Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/10—Adhesives in the form of films or foils without carriers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/35—Heat-activated
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • 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
  • H10K50/842—Containers
  • H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants
• • 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
• • 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
  • H10K50/846—Passivation; Containers; Encapsulations comprising getter material or desiccants
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
  • H10K77/10—Substrates, e.g. flexible substrates
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J153/005—Modified block copolymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J153/02—Vinyl aromatic monomers and conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09J157/02—Copolymers of mineral oil hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
  • C09J177/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2400/00—Presence of inorganic and organic materials
  • C09J2400/20—Presence of organic materials
  • C09J2400/22—Presence of unspecified polymer
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2453/00—Presence of block copolymer
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2463/00—Presence of epoxy resin
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2477/00—Presence of polyamide
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
  • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
  • H01L2924/161—Cap
  • H01L2924/1615—Shape
  • H01L2924/16195—Flat cap [not enclosing an internal cavity]
• • 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 present invention relates to an adhesive tape for the encapsulation of an organic electronic device and a method for its use.
• Optoelectronic arrangements are increasingly used in commercial products or are about to be launched on the market.
• Such arrangements include inorganic or organic electronic structures, for example organic, organometallic or polymeric semiconductors or combinations thereof.
• the corresponding products are rigid or flexible depending on the desired application, whereby there is an increasing demand for flexible arrangements.
• non-impact printing such as thermal transfer printing, inkjet printing or digital printing
• vacuum processes such as chemical vapor deposition (CVD), physical vapor deposition (PVD), plasma-assisted chemical or physical deposition (PECVD), sputtering, (plasma) etching or vapor deposition are used.
• Electrophoretic or electrochromic structures or displays, organic or polymeric light-emitting diodes (OLEDs or PLEDs) in display and display devices or as illumination, as well as electroluminescent lamps, light-emitting electrochemical cells, may be mentioned as examples of optoelectronic applications that are already commercially available or interesting in their market potential (LEECs), organic solar cells such as dye or polymer solar cells, inorganic thin-film solar cells, for example based on silicon, germanium, copper, Indium and selenium, organic field effect transistors, organic switching elements, organic optical amplifiers, organic laser diodes, organic or inorganic sensors or organically or inorganic based RFI D transponder listed.
• an organic electronic arrangement is understood to mean an electronic arrangement which comprises at least one electronically functional, at least partially organic constituent - eg organometallic compounds - or whose electronically functional structure has a thickness of less than 20 ⁇ m.
• inorganic thin film solar cells e.g. inorganic thin film solar cells and inorganic electrochromic layer structures.
• Thicker electroluminescent structures with inorganic particles are also included, as long as organic, e.g. polymers, layers or matrix materials are used for embedding the particles, since here take over the organic materials as a dielectric electronic function.
• electronic-functional components are to be understood as meaning at least but not exclusively all materials lying in an electronic structure between the contact electrodes (for example anode and cathode) and any other electrically conductive layers used.
• organic electronic device does not include conventional semiconductor wafer-based electronic devices, since their structure is generally thicker than 20 ⁇ m.
• a variety of optoelectronic arrangements - especially when using organic materials - are sensitive to both water vapor and oxygen. During the lifetime of the electronic devices protection by an encapsulation is therefore required, otherwise the performance wears off over the period of use. Otherwise, for example, by an oxidation of the components of light-emitting devices such as electroluminescent lamps (EL lamps) or organic light-emitting diodes (OLED) the luminosity, in electrophoretic displays (EP displays) the contrast or in solar cells efficiency within a short time drastically reduce.
• EL lamps electroluminescent lamps
• OLED organic light-emitting diodes
• EP displays electrophoretic displays
• This cover which is impermeable to permeable substances, they can be kept away from the electronic device.
• This cover is usually adhered to the electronic device and / or on the electronic assembly adjacent areas of the substrate on which the arrangement is present.
• Impermeable coverings for impermeable substances may, for example, be present in the form of an impermeable layer of an adhesive which may need to be post-treated, stabilized or covered, or in the form of an impermeable layer of a rigid or flexible material adhered over the entire surface or at least in the edge regions and so encapsulated the electronic arrangement.
• liquid adhesives also brings a number of undesirable effects.
• low molecular weight components VOCs - volatile organic compounds
• the adhesive must be applied consuming on each individual component of the arrangement.
• the purchase of expensive dispensers and fixators is necessary to ensure accurate positioning.
• the type of application also prevents a fast continuous process. In the subsequently required lamination step, it may be difficult to achieve a defined layer thickness and bond width due to the low viscosity.
• PSAs preference is given to using those which can be crosslinked after the bonding by introduced energy (for example actinic radiation or heat).
• energy for example actinic radiation or heat.
• Such compositions are described for example in US 2006/0100299 A1 and WO 2007/087281 A1.
• Their advantage lies in the fact that the barrier effect of the adhesives can be improved by the crosslinking.
• hot melt adhesives is known in the art.
• copolymers of ethylene are used here, for example ethylene-ethyl acetate (EEA), ethylene-acrylic acid copolymer (EAA), ethylene-butyl acrylate (EBA) or ethylene-methyl acrylate (EMA).
• ethylene-vinyl acetate (EVA) copolymers are used for silicon wafer based solar cell modules.
• EVA ethylene-vinyl acetate
• Hot-melt adhesives based on block copolymers or functionalized polymers are described, for example, in WO 2008/036707 A2, WO 2003/002684 A1, JP 2005-298703 A and US 2004/0216778 A1.
• the getter material is in direct contact with a full or partial coverage of the electronic device and may damage it due to its reactivity.
• the effect of the getter materials in turn being able to attack the adhesives themselves as well as the electronic device over time implies that the presence of getter materials promotes the aging of PSAs and reduces the life of the electronic device they are intended to protect , although this does not happen to the extent that would be the case with the permeates.
• the addition of getter materials to adhesives usually also leads immediately to a Lowering the bond strength, as is regularly observed when adding higher amounts of additives.
• the object of the invention is therefore to offer an adhesive which can contribute to reducing the disadvantages of the prior art, which in particular allows a longer life of an organic electronic device than such adhesives, which according to the prior art for the adhesion of covers for protection electronic arrangements are used, and further have particularly long sealing effect in said application.
• the properties of the adhesive tape in particular adhesive properties, should not be adversely affected by a corresponding modification of the adhesive, and further advantageously no significant change in these properties should be noted over the period of application of the adhesive tape.
• the object could be achieved by the encapsulation of the sensitive, located on a substrate organic electronic device by means of a cover, which is fixed by means of a - in particular largely permeat990 - adhesive tape comprising at least one layer of an adhesive, the
• the main claim relates to a method for protecting an organic electrical arrangement arranged on a substrate, wherein a cover is applied to the electronic arrangement such that the electronic arrangement is at least partially covered by the cover, wherein furthermore the cover at least partially on the substrate and / or is glued to the electronic assembly, wherein the bonding is effected by means of at least one layer of an adhesive.
• the adhesive layer is in this case in particular as a layer of an adhesive tape.
• the method according to the invention is characterized in that the adhesive comprises a getter capable of sorbing at least one permeable substance, wherein the getter material is present in a proportion of not more than 2 wt .-%, based on the adhesive with the getter, in the adhesive.
• the adhesive has been used which already inherently possesses a low permeate permeability (referred to below as an adhesive having an inherent barrier effect).
