WO2013007711A1 - Dispositif comprenant une couche polymère - Google Patents

Dispositif comprenant une couche polymère Download PDF

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Publication number
WO2013007711A1
WO2013007711A1 PCT/EP2012/063454 EP2012063454W WO2013007711A1 WO 2013007711 A1 WO2013007711 A1 WO 2013007711A1 EP 2012063454 W EP2012063454 W EP 2012063454W WO 2013007711 A1 WO2013007711 A1 WO 2013007711A1
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composition
μηη
metal oxide
layer
pla
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PCT/EP2012/063454
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English (en)
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Olivier Lhost
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Total Petrochemicals Research Feluy
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Publication of WO2013007711A1 publication Critical patent/WO2013007711A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/206—Filters comprising particles embedded in a solid matrix
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/88—Passivation; Containers; Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the invention relates to a device comprising at least one conductive or semiconductive layer and further comprising at least one additional polymer layer.
  • Organic semiconductors and organic conductors are increasingly used in the development of photovoltaic cells, light-emitting diodes, flat panel displays, polymer field effect transistors, and the like. Such devices usually correspond to a multilayer structure: the "active" part of the structure is constituted by an organic layer, which may be sandwiched between two conductive layers. Additional layers are often introduced as support, barrier layers, adhesive layers, or the like.
  • UV-light in particular is often responsible for degradation of the organic component, and thus reduces the life time of the device.
  • the problem of UV degradation is a common problem in many products exposed to sunlight. Continuous exposure is a more serious problem than intermittent exposure, since attack is dependent on the extent and degree of exposure, making UV degradation a particularly serious problem for photovoltaic cells, and even more so for organic photovoltaic cells.
  • Organic photovoltaic devices currently have a shelf life of several years (typically between 1 and 5 years). They can thus not compete in terms of shelf life to silicon-based devices, which are known to have a much higher shelf life (typically of at least 25 years). Therefore, there is a need for organic photovoltaic devices to improve their shelf life, or they will remain limited to niche applications..
  • UV-protective layer For flexible solar cells and films in particular, such a UV-protective layer needs to be also flexible, as thin as possible and as cheap as possible. Furthermore, such a UV-protective layer needs to block UV-C (with a wavelength of approximately 100-280 nm) and UV-B (280-315 nm) parts of the spectrum, which may be achieved by using for example a PET layer. Improvement has mainly to be done to block UV-A (315-400 nm) rays which may nevertheless be passed through the protective layer.
  • a first aspect of the present invention concerns the use of a composition comprising polylactic acid (PLA) and at least one coated metal oxide particle, as a UV filter for a device comprising at least one conductive or semiconductive layer.
  • PLA polylactic acid
  • said composition is used as a UV-A filter for a device comprising at least one conductive or semiconductive layer.
  • a polylactic acid (PLA) composition comprising metal oxide particles, whereby the particles are coated to prevent degradation of the PLA, can provide optimal UV absorption for an electric, an electronic, an optic, a photoelectric or a photovoltaic device, while minimizing loss of mechanical and thermal properties which is otherwise due to intensive degradation of the polymer matrix.
  • the UV absorption can be tailored to include strong absorption in the UV range of the spectrum, as well as strong absorption in the UV-A sub-range of the spectrum, but only limited absorption in the visible range of the spectrum.
  • the present invention also encompasses a device comprising at least one conductive or semiconductive layer, and at least one additional layer, said additional layer having a composition comprising polylactic acid (PLA) and at least one coated metal oxide particle.
  • PLA polylactic acid
  • the layer composition comprising polylactic acid (PLA) and at least one coated metal oxide particle has the advantages of blocking most of all UV light with a wave length up to about 400 nm, and hardly blocking any light with a wavelength in the visible part of the spectrum.
  • This composition is particularly useful for devices comprising conductive or semiconductive layers.
  • the device is selected from the group comprising an electric, an electronic, an optic, a photoelectric and a photovoltaic module or device. More preferably, the device is selected from the group comprising a photovoltaic cell, a light-emitting diode, a fuel cell, a battery, a sensor, a field effect transistor and a display, preferably wherein the device is a photovoltaic cell. Preferably, the device is an organic photovoltaic cell.
  • Figure 1 represents a graph plotting the transmission (T) of UV-visible spectra as a function of the wavelength for the films of examples 2 to 5.
  • endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g. 1 to 5 can include 1 , 2, 3, 4 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.75 and 3.80, when referring to, for example, measurements).
  • the recitation of end points also includes the end point values themselves (e.g. from 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein.
  • the present invention concerns the use of a composition comprising a PLA polymer and at least one coated metal oxide particle, as a UV filter for a device, said device comprising at least one conductive or semiconductive layer.
