EP3898713A1 - Crosslinkable electroactive fluorinated polymers comprising photoactive groups - Google Patents
Crosslinkable electroactive fluorinated polymers comprising photoactive groupsInfo
- Publication number
- EP3898713A1 EP3898713A1 EP19845701.2A EP19845701A EP3898713A1 EP 3898713 A1 EP3898713 A1 EP 3898713A1 EP 19845701 A EP19845701 A EP 19845701A EP 3898713 A1 EP3898713 A1 EP 3898713A1
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- acrylate
- copolymer
- monomers
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
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- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
- C08F214/222—Vinylidene fluoride with fluorinated vinyl ethers
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- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/182—Monomers containing fluorine not covered by the groups C08F214/20 - C08F214/28
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- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
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- C08F8/00—Chemical modification by after-treatment
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- C08F8/00—Chemical modification by after-treatment
- C08F8/06—Oxidation
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- 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
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- 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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- 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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- 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
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- 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
- C09D127/22—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 modified by chemical after-treatment
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
- H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
- H10N30/077—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition
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- 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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
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- C08F2810/00—Chemical modification of a polymer
- C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Definitions
- the present invention relates to crosslinkable electroactive fluoropolymers comprising photoactive groups, a process for their preparation, as well as films made therefrom.
- Electroactive fluoropolymers or PFEAs are mainly derivatives of polyvinylidene fluoride (PVDF). See in this regard the article Vinylidene fluoride- and trifluoroethylene-containing fluorinated electroactive copolymers. How does chemistry impact properties? de Soulestin et al. in Prog. Polym. Sci. 2017 (DOI: 10.1016 / d. Progpolymsci.2017.04.004). These polymers have particularly advantageous dielectric and electro-mechanical properties.
- the fluorinated copolymers formed from vinylidene fluoride (VDF) and trifluoroethylene (TrFE) monomers are particularly advantageous thanks to their piezoelectric, pyroelectric and ferroelectric properties. They allow in particular to convert mechanical or thermal energy into electrical energy or vice versa.
- Electroactive fluoropolymers are shaped as films, usually by deposition from a so-called "ink" formulation.
- insoluble When manufacturing electroactive devices, it may be necessary to make part or all of the film insoluble according to a predefined pattern. Indeed, it is often necessary to deposit other layers on top of the polymer film, in order to manufacture the desired device. This deposition of other layers often involves the use of a solvent. If the electroactive fluoropolymer is not crosslinked, it can be damaged by this solvent when the other layers are deposited.
- Tan’s article was published in J. Mat. Chem. > 42013 (p.10353-10361) describes the crosslinking of a copolymer P (VDF-TrFE) by heat treatment in the presence of a peroxide compound.
- crosslinking by heat treatment presents the risk of destroying one or more layers of a multilayer electronic device because of the treatment by heating the device.
- the heat treatment does not make it possible to obtain films having defined patterns, since this mode of crosslinking makes selective crosslinking impossible.
- Such irradiation is very energetic and is therefore capable of causing secondary chemical reactions altering the structure of the polymer chains.
- crosslinking requires the presence of a crosslinking agent in addition to the polymer.
- This agent complicates the preparation of the polymer film and can lead to degradation electroactive properties. It is generally desirable to reduce the number of components used in the formulation for the preparation of the polymer film.
- Document WO 2013/087501 relates to a composition comprising a fluoropolymer comprising units from VDF and TrFE and a crosslinking agent comprising azide groups.
- WO 2010/021962 describes fluoropolymers comprising azide groups, which can be obtained either by reaction of a fluoropolymer with an azide compound, or by polymerization of monomers in the presence of an azide compound.
- fluoropolymers provided in the document are copolymers based on VDF and HFP (hexafluoropropylene), or iodinated-terminated polymers (PVDF-I and 1-iodo-perfluorooctane) reacting with sodium azide.
- the invention relates first of all to a copolymer comprising units derived from fluorinated monomers of formula (I):
- each of Xi, X 2 , X 3 and X4 is independently chosen from H, F and alkyl groups comprising from 1 to 3 carbon atoms which are optionally partially or completely fluorinated, the H and / or F atoms of the fluorinated monomers being partially replaced by photoactive groups of formula -Y-Ar-R, in the copolymer;
- Y representing an O atom, or an S atom, or an NH group
- Ar representing an aryl group, preferably a phenyl group, and R being a monodentate or bidentate group comprising from 1 to 30 carbon atoms.
- the fluorinated monomers of formula (I) include vinylidene fluoride and / or trifluoroethylene, and preferably consist of vinylidene fluoride and trifluoroethylene.
- the copolymer comprises both units derived from vinylidene fluoride monomers and units derived from trifluoroethylene monomers, the proportion of units derived from trifluoroethylene monomers preferably being from 15 to 55 mol.% relative to the sum of the units derived from vinylidene fluoride and trifluoroethylene monomers.
- the group Ar is substituted by the group R in the ortho position relative to Y, and / or in the meta position relative to Y, and / or in the para position relative to Y.
- the group R comprises a carbonyl function and preferably is chosen from an acetyl group, a substituted or unsubstituted benzoyl group, a substituted or unsubstituted phenylacetyl group, a phthaloyl group, and an acyl group of phosphine oxide ; the phosphine being substituted by one or more groups chosen from a methyl group, an ethyl group, and a phenyl group.
