WO2018229435A1 - Composition a base de polymere fluore presentant une adhesion amelioree - Google Patents
Composition a base de polymere fluore presentant une adhesion amelioree Download PDFInfo
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- WO2018229435A1 WO2018229435A1 PCT/FR2018/051395 FR2018051395W WO2018229435A1 WO 2018229435 A1 WO2018229435 A1 WO 2018229435A1 FR 2018051395 W FR2018051395 W FR 2018051395W WO 2018229435 A1 WO2018229435 A1 WO 2018229435A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Definitions
- the invention relates to a fluoropolymer-based ink with improved adhesion to a substrate and to the use of this ink in the manufacture of electronic devices.
- Fluorinated polymers such as polyvinylidene fluoride (PVDF) and copolymers derived therefrom have a large number of uses, in particular wherein they are deposited as a film on a substrate.
- PVDF polyvinylidene fluoride
- the deposition of such fluoropolymers in film form can be performed from a formulation called "ink", consisting of a solution of the fluoropolymer, and optionally additives, in a good solvent.
- the document WO 2009/141559 teaches a composition comprising at least one halogenated vinyl polymer (preferably polyvinyl chloride) and at least one copolymer containing units derived from a first monomer rendering the copolymer compatible with the halogenated vinyl polymer, and a second monomer carrying at least one associative group.
- the document discloses the use of the composition in a variety of applications, from stretch films to toys and shoes, to glues and adhesives.
- the document WO 2009/141560 has a content close to the previous one. It teaches a process for preparing a polymer resin by mixing two latices, one formed from at least one halogenated vinyl polymer, and the other formed from a copolymer containing patterns from a first monomer rendering the copolymer compatible with the halogenated vinyl polymer, and a second monomer carrying at least one associative group.
- the invention relates first of all to a composition
- a composition comprising: a PF polymer comprising units derived from vinylidene fluoride; and
- a polymer PA comprising units derived from a (meth) acrylic monomer and units comprising at least one associative group chosen from imidazolidonyl, azoleyl, tazinyl, bis-ureyl and ureido-pyrimidyl groups;
- the polymer PF comprises units derived from trifluoroethylene, the proportion of units originating from trifluoroethylene being preferably from 15 to 55 mol% relative to the sum of the units derived from vinylidene fluoride and trifluoroethylene.
- the polymer PF further comprises units derived from an additional monomer, said additional monomer being preferably chlorotrifluoroethylene or 1,1-chlorofluoroethylene, and the proportion of units derived from the additional monomer being preferably from 1 to 20 mol%, more preferably from 2 to 15 mol%, based on all the units of the polymer PF.
- the polymer PF comprises units derived from hexafluoropropene, preferably in a proportion of 2 to 50 mol%, more preferably 5 to 40 mol%, relative to all the units of the polymer PF.
- the PA polymer comprises:
- a units derived from a first monomer preferably selected from methyl methacrylate, (methoxy) polyethylene glycol (meth) acrylate and acrylonitrile;
- - B units from a second monomer, said units B having an associative group, which is preferably an imidazolidonyl group, and said second monomer is preferably further selected from ethylimidazolidone methacrylate and ethylimidazolidone methacrylamide;
- C units derived from at least a third monomer preferably chosen from (meth) acrylic acid, its esters, its amides or its salts, itaconic acid, its esters, its amides or its salts, and styrene and its derivatives such as 4-styrene sulfonate; the third monomer is preferably ethyl acrylate.
- the PA polymer comprises a molar proportion of 50 to 99% A units, 1 to 20% B units, and 0 to 49% C units.
- the polymer PF is present in a proportion of 70 to 99.9% by weight, and preferably in a weight proportion of 80 to 99% by weight; and the polymer PA is present in a proportion of 0.1 to 30% by weight, and preferably 1 to 20% by weight; the proportions being given with respect to the sum of the polymer PF and the polymer PA.
- the solvent is chosen from dimethylformamide, dimethylacetamide, dimethylsulfoxide and ketones, in particular acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone, and furans, especially tetrahydrofuran; esters, in particular methyl acetate, ethyl acetate, propyl acetate, butyl acetate and propylene glycol methyl ether, carbonates, especially dimethyl carbonate, phosphates, especially triethylphosphate, and mixtures thereof.
- the invention also relates to a method for preparing a composition as described above, comprising dissolving the polymer PF, dissolving the polymer PA and mixing it in the solvent.
- the polymer PA is dissolved in a first portion of the solvent, the polymer PF is dissolved in a second portion of the solvent, and then the first portion of the solvent and the second portion of the solvent are mixed; the first portion of the solvent and the second portion of the solvent being preferably of different compositions.
- the invention also relates to a method for producing a polymer film, comprising depositing the composition described above on a substrate, and evaporation of the solvent from the composition.
- the invention also relates to an electronic device comprising a substrate coated with a polymer film manufactured according to the method described above.
- the polymer film is an electroactive polymer film; or the polymer film is a protective film.
- the electronic device is an optoelectronic device and / or is selected from transistors, in particular field effect, chips, batteries, photovoltaic cells, light-emitting diodes, in particular organic light-emitting diodes, sensors , actuators, transformers, haptics, microelectromechanical systems and detectors.