• the adhesive has a water vapor permeation rate of less than 50 g / (m 2 -d) and / or an oxygen passage rate of less than 5000 g / (m 2 -d-bar) at a thickness of 50 ⁇ m.
• the invention additionally provides an adhesive tape comprising a layer of an adhesive, wherein the adhesive comprises a getter material capable of sorbing at least one permeable substance, wherein the getter material contains not more than 2% by weight, based on the adhesive Getter material in which adhesive is present.
• the adhesive of the adhesive tape according to the invention and the adhesive of the adhesive tape used in the process according to the invention are very advantageously a pressure-sensitive adhesive, in another preferred embodiment an activatable adhesive. Activatable PSAs are particularly preferably used.
• Adhesive adhesives are adhesives whose set film remains permanently tacky and tacky at room temperature in the dry state. Pressure-sensitive adhesives permit a permanent bond with the primer under relatively low pressure and can be removed again from the primer after use essentially without residue. The adhesiveness of the adhesives is based on their adhesive properties and the removability on their cohesive properties.
• Adhesive compositions are considered as activatable adhesives, in which the bonding takes place by an energy input, for example by actinic radiation or heat.
• (adhesive) adhesive in the sense of "adhesive, especially in the embodiment as a pressure-sensitive adhesive” is used.
• the term “adhesive tape” means “adhesive tape, especially in the form of a pressure-sensitive adhesive tape”.
• the inventive method thus has a separation with respect to the functions that are realized in the prior art by getter materials in high quantities:
• the inherent barrier effect ensures that permeates can not penetrate the encapsulation.
• Getteranteil ensures that in the structure of the organic electronic device already located Permeate - which are present for example due to production or storage due to the encapsulation - intercepted.
• permeates are intercepted, which penetrate into this or have already penetrated into it during manufacture, assembly and / or storage of the (adhesive) adhesive tape.
• This is thus largely kept free of permeates.
• the proportion of the getter material in the (adhesive) adhesive is not more than 1% by weight, preferably not more than 0.5% by weight.
• the proportion of the getter material in the (adhesive) adhesive is at least 0.01% by weight, preferably at least 0.05% by weight.
• an adhesive tape in particular a pressure-sensitive adhesive tape, is used, which is used in the form of a single layer of the corresponding (adhesive) adhesive.
• Such single-layer adhesive tapes are referred to as "transfer tapes" and often offered on one or both sides with a temporary carrier for ease of handling, which is removed again for use temporary carriers are for example anti-adhesive films and papers suitable, such as siliconized films and papers.
• the method according to the invention can advantageously be carried out by first applying the (adhesive) adhesive layer, optionally as part of a double-sided adhesive tape comprising further layers, and in a subsequent step the cover to the substrate and / or the electronic device.
• the (adhesive) adhesive layer, optionally as part of a double-sided adhesive tape comprising further layers, and the cover are applied together to the substrate and / or the electronic device.
• the transfer adhesive tape can thus be first connected to the substrate or the electronic arrangement or first to the cover.
• the method according to the invention can be performed such that the cover and / or the (adhesive) adhesive layer, in particular as transfer adhesive tape, completely cover the electronic arrangement.
• the method according to the invention is preferably performed in such a way that a region of the substrate around the electronic arrangement is completely or partially covered by the cover, whereby the adhesive tape can cover the entire surface of the electronic assembly for bonding - and likewise preferably a region of the substrate around the Covered electronic array, preferably the same area as the cover - or may be applied partially, such as a frame around the electrical arrangement around - preferably in the area, which is also covered by the cover is covered -, and optionally additionally in an edge region on the electronic assembly.
• the getter material may be dispersed in the adhesive layer or as a layer within or on one side of the adhesive layer.
• the getter material is present as a dispersed phase in the adhesive.
• the term "dispersed phase” is understood to mean that the getter material is finely distributed in the adhesive composition Basically, the shape and size of the getter material particles - of course within the limits resulting from the structure and function of the adhesive layer - have no limits Feature "present as a dispersed phase” includes a molar dispersion of the getter material and thus a true (molecular) solution of the getter material in the adhesive as well as a dispersion of getter material primary particles, getter material aggregates and getter material agglomerates.
• the getter particles may be spherical, rod-shaped, or platelet-shaped in structure. In particular, platelet-shaped materials are preferably substantially isolated and not in the form of a platelet stack.
• the feature "present as a dispersed phase” means that the getter material does not form a self-contained, continuous layer but is generally in the form of several dispersed particles, but does not mean that there must be an ideal distribution of the getter material particles in the adhesive layer However, this can be so, for example the getter material particles can certainly concentrate in certain areas within the layer or certain areas in the layer of adhesive layer can also be free of getter material.
• the size of the particles of the getter material is limited by the requirements of the thickness of the layer containing it, for example the adhesive layer.
• the size of the particles can therefore be considered about 200 ⁇ , but preferably getter in the form of particles having a particle size of at most 50 ⁇ , particularly preferably used in the form of particles having a particle size of at most 10 ⁇ .
• the getter material is preferably present in the form of particles in a particle size distribution in which a maximum of 1% by volume of the getter material exceeds the average layer thickness of the getter material-containing layer. This has the advantage that the getter particles do not protrude from the respective layer and thus strongly influence the surface properties negatively.
• the entire getter material contained in the transfer adhesive tape according to the invention is present in a particle size distribution in which a maximum of 1% by volume of the getter material exceeds the average layer thickness of the getter material-containing layer.
• particles are understood as meaning primary particles, aggregates and agglomerates of the getter material or getter materials.
• Particle size is understood to be the maximum extent of a particle. The determination of the particle size is preferably carried out by means of laser diffraction according to ISO 13320 (wherein agglomerates are dispersed in the dispersion step, but not aggregates), but other methods known to the person skilled in the art are also suitable.
• all getter materials are nanoscale, that is to say the maximum extent in at least one dimension is less than 500 nm, very particularly preferably less than 200 nm, for example less than 100 nm.
• getter materials are dispersed pyrogenic silica such as Aerosil from Evonik, Calcium Oxide Nanopowder from Sigma-Aldrich, calcium chloride CA-CI-02-NP from American Elements (Los Angeles), nanozeolite LTA or FAU from Nanoscape (Planegg-Martinsried ) or nanoscale zeolite Lucidot NCL 40 from Clariant (Frankfurt).
• pyrogenic silica such as Aerosil from Evonik, Calcium Oxide Nanopowder from Sigma-Aldrich, calcium chloride CA-CI-02-NP from American Elements (Los Angeles), nanozeolite LTA or FAU from Nanoscape (Planegg-Martinsried ) or nanoscale zeolite Lucidot NCL 40 from Clariant (Frankfurt).
• the transfer adhesive tape can consist of further layers beyond the layer of adhesive layer and possibly also a getter material layer. This can e.g. be further Klebemassetiken, carrier material or liner.
• Such a further layer is preferably a carrier material, in particular a polymeric carrier material, since this improves the stampability or applicability of the structure.
• the carrier material used may be textile fabrics, papers, plastic-coated papers or films, with films, in particular dimensionally stable plastic or metal foils, being preferred.
• a carrier layer therefore preferably consists of polyesters, in particular of polyethylene terephthalate, for example of biaxially oriented polyethylene terephthalate, or of polyolefins, in particular of polybutene, cyclo-olefin copolymer, polymethylpentene, polypropylene or polyethylene, for example of monoaxially oriented polypropylene, biaxially oriented polypropylene or biaxially stretched polyethylene.