- the group Ar is a phenyl substituted in the meta position and the group R is an unsubstituted benzoyl group, or the group Ar is a phenyl substituted in the para position and the group R is a non-substituted benzoyl group , or the group Ar is a phenyl substituted in the para position and the group R is a benzoyl group substituted in the para position by a hydroxy group, or the group Ar is a phenyl substituted in the meta position and the group R is an acetyl group, or the group Ar is a phenyl substituted in the para position and the group R is an acetyl group, or the group Ar is a phenyl substituted in the ortho position and the group R is a phenylacetyl group substituted in the position a of the carbonyl group by a hydroxy group, or the group Ar is a phenyl substituted in the meta position and the group R is a
- the molar proportion of H and F atoms of the fluorinated monomer of formula (I) in the copolymer replaced by photoactive groups of formula -Y-Ar-R is from 0.1 to 20%, preferably from 1 to 10%, and more preferably from 2 to 8%.
- the invention also relates to a process for the preparation of a copolymer as described above, comprising:
- CXiX2 CX3X4 in which each of the Xi, X2, X3 and X4 is independently chosen from H, F and alkyl groups comprising from 1 to 3 carbon atoms which are optionally partially or completely fluorinated;
- the photoactive molecule being of formula FIY-Ar-R in which Y represents an O atom, or an S atom, or an NH group, Ar represents an aryl group, preferably a phenyl group and R a monodentate or bidentate group comprising from 1 to 30 carbon atoms.
- the contacting is carried out in a solvent preferably chosen from: dimethylsulfoxide; dimethylformamide; dimethylacetamide; ketones, including acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone; furans, especially tetrahydrofuran; esters, including methyl acetate, ethyl acetate, propyl acetate, butyl acetate and propylene acetate glycol methyl ether; carbonates, in particular dimethylcarbonate; phosphates, in particular triethylphosphate.
- a solvent preferably chosen from: dimethylsulfoxide; dimethylformamide; dimethylacetamide; ketones, including acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone; furans, especially tetrahydrofuran; esters, including methyl acetate, ethyl acetate, propyl
- the method further comprises a step of reacting the photoactive molecule with a base before bringing the starting copolymer into contact with the photoactive molecule, the base preferably being potassium carbonate.
- the contacting of the starting copolymer with the photoactive molecule is carried out at a temperature of 20 to 120 ° C, and preferably from 30 to 90 ° C.
- the invention also relates to a composition
- a composition comprising the copolymer as described above, in which the composition is a solution or dispersion of the copolymer in a liquid vehicle.
- the composition also comprises a second copolymer comprising units derived from fluorinated monomers of formula (I):
- each of Xi, X 2 , X 3 and X4 is independently chosen from H, F and alkyl groups comprising from 1 to 3 carbon atoms which are optionally partially or completely fluorinated.
- the fluorinated monomers of formula (I) of the second copolymer comprise vinylidene fluoride and / or trifluoroethylene, and preferably consist of vinylidene fluoride and trifluoroethylene.
- the second copolymer comprises both units originating from vinylidene fluoride monomers and units originating from trifluoroethylene monomers, the proportion of units originating from trifluoroethylene monomers preferably being from 15 to 55 mol. % relative to the sum of the units derived from vinylidene fluoride and trifluoroethylene monomers.
- the composition comprises from 5 to 95% by weight of copolymer as described above and from 5 to 95% by weight of second copolymer; preferably from 30 to 70% by weight of copolymer as described above and from 30 to 70% by weight of second copolymer; the contents being expressed relative to the sum of the copolymer as described above and of the second copolymer.
- the composition also comprises at least one bi or polyfunctional (meth) acrylic monomer in terms of reactive double bonds.
- said bi or polyfunctional (meth) acrylic monomer in terms of reactive double bonds is a monomer or an oligomer containing at least two reactive double bonds of (meth) acrylic type or a bi (meth) acrylic monomer or oligomer or polyfunctional chosen from diols, triols or polyols, polyesters, ethers, polyethers, polyurethane, epoxies, cyanurates or iso-cyanurates.
- said (meth) acrylic monomer is chosen from the list of following compounds: dodecane dimethacrylate, 1, 3-butylene glycol di (meth) acrylate, butanediol di (meth) acrylate, 1, 6-hexanediol di ( meth) acrylate, hexanediol alkoxylated di (meth) acrylate, neopentyl glycol alkoxylated di (meth) acrylate, dodecyl di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, linear alkanes di (meth) acrylate, bisphenol A ethoxylated di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclo
- the invention also relates to a process for manufacturing a film, comprising:
- the crosslinking is carried out according to a predefined pattern, the method then comprising the elimination of parts of copolymer or of non-crosslinked composition (e), by contacting with a solvent.
- the invention also relates to a film obtained by the above process.
- the invention also relates to an electronic device comprising a film as described above, the electronic device preferably being chosen from field effect transistors, memory devices, capacitors, sensors, actuators, electromechanical microsystems and haptic devices.