- the present invention makes it possible to meet the need of the state of the art. More particularly, it provides an ink composition comprising a fluoropolymer dissolved in a solvent, which allows a fluoropolymer film (i.e., a layer) to be manufactured in a simple manner on a substrate having improved adhesion compared to in the state of the art, and with little or no alteration of the properties of the film.
- a fluoropolymer film i.e., a layer
- This is achieved by combining the fluoropolymer with an additional polymer of (meth) acrylic type having associative groups.
- the present inventors have indeed found that many solvents used for the preparation of inks based on fluoropolymers also allow the dissolution of such polymers. The two polymers can therefore be mixed in a simple manner, without resorting to dry mixing techniques such as extrusion or injection.
- the presence of the additional polymer does not substantially affect the properties of the fluoropolymer films, whether they are electroactive properties or planarization or passivation properties. example, depending on the case.
- Another advantage of the invention is that, in certain embodiments, the fluoropolymer layers obtained undergo essentially no discoloration and in particular yellowing, as may be the case with certain adhesion promoters.
- composition according to the invention comprises a polymer PF and a polymer PA, dissolved in a solvent.
- the PF polymer has structural units (or units, or repeating units, or units) that are derived from (i.e. obtained by polymerization of) vinylidene fluoride (VDF) monomers.
- VDF vinylidene fluoride
- the PF polymer is a PVDF homopolymer.
- the polymer PF is a copolymer (in the broad sense), that is to say that it comprises units derived from at least one other X monomer than the VDF.
- a single monomer X may be used, or several different X monomers, depending on the case.
- the monomer X may be of formula wherein each group X1, X2, X3 and X 4 is independently selected from H, Cl, F, Br, I and C1 -C3 alkyl (preferably 01 -02), which are optionally partially or fully halogenated - this monomer X being different from VDF (that is to say that if X1 and X2 represent H, at least one of X 3 and X 4 is not F; and when X1 and X2 represent F, at least one of X 3 and X 4 is not H).
- each X1, X2, X3 and X4 group independently represents an H, F, Cl, I or Br atom, or a methyl group optionally comprising one or more substituents selected from F, Cl, I and Br.
- X4 independently represents an H, F, Cl, I or Br atom.
- only one of X 1, X 2, X 3 and X 4 represents a Cl or I or Br atom, and the other groups X 1, X 2, X 3 and X 4 independently represent: H or F atom or an alkyl group.
- 01 -C3 optionally comprising one or more fluorine substituents; preferably, an H or F atom or a C 1 -C 2 alkyl group optionally comprising one or more fluorine substituents; and more preferably, an H or F atom or a methyl group optionally comprising one or more fluorine substituents.
- the X monomer has a chlorine or bromine atom. It may in particular be chosen from bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene and chlorotrifluoropropene.
- Chlorofluoroethylene may designate either 1-chloro-1-fluoroethylene or 1-chloro-2-fluoroethylene.
- the 1-chloro-1-fluoroethylene isomer (CFE) is preferred.
- the chlorotrifluoropropene is preferably 1-chloro-3,3,3-trifluoropropene (in cis or trans form, preferably trans) or 2-chloro-3,3,3-trifluoropropene.
- the polymer PF comprises units derived from VDF and HFP, or is a polymer P (VDF-HFP) consisting of units derived from VDF and HFP.
- Such a polymer PF is particularly useful for the manufacture of planarization or passivation layers of electronic devices.
- Such a polymer PF may also be useful for the production of electroactive layers.
- the molar proportion of repeating units resulting from HFP is preferably from 2 to 50%, especially from 5 to 40%.
- the copolymer P (VDF-HFP) may especially be as described in the documents WO 01/32726 and US Pat. No. 6,586,547, to which reference is expressly made.
- the PF polymer comprises units derived from VDF and CFE, or CTFE, or TFE, or TrFE, or TFE.
- the molar proportion of repeating units originating from monomers different from VDF is preferably less than 30%, more preferably less than 20%.
- Such a polymer PF is particularly useful for the production of electroactive layers.
- the PF polymer comprises units derived from VDF and TrFE, or is a P (VDF-TrFE) polymer consisting of units derived from VDF and TrFE.
- Such a polymer PF is particularly useful for the production of electroactive layers.
- the polymer PF comprises units derived from VDF, TrFE and another monomer X as defined above, different from VDF and TrFE, or else is a polymer P (VDF-TrFE X) consisting of units derived from VDF, TrFE and another monomer X as defined above, different from VDF and TrFE.
- the other monomer X is chosen from TFE, HFP, trifluoropropenes and in particular 3,3,3-trifluoropropene, tetrafluoropropenes and in particular 2,3,3,3-tetrafluoropropene or 1, 3,3,3-tetrafluoropropene (in cis or preferably trans form), bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene and chlorotrifluoropropene.
- CTFE or CFE are particularly preferred.
- Such a polymer PF is particularly useful for the production of electroactive layers.
- the proportion of units derived from TrFE is preferably from 5 to 95 mol% relative to the sum of the units derived from VDF and TrFE, and in particular: from 5 to 10 mol.%; or from 10 to 15 mol%; or from 15 to 20 mol%; or from 20 to 25 mol%; or from 25 to 30 mol%; or from 30 to 35 mol%; or 35 to 40 mol%; or from 40 to 45 mol%; or 45 to 50 mol%; or from 50 to 55 mol%; or from 55 to 60 mol%; or from 60 to 65 mol%; or from 65 to 70 mol%; or from 70 to 75 mol%; or from 75 to 80 mol%; or from 80 to 85 mol%; or from 85 to 90 mol%; or from 90 to 95 mol%.