• Polyester films have the advantage that they provide for temperature stability and bring in increased mechanical stability. It is therefore very particularly preferable for a carrier layer in a liner according to the invention to consist of a polyester film, for example of biaxially oriented polyethylene terephthal
• the carrier material also contains a barrier function against one or more specific permeate (s), in particular against water vapor and oxygen.
• a barrier function may consist of organic or inorganic materials.
• Support materials having a barrier function are described in detail in EP 2 078 608 A1.
• the support material particularly preferably contains at least one inorganic barrier layer.
• inorganic barrier layers are particularly well in vacuum (for example by evaporation, CVD, PVD, PECVD) or under atmospheric pressure (for example by means of atmospheric plasma, reactive corona discharge or flame pyrolysis) deposited metals such as aluminum, silver, gold, nickel or metal compounds such as Metal oxides, nitrides or hydronitrides, for example oxides or nitrides of silicon, boron, aluminum, zirconium, hafnium or tellurium or indium-tin oxide (ITO).
• ITO indium-tin oxide
• a particularly suitable method for applying an inorganic barrier layer is high-power impulse magnetron sputtering and atomic layer deposition, which allow particularly permeation-proof layers to be realized with a low temperature load on the carrier layer.
• WVTR water vapor
• OTR oxygen
• the carrier material is equipped with a barrier function as described above, it can also be regarded as a cover in the method according to the invention.
• the adhesive is first applied to the cover.
• Adhesive tapes which are coated with adhesives on one or both sides, are usually wound into a roll in the form of an Archimedean spiral at the end of the production process.
• the adhesive tapes before wrapping with a cover material also referred to as a release material
• cover material also referred to as a release material
• cover materials are familiar with such cover materials under the name of liners or release liners.
• liners are also used to cover pure adhesives (transfer adhesive tape) and adhesive tape sections (for example labels).
• the adhesive tape according to the invention and the adhesive tape used for the method according to the invention contain at least one getter material capable of sorbing at least one permeable substance
• “Sorption” is understood to mean the process of selectively taking up a substance or several substances by another substance, according to the invention, by the getter material
• the sorption of the permeable substance (s) by the getter material can take place, for example, by absorption or adsorption, with adsorption both in the form of chemisorption as well as physisorption.
• a "permeation-capable substance” is understood as meaning a substance which, as gaseous or liquid, if appropriate also as solid substance, is to be protected in the substance Adhesive penetrate and this can penetrate below.
• Such substances are hereinafter referred to as “permeates” - as has already been done several times in the present text
• the permeates can originate from the adhesive itself or from the environment, for example also from the carrier material of an adhesive tape coated with the adhesive
• Adhesive tapes themselves often contain low-molecular-weight organic compounds such as residual solvents, residual monomers, oils, resin components, plasticisers and water.
• the environment is often made up of water, volatile organic compounds (VOCs), low molecular weight hydrocarbons and oxygen.
• VOCs volatile organic compounds
• butyl ester t-butyl acetate
• ethanol methanol, n-hexane, n-heptane, 3-hexanone
• 2-propanol isopropanol
• 3-methyl-1-butanol isoamyl alcohol
• methylene chloride dichloromethane
• methyl ethyl ketone butanone
• Methyl isobutyl ketone nitromethane (nitrocarbole), n-pentane, 2-pentanone, 3-pentanone
• petroleum ether light gasoline
• gasoline propanol
• pyridine azine
• tert-butyl methyl ether tetrachloroethene (perchlorethene), tetrahydrofuran, toluene, trichloroethane
• Triethylamine Triethylamine, xylene, oxygen, methane, ethane
• a “getter material” is understood as meaning a material which, in the sense of the process defined above as “sorption”, can selectively or non-selectively take up at least one permeable substance.
• the getter material could therefore also be referred to as a "sorbent” or as a "sorbent”.
• the getter material is at least capable of sorbing water.
• Suitable getter materials are, for example: salts such as cobalt chloride, calcium chloride, calcium bromide, lithium chloride, lithium bromide, magnesium chloride, barium perchlorate, magnesium perchlorate, zinc chloride, zinc bromide, silicic acids (for example silica gel), aluminum sulfate, calcium sulfate, copper sulfate, barium sulfate, magnesium sulfate, lithium sulfate, sodium sulfate, Cobalt sulfate, titanium sulfate, sodium dithionite, sodium carbonate, sodium sulfate, potassium bisulfite, potassium carbonate, magnesium carbonate, titanium dioxide, diatomaceous earth, zeolites, layered silicates such as montmorillonite and bentonite, Metal oxides such as barium oxide, calcium oxide, iron oxide, magnesium oxide, sodium oxide, potassium oxide, strontium oxide, aluminum oxide (activated alumina); further carbon nanotubes, activated carbon,
• mixtures of two or more getter materials can also be used.
• the getter materials are preferred according to their function as substantially permeate-free materials used, for example anhydrous. This distinguishes getter materials from similar materials used as fillers.
• silica is often used as a filler in the form of fumed silica. However, if this filler is stored as usual under ambient conditions, it already absorbs water from the environment and is no longer technically usable as getter material. Only dried or dry-held silica can be used as getter material.
• Silica acids are, as described above, compounds of the general formula (SiO 2) m * nH20 understood. These are wet-chemical, thermal or fumed silica.
• silica gels or silica gels for example cobalt compounds impregnated with cobalt compounds as moisture indicator, (blue gel) and pyrogenic silicas are suitable getter materials.
• diatomaceous earth is also suitable, but this is generally not attributed to the silicic acids
• Silanes are understood to mean compounds of the general formula R a -Si-X 4 -a or their partial condensation products
• a is an integer from 0 to 3 and preferably 0 or 1.
• X is a hydrolyzable group, for example, and preferred for a halogen atom, in particular chlorine, an alkoxy group such as a methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy or tert-butoxy group
• R is an optionally substituted hydrocarbon radical, for example for a methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl group, a pentyl group and their branched isomers,
• the hydrocarbon radicals can also contain annular and / or aromatic components. Representative structures for this are cyclohexyl, phenyl and benzyl groups.
• the hydrocarbon radical (s) R contains, for example, one or more heteroatom-containing substituents such as amino groups, aminoalkyl groups, glycidyloxy groups, (meth) acryloxy groups and the like. If several substituents R are present, they may be the same or different.
• a silane usable as getter material is preferably selected from the group comprising N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 Aminopropyldiethoxymethylsilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane, (N-butyl) -3-aminopropyltrimethoxysilane, 3- (N -ethylamino) -2-methylpropyltrimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, 4-amino- 3,3-dimethylbutyldimethoxymethylsilane, (N-cyclohex
• Triethoxysilylpropylsuccinic anhydride 3-glycidyloxypropyltrimethoxysilane, 3- glycidyloxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- Glycidyloxypropyldiethoxymethylsilan, 3-methacryloyloxypropyltrimethoxysilane, 3- methacryloyloxypropyltriethoxysilane, 3-Methacryloyloxypropyltriisopropoxysilan, 3- methacryloyloxypropyldimethoxymethylsilane, 3-methacryloyloxypropyldiethoxymethylsilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3
• the getter material is selected from the group consisting of cobalt chloride, calcium chloride, calcium bromide, lithium chloride, lithium bromide, magnesium chloride, barium perchlorate, magnesium perchlorate, zinc chloride, zinc bromide, aluminum sulfate, calcium sulfate, copper sulfate, barium sulfate, magnesium sulfate, lithium sulfate, sodium sulfate, cobalt sulfate, titanium sulfate, sodium carbonate, sodium sulfate , Potassium carbonate, magnesium carbonate as well
• Polyolefin copolymers Polyamide copolymers, PET copolyesters,
• the getter material is preferably selected from the group consisting of iron, sodium dithionite, barium oxide, iron (II, III) oxide, carbohydrazide, activated alumina, zeolite, activated carbon, sulfites, ascorbates, hydrazine, morpholine, 2-butanone oxime, Diethylhydroxylamine, glucose, gallic acid, unsaturated fats and oils.