- the present invention overcomes the drawbacks of the state of the art. It more particularly provides electroactive fluorinated polymers having the useful properties mentioned above (piezoelectric, pyroelectric and ferroelectric), which can subsequently be effectively crosslinked while essentially retaining these useful properties after crosslinking.
- the invention makes it possible to obtain insoluble polymer films, with predefined patterns. These predefined patterns can be obtained for example by means of UV irradiation which allows the crosslinking of a part of the polymer film, followed by a development step so as to eliminate the non-crosslinked parts.
- the invention makes it possible to carry out crosslinking without resorting to excessive energy irradiation, thus avoiding the degradation of other layers in multilayer electrical devices, and without necessarily adding a crosslinking agent.
- the presence of a crosslinking co-agent can be advantageous since the photoactive groups present in the copolymer can make it possible to initiate a radical polymerization reaction.
- the invention is based on the use of copolymers comprising units derived from fluorinated monomers of formula (I). Part of the H and / or F atoms of the copolymer is replaced by photoactive groups of formula -Y-Ar-R, which allow crosslinking. This replacement can be carried out in a simple manner by reaction of the copolymer with a photoactive molecule which contains a photoactive group. The rest of the H and / or F atoms are retained.
- An advantage of the invention is that it makes it possible to obtain crosslinkable polymers from ranges of existing polymers, the synthesis of which is perfectly mastered, without therefore having to develop new polymerization processes.
- FIG. 1 represents a graph showing the infrared spectra in absorbance of polymer according to Example 1 before (A) and after (B) modification with the photoactive groups of formula -O-Ar-R.
- the wave number in cm 1 is indicated on the abscissa axis.
- FIG. 2 represents a graph showing the 1 H NMR spectra of the polymer according to Example 1 before (A) and after (B) modification with the photoactive groups of formula -O-Ar-R. The chemical displacement in ppm is indicated on the abscissa axis.
- FIG.3 represents a photo under an optical microscope of the layer of crosslinked modified polymer according to Example 2.
- FIG. 4 represents the ferroelectric hysteresis measured at 20 ° C, 0.1 Hz and 2000 V, of the layer of crosslinked modified polymer according to example 2.
- the ordinate axis corresponds to the displacement in pC.cnr 2 and the abscissa axis at V voltage.
- PF polymers fluoropolymers
- These PF polymers can be used as starting polymers and modified to graft photoactive groups of formula -Y-Ar-R therefrom; the fluorinated polymers thus modified are designated PFM polymers below.
- a PF polymer comprises units derived from fluorinated monomers of formula (I):
- each of Xi, X 2 , X 3 and X4 is independently chosen from H, F and alkyl groups comprising from 1 to 3 carbon atoms which are optionally partially or completely fluorinated.
- the fluorinated monomer of formula (I) contains at least one fluorine atom.
- the fluorinated monomer of formula (I) preferably has at most 5 carbon atoms, more preferably at most 4 carbon atoms, more preferably at most 3 carbon atoms, and more preferably it has 2 carbon atoms.
- each group Xi, X2, X3, X4 independently represents an H, F atom, or a methyl group optionally comprising one or more substituents chosen from H and F.
- each group X1, X2, X3, X4 independently represents an H or F atom.
- the fluorinated monomer of formula (I) is chosen from vinyl fluoride (VF), vinylidene fluoride (VDF), trifluoroethylene (TrFE), tetrafluoroethylene (TFE), hexafluoropropylene (HFP) , trifluoropropenes and in particular 3,3,3-trifluoropropene, tetrafluoropropenes and in particular 2,3,3,3-tetrafluoropropene or
- the most preferred fluorinated monomers of formula (I) are vinylidene fluoride (VDF) and trifluoroethylene (TrFE).
- the polymer PF is a polymer P (VDF).
- the polymer PF is a polymer P (TrFE).
- units from two or more different fluorinated monomers of formula (I) may be present in the polymer PF.
- the PF polymer comprise units from both VDF and TrFE.
- the polymer PF is a copolymer P (VDF-TrFE).
- the proportion of units from TrFE is preferably from 5 to 95 mol.% Relative to the sum of the units 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 from 35 to 40 mol.%; or from 40 to 45 mol.%; or from 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 85 at 90 mol.%; or from 90 to 95 mol.%.
- a range of 15 to 55 mol.% Is particularly preferred.
- the polymer PF consists of units derived from fluorinated monomers of formula (I).
- the molar composition of the units in the PF polymers can be determined by various means such as infrared spectroscopy or RAMAN spectroscopy. Conventional methods of elementary analysis of carbon or fluorine elements, such as X-ray fluorescence spectroscopy, allow the mass composition of polymers to be calculated unambiguously, from which the molar composition is deduced.
- the group -CFH- of TrFE for example gives characteristic and well isolated signals in NMR of fluorine.
- the combination of the relative integrations of the different signals obtained in proton NMR and in fluorine NMR leads to a system of equations whose resolution leads to the obtaining of molar concentrations of the units derived from the different monomers.
- a person skilled in the art thus has a range of methods or a combination of methods allowing him to determine without ambiguity and with the necessary precision the composition of the PF polymers.
- the polymer PF is preferably random and linear.
- thermoplastic and little or no elastomeric (as opposed to a fluoroelastomer).
- the polymer PF can be homogeneous or heterogeneous.
