DE102012224319A1 - Removing permeate from a flat structure, comprises affixing an adhesive tape containing getter material to flat structure, storing composite containing adhesive tape and flat structure, and removing adhesive tape from the flat structure - Google Patents

Abstract

Removing permeate from a flat structure, comprises affixing an adhesive tape containing at least one getter material to the flat structure, storing the obtained composite containing adhesive tape and flat structure, and removing part of the adhesive tape containing the getter material from the flat structure. An independent claim is also included for an adhesive tape, comprising a support layer with a water vapor permeation rate of less than 1 g/(m 2>.d) (as measured by ASTM F-1249 at 38[deg] C and 90% relative humidity), an adhesive compound, and a getter material arranged between the substrate layer and the adhesive compound or contained in the adhesive compound and capable of absorbing at least one substance capable of permeation, where the adhesive compound is reversible.

Description

The invention relates to the technical field of functionalized tapes. A method is proposed for removing permeates from a sheet and a suitable adhesive tape.

Optoelectronic devices are increasingly being 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. The production of such arrangements is often carried out by printing processes such as high pressure, gravure, screen printing, planographic printing or so-called "non impact printing" such as thermal transfer printing, inkjet printing or digital printing. In many cases, however, vacuum processes such as chemical vapor deposition (CVD), physical vapor deposition (PVD), plasma-enhanced chemical or physical deposition methods (PECVD), sputtering, (plasma) etching or vapor deposition are used. The structuring is usually done by masks.

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 solar cells, in particular 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 RFID transponder listed.

As a technical challenge for the realization of a sufficient life and function of optoelectronic arrangements in the field of inorganic and organic optoelectronics, especially organic optoelectronics, a protection of the components contained therein is to be seen before permeates. As permeate gaseous or liquid substances are generally considered, which penetrate into a solid and penetrate or walk through this, if necessary. Accordingly, many low molecular weight organic or inorganic compounds may be permeates, with water vapor and oxygen being of particular importance in the context described herein.

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. In the case of inadequate protection, the luminosity can be reduced, for example, by oxidation or hydrolysis processes in the case of electroluminescent lamps (EL lamps) or organic light-emitting diodes (OLED), in the case of electrophoretic displays (EP displays) or in the case of solar cells, the efficiency can be drastically reduced within a short time.

In addition to the protection against penetrating permeates but also the removal of harmful permeates from many materials used in the construction of the electronic device itself is absolutely necessary. In particular, the polymeric substrate, cover or adhesive films frequently used in flexible constructions themselves often contain harmful permeate, in particular water, so that these materials have to be dried consuming.

Furthermore, especially in the continuous production of flat electronic devices, materials are used which only function as auxiliary materials, such as e.g. temporary support materials bearing e.g. discrete units are placed and transported through successive processing stages.

Also auxiliary materials, of which only parts remain in the electronic structure, are used and are accordingly to provide permeatfrei available.

In particular, to provide permeate-free is, for example, a carrier film, as used in "Laser Induced Thermal Imaging" (LITI) for providing and transfer of the organic light-emitting layer, since it is in direct contact with the sensitive materials.

Furthermore, intermediates in the production of planar electronic structures are sometimes coated or printed with materials which are present in aqueous dispersion. Thus, e.g. Electron or hole transport layers made from intrinsically conductive polymers such as Clevios (PEDOT: PSS; Heraeus Precious Metals). Such layers must be laboriously liberated to a high degree from the water, since they are in direct contact with the sensitive materials.

However, processes for drying or keeping dry sheets are also used in other fields of application, e.g. in pharmacy in the manufacture and storage of active ingredient patches or medical diagnostic strips; in the chemical analysis in the extraction of substances to be analyzed or in general to cover sensors.

Drug-containing patches or Transdermal Therapeutic Systems (TTS, TDS) were launched in 1979 and are now widely used with a range of drugs. With these systems, which are comparable to purely optically conventional plasters, active ingredients (eg hormones, nicotine and others) are transdermally administered through the skin. The advantage of this dosage form is the transition of the drug into the blood vessels, bypassing the gastrointestinal tract. This protects the gastrointestinal system and reduces the metabolism of the active substance by the hepatic system before reaching the site of action. Furthermore, the patient acceptance (compliance) is improved, because the application of the systems is not daily, but only at longer intervals. The situation is similar with oral soluble films (oral dissolvable films, ODF).

The benefits of TTS and ODF could be even more pronounced if drug delivery from such systems was interactive and controlled. This includes e.g. the release or mobilization of drugs by permeates, e.g. Water vapor or oxygen, which may only enter the system after application. Accordingly, there is a need to release such drug patches after the production of permeate and to keep permeatfrei as well as to provide the patient.

Methods of incorporating permeates of certain materials by means of adhesives are well known in the art.

US 6,103,141 describes, for example, a desiccant-filled hot-melt adhesive which is provided in the form of an adhesive tape. This tape is glued to the inside of a container to keep the container space dry. In a preferred embodiment, the desiccant-filled hot melt adhesive is coated on one side of a substrate and the other side of the substrate is coated with a desiccant-filled adhesive which then makes the connection to the vessel wall in use.

US 6,139,935 describes an oxygen-absorbing label which is adhered to the inside of a container and keeps the container interior of oxygen free.

In DE 199 13 761 A1 For example, a sheet-like and activatable drying device for reducing the moisture content of a gas space surrounding the device and a production method for such a device are described. The desiccant may also be incorporated into a pressure-sensitive adhesive layer.

Subject of the EP 0 582 968 B1 is a film composite with water vapor barrier, which consists of a first plastic film, an adhesive layer formed by a solvent-containing or solvent-free adhesive or a hot melt adhesive containing 10 to 50 wt .-% finely divided water-absorbing polymer powder (SAP), and one of these adhesive layer with the first Plastic film connected second plastic film consists. Such a film composite is used for packaging moisture-sensitive products. The water-absorbent adhesive layer filled with desiccant delays the passage of water through the film composite. It is thus substantially reduced the penetration of water into the package.

JP 2001072946 A describes an adhesive tape having a substrate and a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer contains a hygroscopic powder and a moisture-absorbing substance. At the Hygroscopic powders are hydroxy acid or its salts, which act as a hardening retarder for mortar or concrete. The desiccant should cause a better dispersibility of these retarders in the adhesive composition, so keep the retarder dry. Mortar or concrete, which, due to an uneven surface of tiles, runs into the gap between tile and adhesive tape, is prevented from curing by the retarder contained in the adhesive, so that it is easily wiped off the produced composite after removal of the adhesive tape can.

US 6,112,888 discloses a hot melt adhesive composition of a polymer and a desiccant used to maintain or produce a dry packing atmosphere. The composition is applied from the melt, for example by extrusion or spraying, in the interior of a package, but can also be applied directly to the contents.

US 6,936,131 describes an encapsulation process for organic electronic devices in which a desiccant-containing transfer adhesive tape is used to bond substrate and cover. The desiccant delays the permeation of water vapor through the bond line to the electronic structure.