  • a composition comprising a PLA polymer and at least one coated metal oxide particle, as a UV filter for a device, said device comprising at least one conductive or semiconductive layer.
  • said composition is used as a UV-A filter in a device comprising at least one conductive or semiconductive layer.
  • the present invention also encompasses the use of such a composition for preparing a device comprising at least one conductive or semiconductive layer, and at least one additional layer having a composition as described in the first aspect of the invention.
  • said additional layer is a UV filter.
  • said additional layer is a UV-A filter.
  • the present invention also encompasses a device comprising at least one conductive or semiconductive layer, and at least one additional layer, said additional layer having a composition comprising polylactic acid (PLA) and at least one coated metal oxide particle.
  • the present invention also encompasses a device comprising at least one conductive or semiconductive layer, and at least one UV filter, preferably a UV-A filter, said filter having a composition comprising polylactic acid (PLA) and at least one coated metal oxide particle.
  • the terms "polylactic acid” or “polylactide” or “PLA” are used interchangeably and refers to poly (lactic acid) polymers containing repeat units derived from lactic acid.
  • PLA suitable for the present invention can be prepared according to any method known in the state of the art.
  • the PLA can be prepared by ring-opening polymerization of raw materials having required structures selected from lactide, which is a cyclic dimer of lactic acid, glycolide, which is a cyclic dimer of glycolic acid, and caprolactone and the like.
  • Lactide includes L-lactide, which is a cyclic dimer of L-lactic acid, D-lactide, which is a cyclic dimer of D-lactic acid, meso-lactide, which is a cyclic dimer of D-lactic acid and L- lactic acid, and DL-lactide, which is a racemate of D-lactide and L-lactide.
  • the PLA polymers used in the present invention can be derived from D-lactic acid, L-lactic acid, or a mixture thereof. A mixture of two or more PLA polymers can be used.
  • the PLA for use in the present invention may comprise the product of polymerization reaction of a racemic mixture of L-lactides and D-lactides, also known as poly-DL-lactide (PDLLA).
  • the PLA for use in the present invention may comprise the product of polymerization reaction of mainly D-lactides, also known as poly-D-lactide (PDLA).
  • PDLA poly-D-lactide
  • the PLA for use in the present invention may comprise the product of polymerization reaction of mainly L-lactides (or L, L-lactides), also known as poly-L-lactide (PLLA).
  • Other suitable PLA can be copolymers of PLLA with some D lactic acid units.
  • PLLA-PDLA stereocomplexes can also be used.
  • Copolymeric components other than lactic acid may be used and include dicarboxylic acid, polyhydric alcohol, hydroxycarboxylic acid, lactone, or the like, which have two or more functional groups each capable of forming an ester bonding. These are, for example, polyester, polyether, polycarbonate, or the like which have the two or more unreacted functional groups in a molecule.
  • the hydroxycarboxylic acids may be selected from the list comprising glycolic acid, hydroxybutyric acid, hydroxy valeric acid, hydroxypentanoic acid, hydroxycaproic acid, and hydroxyheptanoic acid.
  • copolymers include poly-ester-urethanes, as disclosed in US 2010/01 13734 A1 , which is hereby incorporated by reference in its entirety, or lactide - amino-acid comonomers.
  • PLLA-PDLA stereocomplexes or copolymer stereocomplexes like poly-ester-urethane stereocomplexes can also be used in the present invention.
  • R 1 , R 2 and R 3 are an alkylene or an arylene group containing from 3 to 20 carbon atoms, preferably from 3 to 13 carbon atoms, more preferably from 6 to 13 carbon atoms.
  • the alkyl or the aryl group may be substituted or not.
  • the alkyl group may be linear, cyclic, saturated or unsaturated.
  • R 1 , R 2 and R 3 are an arylene group.
  • Suitable diamines include 1 ,4-butanediamine, 1 ,6-hexanediamine, 1 ,4- cyclohexanediamine, 1 ,4-phenyldiamine, 4,4'-diaminodiphenylmethane, preferably 1 ,4- phenyldiamine or 4,4'-diaminodiphenylmethane.
  • Suitable diols include 1 ,3- propandiol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,6-hexanediol, 1 ,7-heptanediol, 1 ,8- octanediol, and preferably xylene glycol.
  • the lactide used to obtain a polylactide-urethane copolymer can be a compound formed by the cyclic dimerization of the lactic acid.
  • the lactide may exist in a variety of isomeric forms such as L, L-lactide, D, D-lactide and D, L-lactide.
  • L, L-lactide can be used.
  • suitable diisocyanates include 1 ,6-hexamethylene diisocyanate (HMDI), 4,4'-dicyclohexylmethane diisocyanate, 4,4'-methylene diphenylisocyanate (MDI), toluene diisocyanate (TDI), and p-phenylene diisocyanate.