- a homogeneous polymer has a uniform chain structure, the statistical distribution of the units from the different monomers practically not varying between the chains.
- the chains have a distribution in units from the different monomers multimodal or spread type.
- a heterogeneous polymer therefore comprises chains richer in a given unit and chains poorer in this unit.
- An example of a heterogeneous polymer is given in document WO 2007/080338.
- the PF polymer is an electroactive polymer.
- the senor has a maximum dielectric permittivity of 0 to 150 ° C, preferably of 10 to 140 ° C.
- this maximum is called “Curie temperature” and corresponds to the transition from a ferroelectric phase to a paraelectric phase.
- This maximum temperature, or transition temperature can be measured by differential scanning calorimetry or by dielectric spectroscopy.
- the melting temperature has a melting temperature of 90 to 180 ° C, more particularly from 100 to 170 ° C.
- the melting temperature can be measured by differential scanning calorimetry according to standard ASTM D3418.
- the PF polymer can be produced using any known method, such as emulsion polymerization, suspension polymerization and solution polymerization.
- the weight average molecular weight Mw of the polymer is preferably at least 100,000 g. mol 1 , preferably at least 200,000 g. mol 1 and more preferably at least 300,000 g. mol 1 or at least 400,000 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) in dimethylformamide (DMF) as eluent, with a set of 3 columns of increasing porosity.
- the stationary phase is a styrene-DVB gel.
- the detection process is based on a measurement of the refractive index, and the calibration is carried out with polystyrene standards.
- the sample is dissolved in 0.5 g / L in DMF and filtered through a 0.45 ⁇ m nylon filter.
- the PFM polymer can be produced from a PF polymer by reaction with a photoactive molecule of formula HY-Ar-R, so that integrate into the polymer chain photoactive groups of formula -Y-Ar-R, in which Y represents an O atom, or an S atom, or an NH group, Ar represents an aryl group, preferably a phenyl group and R is a monodentate or bidentate grouping comprising from 1 to 30 carbon atoms.
- single-toothed group is meant a group which binds to the group Ar via a single atom of this group R.
- identity group is meant a group which binds to the group Ar via two different atoms of this group R, preferably at two different positions of the group Ar.
- the group Ar may be substituted by the group R in the ortho position relative to Y, and / or in the meta position relative to Y, and / or in the para position relative to Y.
- the group R may in particular comprise from 2 to 20 carbon atoms, or from 3 to 15 carbon atoms, or from 4 to 10 carbon atoms, and more preferably still from 6 to 8 carbon atoms.
- the group R may comprise an substituted or unsubstituted alkyl or aryl or arylalkyl or alkylaryl chain. It can include one or more heteroatoms chosen from: O, N, S, P, F, Cl, Br, I.
- the group R may preferably comprise a carbonyl function and preferably may be chosen from an acetyl group, a substituted or unsubstituted benzoyl group, a substituted or unsubstituted phenylacetyl group, a phthaloyl group, and an acyl group of phosphine oxide, the phosphine being optionally substituted in particular by one or more groups chosen from a methyl group, an ethyl group, and a phenyl group.
- the group Ar has as sole substituent the group R. In other embodiments, it may also comprise one (or more) additional substituents, comprising from 1 to 30 carbon atoms.
- the additional substituent can comprise one or more heteroatoms chosen from: O, N, S, P, F, Cl, Br, I.
- the additional substituent can be, for example, an aliphatic carbon chain.
- the additional substituent can be a substituted or unsubstituted aryl group, preferably a phenyl group, or an aromatic heterocycle or not.
- the group Ar is a phenyl substituted in the meta position and the group R is a non-substituted benzoyl group, or the group Ar is a phenyl substituted in the para position and the group R is an unsubstituted benzoyl group, or the group Ar is a phenyl substituted in the para position and the group R is a benzoyl group substituted in the para position by a hydroxy group, or the group Ar is a phenyl substituted in the position meta and the group R is an acetyl group, or the group Ar is a phenyl substituted in the para position and the group R is an acetyl group, or the group Ar is a phenyl substituted in the ortho position and the group R is a substituted phenylacetyl group in position a of the carbonyl group by a hydroxy group, or the group Ar is a phenyl substituted in the meta position and the group R is a phen
- Y is an oxygen atom.
- the photoactive molecules can for example be chosen from 3-hydroxybenzophenone, 4-hydroxybenzophenone,
- the photoactive molecules can also be chosen from:
- Y can be an NH group.
- the photoactive molecules can also be chosen from: 2-hydroxy-2-methyl-1-phenyl-propan-1-one, the phenyl group being further substituted by an amine group in the ortho, meta or para position relative to the carbonyl group; 2,4,6-trimethylbenzoyl-diphenylphosphineoxide, the phenyl group being further substituted by an amine group in the meta position relative to the carbonyl group; 2,4,6-trimethylbenzoylethylphenylphosphinate, the phenyl group being further substituted by an amine group in the meta position relative to the carbonyl group; 1-hydroxy-cyclohexyl-phenyl-ketone, the phenyl group being further substituted by an amine group in the ortho, meta or para position relative to the carbonyl group; bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentyl phosphine oxide, the phenyl group being further substituted by an amine group in the
- Y can be a sulfur atom.