Thus, it is known in the art to use adhesive tapes for drying gas spaces or as a permeation barrier in adhesive joints. In addition, however, there is also a need for methods for drying fabrics.

Area-shaped structures, in particular those which are produced or processed in web form in a continuous process, are difficultly permeate-free, in particular dry, to produce, or to be free of permeate, owing to their often large dimensions and their frequent presence in wound form. Because of their high surface area / volume ratio, they also easily pick up permeate from the environment, so they must be freed from permeate before being placed in a permeate-free environment or before contact with permeable materials.

The object of the invention is therefore to provide an easy to carry out and effective method and apparatus for receiving permeates from fabrics available.

The solution of the task is based on the idea to realize this via a correspondingly equipped adhesive tape.

A first subject of the invention is therefore a method for removing permeates from a sheet, which comprises adhering an adhesive tape containing at least one getter material to the sheet, storing the composite of adhesive tape and sheets thus obtained, and removing the adhesive tape from the sheet, wherein the adhesive tape can at least partially accommodate at least one permeate from the sheet.

A "sheet" is understood to mean a planar arrangement of a system whose dimensions are significantly smaller in one spatial direction (thickness or height) than in the two other spatial directions defining the main dimension (length and width). Such a sheet may according to the invention be made compact or perforated and consist of a single material or of different materials. A fabric may have a constant thickness over its entire surface area or different thicknesses. It may moreover consist of a single layer or of several layers which may be arranged congruently or at least partially not covering.

The fabric is, for example, a film, in particular a substrate, cover and / or adhesive film and / or a carrier film, a layer which may also be arranged on a carrier film and / or may be part of a multilayer composite, and / or an active substance plaster.

An adhesive tape is understood as meaning a carrier material coated with at least one pressure-sensitive adhesive or at least one activatable adhesive or a pressure-sensitive adhesive or activatable adhesive which is in the form of a permanent structure. An adhesive tape is basically considered in its shape as a sheet. Extended length and limited width tapes, tape sections, labels, diecuts, and the like are thus encompassed by the term "adhesive tape." On the other hand, it does not include hardened and not yet cured liquid adhesives or adhesions produced therewith.

Preferably, the adhesive applied to the fabric of the adhesive tape used in the process according to the invention is a pressure-sensitive adhesive or an activatable adhesive. Particularly preferably, the adhesive applied to the fabric of the adhesive tape used in the process according to the invention is an activatable pressure-sensitive adhesive. Adhesive adhesives are adhesives whose set film remains permanently tacky and tacky at room temperature in the dry state. Pressure-sensitive adhesives allow a permanent connection with the primer under relatively low pressure.

In general, a distinction is made between PSAs for permanent applications and for reversible applications (reversibly adjusted PSAs). While the former usually only with great effort and often with destruction of the substrate or the adhesive tape can be replaced again, the latter can be replaced with relatively little effort and without destroying the primer usually completely residue-free again.

According to the invention, the adhesive applied to the fabric of the adhesive tape used in the method according to the invention is preferably set reversibly.

The reversibility of a PSA can be described by means of its viscoelastic properties.

With regard to its viscoelastic properties, a substance is generally considered to be suitable for pressure-sensitive adhesive applications if, at room temperature in the frequency range from 10 ⁰ to 10 ¹ rad / s, ideally in the frequency range from 10 ^-1 to 10 ² rad / s, the storage modulus G 'is within the range from 10 ³ to 10 ⁶ Pa and when the loss modulus G "is also within this range. Within this range, which can also be referred to as a viscoelastic window for pressure-sensitive adhesive applications or as a pressure-sensitive adhesive window according to viscoelastic criteria in a matrix application of G 'and G''(G' as a function of G ''), there are again different sectors or Quadrants that characterize the expected pressure-sensitive adhesive properties of the respective substances in more detail. After Chang ( J. Adhesion, 1991, vol. 34, pp. 189-200 ) are reversible PSAs characterized by G 'in the range of 10 ³ -3 × 10 ⁴ Pa and G "in the range of 10 ³ - 3 × 10 ⁴ Pa each at room temperature and a measurement frequency of 10 ^-2 rad / s.

Storage modulus and loss modulus for PSAs are determined here in the oscillatory shear experiment (dynamic mechanical analysis, DMA) under torsional stress at a temperature of 23 ° C. and a frequency of 0.01 rad / s. The test serves to study rheological Properties and is in Pahl et al. "Practical rheology of plastics and elastomers", VDI-Verlag, 1995, pages 57 to 60 and 119 to 127 ) described in detail. The test is run in a shear rate controlled rheometer under torsional loading using a plate-plate geometry with a plate diameter of 25mm.

According to the invention, an adhesive is generally considered to be reversible when it has an adhesion to steel of <3 N / cm, preferably of <2.2 N / cm.

According to the invention, it is possible to use all PSAs known to the person skilled in the art in the process according to the invention, that is to say, for example, those based on acrylates and / or methacrylates, polyurethanes, natural rubbers, synthetic rubbers; Styrene block copolymer compositions comprising an elastomeric block of unsaturated or hydrogenated polydiene blocks such as polybutadiene, polyisoprene, copolymers of both, polybutylene, especially polyisobutylene, and other elastomeric blocks familiar to those skilled in the art; Polyolefins, in particular poly-α-olefins and / or polyisobutylenes; Fluoropolymers and / or silicones. The term "pressure-sensitive adhesive" also includes other compositions which have pressure-sensitively adhesive properties in accordance with the "Handbook of Pressure Sensitive Adhesive Technology" by Donatas Satas (Satas & Associates, Warwick 1999) have.

If 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.

Adhesive compositions are considered as activatable adhesives, in which the production of an adhesive force at all or the increase or decrease in the adhesive force by an energy input, for example by actinic radiation or heat, or a material interaction takes place. The activation is preferably used to produce a reversibility of the bond, in particular if a PSA is not to be assigned to the reversible PSAs according to Chang before their activation. Such pressure-sensitive adhesives are known, for example, from the field of the grinding and dicing adhesive tapes used in wafer processing.

As activatable adhesive, it is possible in principle to use all customary adhesively bonded adhesive systems that are activated. The activation is carried out according to the invention preferably usually via an energy input, for example and particularly preferably by actinic radiation or heat (heat-activated adhesive adhesives).

According to the invention, so-called "autoadhesive" layers are also regarded as reversibly adjusted PSAs. Autoadhesive layers are used, for example, in screen protectors. They show very little or no tack, but are particularly liable to very smooth surfaces. Autoadhesive layers are for example in WO 2005/044560 A1 or DE 19742805 A1 described.

The adhesive tape used in the process according to the invention contains at least one getter material. A "getter material" is understood to mean a substance which is capable of absorbing (sorbing) one or more permeable substance (s). The sorption of the permeable substance (s) by the getter material can be effected for example by absorption or adsorption, wherein adsorption can occur both in the form of chemisorption and physisorption. The getter material could therefore also be referred to as a "sorbent" or as a "sorbent".