- a range of 15 to 55 mol% is particularly preferred.
- the proportion of units derived from this other monomer X in the polymer PF can vary for example from 0.5 to 1 mol%; or from 1 to 2 mol%; or from 2 to 3 mol%; or from 3 to 4 mol%; or from 4 to 5 mol%; or from 5 to 6 mol%; or from 6 to 7 mol%; or from 7 to 8 mol%; or from 8 to 9 mol%; or from 9 to 10 mol%; or from 10 to 12 mol%; or from 12 to 15 mol%; or from 15 to 20 mol%; or from 20 to 25 mol%; or from 25 to 30 mol%; or from 30 to 40 mol%; or from 40 to 50 mol%. Ranges of 1 to 20 mol%, and preferably 2 to 15 mol%, are particularly suitable.
- the molar composition of the units in the fluorinated polymers can be determined by various means such as infrared spectroscopy or RAMAN spectroscopy. Conventional methods for elemental analysis in carbon, fluorine and chlorine or bromine or iodine elements, such as X-ray fluorescence spectroscopy, make it possible to calculate without ambiguity the mass composition of the polymers, from which the molar composition is deduced.
- Multi-core NMR techniques can also be performed by analyzing a solution of the polymer in a suitable deuterated solvent.
- the NMR spectrum is recorded on an FT-NMR spectrometer equipped with a multi-nuclear probe.
- the specific signals given by the different monomers in the spectra made according to one or the other nucleus For example, the unit derived from TrFE gives proton NMR a specific signal characteristic of the CFH group (at about 5-7 ppm, when the solvent is pyridine for example). It is the same for the Chb groups of VDF (massive between 2 - 4 ppm, when the solvent is pyridine for example).
- the relative integration of the two signals gives the relative abundance of the units resulting from the two monomers, that is to say the VDF / TrFE molar ratio.
- the group CF3 for example gives characteristic and well isolated signals in NMR of fluorine.
- the combination of the relative integrations of the different signals obtained by proton NMR and by fluorine NMR leads to a system of equations whose resolution leads to obtaining the molar concentrations of the units resulting from the different monomers.
- the content of units derived from CTFE in a P terpolymer can be determined by a measurement of the chlorine content by elemental analysis.
- the skilled person thus has a range of methods or combination of methods allowing him to determine without ambiguity and with the necessary precision the composition of fluoropolymers.
- the viscosity of the polymer PF is preferably from 0.1 to 100 kPo (kiloPoise) by measuring at 230 ° C. and at 100 s -1 shear rate (according to ASTM D4440, using a PHYSICA MCR301 equipped with two parallel trays).
- the polymer PF is preferably random and linear.
- the polymer PF may be homogeneous or heterogeneous.
- a homogeneous polymer has a uniform chain structure, the statistical distribution of the units from different monomers does not vary substantially between the chains.
- the chains have a distribution in units resulting from the different monomers of the multimodal or spreading type.
- a heterogeneous polymer therefore comprises richer chains in a given unit and poorer chains in this unit.
- An example of a heterogeneous polymer is disclosed in WO 2007/080338.
- the PF polymer can be produced using any known method, such as emulsion polymerization, suspension polymerization and solution polymerization.
- the fluoropolymer comprises units derived from VDF and / or TrFE and another monomer X as described above, it is preferable to use the process described in WO 2010/1 16105. This process allows to obtain polymers of high molecular weight and suitable structuring.
- the preferred method comprises the following steps:
- the radical polymerization initiator may in particular be an organic peroxide of the peroxydicarbonate type. It is generally used in an amount of 0.1 to 10 grams per kilogram of the total monomer charge. Preferably, the amount used is 0.5 to 5 g / kg.
- the initial mixture advantageously comprises only VDF and / or TrFE in a proportion equal to that of the desired final polymer.
- the second mixture preferably has a composition which is adjusted so that the total monomer composition introduced into the autoclave, including the initial mixture and the second mixture, is equal to or approximately equal to the desired final polymer composition.
- the weight ratio of the second mixture to the initial mixture is preferably 0.5 to 2, more preferably 0.8 to 1.6.
- the pressure in the autoclave reactor is preferably 80 to
- the temperature is maintained at a level of preferably 40 ° C to 60 ° C.
- the second mixture can be injected continuously into the autoclave. It can be compressed before being injected into the autoclave, for example by using a compressor or two successive compressors, generally at a pressure higher than the pressure in the autoclave.
- the polymer can be washed and dried.
- the weight average molar mass Mw of the polymer PF is preferably at least 100,000 g. mol “1 , preferably at least 200000 g, mol " 1 and more preferably at least 300000 g. mol “1 or at least 400000 g mol " 1 . It can be adjusted by modifying certain process parameters, such as the temperature in the reactor, or by adding a transfer agent.
- the molecular weight distribution can be estimated by SEC (size exclusion chromatography) with dimethylformamide (DMF) as eluent, with a set of 3 columns of increasing porosity.
- the stationary phase is a styrene-DVB gel.