- the photoactive molecules can also be chosen from: 2-hydroxy-2-methyl-1-phenyl-propan-1-one, the phenyl group being further substituted by a thiol group in the ortho, meta or para position relative to the carbonyl group; 2,4,6-trimethylbenzoyl-diphenylphosphineoxide, the phenyl group being further substituted by a thiol group in the meta position relative to the carbonyl group; 2,4,6-trimethylbenzoylethylphenylphosphinate, the phenyl group being further substituted by a thiol group in the meta position relative to the carbonyl group; 1-hydroxy-cyclohexyl-phenyl-ketone, the phenyl group being further substituted by a thiol group in the ortho, meta or para position relative to the carbonyl group; bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-penty
- the conversion of the PF polymer to the PFM polymer can be carried out by bringing the PF polymer into contact with the photoactive molecule in a solvent in which the PF polymer is dissolved.
- dimethylformamide dimethylacetamide; dimethyl sulfoxide
- ketones including acetone, methyl ethyl ketone (or butan-2-one), methyl isobutyl ketone and cyclopentanone
- furans especially tetrahydrofuran
- esters including methyl acetate, ethyl acetate, propyl acetate, butyl acetate and propylene acetate glycol methyl ether
- carbonates in particular dimethylcarbonate
- phosphates in particular triethylphosphate. Mixtures of these compounds can also be used.
- the photoactive molecule can be reacted with a base before bringing the PF polymer into contact with the photoactive molecule in the solvent, in order to deprotonate the photoactive molecule and form an anion photoactive of formula ⁇ -Ar-R, in which Y, Ar and R are as defined above.
- the base used for deprotonation of the photoactive molecule may have a pKa of 9 to 12.5 and preferably of 10 to 12.
- the base used for deprotonation of the photoactive molecule is preferably chosen from potassium carbonate, calcium carbonate and sodium carbonate, and it is preferably potassium carbonate.
- the base can be used in a molar amount of 1 to 1.25 equivalents, or from 1.25 to 1.5 equivalents, or from 1.5 to 2.0 equivalents, or from 2.0 to 3.0 equivalents, or 3.0 to 4.0 equivalents, or 4.0 to 5.0 equivalents, or 5.0 to 6.0 equivalents, or 6.0 to 7.0 equivalents, or 7.0 to 8 , 0 equivalents compared to the photoactive molecule.
- the reaction of the photoactive molecule with the base can be carried out in a solvent, as mentioned above.
- the solvent used for reacting the photoactive molecule with the base can be the same or different from the solvent used for bringing the PF polymer into contact with the photoactive molecule.
- the solvent used for reacting the photoactive molecule with the base is the same with that used for bringing the PF polymer into contact with the photoactive molecule.
- the reaction of the photoactive molecule with the base can be carried out at a temperature of 20 to 80 ° C, more preferably from 30 to 70 ° C.
- the duration of the reaction of the photoactive molecule with the base can be, for example, from 5 minutes to 5 hours, preferably from 15 minutes to 2 hours, more preferably from 30 minutes to 1 hour.
- the step of reacting the photoactive molecule with the base can be followed by a step of removing the base which is in excess.
- the concentration of polymer PF introduced into the reaction medium can for example be from 1 to 200 g / L, preferably from 5 to 100 g / L, more preferably from 10 to 50 g / L.
- the quantity of photoactive molecules introduced into the reaction medium can be adjusted according to the degree of replacement of the H and / or F atoms by the photoactive groups which is desired. Thus, this quantity can be from 0.1 to 0.2 molar equivalents (of photoactive groups introduced into the reaction medium, relative to the H and F atoms present in the polymer PF); or from 0.2 to 0.3 molar equivalents; or from 0.3 to 0.4 molar equivalents; or from 0.4 to 0.5 molar equivalents; or from
- the reaction of the polymer PF with the photoactive molecule is preferably carried out with stirring.
- the reaction of the polymer PF with the photoactive molecule is preferably carried out at a temperature of 20 to 120 ° C, more preferably from 30 to 90 ° C, and more particularly from 40 to 70 ° C
- the reaction time of the PF polymer with the photoactive molecule can be, for example, from 15 minutes to 96 hours, preferably from 1 hour to 84 hours, more preferably from 2 hours to 72 hours.
- the PFM polymer can be precipitated in a non-solvent, for example deionized water. It can then be filtered and dried.
- a non-solvent for example deionized water.
- composition of the PFM polymer can be characterized by elemental analysis and by NMR, as described above, as well as by infrared spectrometry.
- valence vibration bands characteristic of the aromatic and carbonyl functions are observed between 1500 and 1900 cm 1 .
- the H and / or F atoms of the starting PF polymer are only partially replaced by photoactive groups in the PFM polymer.
- the molar proportion of H and / or F atoms replaced by photoactive groups is from 0.1 to 20%, preferably from 1 to 10%, and preferably from 2 to 8%.
- the molar proportion of H and / or F atoms replaced by photoactive groups can be 0.1 to 0.5 mol.%; or from 0.5 to 1 mol.%; or from 1 to 2 mol.%; or from 2 to 4 mol.%; or from 4 to 6 mol.%; or from 6 to 8 mol.%; or from 8 to 10 mol.%; or from 10 to 15 mol.%; or from 15 to 20 mol.%.