A "permeable substance" is understood as meaning a substance which, as gaseous or liquid, if appropriate also as solid substance, can penetrate into the fabric and subsequently penetrate it. Such substances have been mentioned above and will also be referred to hereinafter as "permeates". The permeates may originate from the fabric itself or from the environment. In the fabric itself are often low molecular weight organic compounds such as solvent residues, residual monomers, oils, resin components, plasticizers and water. From the environment often come water, volatile organic compounds (VOCs), low molecular weight hydrocarbons and oxygen. As "permeable substances" or "permeates" in particular the following substances are considered:
Acetonitrile, 1-butanol, chlorobenzene, chloroform (trichloromethane), cyclohexane, diethyl ether, 1,4-dioxane, glacial acetic acid (acetic acid), acetic anhydride, ethyl acetate (ethyl acetate, ethyl acetate), n-butyl acetate (n-butyl acetate), acetic acid tert-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, xylene, oxygen, methane, ethane, propane, propene, butane, butene, carbon dioxide, ozone, sulfur dioxide, water.

Preferably, in the context of the method according to the invention, the adhesive tape at least partially absorb water from the fabric at least.

Suitable getter materials include: salts such as 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 dithionite, sodium carbonate, sodium sulfate , Potassium disulfite, potassium carbonate, magnesium carbonate; Phyllosilicates 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) and titanium dioxide; further carbon nanotubes, activated carbon, phosphorus pentoxide and silanes; readily oxidizable metals such as iron, calcium, sodium and magnesium; Metal hydrides such as calcium hydride, barium hydride, strontium hydride, sodium hydride and lithium aluminum hydride; Hydroxides such as potassium hydroxide and sodium hydroxide; Metal complexes such as aluminum acetylacetonate; furthermore silicas such as silica gel; diatomaceous earth; zeolites; furthermore organic absorbers, for example polyolefin copolymers, polyamide copolymers, PET copolyesters, anhydrides of simple and multiple carboxylic acids such as acetic anhydride, propionic anhydride, butyric anhydride or methyltetrahydrophthalic anhydride or other absorbers based on hybrid polymers, which are usually used in combination with catalysts such as cobalt ; carbodiimides; other organic absorbers such as weakly crosslinked polyacrylic acid, polyvinyl alcohol, ascorbates, glucose, gallic acid or unsaturated fats and oils. Advantageously used, in particular for the binding of oxygen, are also organometallic oxidation additives based on chelating amines and transition metal complexes, especially in conjunction with oxidizable substrate materials. According to the invention, 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. For example, 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. It is according to the invention, however, also possible to use already partially with permeate complexed materials, for example CaSO ₄ · 1 / 2H ₂ O (calcium sulphate hemihydrate), or partially hydrogenated silicas, which by definition as compounds of the general formula (SiO _{2) m} × nH ₂ O present.

By "silanes" is meant compounds of the general formula R _a -Si-X _4-a or their partial condensation products. In the formula, a is an integer from 0 to 3 and preferably 0 or 1. X is a hydrolyzable group, for example and preferably a halogen atom, especially chlorine, an alkoxy group such as methoxy, ethoxy , n-propoxy, iso-propoxy, n-butoxy, sec-butoxy or tert-butoxy group or an acetoxy group. Further examples of hydrolyzable groups known to the person skilled in the art are likewise usable for the purposes of the present invention. If several substituents X are present, they may be the same or different. R is an optionally substituted hydrocarbon radical, for example a methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, pentyl and branched Isomers, a hexyl group and the branched isomers, a heptyl group and the branched isomers, an octyl group and the branched isomers, a nonyl group and the branched isomers, a decyl group and the branched isomers, an undecyl group Group and the branched isomers, a dodecyl group and the branched isomers, a tetradecyl group and the branched isomers, a hexadecyl group and the branched isomers, an octadecyl group and the branched isomers or an eicosyl group and the branched isomers , The hydrocarbon radicals can also contain annular and / or aromatic components. Representative structures for this are cyclohexyl, phenyl and benzyl groups. Optionally, 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-cyclohexyl) aminomethyldimethoxymethylsilane, (N-cyclohexyl) aminomethyltrimethoxysilane, (N-phenyl) -3-aminopropyltrimethoxysilane, (N-phenyl) aminomethyldimethoxymethylsilane, (N-benzyl-2-aminoethyl) -3-aminopropyltrimethoxysilane, [2- (N-Benzyl-N-vinylamino) ethyl] -3-aminopropyltrimethoxysilane Hydrogen chloride, [2- (N-benzyl-N-vinylamino) ethyl] -3-aminopropyltrimethoxysilane, bis (3-propyltriethoxysilyl) amine , Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, vinylt riisopropoxysilan, vinyldimethoxymethylsilane, vinyltriacetoxysilane, 3-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-isocyanatopropyltriethoxysilane, isocyanatomethyltrimethoxysilane, isocyanatomethyldimethoxymethylsilane, tris [3- (trimethoxysilyl) -propyl] -isocyanurate, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 2-hydroxy 4- (3-triethoxysilylpropoxy) benzophenone, 4- (3'-chlorodimethylsilylpropoxy) benzophenone, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, bis (3-triethoxysilylpropyl) disulfane, B is- (3-triethoxysilylpropyl) tetrasulfane, bis (triethoxysilylpropyl) polysulfan and octadecylaminodimethyltrimethoxysilylpropylammonium chloride.

Preferably, 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 and kieselguhr, silicic acids (silica), zeolites, phyllosilicates and iron, calcium, sodium, magnesium, barium oxide, calcium oxide, iron oxide, magnesium oxide, sodium oxide, titanium dioxide, potassium oxide, strontium oxide, activated aluminum oxide and carbon nanotubes, activated carbon, phosphorus pentoxide, silanes and calcium hydride, Barium hydride, strontium hydride, sodium hydride and lithium aluminum hydride, potassium hydroxide, sodium hydroxide and aluminum acetylacetonate; and polyolefin copolymers, polyamide copolymers, PET copolyesters, acetic anhydride, propionic anhydride, butyric anhydride, methyltetrahydrophthalic anhydride, polyacrylic acid and polyvinyl alcohol, since these materials are particularly useful as water-getters.

From the aspect of a particularly pronounced binding action towards oxygen, the getter material is preferably selected from the group comprising iron, sodium dithionite, barium oxide, iron (II, III) oxide, carbohydrazide, activated alumina, zeolites, activated carbon, sulfites, ascorbates, hydrazine, morpholine, 2-butanone oxime, diethylhydroxylamine, glucose, gallic acid, unsaturated fats and oils, and organometallic oxidation additives based on chelating amines and transition metal complexes, in particular in conjunction with oxidizable substrate materials.