• organometallic oxidation additives based on chelating amines and transition metal complexes, in particular in conjunction with oxidizable substrate materials.
• the getter material is selected from the group consisting of cobalt chloride, calcium chloride, calcium bromide, lithium chloride, lithium bromide, magnesium chloride, barium perchlorate, magnesium perchlorate, zinc chloride, zinc bromide, aluminum sulfate, calcium sulfate, copper sulfate, barium sulfate, magnesium sulfate, lithium sulfate, sodium sulfate, cobalt sulfate, titanium sulfate, sodium carbonate, sodium sulfate , Potassium carbonate, zeolites, calcium, magnesium, barium oxide, calcium oxide, magnesium oxide, sodium oxide, potassium oxide, strontium oxide, activated carbon, phosphorus pentoxide, silanes, calcium hydride, barium hydride, strontium hydride, sodium hydride and lithium aluminum hydride, potassium hydroxide, sodium hydroxide, acetic anhydride, propionic anhydride, butyric anhydride, potassium hydro
• These getter materials have the advantage of being easily incorporated into the adhesive, a high sorptivity
• These are understood to be substances which can release released permeates, for example water, under certain conditions and thereby reach a state which makes them capable of renewed permeate uptake, thus enabling a process in which the getter-containing transfer adhesive tape before contacting with the adhesive is largely freed from optionally up to this time recorded per
• the getter material is selected from calcium oxide, calcium sulfate, calcium chloride and zeolites and mixtures of two or more of the above substances. These materials have particularly high capacities for the absorption of water and other permeates, are largely regenerable, can be incorporated into the adhesive outstandingly and do not affect the function of this layer in the amount according to the invention or only in a negligible manner.
• the getter material is calcium oxide.
• this substance allows conclusions to be drawn regarding the permeate content of the adhesive, for example by changing from white to a transparent appearance with increasing water absorption. As long as free getter capacity can still be identified on the basis of the optical appearance of the transfer adhesive tape, this can be taken as an indication that no or at most little permeate has yet diffused into the adhesive.
• Even metallic calcium loses its metallic-opaque appearance and becomes increasingly transparent, another example is Colbaldchlorid, which changes its color when absorbed from blue to pink.
• the getter material binds the permeate by chemisorption. This process is slower than physisorption due to the generally higher activation energy.
• a well-known example here is calcium oxide, which is converted by the permeate water into calcium hydroxide.
• the getter material is molecularly dispersed in the matrix material, since both the transparency and the surface roughness are less affected compared to particles.
• the getter material in particular isocyanates, metal complexes and organic metal compounds are used, preferably those organometallic Lewis acids which do not form an alcohol in a reaction with water. This is preferred because the alcohol, like water, can cause degradation of the organic electronic structure.
• Examples of such compounds are Al (C 2 H 5 ) 3, Al (C 4 H 9 ) 3, B (C 4 H 9 ) 3 , Zn (C 4 H 9 ) 2 , Al (t-butyl) 3 , Ti (t-butyl) 4 , Mg (t -butyl) 2 , Al (C 4 H 9 ) 2 (N (C 6 H 5 ) 2 ), Al (C 4 H 9 ) (N (C 6 H 5 ) 2 ) 2 , as well as others as described in US2006 / 0087230.
• a getter material is preferred which already has high activity at low permeate concentration.
• such getter materials are preferably used via the saturated aqueous solution at 20 ° C and an air pressure of 1013 mbar a relative humidity of less than 20% sets.
• the getter material is preferably selected from the group comprising sodium hydroxide, potassium hydroxide, lithium bromide, zinc bromide, lithium chloride, calcium bromide, lithium iodide and calcium acetate.
• the introduction of the getter material or the getter materials into the adhesive can be carried out by all methods known to the person skilled in the art.
• the getter material may be present in solution, dispersion, melt or as a fluid.
• the adhesive layer contains no more than 2% by weight of getter material. The content depends essentially on the desired absorption capacity for the respective permeates.
• the adhesive layer therefore contains 0.01 to 0.5 wt .-% getter material.
• this therefore contains 0.5 to 1, 9 wt .-%.
• a getter material with a high absorption capacity (maximum absorbable permeate weight> 25% of the getter weight) is preferred, since it makes it possible to keep the getter content low.
• the absorption capacity is determined after storage of the getter over 100 h at 23 ° C and 50% relative humidity for the permeate water vapor or at 23 ° C in a saturated atmosphere in other gaseous permeates.
• the permeate content of the getter after storage can be determined gravimetrically.
• the getter material is preferably selected from the group consisting of zeolite, copper sulfate, calcium oxide and calcium chloride.
• the transfer adhesive tape is transparent, that is, the transmission measured according to ASTM D1003-00 (Procedure A, in a modification, however, standard illuminant D65) is greater than 50%, preferably greater than 75%.
• ASTM D1003-00 Procedure A, in a modification, however, standard illuminant D65
• the sheet can be more easily positioned in the application and in applications where transparency is required, such as light emitting electronic assemblies or solar cells, for a at least partial, but also full-surface gluing the electronic structure can be used.
• the transfer adhesive tape is UV light impermeable, that is, the transmission in a wavelength range of 300 to 400 nm, measured according to ASTM D1003-00 (Procedure B, in a modification, however, standard illuminant D65) is less than 25%, preferably less than 10 %.
• a UV-impermeable fabric an electronic structure can be protected from changes (for example, chemical reactions, aging, cross-linking) by exposure to UV light.
• the getter is at the same time a UV absorber, since then can be dispensed with the additional addition of a UV absorber.
• the adhesive is preferably a pressure-sensitive adhesive or an activatable adhesive and in particular an activatable pressure-sensitive adhesive.
• acrylate-based pressure-sensitive adhesives are mentioned in the context of this document, they should include PSAs based on methacrylates and on the basis of acrylates and methacrylates, even without explicit mention, unless expressly stated otherwise. Also within the meaning of the invention are combinations and mixtures of several base polymers as well as adhesive resins, fillers, anti-aging agents and crosslinkers additivtechnischtechnisches used, the list of additives is to be understood only as an example and not limiting.
• Very preferably adhesives are used which can be kept anhydrous or which, due to their chemical nature, contribute to keeping the water content as low as possible. This can be achieved in particular by the use of pressure-sensitive adhesives having nonpolar properties.
• Very advantageous according to the invention are therefore pressure-sensitive adhesives based on synthetic rubbers; Styrene block copolymer compositions having an elastomeric block of unsaturated or hydrogenated polydiene blocks such as polybutadiene, polyisoprene, copolymers of both as well as other, familiar to the expert elastomeric blocks; PSAs based on polyolefins used.