- the proportion of structural units comprising a photoactive group can be for example 0.1 to 0.5 mol.%; or from 0.5 to 1 mol.%; or from 1 to 2 mol.%; or from 2 to 4 mol.%; or from 4 to 6 mol.%; or from 6 to 8 mol.%; or from 8 to 10 mol.%; or from 10 to 15 mol.%; or from 15 to 20 mol.%.
- Film preparation can be for example 0.1 to 0.5 mol.%; or from 0.5 to 1 mol.%; or from 1 to 2 mol.%; or from 2 to 4 mol.%; or from 4 to 6 mol.%; or from 6 to 8 mol.%; or from 8 to 10 mol.%; or from 10 to 15 mol.%; or from 15 to 20 mol.%.
- a fluoropolymer film according to the invention can be prepared by deposition on a substrate: either of one or more PFM polymers only; or at least one PF polymer and at least one PFM polymer.
- a PF polymer can be combined with a PFM polymer obtained from the PF polymer in question.
- the mass proportion of PF polymer (s) relative to all of the PF and PFM polymers can in particular be from 5 to 10%; or from 10 to 20%; or from 20 to 30%; or from 30 to 40%; or from 40 to 50%; or from 50 to 60%; or from 60 to 70%; or from 70 to 80%; or from 80 to 90%; or 90 to 95%.
- the production of the film may include a step of depositing PFM polymers (or PFM and PF) on a substrate, followed by a crosslinking step.
- the PFM polymers (or PFM and PF) can also be combined with one or more other polymers, in particular fluoropolymers.
- the substrate may in particular be a surface of glass, or of silicon, or of polymer material, or of metal.
- a preferred method consists in dissolving or suspending the polymer (s) in a liquid vehicle, to form a so-called ink composition before depositing it on the substrate.
- the liquid vehicle is a solvent.
- this solvent is chosen from: dimethylformamide; dimethylacetamide; dimethyl sulfoxide; ketones, including acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone; furans, especially tetrahydrofuran; esters, including methyl acetate, ethyl acetate, propyl acetate, butyl acetate and propylene acetate glycol methyl ether; carbonates, in particular dimethylcarbonate; phosphates, in particular triethylphosphate. Mixtures of these compounds can also be used.
- the total mass concentration of polymers in the liquid vehicle can in particular be from 0.1 to 30%, preferably from 0.5 to 20%.
- the ink may optionally include one or more additives, in particular chosen from agents modifying surface tension, agents modifying rheology, agents modifying aging resistance, agents modifying adhesion, pigments or dyes , the charges (including nanofillers).
- Preferred additives are in particular the co-solvents which modify the surface tension of the ink. In particular, it may be, in the case of solutions, organic compounds miscible with the solvents used.
- the ink composition may also contain one or more additives having served for the synthesis of the polymer (s).
- the present invention does not use a photoinitiator additive. Indeed, thanks to the presence of photoactive groups on the PFM polymer, the addition of a photoinitiator additive is not necessary.
- the ink comprises at least one crosslinking aid additive, preferably a crosslinking agent.
- the presence of a crosslinking agent has the advantage of forming covalent bonds with the polymer, resulting in improvement of the resistance of the polymer to the solvent.
- the crosslinking agent can for example be chosen from molecules, oligomers, polymers carrying at least two reactive double bonds such as triallylisocyanurate (TAIC), polybutadiene; compounds carrying at least two triple reactive bonds of carbon-carbon or carbon-nitrogen type such as tripropargyl amine; their derivatives, and mixtures thereof.
- TAIC triallylisocyanurate
- polybutadiene compounds carrying at least two triple reactive bonds of carbon-carbon or carbon-nitrogen type such as tripropargyl amine; their derivatives, and mixtures thereof.
- the crosslinking agent can also and preferably be a bi or polyfunctional (meth) acrylic monomer in terms of reactive double bonds.
- the crosslinkable composition may contain one or more monomers of this type.
- Said bi or polyfunctional (meth) acrylic monomer in terms of reactive double bonds can be a bi or polyfunctional (meth) acrylic monomer or oligomer.
- monomers useful for the invention mention may be made of monomers and oligomers containing at least two reactive double bonds of (meth) acrylic type. It is these reactive double bonds which, using a radical polymerization initiator, will allow the polymerization and crosslinking of the (meth) acrylic network within the structure [fluorinated electroactive copolymer-crosslinked (meth) acrylic network]. Therefore, any purely (meth) acrylic monomer bi or polyfunctional such as, for example dodecane di methacrylate is useful for the invention.
- (meth) acrylic monomers or oligomers have chemical structures derived from functions other than pure alkane chemistry, such as diols, triols or polyols, polyesters, ethers, polyethers, polyurethane, epoxies, cyanurates or iso-cyanurates.
- these monomers comprising at least two reactive (meth) acrylic functions in radical polymerization, they become useful for the invention.
- the bi or polyfunctional (meth) acrylic monomer or oligomer can be chosen from: trimethylolpropane triacrylate (such as that sold by the company Sartomer under the reference SR351), trimethylolpropane triacrylate ethoxylated (such as that sold by the company Sartomer under the reference SR454), the aliphatic urethane modified polyacrylate (such as that sold by the company Sartomer under the reference CN927).