The getter material is particularly preferably selected from the group comprising 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, methyltetrahydrophthalic anhydride and Carbodiimides and mixtures of two or more of the above substances. These materials have a high sorption capacity against at least one of the abovementioned permeates and in particular also with respect to water.

"Carbodiimides" are understood to mean compounds of the general formula R ¹ -N = C =NH ² , where R ¹ and R ^{2 are} organic radicals, in particular alkyl or aryl radicals, which may be identical or different.

Very particular preference is given to the getter material selected from the group comprising barium, calcium, calcium sulfate, calcium chloride, calcium oxide, sodium sulfate, potassium carbonate, copper sulfate, magnesium perchlorate, magnesium sulfate, lithium chloride, silicic acids and zeolites and mixtures of two or more of the above substances. These getter materials have the advantage of being easy to incorporate into the particular layer of adhesive tape, of high sorptivity, and of being regenerable getter materials. This is understood to mean 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. This allows for a process in which the getter-containing adhesive tape is substantially freed, for example by drying, prior to contacting the sheet with permeates, if any, collected up to that time. As a result, the full getter capacity is advantageously available when using the adhesive tape.

In particular, the getter material is selected from the group comprising calcium oxide, calcium sulfate, calcium chloride, fumed silicas 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 perfectly into the adhesive tape and do not affect the function of the individual layers or only in a negligible manner.

In a particular embodiment of the invention, the getter material is selected from calcium oxide, calcium, iron, barium, lithium chloride and cobalt chloride. These substances allow conclusions on the permeate content of the fabric by changing their optical properties. As long as free getter capacity is still recognizable on the basis of the optical appearance of the adhesive tape, this can be taken as an indication that no or at most only a small amount of permeate has diffused into the fabric to be protected. For example, metallic calcium loses its metallic-opaque appearance and becomes increasingly transparent; Cobalt chloride changes color from blue to pink on water uptake. In particular, the getter material is calcium oxide.

Advantageously, the proportion of the getter material in the layer of the adhesive tape containing the getter material is in each case at least 1% by weight, preferably at least 10% by weight, in each case based on the weight the layer concerned. The maximum proportion of getter material in the getter material-containing layer of the adhesive tape is not limited in each case and may extend to a layer of pure getter material.

The content depends essentially on the desired absorption capacity for the respective permeates.

For example, if only a small capacity is required, it may be sufficient to use a low-capacity getter with a low content. In a preferred embodiment, therefore, the layer containing the getter material or containing the getter material-containing layers contains in each case 1 to 5 wt .-% getter material. If this layer is the adhesive of the adhesive tape, this also has the advantage that the adhesive properties are not significantly impaired by the low proportion of getter material.

However, with a very high required recording capacity of the adhesive tape, a relatively high content of getter material must be used in the getter material-containing layer, and the getter material should also have a high recording capacity. But even a low-capacity getter material can be used if this is suggested by the cost or compatibility aspects. Within the scope of a further preferred embodiment of the sheet according to the invention, this therefore contains from 20 to 99% by weight, based on the total weight of the adhesive tape.

If the layer containing the getter material is an adhesive, then a content of from 10 to 80% by weight is preferred so that adequate adhesive properties are retained. However, if the reversibility of the adhesive is to be increased or only produced, a content of 50-95% by weight is advantageous, in each case based on the total weight of the adhesive containing the getter material.

The adhesive tape preferably has a permeate content of less than 1000 ppm, particularly preferably less than 100 ppm. The indication ppm refers to the relation of the total weight of permeates contained in the weight of the adhesive tape. The permeate content can be determined by gas chromatography according to VDA 277 or in the case of water after 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. At low permeate contents, the capacity of the getter materials of the adhesive tape is not stressed so much by permeates diffusing out of the adhesive tape itself, and the adhesive tape can better fulfill its function as a protective or drying device.

Particularly advantageously, at least one layer of the adhesive tape, more preferably at least one of the outer layers of the adhesive tape, most preferably the adhesive layer provided for support on the fabric has a low permeation rate for the permeate to be immobilized. In the case of water vapor as permeate, the water vapor permeation rate (WVTR) is preferably less than 50 g / (m ² · d), more preferably less than 20 g / (m ² · d), based on a layer thickness of 50 μm. The WVTR is at 38 ° C and 90% relative humidity after ASTM F-1249 , the oxygen permeation rate (OTR) at 23 ° C and 50% relative humidity after DIN 53380 part 3 measured.

Due to the low permeation rate, in particular during the production of the adhesive tape, less permeate from the environment diffuses through the relevant layer (s) into the getter material-containing layer of the adhesive tape, thus fulfilling its function even longer, despite a low getter content, or with an even smaller amount Getter material can be equipped, which saves costs. With particular preference, therefore, at least the two outer layers of the adhesive tape have a low permeation rate for the permeate to be immobilized.

As (adhesive) adhesives with inherent barrier effect, in particular as such (adhesive) adhesives, which at a thickness of 50 microns, a Wasserdampfpermeationsrate of less than 50 g / (m ² · d) and / or an oxygen passage rate of less than 25000 g / (m ² · d · bar), for example - without the intention of limiting to the examples mentioned - such adhesives as used in the writings DE 10 2010 043 871 (A1) . DE 10 2010 043 866 (A1) . DE 10 2008 060 113 A1 . DE 2008 10 062 130 A1 . DE 2008 10 047 964 A1 . DE 2009 10 036 970 A1 . DE 2009 10 036 968 A1 . US 20090026934 (A1) . EP 1 469 054 B1 and EP 0519278 B2 be revealed.

Due to the generally relatively low water vapor permeation rate, preference is given to using adhesives based on synthetic rubbers, in particular based on polyisobutylene and its copolymers, polybutene, butyl rubber, styrene block copolymers with polymer blocks formed by polymerization of 1,3-dienes, in particular butadiene, isobutylene and / or isoprene, which may also contain specific or fully hydrogenated polymer blocks, and polyolefins and their copolymers (see also DE 19742805 A1 ).

Preferably, the adhesive applied to the sheet adhesive of the adhesive tape is free of adhesive resins. As a rule, this further improves the reversibility of the bond.

In one embodiment of the invention, the adhesive tape on a carrier material, since this advantageously the punchability and / or applicability is improved.

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. The carrier layer or the carrier material therefore preferably consists of polyesters, in particular of polyethylene terephthalate, for example of biaxially oriented polyethylene terephthalate; or from polyolefins, in particular from polybutene, cyclo-olefin copolymer, polymethylpentene, polypropylene or polyethylene, for example from monoaxially stretched 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 the carrier layer or the carrier material in the adhesive tape used according to the invention to consist of a polyester film, for example of biaxially oriented polyethylene terephthalate.

In a preferred embodiment, the carrier material also contains a barrier function against one or more specific permeate (s), in particular against water vapor and oxygen, so that the getter material in the adhesive tape does not come from the environment during the production and / or storage of the adhesive tape diffusing permeate is partially or even completely saturated. Such a barrier function may consist of organic or inorganic materials. Furthermore, such a carrier material in the adhesive tape protects the fabric to be freed of permeate from the diffusion of permeate from the environment.