• pressure-sensitive adhesives based on styrene block copolymers, polybutylenes, polyolefins, since these are distinguished by a high permeation barrier against water vapor and a low water content.
• heat-adhesive adhesives can be classified into two categories: thermoplastic heat-activated adhesives (hot-melt adhesives) and reactive heat-activated adhesives (reactive adhesives). Also included are those adhesives which can be assigned to both categories, namely reactive thermoplastic heat-activated adhesive adhesives (reactive hot melt adhesives).
• Thermoplastic adhesives are based on polymers that reversibly soften when heated and solidify again during cooling.
• Particularly suitable thermoplastic adhesives have been found to be advantageous on the basis of polyolefins and copolymers of polyolefins and of their acid-modified derivatives, of ionomers, of thermoplastic polyurethanes, of polyamides and polyesters and copolymers thereof, and also of block copolymers such as styrene block copolymers.
• the activatable adhesives which have non-polar properties are particularly preferably selected, since in this way the water content can be kept low and the barrier action against water vapor is good.
• the adhesives based on polyolefins, based on copolymers of polyolefins and their acid-modified derivatives, based on polyamides, based on polyamide copolymers and based on block copolymers such as styrene block copolymers are therefore particularly preferred.
• reactive heat-activated adhesive adhesives contain reactive components.
• the latter ingredients are also referred to as "reactive resins” in which the heating initiates a crosslinking process which, upon completion of the crosslinking reaction, ensures a durable, stable compound.
• Such adhesives preferably also contain elastic components, for example synthetic nitrile rubbers or styrene block copolymers. Such elastic Due to their high flow viscosity, components give the heat-activated adhesive composition a particularly high dimensional stability even under pressure.
• reactive heat-activated adhesive adhesives are those based on styrene block copolymers due to their non-polar character.
• Radiation activated adhesives are also based on reactive components.
• the latter constituents may comprise, for example, polymers or reactive resins in which the irradiation initiates a crosslinking process which, upon completion of the crosslinking reaction, ensures a permanent stable compound.
• Such adhesives preferably also contain elastic components, as stated above.
• activatable adhesives based on (meth) acrylates can also be used here; However, activatable adhesives based on epoxides, oxetanes or modified styrene block copolymers are preferably used.
• the adhesive according to the invention itself preferably has a permeate content of less than 1000 ppm, more preferably less than 500 ppm.
• the indication ppm refers to the relation of the total weight of permeates contained to the examined adhesive mass weight.
• the permeate content can be determined by means of gas chromatography according to VDA 277 or in the case of water according to DIN EN ISO 62 (gravimetric method, method 4) or DIN 53715 (Karl Fischer titration) after storage of the test specimen for 24 hours at 23 ° C and 50% relative humidity.
• the capacity of the getter materials is not so much claimed by contained in the adhesive permeates, but the tape can fulfill its function as permeates from the electronic assembly itself binding or even protect against permeables from the environment cover better.
• a getter material-containing adhesive with a low permeate content, it is advantageous to free the adhesive from a substantial proportion of the permeate contained in the composition itself before introducing the getter material. This is particularly important when adhesive tapes according to the invention are produced with a small proportion of material. This is achieved particularly advantageously by a further getter material, which also acts as a sorbent for the permeate, but is removed from the adhesive during the manufacturing process of the adhesive tape.
• Claimed is therefore a method for producing a gettermaterial restroomn adhesive tape, in which first a first getter material is added to the adhesive, and then add a second getter material, wherein the first getter material before or after the addition of the second getter material is removed from the mass, and then an adhesive tape is formed.
• the process according to the invention offers the advantage that permeate is simultaneously removed from essentially all constituents of an adhesive composition and thus the expense is less. Furthermore, such permeate is detected, which is introduced via manufacturing and / or transport devices in the adhesive.
• the method according to the invention is not intended to exclude the addition of further components of the adhesive to the adhesive composition after addition or removal of the first getter material or after addition of the second getter material. These can also be freed separately from permeate.
• This process is preferably carried out in a fluid state of the adhesive. Preference is given to a melt, a solution or a dispersion. In this state, the getter materials can be easily distributed and also the separation of the first getter material is easy to carry out with separation techniques known to those skilled in the art, e.g. Filtering, settling and decanting, precipitation or centrifugation, wherein a chemical reaction of the getter - regardless of any chemical reaction occurring by the permeate - should not be excluded before separation ..
• the first and the second getter material can be the same or different (chemically). If they are the same, it is preferred that they have at least one feature by which they can be separated, eg, different particle size or density. But this is not absolutely necessary, because the first getter material According to the invention can be removed from the adhesive again before the addition of the second getter material.
• the first getter material has a larger particle size than the second getter material. Then the first getter material can easily be filtered out.
• zeolite spheres having a diameter of more than 100 ⁇ m, preferably more than 500 ⁇ m, can be used for binding water, as is explained in the examples.
• getter materials basically all previously mentioned getter materials can be used.
• the first getter material is present as a disperse phase, more preferably as a particulate dispersed phase and not as a molar dispersed phase.
• the adhesive has a low permeation rate for the permeate to be immobilized.
• the water vapor permeation rate is preferably less than 50 g / (m 2 d), more preferably less than 20 g / (m 2 d), based on an adhesive composition thickness of 50 ⁇ m.
• the WVTR is measured at 38 ° C and 90% relative humidity according to ASTM F-1249, the oxygen permeation rate (OTR) at 23 ° C and 50% relative humidity according to DIN 53380 Part 3.
• 5000 g / (m 2 -d-bar) can be, for example - without the intention of
• Adhesives based on vinylaromatic block copolymers Adhesives based on vinylaromatic block copolymers
• PSA polymer blocks formed from vinyl aromatics, in particular of styrene; Furthermore, they advantageously contain polymer blocks which are formed by polymerization of 1,3-dienes, in particular butadiene and / or isoprene, and / or specifically or completely hydrogenated polymer blocks
• the polyvinylaromatic fraction of the block copolymers is advantageously from 10% by weight to 35% by weight. %.
• the pressure-sensitive adhesive comprises a proportion of the vinylaromatic block copolymers of at least 20% by weight, preferably at least 30% by weight, more preferably at least 35% by weight; and / or it has a proportion of vinylaromatic block copolymers of not more than 80% by weight, preferably not more than 65% by weight, more preferably not more than 60% by weight.
• the pressure-sensitive adhesive may comprise one or more resins or one or more resin mixtures, preferably hydrogenated resins having a degree of hydrogenation of at least 90%, more preferably of at least 95%.
• the PSA contains at least one resin which has a DACP of more than 30 ° C and a MMAP of more than 50 ° C, preferably a DACP of more than 37 ° C and a MMAP value greater than 60 ° C, and / or the PSA contains at least one resin having a softening temperature greater than 95 ° C, in particular greater than 100 ° C. It may contain one or more additives, preferably selected from the group consisting of: plasticizers, primary antioxidants, secondary antioxidants, process stabilizers, light stabilizers, processing aids,
• Endblocker resins polymers, in particular of an elastomeric nature. It is advantageous if the pressure-sensitive adhesive, in particular after crosslinking, has an elongation at break of at least 20%,
• partially crosslinked pressure-sensitive adhesive compositions based on acid or acid anhydride-modified vinylaromatic block copolymers may be mentioned.