- trimethylolpropane triacrylate such as that sold by the company Sartomer under the reference SR351
- trimethylolpropane triacrylate ethoxylated such as that sold by the company Sartomer under the reference SR454
- the aliphatic urethane modified polyacrylate such as that sold by the company Sartomer under the reference CN927.
- no crosslinking aid additive such as a crosslinking agent, is present in the ink deposited on the substrate.
- the deposition can be carried out in particular by coating by centrifugation (“spin-coating”), by spraying or atomization (“spray coating ”), by coating in particular with a bar or film puller (“ bar coating ”), by immersion (“ dip coating ”), by roller printing (“ roll-to-roll printing ”), by screen printing or by lithographic printing or by inkjet printing.
- the liquid vehicle is evaporated after deposition.
- the fluoropolymer layer thus formed can in particular have a thickness of 10 nm to 1 mm, preferably from 100 nm to 500 ⁇ m, more preferably from 150 nm to 250 ⁇ m, and more preferably from 50 nm to 50 ⁇ m.
- the crosslinking step can be carried out in particular by heat treatment and / or exposure to electromagnetic radiation, and preferably by UV irradiation.
- photoactive groups tend to decompose to form radicals. These are capable of reacting with C-F or C-H groups and / or of recombining with each other, which leads to crosslinking of the polymer (s).
- a crosslinking co-agent when a crosslinking co-agent is present, it is thought without wishing to be bound by a theory that the photoactive groups tend to decompose to form radicals. These are capable of reacting with the crosslinking co-agent by a radical polymerization mechanism, which leads to crosslinking of the polymer (s).
- the heat treatment can be carried out by subjecting the film for example to a temperature of 40 ° C to 200 ° C, preferably from 50 to 150 ° C, preferably from 60 to 140 ° C, for example in a ventilated fcur or on a hot plate.
- the duration of the heat treatment can in particular be from 1 minute to 4 hours, preferably from 2 minutes to 2 hours, and preferably from 5 to 20 minutes.
- UV irradiation means irradiation with electromagnetic radiation at a wavelength of 200 to 650 nm, and preferably from 220 to 500 nm. Wavelengths from 250 to 450 nm are particularly preferred.
- the radiation can be monochromatic or polychromatic.
- the total dose of UV irradiation is preferably less than or equal to 40 J / cm 2 , more preferably still less than or equal to 20 J / cm 2 , more preferably still less than or equal to 10 J / cm 2 , more preferably less than or equal to 5 J / cm 2 , and more preferably less than or equal to 3 J / cm 2 .
- a low dose is advantageous to avoid degrading the surface of the film.
- the treatment is carried out essentially in the absence of oxygen, always in order to avoid any degradation of the film.
- the treatment can be carried out under vacuum, or in an inert atmosphere, or by protecting the film from ambient air with a physical barrier impermeable to oxygen (glass plate or polymer film for example).
- a thermal pre-treatment and / or a thermal post-treatment, before and / or after the UV irradiation, can be carried out.
- the heat pre-treatment and the heat post-treatment can in particular be carried out at a temperature of 20 to 250 ° C., preferably from 30 to 150 ° C., and preferably from 40 to 110 ° C. and for example about 100 ° C for a period of less than 30 minutes, preferably less than 15 minutes, and more preferably less than 10 minutes.
- a development step can then be carried out, so as to eliminate the non-crosslinked parts of the film and to reveal the desired geometric pattern for the film.
- Development can be carried out by contacting the film with a solvent, preferably by immersion in a solvent bath.
- the solvent can preferably be chosen from dimethylformamide; dimethylacetamide; dimethyl sulfoxide; ketones, including acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone; furans, especially tetrahydrofuran; esters, including methyl acetate, ethyl acetate, propyl acetate, butyl acetate and propylene acetate glycol methyl ether; carbonates, in particular dimethylcarbonate; phosphates, in particular triethylphosphate. Mixtures of these compounds can also be used.
- the non-solvent liquid can in particular be any solvent which is different from the following solvents: dimethylformamide; dimethylacetamide; dimethyl sulfoxide; ketones; furans; esters; carbonates; phosphates.
- a protic solvent that is to say a solvent comprising at least one H atom bonded to an O atom or to an N atom.
- an alcohol such as as ethanol or isopropanol
- demineralized water demineralized water.
- Mixtures of non-solvents can also be used.
- the presence of a non-solvent in combination with the solvent can make it possible to further improve the sharpness of the patterns obtained, compared with the assumption that the non-solvent is only used during rinsing.
- the development can be carried out preferably at a temperature of 10 to 100 ° C, preferably from 15 to 80 ° C, and more preferably from 20 to 60 ° C.
- the duration of the development is preferably less than 15 minutes, from preferably still less than 10 minutes.
- the film can be rinsed with a non-solvent liquid for the fluoropolymer, miscible with the solvent or the solvent / non-solvent mixture.
- a non-solvent liquid for the fluoropolymer miscible with the solvent or the solvent / non-solvent mixture.
- It may in particular be a practical solvent, that is to say a solvent comprising at least one H atom bonded to an O atom or to an N atom.
- an alcohol such as as ethanol or isopropanol
- demineralized water demineralized water.