The support material particularly preferably contains at least one inorganic barrier layer. As 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). Likewise suitable are doped layers of the abovementioned variants with further elements.

A particularly suitable method for applying an inorganic barrier layer is high-power impulse magnetron sputtering and atomic layer deposition, by means of which particularly permeation-proof layers can be realized with low thermal stress on the carrier layer. Preference is given to a permeation barrier of the carrier layer with barrier function or of the composite of carrier layer and barrier layer against water vapor (WVTR) of <1 g / (m ² · d) and / or oxygen (OTR) of <1 cm ³ / (m ² · d Bar), wherein the value is related to the thickness of the carrier layer used in each case in the fabric, ie is not normalized to a specific thickness. The WVTR is at 38 ° C and 90% relative humidity after ASTM F-1249 and the OTR at 23 ° C and 50% relative humidity after DIN 53380 part 3 measured.

The tape can be covered with a liner. 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. In order to prevent double-sided adhesive tapes that the adhesives come into contact with each other, or to prevent sticking of the adhesive on the carrier in one-sided adhesive tapes, the adhesive tapes before wrapping with a cover material (also referred to as a release material) are covered is wound up together with the adhesive tape. The person skilled in the art is familiar with such cover materials under the name of liners or release liners. In addition to covering single-sided or double-sided adhesive tapes, liners are also used to cover pure adhesives (transfer adhesive tape) and adhesive tape sections (for example labels).

A liner is accordingly understood to mean a covering material which has an anti-adhesive (abhesive) surface and is applied directly to the composition for the temporary protection of an adhesive and usually immediately before application of the adhesive can be removed by simply peeling off. Advantageously, an adhesive tape used in the process according to the invention or an adhesive tape according to the invention is covered with a release liner which can be removed before carrying out the process. However, the release liner is not considered according to the invention as part of the adhesive tape, but only as an aid to its storage and / or use. Particularly preferably, the release liner has the same permeation barrier properties as mentioned above for the carrier material, so that the getter material in the adhesive tape is not already partially or completely saturated by permeate which diffuses from the environment during the production and / or storage of the adhesive tape.

The thickness of the adhesive tape used in the process according to the invention may comprise all customary thicknesses, that is to say from about 1 .mu.m to 3000 .mu.m. Preference is given to a thickness of between 25 and 100 μm, since adhesion and handling properties are particularly favorable in this area. Another preferred range is a thickness of 3 to 25 microns, since in this area the total thickness of the to be dried / protective sheet and the adhesive tape is not very increased and the overall structure is only slightly impaired in its flexibility.

For producing an adhesive tape or adhesive tape according to the invention, the carrier of the adhesive tape or a liner is preferably coated or printed on one side with a preferably getter-material-containing adhesive of solution or dispersion or 100% (for example melt), or the adhesive tape becomes produced by (co) extrusion. Alternatively, a production by transfer of a preferably getter material-containing adhesive layer by lamination to a support material or a liner is possible. The adhesive layer can be crosslinked by heat or high-energy radiation. In such processes, structures are also advantageously produced in which the getter material is present in a layer other than the adhesive.

The layer containing the getter material can in principle be applied directly from the solution, emulsion or dispersion by methods known to those skilled in the art. The dissolving, emulsifying or dispersing agent used can then be evaporated in this case in a commercially available dryer. Likewise, a solventless coating, e.g. by means of littering, flocking or powdering methods.

The layer containing the getter material can also be printed according to the invention. Deep and screen printing processes are suitable for this purpose according to the prior art. Rotary printing processes are preferably used here. Furthermore, coatings can also be applied by spraying. This can be done by rotary spraying, optionally also electrostatically.

Preferably, this production process takes place in an environment in which the specific permeate is present only in low concentration or almost not at all. As an example, a relative humidity of less than 30%, preferably less than 15%, may be mentioned.

To optimize the properties, the adhesive used can be blended with one or more additives, such as tackifiers (resins), plasticizers, fillers, pigments, UV absorbers, light stabilizers, aging inhibitors, crosslinking agents, crosslinking promoters and / or elastomers.

The amount of an adhesive layer in the adhesive tape is preferably 1 to 200 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.

The process of the invention preferably finds application in the removal of permeates from feedstocks or intermediates in the production of organic electronic structures, in particular / for example from substrate or cover materials, in particular printed anodes or cathodes, in particular printed conductive layers or conductor tracks, hole injection layers -layers (HIL), in particular those based on aqueous dispersions of intrinsically conductive polymers such as PEDOT: PSS, and in particular printed organic light-emitting or -absorbierenden layers, in particular LITI films, and from drug patches.

The process according to the invention is particularly preferably used for removing permeates from substrate or cover films, from hole injection layers and from organic light-emitting or -absorbing layers.

Another object of the invention is an adhesive tape, which has a carrier layer with a Wasserdampfpermeationsrate of <1 g / (m ² · d) (measured according to ASTM F-1249 at 38 ° C and 90% relative humidity), an adhesive and at least one in a disposed between the support layer and adhesive layer or contained in the adhesive, for sorption of at least one permeable substance capable of getter material comprises and which is characterized in that the adhesive is reversible is. With such an adhesive tape, it is possible to remove permeate from a fabric in a particularly efficient manner and at the same time to prevent the absorption of permeates, in particular of water, from the surrounding atmosphere. The getter material is preferably contained in a layer arranged between the carrier layer and the adhesive.

Of course, embodiments of the adhesive tape used in the context of the description of the method according to the invention also apply to the adhesive tape according to the invention, provided that they do not contradict this. In particular, the adhesive of the adhesive tape according to the invention is therefore a reversibly adjusted adhesive. Conversely, embodiments of the adhesive tape according to the invention also represent possible embodiments of adhesive tapes that can be used in the method according to the invention.

If the getter material is present in a layer arranged between the carrier layer and the adhesive, this layer can contain the getter material in a matrix, for example as a disperse material. The layer can also be formed by the getter itself and thus consist of this. The carrier layer may also contain the getter material or be formed by it itself.

In one embodiment of the adhesive tape of the invention, the getter material is contained in a layer arranged between the carrier layer and the adhesive and / or in the adhesive as the dispersed phase. By "contained as a dispersed phase" is meant that the getter material is finely dispersed in the particular layer (s) of the adhesive tape. In principle, the shape and size of the getter material particles - of course, within the limits resulting from the structure and function of the adhesive tape or the layers - have no limits. The term "contained as a dispersed phase" includes a molar dispersion and thus a true (molecular) solution of the getter material in the material of the respective layer as well as a dispersion of getter material primary particles, getter material aggregates and getter material agglomerates. Preferably, the getter material is contained in the adhesive as a dispersed phase.