- the detection method is based on a measurement of the refractive index, and the calibration is performed with polystyrene standards.
- the sample is dissolved in 0.5 g / l in DMF and filtered through a 0.45 ⁇ m nylon filter.
- the polymer PA is an acrylic polymer, that is to say that it comprises at least units derived from a (meth) acrylic monomer.
- the polymer PA comprises units comprising at least one associative group chosen from imidazolidonyl, azazolyl, triazinyl, bis-ureyl and ureido-pyrimidyl groups.
- the units comprising this associative group are preferably themselves derived from a (meth) acrylic monomer.
- the polymer PA comprises at least 50 mol%, more preferably at least 60 mol%, or at least 70 mol%, or at least 80 mol%, or at least 90 mol%, or minus 95 mol%, or at least 98 mol%, of (meth) acrylic monomers.
- the all the polymer PA consists of units derived from (meth) acrylic monomers.
- (meth) acrylic monomer is meant acrylic acid or methacrylic acid and their derivatives, and in particular: alkyl acrylates and methacrylates, hydroxyalkyl acrylates and methacrylates, amides derived from acrylic acid or methacrylic acid, acrylonitrile, glycidyl acrylates and methacrylates ...
- the PA polymer comprises:
- C units derived from at least one third monomer optionally, C units derived from at least one third monomer.
- the first monomer is a (meth) acrylic monomer.
- the first monomer is preferably selected from methyl methacrylate, (methoxy) polyethylene glycol (meth) acrylate and acrylonitrile.
- it is methyl methacrylate.
- the units A derived from the first monomer are preferably present in the polymer PA in a molar proportion of 50 to 99%, more preferably 60 to 97%, more preferably 70 to 95%, and more preferably 80 to 100%. 90%.
- B units carry at least one associative group.
- associative groups is meant groups capable of associating with each other by hydrogen bonds or by pi stacking, or by ionic bonds, or non-Van der Waals bonds, or by halogen bonds, and advantageously by 1 with 6 hydrogen bonds.
- the associative groups used according to the invention are more specifically chosen from imidazolidonyl, azolyl, azinyl, bisureyl and ureido-pyrimidyl groups, and the combinations thereof. Imidazolidonyl groups are preferred.
- the second monomer is a (meth) acrylic monomer.
- the second monomer is more preferably chosen from ethylimidazolidone methacrylate and ethylimidazolidone methacrylamide.
- the units B are preferably present in the polymer PA in a molar proportion of 1 to 20%, more preferably 2 to 15%, more preferably 3 to 12%, and more preferably 5 to 10%.
- the third monomer is preferably a (meth) acrylic monomer as defined above, or itaconic acid, one of its esters, amides or salts, or styrene or one of its derivatives such as 4 styrene sulfonate, or a combination thereof (when the C units are formed from more than one monomer). More preferably, the third monomer is a (meth) acrylic monomer, such as, for example, ethyl acrylate.
- the units C are preferably present in the polymer PA in a molar proportion of 0 to 49%, more preferably 1 to 30%, more preferably 2 to 20%, and more preferably 5 to 10%.
- the polymer PA comprises, in molar proportions:
- the associative groups may be introduced during the polymerization of the PA polymer.
- the polymer PA is thus capable of being obtained by copolymerization of the first monomer with the second monomer bearing the associative groups, and optionally one or more third monomers C.
- Such a polymer PA may be prepared according to known methods of radical polymerization in solution in solvents such as chloroform or tetrahydrofuran or in dispersed medium such as, in particular, in suspension or in aqueous emulsion.
- radical polymerization in suspension or in aqueous emulsion.
- the polymerization can be initiated using free-radical polymerization initiators soluble in the monomer mixture.
- radical generation mechanisms can be implemented such as, for example, thermal decomposition, oxidation-reduction reactions, decomposition caused by electromagnetic radiation and, in particular, radiation in the ultraviolet.
- WO 2009/141559 in particular with regard to:
- examples of possible initiators which may be used in particular at a content of 0.05 to 10% by weight relative to the total weight of the monomers;
- chain transfer agents which are optional (and which are generally used at a content of 0.01 to 10%, and preferably from 0.5 to 2% by weight relative to the total weight of the monomers);
- antioxidants examples include antioxidants, biocides and / or activators of polymerization initiators (which are generally used at a content of 0.01% and 5% by weight relative to the total weight of the monomers);
- suspending agents in the case of suspension polymerization (which are generally used at a content of from 0.05 to 10%, preferably from 0.1 to 5% by weight relative to the total weight of the dispersed phase containing the monomers);
- salts or pH regulators which can be used in combination with the suspending agents (which are generally used at a content of from 0.05 to 5% by weight relative to the total weight of the continuous aqueous phase);
- surfactants or stabilizers useful for aqueous emulsion polymerization which are generally used at a content of 0.1 to 10% by weight relative to the total weight of the monomers
- the polymer PA may be obtained by grafting the associative groups onto an already constituted polymer comprising units A and optionally C, as well as units B 'comprising at least one reactive function, such as a functional group.
- WO 2009/141559 concerning inter alia the conditions of the reaction, and in particular the use of catalysts and additives, the contents of the different species, as well as examples of modification.