• the PSA very advantageously contains polymer blocks formed from vinylaromatics, in particular styrene.
• pressure-sensitive adhesives based on acid or acid anhydride-modified vinylaromatic block copolymers which comprise polymer blocks formed by polymerization of 1,3-dienes, in particular butadiene and / or isoprene, and / or specific or fully hydrogenated polymer blocks.
• PSAs may advantageously be crosslinked with amines and / or epoxy resins and / or metal chelates.
• metal chelates may preferably such which can be represented by the formula (R 10) n M (XR 2 Y) m , where M is a metal of the 2nd, 3rd, 4th and 5th main groups or a transition metal; Ri is an alkyl or aryl group such as methyl, ethyl, butyl, isopropyl or benzyl; n is zero or a larger integer; X and Y are oxygen or nitrogen, each of which may also be bonded to R2 by a double bond; R 2 is an alkylene group linking X and Y, which may be branched or may also contain oxygen or other heteroatoms in the chain; m is an integer, but at least 1.
• the chelate may be an acetylacetonate, especially aluminum acetylacetonate.
• the block copolymers have a Polyvinylaromatenanteil of 10 wt .-% to 35 wt .-%.
• the proportion of the vinylaromatic block copolymers in the pressure-sensitive adhesive is preferably at least 30% by weight, preferably at least 40% by weight, more preferably at least 45% by weight.
• the proportion of vinylaromatic block copolymers in the pressure-sensitive adhesives should not exceed 80% by weight, preferably 70% by weight.
• the pressure-sensitive adhesive may contain a resin or a mixture of resins, preferably hydrogenated resins having a degree of hydrogenation of at least 90%, more preferably of at least 95%.
• the PSA may contain one or more additives, preferably selected from the group comprising plasticizers, primary antioxidants, secondary antioxidants, process stabilizers, light stabilizers, processing aids, endblocker resins, polymers, in particular of an elastomeric nature.
• the PSA may contain one or more fillers, such as nanoscale fillers, transparent fillers.
• the fillers are nanoscale in at least one dimension.
• Adhesives based on polyolefin in particular as described for example in DE 10 2008 062 130 A.
• Pressure-sensitive adhesives based on a partially crystalline polyolefin are particularly preferred, the polyolefin having a density of between 0.86 and 0.89 g / cm, preferably between 0.86 and 0.88 g / cm 3 , very preferably between 0.86 and 0, 87 g / cm 3 , and a crystallite melting point of at least 90 ° C, preferably of at least 1 15 ° C, very preferably of at least 135 ° C.
• the polyolefin is combined with at least one tackifier resin, wherein preferably the amount of tackifier resin is 130 to 350 phr, more preferably 200 to 240 phr.
• the PSA comprises a hydrogenated resin, preferably with a degree of hydrogenation of at least 90%, more preferably of at least 95%.
• One or more additives may be included preferably selected from the group consisting of: plasticizers, primary antioxidants, secondary antioxidants, process stabilizers, light stabilizers, processing aids, UV blockers.
• Adhesives based on isobutylene and / or based on Butylenblockcopolymerbasis in particular those, for example, according to DE 10 2008 060 1 13 A.
• Particularly preferred are pressure-sensitive adhesives based on isobutylene block copolymers.
• the PSA preferably comprises polymer blocks formed from vinylaromatics, in particular styrene, and polymer blocks which are formed by polymerization of isobutylene or of isobutylene in combination with n-butene and / or 1,3-dienes, in particular butadiene and / or isoprene.
• the block copolymers preferably have a Polyvinylaromatenanteil of 10 wt .-% to 35 wt .-%.
• the proportion of the block copolymers in the pressure-sensitive adhesive is preferably at least 20% by weight, preferably at least 30% by weight, more preferably at least 35% by weight, and / or at most 90% by weight, preferably at most 75% by weight. , more preferably at most 70% by weight. It is advantageous if the proportion of the isobutylene block copolymers in the total proportion of the block copolymers is at least 40% by weight, preferably at least 55% by weight.
• the pressure-sensitive adhesive may contain a resin or a mixture of resins; preferably it contains hydrogenated resins having a degree of hydrogenation of at least 90%, more preferably of at least 95%.
• the resin contained in the PSA preferably has a DACP of greater than 30 ° C and a MMAP greater than 50 ° C, preferably a DACP greater than 37 ° C and a MMAP greater than 60 ° C, and / or a softening temperature of more than 95 ° C, in particular of more than 100 ° C. It may contain one or more additives, preferably selected from the group consisting of: plasticizers, primary antioxidants, secondary antioxidants, process stabilizers, light stabilizers, processing aids,
• Endblocker resins polymers, in particular of an elastomeric nature
• activatable adhesives in particular as they are shown in DE 10 2009 036 986 A.
• thermally activatable adhesive or hot-melt adhesives which can be activated advantageously by heat generated by ultrasound or magnetic induction, in particular the heat is generated by suitable activatable additives in the interior of the adhesive.
• suitable activatable additives for this purpose, in the adhesive, for example, iron oxide particles which are enveloped by silicon dioxide may be provided.
• this reference shows photocurable compositions comprising (A) an epoxy resin having at least two glycidyl groups in each molecule and having a number average molecular weight Mn of from 200 to 7,000, (B) an epoxy resin having at least one glycidyl group in each molecule and having a number average molecular weight of from 20,000 to 100000, (C) a latently acidic photocatalyst capable of activating acid functionality by irradiation, and (D) a silane coupling agent having at least one glycidyl group in each molecule, wherein the amount of component (B) is 30 to 150 parts by weight, based on 100 parts by weight of component (A), and wherein the amounts of components (C) and (D) are each 0.1 to 10 parts by weight, based on 100 parts by weight of components (A) and (B) together, and wherein the composition is non-flowable at 25 ° C but fluid in a range of 50 ° C to 100 ° C.
• Adhesives based on polyamide in particular as presented for example in DE 10 2006 047 739 A.
• This document shows heat-activatable adhesives which consist at least of a) a polyamide having amino and / or acid end groups, b) an epoxy resin, and c) optionally a plasticizer, wherein the polyamide reacts with the epoxy resin at temperatures of at least 150 ° C and the Ratio in parts by weight of a) and b) is between 50:50 to 99: 1.
• the polyamide is advantageously a non-crystalline copolyamide such as PA 6,6 / 6,12 or PA 6,6 / 6,1.
• the viscosity number of the polyamide in 96% sulfuric acid measured according to ISO 307 is preferably 100 to 130 ml /G.
• plasticizers for example, phthalates, trimellitates, phosphoric acid esters, natural oils, polyalkylene oxides, rosin resins and / or polyethylene glycol can be selected.
• the proportion of plasticizer is preferably between 5 wt .-% and 45 wt .-% of the total mass of the adhesive.
• the adhesive may advantageously be admixed with additives, such as accelerators, dyes, carbon black and / or metal powder.