In addition, the feature "contained as dispersed phase" means that the getter material in question does not form a self-contained, continuous layer but is generally in the form of several, distributed particles. It does not mean, however, that an ideal or statistical distribution of the getter material particles must be present in the layer material. For example, the getter material particles may well concentrate in certain areas within the layer or certain areas of a getter-containing layer of the liner may also be free of getter material. The distribution of the getter material as a dispersed phase in a layer of the adhesive tape has the advantage over a continuous, independent getter material layer that the specific surface area for receiving permeates is greater than in the case of a continuous layer and thus higher absorption capacities for permeates can be realized ,

Basically, the size of the particles of the getter material is limited by the requirements of the thickness of the respective layer containing them. As an upper limit for the size of the particles, therefore, about 200 microns can be considered, but preferably getter material is used in the form of particles having a grain size of 50 microns maximum.

In the adhesive tape according to the invention, it is quite possible for a plurality of layers, for example a carrier layer and the adhesive layer and possibly also further layers, to contain the same or different getter material (s).

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. In a particularly preferred embodiment, the entire getter material contained in the adhesive tape of 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 respective layer containing the material containing the material.

In an alternative preferred variant, the getter material is present in the form of particles in a particle size distribution in which at least 10% by volume exceeds the average layer thickness of the getter material-containing layer. This leads to a rough surface and can improve the anchoring of the various layers in the layer composite of the adhesive tape or increase the reversibility on the fabric. If these particles are arranged in the adhesive layer that is in contact with the fabric, they are covered to a lesser extent with the adhesive, so they have almost immediate contact with the fabric and can bind permeates even more efficiently. Particularly preferably, the entire getter material contained in the adhesive tape according to the invention is present in a particle size distribution in which at least 10% by volume exceed the average layer thickness of the respective layer containing the material containing the gate material.

Under "particles" are in the sense of DIN 53206-1: 1972-08 Primary particles, aggregates and agglomerates of the getter material or getter materials understood. By "particle size" is meant the maximum extent of a particle. The determination of the particle size is preferably carried out by means of laser diffraction ISO 13320 (Agglomerates are dispersed in the dispersion step, but not aggregates), but other methods known to those skilled in the art are also suitable.

Particularly preferably, 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.

Such getter materials can be, for example, dispersed pyrogenic silica such as Aerosil from Evonik, Calcium Oxide Nanopowder from Sigma-Aldrich, calcium chloride CA-Cl-02-NP from American Elements (Los Angeles), nanozeolite LTA or FAU from Nanoscape (Planegg-Martinsried ) or nanoscale zeolite Lucidot NCL 40 from Clariant (Frankfurt).

In a further embodiment, the adhesive tape according to the invention comprises at least one layer of a getter material arranged between carrier layer and adhesive.

The getter material layer is preferably formed as a coherent, continuous and uninterrupted layer. However, it can also be present as a discontinuous layer or have holes. According to the invention, it is possible to apply a full-area or perforated layer of pulverulent getter material to a further layer provided in the construction of the adhesive tape, for example onto a carrier material, and to bind it with the layer material, for example by a thermal and / or mechanical process such as hot rolling. An openwork layer has the advantage that allowed permeates can pass the layer more easily, but permeates to be bound are intercepted. Furthermore, a perforated layer, for example made of particles, has a higher surface area than a full-surface, smooth layer, so that the sorption capacity of the getter material is even better utilized.

The thickness of the getter material layer depends in particular on the desired absorption capacity for the particular permeate. The lower limit is the minimum thickness of a continuous layer of a high-receptivity getter material, for example a calcium layer, which can be estimated to be about 20 nm. The upper limit is the thickness of a foil made of metallic getter material, for example of a barium-zinc alloy, which still allows the stiffness of the winding of an adhesive tape. Such a layer thickness can be estimated at about 100 μm.

The getter material layer is preferably made of the pure getter material. For example, this is a vapor-deposited or sputtered layer of a getter material. In a further embodiment, at least one further material is dispersed in the getter layer. For example, this further material is a gas, so that the getter layer is particularly advantageously present as a foam, in particular as an open-cell foam. This has the advantage of a particularly large active surface of the getter layer. Also materials in solid or liquid state may be dispersed in the getter material layer. These may be, for example, materials which bind a getter material liquefying under permeate uptake, for example lithium chloride, or liberated gases, for example hydrogen in the reaction of barium with water. Pore formers which are removed again after the formation of the getter material layer can also form the material dispersed in the getter layer. These may be, for example, organic materials which are initially incorporated in an electrochemical deposition of a getter material layer, but are dissolved out in a subsequent step, thus leaving a porous getter material structure.

A getter material which is dispersed (as dispersed phase) in a layer of the adhesive tape does not constitute a "layer of getter material" within the meaning of the invention. A "getter material layer" according to the invention is present only if the layer is essentially of the getter material itself is formed, for example, as the exclusive material of the layer or as a continuous phase of a dispersion. As a continuous phase of a dispersion in the context of the invention also percolated particles apply. By "percolated particles" is meant particles that interact with each other to form contiguous regions or clusters. Since the presence of percolation is not immediately apparent, alternatively, a 50% weight fraction of the getter material within a dispersion is defined as the percolation threshold.

Advantageously, the intended for resting on the fabric adhesive of the adhesive tape according to the invention is covered before application with a liner. The liner also particularly preferably contains a barrier function against one or more specific permeate (s), in particular against water vapor and oxygen, so that the getter material in the adhesive tape does not become permeable during the production and / or storage of the adhesive tape by permeate which diffuses from the environment partially or completely saturated. Such a barrier function may consist of organic or inorganic materials. Preference is given to a permeation barrier of the carrier layer of the liner with barrier function or of the composite of carrier layer and barrier layer of the liner against water vapor (WVTR) of <1 g / (m ² · d) and / or oxygen (OTR) of <1 cm ³ / ( m ² · d · bar), the value being based on the thickness of the carrier layer used in each case in the liner, that is to say not normalized to a specific thickness. The WVTR is at 38 ° C and 90% relative humidity after ASTM F-1249 and the OTR at 23 ° C and 50% relative humidity after DIN 53380 part 3 measured.

Possible embodiments of an adhesive tape according to the invention are in the 1 and 2 shown. In this mean:

LIST OF REFERENCE NUMBERS

10

reversible Klebemasse

20

Schicht enthaltend Gettermaterial

30

Trägermaterial mit WVTR < 1 g/m²d bei 38°C und 90% rF bezogen auf die eingesetzte Trägermaterialdicke

Fig. 2:

11

reversible Klebemasse enthaltend Gettermaterial, wobei die Klebemasse eine geringe Permeationsrate für das zu immobilisierende Permeat aufweist.

30

Trägermaterial mit WVTR < 1 g/m²d bei 38°C und 90% rF bezogen auf die eingesetzte Trägermaterialdicke.

Fig. 1:

10

reversible adhesive

20

Layer containing getter material

30

Carrier material with WVTR <1 g / m ² d at 38 ° C. and 90% relative to the carrier material thickness used

Fig. 2:

11

reversible adhesive comprising getter material, wherein the adhesive has a low permeation rate for the permeate to be immobilized.