- the polymer PA is chosen so as to be compatible with the polymer
- the two polymers form a homogeneous mixture, in that they have a miscibility such that at least the amorphous phase of the polymer PF and the amorphous phase of the polymer PA form only one phase.
- Miscibility can be identified by different analytical methods such as scanning electron microscopy (SEM) or transmission electron microscopy (TEM) or atomic force microscopy (AFM), which allow the identification of inhomogeneities of mixtures in the form of size domains. characteristic greater than 1 micron, which is a sign of immiscibility. It can also be identified by measurements of glass transition temperature (Tg) of the mixture of the two polymers: the miscibility then results in the existence of a single Tg for the mixture.
- Tg glass transition temperature
- Methods for measuring the Tg of polymers and polymer blends include differential scanning calorimetry (DSC), volumetry or dynamic mechanical analysis (DMA).
- PA polymer based on methyl methacrylate is particularly favorable for the polymer PA to be compatible with the polymer PF.
- the polymer PA preferably has a number-average molecular weight of between 5,000 g / mol and 500,000 g / mol, more preferably between 15,000 g / mol and 100,000 g / mol, and particularly preferably between 25,000 g / mol and 50000 g / mol.
- the PA and PF polymers are dissolved in a solvent.
- solution is meant a homogeneous dispersion of the polymers in the solvent, at the molecular level.
- solution is used herein as opposed to a suspension of polymer particles in a liquid vehicle, and as opposed to an emulsion or polymer latex.
- composition comprising the solvent and the polymers PA and PF (and optionally additional compounds such as additives) is also called ink.
- the solvent is chosen from: dimethylformamide; dimethylacetamide; dimethylsulfoxide; ketones, especially acetone, methyl ethyl ketone (or butan-2-one), methyl isobutyl ketone and cyclopentanone; furans, especially tetrahydrofuran; esters, especially methyl acetate, ethyl acetate, propyl acetate, butyl acetate and propylene glycol methyl ether; carbonates, especially dimethyl carbonate; phosphates, especially triethylphosphate. Mixtures of these compounds can also be used.
- the weight proportion of polymer (s) PF relative to the sum of the polymer (s) PA and PF in the composition may be in particular: from 50 to 60%, or from 60 to 70%, or from 70 to 75%, or 75 to 80%, or 80 to 85%, or 85 to 90%, or 90 to 95%, or 95 to 98%, or 98 to 99%, or 99 to 99.9%.
- the mass proportion of polymer (s) PA relative to the sum of the polymer (s) PA and PF in the composition may be in particular: from 0.1 to 1%, or from 1 to 2%, or from 2 to 5%, or 5 to 10%, or 10 to 15%, or 15 to 20%, or 20 to 25%, or 25 to 30%, or 30 to 40%, or 40 to 50% %.
- the composition preferably contains from 0.1 to 60%, preferably from 0.5 to 30%, more preferably from 1 to 20%, more preferably from 3 to 15% by weight of polymers PA and PF (together). , relative to the total composition.
- the ink may optionally comprise one or more additives, especially chosen from surface-tension modifiers, rheology-modifying agents, aging-modifying agents, adhesion-modifying agents, pigments or dyes. , charges (including nanofillers).
- Preferred additives include co-solvents modifying the surface tension of the ink. In particular, it may be organic compounds miscible with the solvents used. Examples are compounds of the family of linear or cyclic alkanes such as heptane and cyclohexane, decane or dodecane, and aromatic compounds such as toluene or ethylbenzene.
- the ink composition may also contain one or more additives used for the synthesis of the polymer (s).
- the ink comprises at least one crosslinking aid additive preferably chosen from radical initiators, co-agents such as bifunctional molecules. or polyfunctional in terms of reactive double bonds, basic crosslinking agents such as di-amines, and combinations thereof.
- crosslinking aid additive preferably chosen from radical initiators, co-agents such as bifunctional molecules. or polyfunctional in terms of reactive double bonds, basic crosslinking agents such as di-amines, and combinations thereof.
- a photoinitiator may be used, for example chosen from 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyl-diphenylphosphineoxide, 2,4, 6-trimethylbenzoylphenyl phosphinate, 1-hydroxy-cyclohexyl-phenyl-ketone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentyl phosphine oxide, 1- [4- (2-hydroxyethoxy) - phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1 [4- (methylthio) phenyl] Morpholinopropan-1-one, 2,4-diethylthioxanthone, their derivatives, and mixtures thereof.
- bi- or polyfunctional (meth) acrylic monomers or oligomers in terms of reactive double bonds.
- These bi- or polyfunctional (meth) acrylic monomers or oligomers may have chemical structures derived from functions other than the strict alkane chemistry, such as diols, triols or polyols, polyesters, ethers, polyethers, polyurethanes, epoxys, cyanurates or isocyanates. cyanurates.
- no crosslinking aid additive such as a photoinitiator or a crosslinking agent, is present in the ink.
- the total content of additives is preferably less than 20% by weight, more preferably less than 10% by weight, based on total PA, PF polymers and additives.
- the ink preferably has a nonvolatile solids content of 0.1 to 60%, preferably 0.5 to 30%, more preferably 1 to 20%, more preferably 3 to 15% by weight. .
- the ink composition according to the invention can be prepared by dissolving the polymer PA, dissolving the polymer PF, and mixing.
- the dissolution of the polymers PA and PF may be simultaneous or not as described below.