  • HMDI 1,6-hexamethylene diisocyanate
  • MDI 4,4'-dicyclohexylmethane diisocyanate
  • MDI 4,4'-methylene diphenylisocyanate
  • TDI toluene diisocyanate
  • p-phenylene diisocyanate Preferably, 4,4'-methylene diphenylisocyanate can be used.
  • the PLA for use in the present invention comprises PLLA.
  • the PLA for use in the present invention can comprise a physical polymer blend of PLA and at least one other polymer.
  • the at least one other polymer is poly(methyl methacrylate) (PMMA). Therefore, the invention also encompasses a device wherein the composition further comprises poly(methyl methacrylate) (PMMA).
  • the composition comprises at least 50 wt% of PLA based on the total weight of the composition. In a preferred embodiment of the invention, the composition comprises at least 80 wt% of PLA based on the total weight of the composition. In a more preferred embodiment of the invention, the composition comprises at least 90 wt% of PLA based on the total weight of the composition.
  • the PLA for use in the invention has a mean molecular weight Mn higher than 20000 Da, preferably higher than 50000, more preferably higher than 100000 Da, more preferably higher than 200000 Da.
  • UV refers to the band of electro-magnetic radiation with a wavelength of 100 nm to 400 nm.
  • visible light refers to the band of electro-magnetic radiation with wavelengths approximately in the 400 nm to 750 nm range.
  • UV-A also referred to as UVA, Ultraviolet A, long wave, or black light
  • UV-B also referred to as UVB, Ultraviolet B, or medium wave
  • UVC also referred to as UVC, Ultraviolet C, short wave, or germicidal
  • UVC refers to the band of electro-magnetic radiation with a wavelength of 100 nm to 280 nm.
  • UV filter refers to a substance which is able to absorb ultraviolet rays and give off the absorbed energy again in the form of longer-wave radiation, e.g. heat.
  • light transmittance refers to the amount of light that is transmitted or passes through a substance or product, expressed as a percentage.
  • UV light transmittance of the UV filter suitable for use in the invention is less than 30%. In preferred embodiment of the invention, the UV light transmittance of the UV filter is less than 20%. In a more preferred embodiment of the invention, the UV light transmittance of the UV filter is less than 10%. In an even more preferred embodiment of the invention, the UV light transmittance of the UV filter is less than 5%.
  • UV-A light transmittance of the UV-A filter suitable for use in the invention is less than 30%. In preferred embodiment of the invention, the UV-A light transmittance of the UV-A filter is less than 20%. In a more preferred embodiment of the invention, the UV-A light transmittance of the UV-A filter is less than 10%. In an even more preferred embodiment of the invention, the UV-A light transmittance of the UV-A filter is less than 5%.
  • the UV filter or UV-A filter has limited absorption for light in the visible range of the spectrum.
  • the UV filter or the UV-A filter suitable for use in the present invention has a visible light transmittance of about 50% or greater.
  • the UV filter or the UV-A filter has a visible light transmittance of about 60% or greater.
  • the UV filter or the UV-A filter has a visible light transmittance of about 70% or greater.
  • the UV filter or the UV-A filter has a visible light transmittance of 75% or greater.
  • metal oxide refers to a solid compound that contains a metal cation and an oxide anion.
  • the metal can be selected from the group comprising Ca, Mg, Ni, Cu, Ag, Si, Ti and Zn, and combinations thereof. In a preferred embodiment of the invention, the metal is selected from the group comprising Ca, Mg, or Zn.
  • the at least one metal oxide particle is a zinc oxide (ZnO) particle.
  • the composition comprises between 0.01 wt% and 10 wt% of metal oxide based on the total weight of the composition, preferably between 0.5 wt% and 3 wt% based on the total weight of the composition, more preferably between 0.5 wt% and 1 .5 wt% based on the total weight of the composition.
  • the composition can comprises between 0.01 wt% and 10 wt% of zinc oxide based on the total weight of the composition, preferably between 0.5 wt% and 3 wt% based on the total weight of the composition, more preferably between 0.5 wt% and 1.5 wt% based on the total weight of the composition.
  • Nano-sized particles are preferred in order to obtain the best available dispersion with the lowest total amount of product. It thus allows optimizing other relevant properties of the material such as optical and/or mechanical properties.
  • nano-particles or “nano-sized particles” are particles having at least one of its average dimensions (diameter, width, thickness or length) ranging between 1 nanometer and 300 nanometers. In a preferred embodiment, the nano-particles have an average particle size of between 1 nanometer and 300 nanometers.