- This rinsing step improves the clarity of the film patterns and the roughness of their surface.
- Rinsing can be carried out in particular by spraying the non-solvent on the crosslinked film. Rinsing can also be carried out by immersion in a non-solvent bath.
- the temperature during the rinsing can be from 5 to 80 ° C, more preferably from 10 to 70 ° C and particularly at room temperature from 15 to 35 ° C.
- the duration of the rinsing step is less than 10 minutes, more preferably less than 5 minutes and particularly less than 1 minute.
- the film can be dried in air, and optionally undergo a post-crosslinking heat treatment, by exposing it to a temperature ranging, for example, from 30 to 150 ° C., preferably from 50 to 140 ° C.
- the film according to the invention is preferably characterized by a dielectric constant (or relative permittivity) at 1 kHz and at 25 ° C which is greater than or equal to 8, and preferably greater than or equal to 10.
- the dielectric constant can be measured using an impedance meter capable of measuring the capacity of the material in knowing the geometric dimensions (thickness and facing surfaces). Said material is placed between two conductive electrodes.
- the film according to the invention can be characterized by a piezoelectric coefficient d33 greater than 15 pC / N, and preferably greater than 20 pC / N.
- the piezoelectric coefficient measurement can be performed using a Piezometer PM300.
- the film according to the invention is characterized by a coercive field of 40 to 60 MV / m.
- the film according to the invention can also be characterized by a remanent polarization greater than 30 mC / m 2 , preferably greater than 50 mC / m 2 and preferably greater than 65 mC / m 2 ; measured at an electric field of 150 MV / m and at 25 ° C.
- Coercive field and remanent polarization measurements can be obtained by measuring the polarization curves of the material. Said film is placed between two conductive electrodes and then a sinusoidal electric field is applied. The measurement of the current passing through said film makes it possible to go back to the polarization curve.
- the film according to the invention can be used as a layer in an electronic device.
- one or more additional layers can 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.
- electronic device is meant either a single electronic component, or a set of electronic components, capable of performing one or more functions in an electronic circuit.
- 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 if appropriate optoelectronic, concerned by the present invention are the transistors (in particular field effect), the chips, the batteries, the photovoltaic cells, the light-emitting diodes (LED), the organic light-emitting diodes ( OLED), sensors, actuators, transformers, haptics, electromechanical microsystems, electro-caloric devices and detectors.
- the film according to the invention can be used in a sensor, in particular a piezoelectric sensor, as an active layer comprised between two metallic or polymer electrodes.
- Electronic and optoelectronic devices are used and integrated in many electronic devices, equipment or sub-assemblies and in many objects and applications such as televisions, mobile phones, rigid or flexible screens, thin-film photovoltaic modules, light sources, energy sensors and converters, etc.
- the final product was characterized by FTIR, CES and 1 H liquid NMR.
- the final polymer contains 4.4 mol.% Of benzophenone groups.
- the infrared spectrum of the polymer was measured before (A) and after (B) the modification.
- the 1 H liquid NMR spectrum of the polymer was also measured before (A) and after (B) the modification.
- the modified copolymer according to Example 1 was dissolved in cyclopentanone at a rate of 4% by mass at room temperature and with magnetic stirring for 24 h.
- a film of modified copolymer was prepared by “spin-coating” at 1000 rpm on a silicon wafer. The deposit was dried at 125 ° C for 5 min, then irradiated, selectively using a mask, with a Mercury lamp at a dose of 6 J. cm 2 under a stream of nitrogen. Annealing was then carried out at 110 ° C for 5 min.
- the product was then developed in an acetone bath for 1 min and then rinsed with isopropanol.
- the irradiated, cross-linked areas are insoluble.
- the non-irradiated areas are soluble and have been removed from the substrate.
- Figure 3 presents an optical microscope photo of the crosslinked modified polymer layer.
- the light areas are the irradiated and cross-linked areas, the dark areas correspond to the substrate.
- a pattern corresponding to the mask has been made.
- Figure 4 shows the ferroelectric hysteresis measured at 20 ° C, 0.1 Hz and 2000 V, of the layer of crosslinked modified polymer. It is observed that the layer of crosslinked modified polymer has a remanent polarization greater than 4 pC.cnr 2 . Thus, it is concluded that the crosslinked modified polymer retains good electroactive properties.
- Copolymer comprising units derived from monomers
- each of Xi, X 2 , X 3 and X4 is independently chosen from H, F and alkyl groups comprising from 1 to 3 carbon atoms which are optionally partially or completely fluorinated, the H and / or F atoms of fluorinated monomers being partially replaced by photoactive groups of formula -Y-Ar-R, in the copolymer; Y
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Abstract
Description
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FR1873062A FR3089978B1 (en) | 2018-12-17 | 2018-12-17 | Crosslinkable electroactive fluorinated polymers comprising photoactive groups |
PCT/FR2019/053074 WO2020128265A1 (en) | 2018-12-17 | 2019-12-16 | Crosslinkable electroactive fluorinated polymers comprising photoactive groups |
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KR20060123376A (en) | 2003-12-22 | 2006-12-01 | 코닌클리즈케 필립스 일렉트로닉스 엔.브이. | Method for patterning a ferroelectric polymer layer |
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