- the temperature applied during this preparation is preferably 0 to 60 ° C, more preferably 10 to 50 ° C, more preferably 15 to 40 ° C, and most preferably 20 to 30 ° C.
- the preparation is performed at room temperature.
- the preparation is carried out with moderate agitation.
- the PA polymer is dissolved in the solvent on one side, and the PF polymer is dissolved in the same solvent on the other side, and then the two solutions are mixed.
- the solvent used may be formed by a single compound or a mixture of compounds miscible with each other.
- one of the polymers PA and PF is dissolved in the solvent, then the other PA and PF polymers is added to the solution and dissolved in turn.
- the solvent used may be formed by a single compound or a mixture of compounds miscible with each other.
- the solvent of the ink composition is a mixture of a first solvent and a second solvent of different compositions and miscible with each other.
- the polymer PA is dissolved in the first solvent to form a first solution
- the polymer PF is dissolved in the second solvent to form a second solution
- the first solution and the second solution are mixed to form the ink composition of the invention.
- the first solvent and the second solvent may each be formed by a single compound or a mixture of miscible compounds between them.
- the first solvent and the second solvent may each be formed by mixtures of the same compounds, in different proportions between the first solvent and the second solvent.
- additives When additives are to be added to form the ink composition of the invention, they may be added before, during or after the dissolution of the PA and PF polymers.
- the substrate on which the ink is deposited may in particular be a surface of glass, or of silicon, or of quartz, or of polymeric material (in particular polyethylene terephthalate or polyethylene naphthalate), or of metal, or a mixed surface composed of several materials different.
- the application of the ink may comprise spreading by discrete or continuous means.
- the deposition may be carried out in particular by coating by centrifugation ("spin-coating"), by spraying or atomizing (“spray coating”), by coating, in particular with a bar or a film puller (“bar coating”), by coating with slit, dip coating, roll-to-roll printing, screen printing, flexographic printing, lithographic printing or jet printing ink.
- the solvent is evaporated after the deposition.
- the polymer layer then solidifies to form a continuous film, by interdiffusion of the polymer molecules.
- the evaporation can be carried out at room temperature and / or by heating at a temperature preferably from 30 to 200 ° C, more preferably from 50 to 180 ° C, more preferably from 80 to 160 ° C.
- the layer may be vented to facilitate evaporation.
- the duration of the evaporation can be, for example, from 1 minute to 24 hours, preferably from 5 minutes to 5 hours, more preferably from 10 minutes to 2 hours.
- An annealing step may be carried out after evaporation of the solvent, for example to allow crystallization of the polymer.
- the annealing may in particular be carried out by subjecting the deposited layer to a temperature of 50 to 200 ° C., preferably of 80 to 180 ° C., more preferably of 100 to 160 ° C., in particular of 120 to 150 ° C.
- the fluoropolymer / polymer layer carrying associative units, thus formed may in particular have a thickness of 50 nm to 100 ⁇ m, preferably 200 nm to 50 ⁇ m, and more preferably 500 nm to 20 ⁇ m.
- a crosslinking step can be carried out by subjecting the layer to radiation, such as X, gamma, UV radiation or by thermal activation if the annealing step is not sufficient.
- radiation such as X, gamma, UV radiation or by thermal activation if the annealing step is not sufficient.
- UV irradiation is used.
- all or part of the radiation having a wavelength in a spectral range of 150 to 410 nm, preferably 315 to 410 nm.
- the irradiation comprises wavelengths at 365 nm and / or at 385 nm and / or 405 nm. More preferably, the dose of radiation applied is less than 20 J / cm 2 , or even less than 10 J / cm 2 .
- the film according to the invention can be used as an electroactive layer and / or as a dielectric layer in an electronic device, and in particular when the polymer PF is a P (VDF-TrFE) or P (VDF-TrFE) copolymer -CFE) or P (VDF-TrFE-CTFE) as described above.
- the film according to the invention thus advantageously has a dielectric permittivity at 25 ° C. and 1 kHz greater than 8, preferably greater than 10 and more particularly greater than 12.
- the film advantageously also has a saturation polarization greater than 30 mC / m. 2 , preferably greater than 50 mC / m 2 .
- the dielectric permittivity measurement can be carried out by means of a LCF meter Sefelec LCR 819, which makes it possible to measure a capacitance which is proportional to the permittivity.
- the saturation polarization can be obtained by applying an alternating electric field of increasing amplitude and a frequency of 50 mHz by means of electrodes on a surface of 1 mm 2 of the film.
- the current passing through the sample is measured as a function of the electric field applied via a precision ammeter. The current measurement provides access to the saturation polarization.
- One or more additional layers may be deposited on the substrate provided with the film of the invention, for example one or more layers of polymers, semiconductor materials, or metals, in a manner known per se.
- the term electronic device is either a single electronic component or a set of electronic components, capable (s) to perform one or more functions in an electronic circuit. According to certain variations, the electronic device is more particularly an optoelectronic device, that is to say capable of emitting, detecting or controlling electromagnetic radiation.
- Examples of electronic devices, or possibly optoelectronic devices, concerned by the present invention are transistors (in particular field effect), chips, batteries, photovoltaic cells, light-emitting diodes (LEDs), organic light-emitting diodes ( OLED), sensors, actuators, transformers, haptic devices, electromechanical microsystems and detectors.