• Adhesives comprising (a) at least one copolymer containing at least isobutylene or butylene as comonomer and at least one comonomer species having a softening temperature of greater than 40 ° C as a hypothetical homopolymer, (b) at least one kind of at least partially hydrogenated adhesive resin, (c) at least one type of reactive resin based on cyclic Ethers having a softening temperature of less than 40 ° C, preferably less than 20 ° C; (d) at least one type of photoinitiator for initiating cationic curing; and adhesives comprising (a) at least one copolymer containing at least isobutylene or butylene as comonomer and at least one comonomer which - considered as a hypothetical homopolymer - a softening temperature greater than 40 ° C, (b) at least one kind of at least partially hydrogenated adhesive resin, (e ) at least one type of reactive resin based on acrylates or me
• the copolymer (s) may be, for example, random, alternating, block, star and / or graft copolymers having a molecular weight M w of 300,000 g / mol or less, preferably 200,000 g / mol or less.
• the copolymer (s) Block, star and / or graft copolymers in a preferred embodiment have at least one grade of a first polymer block ("soft block") having a softening temperature of less than -20 ° C and at least one grade of a second polymer block (“hard block”). with a softening temperature greater than +40 ° C.
• the soft block may be constructed in a non-polar manner and contain butylene or isobutylene as the homopolymer block or copolymer block, the latter preferably copolymerized with itself or with one another or with further particularly preferably nonpolar comonomers.
• the hard block is composed of styrene, styrene derivatives and / or of other aromatic or (cyclo) aliphatic hydrocarbon monomers or of methacrylates or of acrylates.
• the at least one block copolymer is a triblock copolymer which is made up of two terminal hard blocks and one medium soft block.
• the adhesive resin (s) preferably has a degree of hydrogenation of at least 70%, more preferably of at least 95%.
• the adhesive may advantageously contain one or more additives, independently selected from the following group: Resins which have a DACP value of more than 30 ° C.
• Reactive resins which carry at least one epoxide or at least one oxetane group;
• Photoinitiators that absorb UV light above 250 nm and below 350 nm ⁇ Plasticizers, ⁇ primary antioxidants, ⁇ secondary antioxidants, ⁇ process stabilizers, ⁇ light stabilizers, ⁇ processing aids, ⁇ endblocker resins, ⁇ polymers, in particular of an elastomeric nature;
• Fillers preferably nanoscale fillers, transparent fillers and / or getter and / or scavenger fillers.
• the adhesive is transparent in the visible light of the spectrum (wavelength range from about 400 nm to 800 nm) and / or exhibits a haze of less than 5.0%, preferably less than 2.5%.
• the facts disclosed in the respective documents are referred to explicitly. The mention of the above examples should not unnecessarily limit the choice of the adhesives of the invention.
• a further subject of the invention is a transfer adhesive tape comprising at least one layer of a getter material-containing PSA or of an activatable adhesive and in particular of an activatable PSA, wherein the adhesive comprises a getter material in an amount of less than 2% by weight, preferably less than 1% by weight. , more preferably less than 0.5 wt .-%.
• the adhesive tape may also contain further layers, for example one or more further adhesive layers or a carrier material.
• Fig. 3 shows a second inventive (opto) electronic arrangement in a schematic representation.
• Fig. 1 shows a first embodiment of an organic electronic device 1 according to the prior art.
• This arrangement 1 has a substrate 2 on which an electronic structure 3 is arranged.
• the substrate 2 itself is formed as a barrier for permeates and thus forms part of the encapsulation of the electronic structure 3.
• an adhesive 5 is provided circumferentially next to the electronic structure 3 on the substrate 2. It is irrelevant whether the adhesive was first connected to the substrate 2 or first with the cover 4.
• the pressure-sensitive adhesive 5 connects the cover 4 with the substrate 2.
• the PSA 5 also allows the spacing of the cover 4 of the electronic structure 3.
• the adhesive 5 is one of the prior art, that is to say an adhesive with a high permeation barrier, which moreover can be filled to a high proportion with getter material.
• the adhesive 5 not only performs the function of connecting the substrate 2 to the cover 4, but also forms a barrier layer for permeation, so as to encapsulate the electronic structure 2 from the side against permeates such as water vapor and oxygen. If the adhesive is applied in the form of a liquid adhesive, a high proportion of getter material is generally not critical, since the fluid form ensures good flow and thus good sealing of the interface.
• the adhesive is a transfer adhesive tape which is tacky or is put into a sticky state by an activation step, eg by heating
• a high proportion of getter material after application generally does not result in complete wetting of the surfaces of the substrate and / or covering, so that the permeation barrier is disturbed at the interface.
• a transfer adhesive tape would also be provided in the form of a stamped product which, because of its filigree geometry, is more difficult to handle than a transfer adhesive tape applied substantially over the entire surface.
• FIG. 2 shows an embodiment of an (opto) electronic device 1 according to the invention.
• the transfer adhesive tape 6 is one based on the transfer adhesive tape according to the invention as described above in a general form and is described in more detail below in exemplary embodiments.
• the transfer adhesive tape consists in the illustrated embodiment only of one layer of an adhesive fraction filled to less than 2% by weight.
• the combination of an adhesive filled with getter material with the full-surface coverage also shows another surprising synergistic effect: the electronic arrangement does not degrade over the entire surface but only slowly from the edge. As a result, a large part of the arrangement can still be used even with the first penetration of permeates. Due to the dense interface between transfer adhesive tape and substrate or cover as well as the electronic arrangement Permeate are forced to permeate through the adhesive itself, in the surprisingly sufficient combination of a small amount of getter with a high permeation barrier, the life to a similar extent extend like a high Gettermaterialanteil.
• the cover 4 does not necessarily have to meet the high barrier requirements since the barrier is already provided by the pressure-sensitive adhesive when the electronic assembly is completely covered by the transfer adhesive tape.
• the cover 4 may, for example, only perform a mechanical protective function, but it may also be additionally provided as a permeation barrier.
• FIG. 3 shows an alternative embodiment of an (opto) electronic device 1.
• two transfer adhesive tapes 6a, b are now provided, which in the present case are identical, but may also be different.
• the first transfer adhesive tape 6a is arranged over the entire surface of the substrate 2.
• the electronic structure 3 which is fixed by the transfer adhesive tape 6a.
• the composite of transfer adhesive tape 6a and electronic structure 3 is then completely covered with the further transfer adhesive tape 6b, so that the electronic structure 3 is encapsulated on all sides by the transfer adhesive tapes 6a, b.
• the cover 4 is provided above the transfer adhesive tape 6b.
• neither the substrate 2 nor the cover 4 necessarily have barrier properties. However, they can still be provided to further restrict the permeation of permeates to the electronic structure 3.
• the transfer adhesive tape here and preferably in each case has a homogeneous layer thickness.
• the transition is fluid and it may remain small un-filled or gas-filled areas. Possibly.
• the adhesive is locally compressed to different degrees, so that a certain compensation of the height difference can be made to the edge structures by flow processes.
• the dimensions shown are not to scale, but rather serve only a better representation.
• the electronic structure itself is usually relatively flat (often less than 1 ⁇ thick).
• the thickness of the transfer adhesive tape may include all conventional thicknesses, that is from about 1 ⁇ up to 3000 ⁇ . Preference is given to a thickness of between 25 and 100 ⁇ m, since adhesion and handling properties are particularly favorable in this area. Another preferred range is a thickness of 3 to 25 ⁇ , since in this area the amount of permeating through the adhesive joint substances can be kept low solely by the small cross-sectional area of the adhesive joint in an encapsulation application.
• the support of the adhesive tape or liner is coated or printed on one side with the getter material-containing adhesive from solution or dispersion or 100% (for example melt), or the adhesive tape is produced by (co) extrusion.