  • the at least one metal oxide particle has an average particle size smaller than or equal to 30 ⁇ , preferably smaller than or equal to 3 ⁇ , preferably smaller or equal to 300 nm, preferably smaller than or equal to 100 nm, more preferably smaller than or equal to 50 nm, more preferably smaller than or equal to 40 nm, more preferably smaller than or equal to 30 nm.
  • the at least one metal oxide particle preferably the zinc oxide particle
  • D99 maximum particle size
  • particle average size may be expressed as "Dxx" where the "xx” is the volume percent of that particle having a size equal to or less than the Dxx.
  • the D99 is defined as the particle size for which ninety nine percent by volume of the particles has a size lower than the D99.
  • the D99 can be measured by sieving, by BET surface measurement, or by laser diffraction analysis, for example using a Malvern analyzer.
  • the term “coated” or “coating” refers to the fact that the at least one metal oxide particle has undergone one or more surface treatments of chemical, electronic, mechanochemical and/or mechanical nature with compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal (e.g. titanium or aluminum) alkoxides, polyethylene, silicones, proteins (collagen or elastin), alkanolamines, silicon oxides, metal oxides, sodium hexa-metaphosphate, alumina, glycerol, silanes, tiophenes or citrates or combination thereof.
  • compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal (e.g. titanium or aluminum) alkoxides, polyethylene
  • Such a surface treatment results in a coating of the metal oxide particle.
  • Said coating can result in partial or complete encapsulation of the metal oxide particle.
  • the at least one metal oxide particle is coated with at least one compound selected from the group comprising silanes, tiophenes, citrates, or combinations thereof.
  • said at least one compound is a silane compound. In an even more preferred embodiment of the invention said at least one compound is an alkoxysilane compound.
  • the present inventors have surprisingly found that the use of uncoated metal oxide particles into PLA composition can lead to significant loss of the thermo-mechanical performances.
  • composition comprising coated metal oxide on the other hand, can prevent or diminish such a reduction in thermo- mechanical performances, whereas good dispersion/distribution of metal oxide remains possible.
  • such composition can be easily extruded into films.
  • the present composition shows very effective anti-UV action, as well as antibacterial protection.
  • the silane compound can be selected from the group comprising alkoxysilanes, silazanes and siloxanes.
  • Non-limiting examples of silazane compound can be hexamethyldisilazane (HMDS or Bis(trimethylsilyl)amine).
  • Non-limiting examples of siloxane compound can be selected from polydimethylsiloxane (PDMS) and octamethylcyclotetrasiloxane.
  • the silane compound is an alkoxysilane.
  • alkoxysilane refers to a compound that comprises a silicon atom, at least one alkoxy group and at least one other organic group, wherein said silicon atom is bonded with said organic group by covalent bond.
  • the alkoxysilane is selected from the group comprising alkylsilanes; acryl-based silanes; vinyl-based silanes; aromatic silanes; epoxy-based silanes; amino-based silanes and amines that possess - NH 2 , -NHCH 3 or -N(CH 3 ) 2 ; ureide-based silanes; mercapto-based silanes; and, in addition alkoxysilanes which have a hydroxyl group (i.e., -OH).
  • An acryl-based silane may be selected from the group comprising [beta]-acryloxyethyl trimethoxysilane; [beta]- acryloxypropyl trimethoxysilane; [gamma]-acryloxyethyl trimethoxysilane; [gamma]- acryloxypropyl trimethoxysilane; [beta]-acryloxyethyl triethoxysilane; [beta]-acryloxypropyl triethoxysilane; [gamma]-acryloxyethyl triethoxysilane; [gamma]-acryloxypropyl triethoxysilane; [beta]-methacryloxyethyl trimethoxysilane; [beta]-methacryloxypropyl trimethoxysilane; [gamma]-methacryloxyethyl trimethoxysilane; [gamma]-methacryloxypropyl trimeth
  • a vinyl- based silane may be selected from the group comprising vinyl trimethoxysilane; vinyl triethoxysilane; p-styryl trimethoxysilane, methylvinyldimethoxysilane, vinyldimethylmethoxysilane, divinyldimethoxysilane, vinyltris(2-methoxyethoxy)silane, and vinylbenzylethylenediaminopropyltrimethoxysilane.
  • An aromatic silane may be selected from phenyltrimethoxysilane and phenyltriethoxysilane.
  • An epoxy-based silane may be selected from the group comprising 3-glycydoxypropyl trimethoxysilane; 3- glycydoxypropylmethyl diethoxysilane; 3-glycydoxypropyl triethoxysilane; 2-(3,4- epoxycyclohexyl)ethyl trimethoxysilane, and glycidyloxypropylmethyldimethoxysilane.