- transistors in particular field effect
- chips batteries, photovoltaic cells, light-emitting diodes (LEDs), organic light-emitting diodes (OCLED), sensors, actuators, transformers, haptic devices, electromechanical microsystems and detectors.
- Electronic and optoelectronic devices are used and integrated in many electronic devices, equipment or subassemblies and in many objects and applications such as televisions, mobile phones, rigid or flexible screens, thin-film photovoltaic modules, lighting sources, energy sensors and converters, etc.
- the layer may be used as a protective coating (or encapsulation) for an electronic device, and especially when the polymer PF is a P copolymer (VDF-HFP) as described above.
- a protective coating may be used alone or in combination with other protective films.
- the electronic device may in particular comprise a substrate and electronic elements supported on it, which may comprise layers of conductive material, semiconductor material and the like.
- the electronic elements are preferably on one side of the substrate but in some embodiments they may be on both sides of the substrate.
- the layer may cover all or part of the electronic elements, and all or part of the substrate.
- the layer covers at least a portion of the substrate and at least a portion of the electronic elements, and performs a planarizing function.
- the layer may cover only one of the two faces of the substrate (preferably the face which comprises the electronic elements), in whole or in part, or alternately the two faces of the substrate, in whole or in part.
- the electronic device When the layer is used as a protective coating for an electronic device, the electronic device may be of the same type as above.
- a stirred glass reactor with a jacket in which circulates a heat transfer fluid for heating the reactor contents and optionally cooling and also provided with a vapor condensation system (reflux) with the aid of a water-cooled refrigerant, and a nitrogen sparge system, are introduced 80.51 g of methyl ethyl ketone (MEK), 13.32 g of an electroactive fluorinated copolymer of relative molar composition determined by spectroscopy nuclear magnetic resonance (NMR) of 80 ⁇ 2% of units derived from VDF and 20 ⁇ 2% of units derived from TrFE, and 0.35 g of a methacrylic copolymer bearing associative groups of relative molar composition determined by spectroscopy of 85 ⁇ 2% nuclear magnetic resonance (NMR) units derived from methyl methacrylate, 7.5 ⁇ 1% of units derived from ethyl acrylate and 7.5 ⁇ 1% of units derived from ethyl methacrylate imidazo lidone (MEIO
- Polymer films are prepared by coating with a bar, a glass plate from the above solution.
- the glass plate is deposited in a ventilated grid, at room temperature, for 30 minutes, to allow at least partial evaporation of the solvent. It is then placed 20 minutes in a ventilated oven previously heated to 140 ° C to allow total evaporation of the solvent.
- Example 2 an ink is made and a polymer layer is deposited in the same manner as in Example 1, but omitting the methacrylic copolymer.
- the polymer layers according to Example 1 and according to Example 2, of approximately 20 ⁇ , are tested as follows.
- the adhesion properties of the layer on the glass plate are evaluated according to the ASTM D3359 ("tape test") test, using an ERICHSEN Model 259 grid comb.
- the measurement of the piezoelectric coefficient d33 performed on a Berlincourt piezometer, makes it possible to check the influence of the addition of the additive on the piezoelectric properties.
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- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Paints Or Removers (AREA)
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- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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KR1020207001043A KR102646306B1 (ko) | 2017-06-15 | 2018-06-13 | 개선된 접착성을 갖는 플루오르화 폴리머-기반 조성물 |
JP2019569240A JP7376365B2 (ja) | 2017-06-15 | 2018-06-13 | 改良された接着性を有するフッ素化ポリマーをベースとするインク |
CN201880039633.XA CN110741042A (zh) | 2017-06-15 | 2018-06-13 | 粘附性提高的基于氟化聚合物的墨 |
US16/622,422 US11827778B2 (en) | 2017-06-15 | 2018-06-13 | Ink based on fluorinated polymer having improved adhesion |
EP18748965.3A EP3638732A1 (fr) | 2017-06-15 | 2018-06-13 | Composition a base de polymere fluore presentant une adhesion amelioree |
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FR1755434A FR3067715B1 (fr) | 2017-06-15 | 2017-06-15 | Encre a base de polymere fluore presentant une adhesion amelioree |
FR1755434 | 2017-06-15 |
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WO2018229435A1 true WO2018229435A1 (fr) | 2018-12-20 |
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PCT/FR2018/051395 WO2018229435A1 (fr) | 2017-06-15 | 2018-06-13 | Composition a base de polymere fluore presentant une adhesion amelioree |