• a preparation by transfer of an adhesive layer according to the invention by lamination to a carrier material or a liner is possible.
• the adhesive layer can be crosslinked by heat or high-energy radiation.
• this production process takes place in an environment in which the specific permeate is present only in low concentration or almost not at all.
• a relative humidity of less than 30%, preferably less than 15% may be mentioned.
• the adhesive used can be blended with one or more additives such as tackifiers (resins), plasticizers, fillers, pigments, UV absorbers, light stabilizers, antiaging agents, crosslinking agents, crosslinking promoters or elastomers.
• the amount of an adhesive layer is preferably 1 to 120 g / m 2 , preferably 10 to 100 g / m 2 , where "amount" is understood to mean the amount after any removal of water or solvent.
• Another object of the present invention is the use of a change in the optical properties of the getter material for the indication of the freedom of the adhesive tape. For example, with increasing water binding, calcium oxide changes its color from white to transparent.
• the SBBS contains about 68% by weight diblock content.
• the solvent used was a mixture of toluene and acetone in the ratio 2: 1.
• Block polystyrene content 36 wt .-% diblock and 1 wt .-% maleic acid Kraton
• the solvent used was methyl ethyl ketone.
• the adhesive was prepared in a process as disclosed in DE102006047739 A1 with ethanol as solvent.
• Acrylate pressure-sensitive adhesive which contained as comonomers 30% by weight of ethylhexyl acrylate, 67% by weight of butyl acrylate and 3% by weight of acrylic acid.
• the individual comonomers were polymerized in a manner known to those skilled in the art in a mixture of gasoline and acetone.
• the water vapor (WVTR) and oxygen permeation rate (OTR) were determined. This was carried out with the activatable adhesives in the activated, ie crosslinked, state.
• the WVTR was measured at 38 ° C and 90% relative humidity according to ASTM F-1249, the OTR at 23 ° C and 50% relative humidity according to DIN 53380 Part 3.
• Adhesive WVTR [g / m 2 d] OTR [cm 3 / m 2 d bar]
• the adhesive tapes were produced in a glove box under a nitrogen atmosphere at 23 ° C. and 1 ppm water content.
• transfer adhesive tapes For the production of transfer adhesive tapes, the different adhesives from a solution were applied to a conventional permeation-tight liner of the type ALU I 38 UV1 Mondi, containing a support made of aluminum foil, applied by means of a laboratory coater and dried.
• the adhesive layer thickness after drying was 25 ⁇ each.
• the drying was carried out in each case at 120 ° C. for 30 minutes in a drying oven.
• the adhesive layers were also covered on the open side with the above-mentioned liner.
• the transfer adhesive tapes produced by way of example according to the invention thus each consisted of only one layer of an adhesive.
• transfer adhesive tapes having getter contents higher than the getter contents according to the invention were produced.
• getter-filled transfer adhesive tapes were sealed immediately after production in vacuum-sealed bags made of a permeation-tight film laminate (polyester film-aluminum foil sealant film) stored in the glove box under a nitrogen atmosphere and removed just before use.
• a permeation-tight film laminate polyyester film-aluminum foil sealant film
• Examples of Examples 1-4 and Comparative Examples V1-V4 and V10-V12 were the bond strengths on steel analogous to ISO 29862 (Method 3) at 23 ° C and 50% relative humidity with a take-off speed of 300 mm / min and a peel angle of 180 ° determined.
• the reinforcing film used was an etched PET film with a thickness of 50 ⁇ m, as available from Coveme (Italy).
• the gluing of the measuring strip was carried out by means of a laboratory laminator at a temperature of 60 ° C. Only the adhesive K2 was glued at a temperature of 120 ° C. The tapes were peeled off 14 days after application.
• a calcium test was used. This is shown in FIG.
• a 20 x 20 mm 2 large, thin calcium layer 23 is deposited on a glass plate 21 in a vacuum and then stored under a nitrogen atmosphere.
• the thickness of the calcium layer 23 is about 100 nm.
• an adhesive tape (26 ⁇ 26 mm 2 ) with the adhesive 22 to be tested and a thin glass pane 24 (35 ⁇ m, Schott) is used as the carrier material.
• the thin-glass pane was laminated with a 100 ⁇ thick PET film 26 by means of a 50 ⁇ thick transfer adhesive tape 25 of an optically highly transparent acrylic PSA.
• the adhesive 22 is applied to the glass plate 21 in such a way that the adhesive 22 covers the calcium mirror 23 with an edge of 3 mm (AA) protruding on all sides. Due to the opaque glass carrier 24 only the permeation through the pressure sensitive adhesive or along the interfaces is determined.
• the application was carried out by means of a roll laminator at specific temperatures for each adhesive.
• irradiation with UV light was subsequently carried out by means of a medium-pressure mercury vapor radiator with a UV-C dose of about 200 mJ / cm 2 (determined with the UV-Power Puck device from EIT (USA) in the wavelength range of 250-260 nm).
• a hot pressing step was carried out at a temperature of 160 ° C. and a pressure of about 1 MPa:
• the test is based on the reaction of calcium with water vapor and oxygen, as described for example by AG Erlat et. al. in the "47th Annual Technical Conference Proceedings Society of Vacuum Coaters", 2004, pages 654 to 659, and by ME Gross et al., in the 46th Annual Technical Conference Proceedings Society of Vacuum Coaters, 2003, Pages 89 to 92 are described.
• the light transmission of the calcium layer is monitored, which increases by the conversion into calcium hydroxide and calcium oxide. This takes place in the described test setup from the edge, so that the visible surface of the calcium level is reduced. It is called the time to halving the light absorption of the calcium level as a lifetime.
• the method captures both the degradation of the surface of the calcium level from the edge and the selective reduction in the area as well as the homogeneous reduction of the layer thickness of the calcium level due to full-scale degradation.
• the measuring conditions used were 60 ° C and 90% relative humidity.
• the samples were glued with a layer thickness of the PSA of 25 ⁇ over the entire surface and without bubbles.
• the measured value (in h) was the average of three individual measurements.
• the transfer adhesive tapes according to the invention show a service life in a similar order of magnitude as adhesive tapes according to the prior art (compare Examples 1 -3 with V1 -V2, 4 vs. V3-V4).
• adhesive tapes according to the invention achieve even longer lifetimes than adhesive tapes, which according to the prior art are already considered to be filled with getter material only to a small extent (compare Examples 5 vs. V5, 6-8 vs. V6-V7, 9-1 vs. V8-V9).
• Comparative Examples V10-V12 show that the synergistic effect does not occur with adhesives which already have a high permeation rate of permeates which lead to a degradation of the calcium in the life test.
• the effect occurs only when using adhesives which already present a high permeation barrier, in particular which at a thickness of 50 ⁇ m has a water vapor permeation rate of less than 50 g / m 2 d and / or an oxygen permeation rate of less than 5000 g / m 2 d bar.

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• Chemical & Material Sciences (AREA)
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• 2012
  • 2012-06-29 DE DE102012211335.5A patent/DE102012211335A1/de not_active Withdrawn
• 2013
  • 2013-05-27 EP EP13727834.7A patent/EP2867318B1/de active Active
  • 2013-05-27 CN CN201380040109.1A patent/CN104508063B/zh active Active
  • 2013-05-27 US US14/411,585 patent/US9543549B2/en active Active
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