  • An amino-based silane may be selected from the group comprising 3-aminopropyl triethoxysilane; 3-aminopropyl trimethoxysilane; 3-aminopropyldimethyl ethoxysilane; 3- aminopropylmethyldiethoxysilane; 4-aminobutyltriethoxysilane; 3-aminopropyldiisopropyl ethoxysilane; 1 -amino-2-(dimethylethoxysilyl)propane; (aminoethylamino)-3- isobutyldimethyl methoxysilane; N-(2-aminoethyl)-3-aminoisobutylmethyl dimethoxysilane; (aminoethylaminomethyl)phenetyl trimethoxysilane; N-(2-aminoethyl)-3- aminopropylmethyl dimethoxysilane; N-(2-aminoeth
  • An ureide-based silane may be 3- ureidepropyl triethoxysilane.
  • a mercapto-based silane may be selected from the group comprising 3-mercaptopropylmethyl dimethoxysilane, 3-mercaptopropyl trimethoxysilane, and 3-mercaptopropyl triethoxysilane.
  • An alkoxysilane having a hydroxyl group may be selected from the group comprising hydroxymethyl triethoxysilane; N-(hydroxyethyl)-N- methylaminopropyl trimethoxysilane; bis(2-hydroxyethyl)-3-aminopropyl triethoxysilane; N-(3-triethoxysilylpropyl)-4-hydroxy butylamide; 1 1 -(triethoxysilyl)undecanol; triethoxysilyl undecanol; ethylene glycol acetal; and N-(3-ethoxysilylpropyl)gluconamide.
  • alkylsilane suitable for the invention can be expressed with a general formula: R n Si(OR') 4 - n wherein: n is 1 , 2 or 3; R is a Ci -2 oalkyl; and R' is an Ci -2 oalkyl.
  • alkyl by itself or as part of another substituent, refers to a straight or branched or cyclic saturated hydrocarbon group joined by single carbon-carbon bonds having 1 to 20 carbon atoms, for example 1 to 10 carbon atoms, for example 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms.
  • the subscript refers to the number of carbon atoms that the named group may contain.
  • Ci -6 alkyl means an alkyl of one to six carbon atoms.
  • alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, ie f-butyl, 2- methylbutyl, pentyl iso-amyl and its isomers, hexyl and its isomers, heptyl and its isomers, octyl and its isomer, decyl and its isomer, dodecyl and its isomers.
  • C 2 - 2 oalkenyl by itself or as part of another substituent, refers to an unsaturated hydrocarbyl group, which may be linear, or branched, comprising one or more carbon- carbon double bonds having 2 to 20 carbon atoms.
  • Examples of C 2-6 alkenyl groups are ethenyl, 2-propenyl, 2-butenyl, 3-butenyl, 2-pentenyl and its isomers, 2-hexenyl and its isomers, 2,4-pentadienyl and the like.
  • An alkylsilane may be selected from the group comprising methyltrimethoxysilane; methyltriethoxysilane; ethyltrimethoxysilane; ethyltriethoxysilane; propyltrimethoxysilane; propyltriethoxysilane; hexyltrimethoxysilane; hexyltriethoxysilane; octyltrimethoxysilane; octyltriethoxysilane; decyltrimethoxysilane; decyltriethoxysilane; dodecyltrimethoxysilane: dodecyltriethoxysilane; tridecyltrimethoxysilane; dodecyltriethoxysilane; hexadecyltrimethoxysilane; hexadecyltriethoxysilane; octadecyl
  • the silane compound is an alkylsilane.
  • said silane compound is selected from triethoxyoctylsilane, trimethoxyoctylsilane or combinations thereof.
  • the coated metal oxide particle is a zinc oxide particle coated with a silane. In a particularly preferred embodiment of the invention, the coated metal oxide particle is a zinc oxide particle coated with an alkylsilane. In a particularly preferred embodiment of the invention, the coated metal oxide particle is a zinc oxide particle coated with octyltrimethoxysilane. In a particularly preferred embodiment of the invention, the coated metal oxide particle is a zinc oxide particle coated with octyltriethoxysilane.
  • the composition may further comprise at least one additive.
  • the invention therefore also encompasses the use as described herein or the device as described herein wherein the composition comprises from 0% to 10 wt% of at least one additive based on the total weight of the composition.
  • said composition comprises less than 5 wt% of additive based on the total weight of the composition, for example 0.1 to 3 wt% of additive based on the total weight of the composition.
  • Said additive may be selected from the group comprising an epoxy-functional styrene acrylic resin, an antioxidant, a thermal stabilizer, an antiacid, a UV-stabilizing agent, a solvent, a weather resistant agent, or an antistatic agent.