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US (1) | US11827778B2 (fr) |
EP (1) | EP3638732A1 (fr) |
JP (1) | JP7376365B2 (fr) |
KR (1) | KR102646306B1 (fr) |
CN (1) | CN110741042A (fr) |
FR (1) | FR3067715B1 (fr) |
TW (1) | TWI770183B (fr) |
WO (1) | WO2018229435A1 (fr) |
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CN114181565A (zh) * | 2021-10-21 | 2022-03-15 | 嘉兴聚鑫隆科技有限公司 | 用于柔性传感器的压电基材及其制造工艺 |
CN117529132A (zh) * | 2022-07-25 | 2024-02-06 | Tcl科技集团股份有限公司 | 复合材料、复合材料薄膜、发光二极管以及显示装置 |
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WO2001032726A1 (fr) | 1999-11-03 | 2001-05-10 | Atofina Chemicals, Inc. | Copolymeres de hexafluoropropylene de fluorure de vinylidene a faible cristallinite |
WO2007080338A2 (fr) | 2006-01-13 | 2007-07-19 | Arkema France | Agent d'extrusion a base d'un pvdf heterogene |
FR2930947A1 (fr) * | 2008-05-07 | 2009-11-13 | Arkema France | Composition renfermant un polymere vinylique halogene et un copolymere porteur de groupes associatifs |
WO2009141560A2 (fr) | 2008-05-07 | 2009-11-26 | Arkema France | Procédé de préparation d'un mélange de polymère halogéné et de copolymère porteur de groupes associatifs |
WO2010116105A1 (fr) | 2009-04-09 | 2010-10-14 | Piezotech | Procede de fabrication de terpolymeres a base de vdf,trfe, et cfe ou ctfe |
FR3031519A1 (fr) * | 2015-01-14 | 2016-07-15 | Arkema France | Composition a base de terpolymere electroactif |
Family Cites Families (8)
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US20040002559A1 (en) * | 2002-04-10 | 2004-01-01 | Malisa Troutman | Flame retardant coatings |
US7399533B2 (en) | 2005-01-21 | 2008-07-15 | Arkema Inc. | Polyvinylidene fluoride coating for metal substrates |
WO2008103226A1 (fr) | 2007-02-22 | 2008-08-28 | Dow Corning Corporation | Films de résine de silicone renforcés |
JP2009227719A (ja) * | 2008-03-19 | 2009-10-08 | Fujifilm Corp | インクジェット記録用水性インク |
CN102083876B (zh) | 2008-07-07 | 2014-01-01 | 阿科玛股份有限公司 | 具有改进的薄膜成形性的氟聚合物水性混杂组合物 |
JP6944247B2 (ja) | 2014-02-20 | 2021-10-06 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングMerck Patent Gesellschaft mit beschraenkter Haftung | 触媒溶液から繊維を調製する方法、およびかかる繊維を含む物品 |
CN106661180B (zh) * | 2014-07-01 | 2020-05-19 | 阿科玛股份有限公司 | 稳定的水性氟聚合物涂料组合物 |
FR3055472B1 (fr) | 2016-08-29 | 2019-03-15 | Arkema France | Protection de dispositifs electroniques |
-
2017
- 2017-06-15 FR FR1755434A patent/FR3067715B1/fr active Active
-
2018
- 2018-05-31 TW TW107118662A patent/TWI770183B/zh active
- 2018-06-13 EP EP18748965.3A patent/EP3638732A1/fr active Pending
- 2018-06-13 CN CN201880039633.XA patent/CN110741042A/zh active Pending
- 2018-06-13 US US16/622,422 patent/US11827778B2/en active Active
- 2018-06-13 KR KR1020207001043A patent/KR102646306B1/ko active IP Right Grant
- 2018-06-13 WO PCT/FR2018/051395 patent/WO2018229435A1/fr unknown
- 2018-06-13 JP JP2019569240A patent/JP7376365B2/ja active Active
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WO2001032726A1 (fr) | 1999-11-03 | 2001-05-10 | Atofina Chemicals, Inc. | Copolymeres de hexafluoropropylene de fluorure de vinylidene a faible cristallinite |
US6586547B1 (en) | 1999-11-03 | 2003-07-01 | Atofina Chemicals, Inc. | Low crystallinity vinylidene fluoride hexafluoropropylene copolymers |
WO2007080338A2 (fr) | 2006-01-13 | 2007-07-19 | Arkema France | Agent d'extrusion a base d'un pvdf heterogene |
FR2930947A1 (fr) * | 2008-05-07 | 2009-11-13 | Arkema France | Composition renfermant un polymere vinylique halogene et un copolymere porteur de groupes associatifs |
WO2009141559A1 (fr) | 2008-05-07 | 2009-11-26 | Arkema France | Composition renfermant un polymère vinylique halogéné et un copolymère porteur de groupes associatifs. |
WO2009141560A2 (fr) | 2008-05-07 | 2009-11-26 | Arkema France | Procédé de préparation d'un mélange de polymère halogéné et de copolymère porteur de groupes associatifs |
WO2010116105A1 (fr) | 2009-04-09 | 2010-10-14 | Piezotech | Procede de fabrication de terpolymeres a base de vdf,trfe, et cfe ou ctfe |
FR3031519A1 (fr) * | 2015-01-14 | 2016-07-15 | Arkema France | Composition a base de terpolymere electroactif |
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Publication number | Publication date |
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FR3067715A1 (fr) | 2018-12-21 |
TWI770183B (zh) | 2022-07-11 |
KR20200019684A (ko) | 2020-02-24 |
FR3067715B1 (fr) | 2019-07-05 |
JP7376365B2 (ja) | 2023-11-08 |
CN110741042A (zh) | 2020-01-31 |
EP3638732A1 (fr) | 2020-04-22 |
US20200207970A1 (en) | 2020-07-02 |
JP2020523460A (ja) | 2020-08-06 |
TW201905072A (zh) | 2019-02-01 |
KR102646306B1 (ko) | 2024-03-08 |
US11827778B2 (en) | 2023-11-28 |
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