30

Carrier material with WVTR <1 g / m ² d at 38 ° C. and 90% relative to the carrier material thickness used.

Another object of the invention is the use of an adhesive tape according to the invention for removing permeates from a sheet, preferably for at least partially removing at least water from a sheet.

example part

Several getter material filled adhesive tapes were made to carry out the process.

Adhesive layers:

For the production of adhesive layers, various adhesives were applied from a solution to a conventional Silanes S75 M371 liner from Siliconature by means of a laboratory coater and dried. The adhesive layer thickness after drying is indicated in each case. The drying was carried out in each case at 120 ° C. for 30 minutes in a laboratory drying cabinet. K1 pressure-sensitive adhesive 100 parts Tuftec P 1500 SBBS with 30 wt .-% block polystyrene content of Asahi. The SBBS contains about 68% by weight diblock content. 100 parts Escorez 5600 Hydrogenated HC resin with a softening point of 100 ° C from Exxon 25 parts Ondina 917 White oil from paraffinic and naphthenic shares of Shell

The solvent used was a mixture of toluene and acetone in the ratio 2: 1. K2: reversible PSA 90 parts Butyl 100 Butyl rubber from Bayer, isoprene content 0.9 mol% 10 parts Hyvis 200 Polybutene from BP Chemical

As a solvent, petroleum gas was used. K3: reversible PSA 80 parts Butyl 100 Butyl rubber from Lanxess, isoprene content 0.9 mol% 10 parts Oppanol B 150 Polyisobutylene (PIB) from BASF, Mn = 425,000 g / mol 10 parts Regalite R 1100 Hydrogenated hydrocarbon resin from Eastman with a softening point of 100 ° C.

As a solvent, petroleum gas was used. K4: reversible PSA 100 parts Levapren 700 Polyethylene vinyl acetate, manufacturer Bayer, proportion of vinyl acetate 70 wt .-%. 30 parts Levapren 800 Polyethylene vinyl acetate, manufacturer Bayer, content of vinyl acetate 80 wt .-%. 25 parts Levapren 450 Polyethylene vinyl acetate, manufacturer Bayer, content of vinyl acetate 45 wt .-%.

The solvent used was methyl ethyl ketone. K5: radiation-activated reversible PSA 59 parts Acrylate copolymer consisting of 56% by weight of butyl acrylate, 40% by weight of methyl acrylate, 2% by weight of acrylic acid and 2% by weight of benzoin acrylate, prepared in free-radical polymerization according to DE 195 20 238 C2 disclosed methods (Example 1) 0.4 parts Aluminum acetylacetonate 28 parts Ebecryl 220 hexafunctional, aromatic urethane-acrylate oligomer from Cytec 12 parts PETIA Pentaerythritol tri-tetraacrylate from Cytec with a tri / tetra ratio of about 1: 1 K6: reversible PSA 85 parts Oppanol B 150 PIB from BASF, Mn = 425,000 g / mol 15 parts Oppanol B 50 PIB from BASF, Mn = 120,000 g / mol

As a solvent, petroleum gas was used.

Storage modulus and loss modulus of the reversible PSAs were determined in the oscillatory shear experiment (dynamic mechanical analysis, DMA) under torsional stress at a temperature of 23 ° C. and a frequency of 0.01 rad / s.

Furthermore, the water vapor permeation rate (WVTR) at 38 ° C and 90% relative humidity was after ASTM F-1249 measured. The specified value is the mean of two measurements.

The bond strengths on steel became analog ISO 29862 (Method 3) at 23 ° C and 50% relative humidity at a take-off speed of 300 mm / min and a deduction angle of 180 ° determined. As the reinforcing sheet, an etched PET film having a thickness of 50 μm, as available from Coveme (Italy), was used. The gluing of the measuring strip was carried out by means of a coiling machine at a temperature of 23 ° C. The tapes were peeled off immediately after application. The specified value is the average of three measurements. description WVTR [g / m ² d] Bond strength / steel [N / cm] K1 (not reversible) 68 7.1 K2 44 1.7 K3 18 2.2 K4 155 1.2 K5 569 1.8 before / 0.23 after UV K6 6 1.0

The determined bond strengths on steel show that the compositions K2-K6 are reversible PSAs.

The carrier material for the adhesive tapes used was a laminate of aluminum foil and BOPP from Novelis, Berlin. The adhesive was coated on the aluminum side of the composite support from the solution and dried.

The following getter materials were used: description description trade name supplier G1 calcium oxide Calcium oxide nanopowders Sigma-Aldrich G2 Zeolite 3A Purmol 3 STH Zeochem

The getter materials were incorporated into the adhesive solutions by means of a high speed dispersing disc of a laboratory agitator. The adhesive mass solutions were previously dried by means of approximately 1 mm zeolite balls, which were filtered out again before the coating process.

Table 1 shows the produced getter material-containing adhesive tapes 2 Overview (T1-T11, T13, T14). The adhesives K1, K4 and K5 are contrary to the description 2 a WVTR of more than 50 g / (m ² · d). Only tape 12 (T12) was after 1 wherein the getter material is dispersed in adhesive 1 and as "layer containing getter material ( 20 ) Was used in a thickness of 50 microns. As an adhesive ( 10 Adhesive 4 was used. Table 1: Getter-filled adhesive tapes: description adhesive Getter material Share getter [weight%] Thick adhesive layer [μm] T1 K2 G1 10 75 T2 K2 G1 20 75 T3 K2 G1 40 75 T4 K3 G1 20 75 T5 K4 G1 20 75 T6 K5 G1 20 50 T7 K2 G2 20 75 T8 K2 G2 40 75 T9 K3 G2 20 75 T10 K4 G2 20 75 T11 K5 G2 20 50 T12 K1 / K4 G2 in K1 20 K1: 50; K2: 20 T13 K1 G2 20 75 T14 K6 G2 20 50

As a permeate to liberating fabric, an approximately 30 microns thick, coated with an inorganic barrier layer polyester film (GX-P-F from Toppan Printing) was used. The film was conditioned for 24 hours at 23 ° C and 50% RH before use.

The produced gettersmaterialhaltigen tapes were immediately laminated after drying on the non-inorganic coated side of the polyester film. With the adhesive tapes T11 and T14, an additional attempt was made to initially store the adhesive tapes open at 23 ° C. and 50% RH for 1 hour and then to laminate them onto the polyester film.

The composites produced in this way were stored for 14 days at 23 ° C. in a permeation-tight packaging (shrink-wrapped in an aluminum composite film). The samples were then removed from their packaging in a glove box (atmosphere: water vapor <5 ppm, oxygen <1 ppm) and the adhesive tape was peeled off the polyester film. The polyester film was immediately sealed in glass containers for water content determination. Patterns with the adhesive K5 were previously crosslinked in the glove box with a UV cube from Hoenle with a UV-C dose of 80 mJ / cm ² (250-260 nm band) to produce the reversibility.