  • Suitable antioxidants include, for example, organophosphites such as bis(2,4-di-t- butylphenyl)pentaerythritoldiphosphite, tris(nonylphenyl)phosphite, tris(2,4-di-t- butylphenyl)phosphite, (2,4,6-tri-tert-butylphenyl)(2-butyl-2-ethyl-l,3- propanediol)phosphite, distearyl pentaerythritol diphosphite or the like; alkylated monophenols or polyphenols; alkylated reaction products of polyphenols with dienes, such as tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane, or the like; butylated reaction products of para-cresol or dicyclopentadiene; alkylated hydroquinones;
  • Preferred antioxidant is ((bis(2,4-di- t-butylphenyl) pentaerythritol diphosphite) (know under the tradename (Ultranox®, 626). Antioxidants are generally used in amounts of about 0.1 to about 5 parts by weight, based on 100 parts by weight of the composition .
  • thermal stabilizer is Biomax Thermal 300 modifier from DuPont or a blend with poly(methyl methacrylate) (PMMA). Thermal stabilizers are generally used in amounts of about 0.1 to about 5 parts by weight, based on 100 parts by weight of the composition.
  • Non-limiting examples of the heat stabilizer and the antioxidant include hindered phenols, hindered amines, sulfur compounds, copper compounds and halides of alkali metals.
  • the composition comprises bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite (Ultranox®, such as Ultranox626A).
  • the composition comprises 1 ,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate.
  • Suitable UV-stabilizing agents include for example, hydroxybenzophenones; hydroxybenzotriazoles; hydroxybenzotriazines; cyanoacrylates; oxanilides; benzoxazinones; 2-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)-phenol (CYASORB 541 1 ); 2-hydroxy-4-n-octyloxybenzophenone (CYASORB 531 ); 2-[4,6-bis(2,4- dimethylphenyl)- 1 ,3,5-triazin-2-yl]- 5-(octyloxy)-phenol (CYASORB 1 164); 2,2'-(1 ,4- phenylene)bis(4H-3,1 -benzoxazin-4-one) (CYASORB UV- 3638); 1 ,3-bis[(2-cyano-3,3- diphenylacryloyl)oxy]-2,2-bis
  • antistatic agents examples include glycerol monostearate, glycerol distearate, glycerol tristearate, ethoxylated amines, primary, secondary and tertiary amines, ethoxylated alcohols, alkyl sulfates, alkylarylsulfates, alkylphosphates, alkylaminesulfates, alkyl sulfonate salts such as sodium stearyl sulfonate, sodium dodecylbenzenesulfonate or the like, quaternary ammonium salts, quaternary ammonium resins, imidazoline derivatives, sorbitan esters, ethanolamides, betaines, polyesteramides polyether-polyamide (polyetheramide) block copolymers, polyetheresteramide block copolymers, polyetheresters, or polyurethanes, each containing polyalkylene glycol moieties polyalkylene oxide units such as polyethylene glycol
  • Such polymeric antistatic agents are commercially available, for example Pelestat 6321 (Sanyo) or Pebax MH1657 (Atofina), Irgastat P18 and P22 (Ciba-Geigy). Antistatic agents are generally used in amounts of about 0.05 to about 20 parts by weight, based on 100 parts by weight of the composition.
  • Non-limiting examples of suitable solvents include chloro-subsituted alkanes (such as dichloro methane and trichloro methane), alkyl acetates (such as ethyl-, propyl- and n- butyl acetate), ethers (such as diethyl ether and tetrahydrofuran), alcohols (such as methanol and ethanol), ketones (such as acetone, methyl ethyl ketone and methyl isobutyl ketone), cyclic hydrocarbons (such as hexane) and aromatic hydrocarbons (such as toluene, o-dichlorobenzene and o-, m-, or p-xylene) or acetonitrile.
  • the solvent is dichloro methane.
  • the present invention also encompasses the use of said composition for the preparation of a film.
  • the present invention also encompasses a device wherein the at least one additional layer is a film.
  • the film has a thickness between 1 ⁇ and 0.5 mm, preferably between 4 ⁇ and 150 ⁇ , more preferably between 30 ⁇ and 50 ⁇ .
  • the PLA composition may optionally include other additives known in the art to improve processing and application of polymer films, e.g., antiblock additives, slip additives and viscosity enhancers. When used to enhance the production of polymer films, it should be noted that these additives are not essential for blowing the PLA films per se, but may be preferentially employed to enhance the processing, performance and look of the final product.
  • the PLA composition comprises a slip agent, preferably erucamide.
  • the PLA composition comprises an antiblock additive, preferably talc or other silica-based products.
  • composition comprising PLA and metal oxide particles can be readily prepared by any method known in the art.
  • the components of the composition can be blended together by melt extrusion or can be admixed together on a conventional mixing machine such as an extruder, a kneader or a continuous mixer.
  • the composition of the present invention can be formed into film using any technique known in the art such as a cast method or blown film method or coating method.
  • the present invention includes a blown film process wherein an extruder having an annular die is used for extruding the composition for use in the present invention. Air is blown in through the extruder die to form a bubble of the composition. After a cooling air stream cures, the film is wound onto rolls. More particularly, a composition as defined hereinabove is introduced into the feed hopper of an extruder that is resistance heated. The film can extruded through the die into a film that is cooled by blowing air onto the surface of the film in a blowing manner. The film can be drawn from the die typically forming a cylindrical film that is cooled, collapsed, optionally slit, and wound to form a roll of film.
  • the film can be obtained using a cast film process, wherein a flat die extruder is used for extruding the composition for use in the present invention. The film is then cast on a chill roll where cooling quenches it.
  • the film can be obtained by extrusion coating process, wherein a flat die extruder is used for extruding the composition for use in the present invention. The film is then cast on a support.
  • the film can be co-extruded with one or more other polymer compositions to form a multi-layered film.
  • the film can also be used in a lamination process.
  • the film can be used as a substrate in production processes used for production of multilayer devices with at least one organic UV-sensitive layer. Such processes can include, for example, spin coating, vacuum thermal evaporation, vapor phase deposition, printing technologies or coating.
  • the film generally has a higher impact strength and a higher gloss than the neat PLA.
  • the film is particularly useful for the preparation of a device comprising at least one at least one conductive or semiconductive layer.
  • this layer or film having a composition as described herein can be multiple: it can serve as a support for the whole structure. It can be used as a barrier layer for example to prevent migration of water, gas, and the like. This layer can be used as external layer, and can provide a very high gloss to the structure. In particular this layer has the advantage of being a UV barrier.
  • the present invention also encompasses a device comprising at least one conductive or semiconductive layer, and at least one additional layer, said additional layer having a composition comprising polylactic acid (PLA) and at least one coated metal oxide particle.
  • PLA polylactic acid
  • the present invention encompasses a device comprising at least one conductive or semiconductive layer, and at least one film having a composition comprising polylactic acid (PLA) and at least one coated metal oxide particle.
  • PLA polylactic acid
  • the term "conductive layer” refers to a layer comprising a conductive material, i.e. a material that does not have a band gap or that has a very small band gap.
  • the term “semiconductive layer” refers to a layer comprising a semiconductive material, i.e. a material with a band gap smaller than 5 eV. In a preferred embodiment of the invention, the band gap of the semiconductive material is smaller than 3 eV. In a more preferred embodiment of the invention, the band gap of the semiconductive material is between 1 and 2 eV.
  • the at least one conductive or semiconductive layer is organic or semi-organic.
  • the conductive or semiconductive layer comprises an organic conductor or semiconductor. More preferably the conductive or semiconductive layer comprises a polymeric organic conductor or semiconductor.
  • the polymeric organic conductor or semiconductor is selected from the list comprising poly(fluorene), polyphenylene, polypyrene, polyazulene, polynaphthalene, poly(pyrrole) (PPY), polycarbazole, polyindole, polyazepine, polyaniline (PANI), poly(thiophene) (PT), poly(3-hexylthiophene), poly(3,4-ethylenedioxythiophene) (PEDOT), poly(dioctyl-bithiophene) (PDOT), poly(p-phenylene sulfide) (PPS), poly(p- phenylene vinylene) (PPV), poly(acetylene) (PAC) and their derivatives.
  • Conductive and semiconductive polymers are lighter, more flexible, and less expensive than inorganic conductors. This makes them a desirable alternative in many applications. It also creates the possibility of new applications that would be impossible using copper or silicon.
  • the organic conductor or semiconductor is a polythiophene derivative, particularly poly (3 hexyl thiophene).
  • the polythiophene derivative is the "donor” component, combined with fullerene based compound, such as, for example, [6,6]-phenyl-C 6 rbutyric acid methyl ester (PC[60]BM), or a carbon nanotube (CNT) based compound as the "acceptor" component.
  • the device is selected from the group comprising an electric, an electronic, an optic, a photoelectric and a photovoltaic module or device.
  • the device is selected from the group comprising a photovoltaic cell, a light-emitting diode, a fuel cell, a battery, a sensor, a field effect transistor and a display.
  • the device is a photovoltaic cell.
  • the device is flexible.
  • the device is an organic electronic device.
  • organic electronic device does not only include devices based on organic semiconductors, but also devices comprising organic dielectrics, conductors and light emitters. Examples of organic electronic devices include organic field-effect transistors (OFET), organic light-emitting diodes (OLED) and organic photovoltaic cell (OPVC).
  • OFET organic field-effect transistors
  • OLED organic light-emitting diodes
  • OPVC organic photovoltaic cell
  • the device is an organic photovoltaic cell (OPVC).