Measurement of water content

The water content was determined after DIN 53715 (Karl Fischer titration). The measurement was carried out on a Karl Fischer Coulometer 851 in conjunction with an ovensampler (oven temperature 140 ° C.). With a weight of about 0.3 g, a triple determination was carried out in each case. The water content is the arithmetic mean of the measurements.

Furthermore, the reversibility of the adhesives was subjectively assessed upon peeling the adhesive tape from the barrier film. Table 2 presents the results: TABLE 2 Results of the drying process and reversibility Name of applied and removed tape Water content of fabrics [ppm] Reversibility ++ very easy to remove + easy to remove o can be removed with a little force - removable with high force - (conditioned film) 3630 n / A T1 57 + T2 7 + T3 <2 * ++ T4 10 + T5 4 + T6 23 ++ T7 12 + T8 <2 * ++ T9 9 + T10 7 + T11 4 ++ T12 7 + T13 10 - T14 13 ++ T11-1 h conditioned 1540 ++ T14-1 h conditioned 22 ++ * Measuring limit

The results show that excellent drying results can be achieved with the method according to the invention.

Surprisingly, the experiments carried out with an inventive adhesive tape with reversible adhesive (T1-T12, T14) no worse exemption from the permeate than the example with a conventional adhesive (T13), although one skilled in the art would expect that a reversible adhesive due to the lower flowability builds less contact with the bonding substrate and thus the mass transport is reduced.

Both getter materials used prove to be well suited. Surprisingly, experiments with a low proportion of getter material in the adhesive tape (T2, T7) also show only slightly reduced effectiveness compared to those with a higher degree of filling (T3, T8).

Surprisingly, an adhesive tape with the structure after 1 (T12), in which the mass transport first has to take place through a slightly permeable layer, no properties that are appreciably worse.

Comparing the methods with the T11 and T14 adhesive tapes, which were laminated to the barrier substrate immediately or after conditioning for one hour, shows the advantage of a low permeation rate adhesive: T11 shows a significant reduction in drying performance after conditioning, while T14 tape shows the much less permeable adhesive barely shows a drop in drying performance.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 6103141 [0015]
• US 6139935 [0016]
• DE 19913761 A1 [0017]
• EP 0582968 B1 [0018]
• JP 2001072946A [0019]
• US 6112888 [0020]
• US 6936131 [0021]
• WO 2005/044560 A1 [0041]
• DE 19742805 A1 [0041, 0065]
• DE 102010043871 A1 [0064]
• DE 102010043866 A1 [0064]
• DE 102008060113 A1 [0064]
• DE 200810062130 A1 [0064]
• DE 200810047964 A1 [0064]
• DE 200910036970 A1 [0064]
• DE 200910036968 A1 [0064]
• US 20090026934 A1 [0064]
• EP 1469054 B1 [0064]
• EP 0519278 B2 [0064]
• DE 19520238 C2 [0108]

Cited non-patent literature

• J. Adhesion, 1991, vol. 34, pp. 189-200 [0034]
• Properties and is in Pahl et al. "Practical Rheology of Plastics and Elastomers", VDI-Verlag, 1995, pages 57 to 60 and 119 to 127 [0035]
• "Handbook of Pressure Sensitive Adhesive Technology" by Donatas Satas (Satas & Associates, Warwick 1999). [0037]
• DIN EN ISO 62 [0061]
• DIN 53715 [0061]
• ASTM F-1249 [0062]
• DIN 53380 part 3 [0062]
• ASTM F-1249 [0071]
• DIN 53380 part 3 [0071]
• ASTM F-1249 [0083]
• DIN 53206-1: 1972-08 [0092]
• ISO 13320 [0092]
• ASTM F-1249 [0100]
• DIN 53380 part 3 [0100]
• ASTM F-1249 [0111]
• ISO 29862 [0112]
• DIN 53715 [0121]

Claims (15)

 A method of removing permeates from a sheet comprising adhering an adhesive tape containing at least one getter material to the sheet, the storage of the thus obtained composite of adhesive tape and fabric as well as the removal of the adhesive tape from the fabric, wherein the adhesive tape can at least partially accommodate at least one permeate from the sheet. A method according to claim 1, characterized in that the adhesive applied to the sheet adhesive of the adhesive tape is a pressure-sensitive adhesive or an activatable adhesive. A method according to any one of the preceding claims, characterized in that the adhesive applied to the sheet adhesive of the adhesive tape is an activatable pressure-sensitive adhesive. Method according to at least one of the preceding claims, characterized in that the adhesive applied to the sheet adhesive of the adhesive tape is set reversibly. A method according to any one of the preceding claims, characterized in that the adhesive applied to the sheet adhesive of the adhesive tape is free of adhesive resins. Method according to at least one of the preceding claims, characterized in that the adhesive tape can at least partially absorb water from the fabric at least in part. A method according to any one of the preceding claims, characterized in that the getter material is selected from the group comprising barium, calcium, calcium sulfate, calcium chloride, calcium oxide, sodium sulfate, potassium carbonate, copper sulfate, magnesium perchlorate, magnesium sulfate, lithium chloride, silicic acids and zeolites and mixtures of two or several of the above substances. Method according to at least one of the preceding claims, characterized in that the getter material is selected from the group comprising calcium oxide, calcium sulfate, calcium chloride, fumed silicas and zeolites and mixtures of two or more of the above substances.  Method according to at least one of the preceding claims for removing permeates from feedstocks or intermediates in the manufacture of electronic constructions, from anodes or cathodes, from conductive layers or printed conductors, from hole injection layers, from organic light emitting or absorbing layers and / or from active ingredient patches. Adhesive tape comprising a support layer having a water vapor permeation rate of <1 g / (m ² · d) (measured according to ASTM F-1249 at 38 ° C and 90% relative humidity), an adhesive and at least one layer disposed between a support layer and adhesive or in the adhesive contained, for the sorption of at least one permeable substance capable of getter material, characterized in that the adhesive is reversible. Adhesive tape according to Claim 10, characterized in that the getter material is contained in a layer arranged between the carrier layer and the adhesive. Adhesive tape according to at least one of claims 10 and 11, characterized in that the getter material is selected from the group consisting of barium, calcium, calcium sulfate, calcium chloride, calcium oxide, sodium sulfate, potassium carbonate, copper sulfate, magnesium perchlorate, magnesium sulfate, lithium chloride, silicic acids and zeolites and mixtures of two or more of the above substances. Adhesive tape according to at least one of claims 10 to 12, characterized in that the getter material is selected from the group consisting of calcium oxide, calcium sulfate, calcium chloride, fumed silicas and zeolites and mixtures of two or more of the above substances.  Use of an adhesive tape according to any one of claims 10 to 13 for removing permeates from a sheet. Use according to claim 13 for the at least partial removal of at least water from a sheet.

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