  • OPVC organic photovoltaic cell
  • the additional layer is used as a support in organic multilayer photovoltaic devices.
  • the organic photovoltaic cell according to an embodiment of the invention can comprise a planar heterojunction (PHJ), a bulk heterojunction (BHJ) or an ordered heterojunction (OHJ).
  • An organic photovoltaic cell according to an embodiment of the invention can be manufactured by any technique known in the art.
  • the photovoltaic cell is manufactured by laminated multiple layers onto a support.
  • the organic photovoltaic cell can comprise multiple layers: a substrate or support layer, a transparent first electrode layer, optionally an interlayer, an active layer and a second electrode layer.
  • the substrate layer or support layer comprises a composition comprising PLA and at least one coated metal oxide particle.
  • any transparent electrode is suitable such as one formed from a layer of transparent conductive oxide, such as indium tin oxide (ITO).
  • ITO indium tin oxide
  • the interlayer comprises a conductive organic material, such as poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (also known as PEDOT:PSS).
  • the interlayer may further comprise any conjugated families, compounds, their derivatives, moieties etc, for example: polyfluorene, polyphenylenevinylene, poly(methyl methacrylate), polyvinylcarbazol (PVK) thiophene and their derivatives which include cross-linkable forms.
  • the interlayer can be arranged between the electrodes and the active layer.
  • the active layer can comprise any electron accepting material, such as a fullerene, and any electron donating material, such as an active polymer, for example polythiophene.
  • the second electrode can comprise any metal, such as aluminium or silver, or a combination of two or more metals, such as calcium and aluminium or calcium and silver or lithium fluoride and aluminium or lithium fluoride and silver.
  • composition is thus an improved UV-filter, and provides an improved shelf-life of the active organic layer in a photovoltaic device.
  • Example 1 Preparation of a PLA layer for use in the device according to an embodiment of the invention
  • the blow-up ratio was 2.5 - 3.
  • Rolling system speed was adjusted to obtain a 40 ⁇ thickness film.
  • the transmittance was smaller than 5 % for all wavelengths smaller than 375 nm
  • the film can thus be used as a substrate e.g. for the production of a photovoltaic organic device.
  • Example 2 Preparation of a PLA layer for use in the device according to an embodiment of the invention
  • a film was prepared using a composition comprising PLA (IngeoTM 4042D commercially available at NatureWorks LLC) and 0.1 % of Zano20 plus (ZnO particles coated with triethoxy caprylylsilane), commercialized by Umicore Zinc Chemicals (Belgium). 0.3 wt% of Ultranox 626 (bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite) supplied by GE Specialty Chemicals was further added to the composition.
  • PLA IngeoTM 4042D commercially available at NatureWorks LLC
  • Zano20 plus ZnO particles coated with triethoxy caprylylsilane
  • Umicore Zinc Chemicals Belgium
  • Ultranox 626 bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite
  • the UV-visible spectrum obtained for this film is illustrated in Figure 1 (b) and compared to the UV-visible spectrum of the same film without Zano20 plus in Figure 1 (a).
  • the film with the Znano20 plus can thus be used as a substrate e.g. for the production of a photovoltaic organic device.
  • Example 3 Preparation of a PLA layer for use in the device according to an embodiment of the invention
  • Example 4 Preparation of a PLA layer for use in the device according to an embodiment of the invention
  • Example 5 Preparation of a PLA layer for use in the device according to an embodiment of the invention
  • the films of examples 3-5 can thus be used as a substrate, e.g. for the production of a photovoltaic organic device.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electromagnetism (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette invention concerne un dispositif comprenant au moins une couche conductrice ou semi-conductrice, et au moins une couche supplémentaire, ladite couche supplémentaire ayant une composition comprenant de l'acide polylactique (PLA) et au moins une particule d'oxyde métallique revêtue.
PCT/EP2012/063454 2011-07-12 2012-07-10 Dispositif comprenant une couche polymère WO2013007711A1 (fr)

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Cited By (2)

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CN104189963A (zh) * 2014-05-13 2014-12-10 奚廷斐 降低可全降解镁合金血管支架降解速率的表面涂层制备方法
TWI609935B (zh) * 2013-09-30 2018-01-01 住友大阪水泥股份有限公司 無機粒子分散液、含無機粒子之組成物、塗膜、附塗膜之塑膠基材、顯示裝置

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TWI609935B (zh) * 2013-09-30 2018-01-01 住友大阪水泥股份有限公司 無機粒子分散液、含無機粒子之組成物、塗膜、附塗膜之塑膠基材、顯示裝置
CN104189963A (zh) * 2014-05-13 2014-12-10 奚廷斐 降低可全降解镁合金血管支架降解速率的表面涂层制备方法

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