WO2012152713A1 - Doppelseitiges klebeband mit einer ersten äusseren haftklebrigen und einer zweiten äusseren hitzeaktivierbaren seite - Google Patents
Doppelseitiges klebeband mit einer ersten äusseren haftklebrigen und einer zweiten äusseren hitzeaktivierbaren seite Download PDFInfo
- Publication number
- WO2012152713A1 WO2012152713A1 PCT/EP2012/058285 EP2012058285W WO2012152713A1 WO 2012152713 A1 WO2012152713 A1 WO 2012152713A1 EP 2012058285 W EP2012058285 W EP 2012058285W WO 2012152713 A1 WO2012152713 A1 WO 2012152713A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- adhesive tape
- double
- sided adhesive
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
- B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
- B29B7/485—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws with three or more shafts provided with screws
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/82—Heating or cooling
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
- C08J5/128—Adhesives without diluent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
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- B29B7/80—Component parts, details or accessories; Auxiliary operations
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- Y10T428/2813—Heat or solvent activated or sealable
- Y10T428/2817—Heat sealable
- Y10T428/2826—Synthetic resin or polymer
Definitions
- the present invention relates to a double-sided adhesive tape having a tack-sensitive and a heat-activatable side.
- double-sided adhesive tapes are very often used to glue two materials together.
- the requirements are very specific for the most diverse application directions, so that high demands are placed on the corresponding adhesive tapes.
- high temperature stability and high resistance to solvents and motor vehicles are very often required. These properties are met in very good shape by cross-linked acrylic adhesives.
- the most diverse substrates can also be glued in the industrial sector.
- US Pat. No. 6,124,032 B1 describes a heat-activatable adhesive tape for sealing cardboard.
- the requirements in this area are very low, since the forces acting on the adhesive tape through the cardboard are relatively low. This manifests itself in the carrier material, which consists of paper. The focus is therefore not on bond strength but on a manufacturing process for a low-priced pressure-sensitive adhesive tape.
- No. 5,593,759 A describes a double-sided pressure-sensitive adhesive tape which is composed of a carrier layer which is coated with two thin pressure-sensitive adhesives.
- the carrier layer consists of a structural adhesive.
- a veneering of the pressure-sensitive adhesive with the structural adhesive occurs and cures this too.
- this pressure-sensitive adhesive tape has a fundamental disadvantage for many applications, since the double-sided pressure-sensitive adhesive tape is already tacky on both sides at the beginning.
- the PSA tape is not sticky at least on one side and thus optimally repositionable. In US 5,593,759 A, this advantage is not given.
- EP 1 262 532 A1 describes a double-functional adhesive tape with a heat-activatable adhesive resin layer of polyolefin and an acrylic pressure-sensitive adhesive, the polyolefin layer N 2 being corona-treated to achieve a good anchoring of the two layers to one another.
- the document describes only acrylate pressure-sensitive adhesives polymerized by irradiation with UV light. The disadvantage of this is the limited coating speed, since the polymerization takes place during the coating process and thus monomer conversion and degree of polymerization are dependent on the coating speed. Another problem may be the relatively high residual monomer contents.
- EP 0 384 598 A1 also describes a double-functional adhesive tape having a heat-activatable adhesive resin layer made from polyolefin and an acrylic pressure-sensitive adhesive polymerized by irradiation with UV light.
- the anchoring to the polyolefin layer is achieved by a grafted monomer.
- the disadvantage here too is the limited coating speed, since here too the polymerization initiated by UV light takes place during the coating process and thus monomer conversion and degree of polymerization are not independent of the coating speed and, moreover, the grafting reaction also takes place during the coating process and thus likewise with the coating speed in a correlation is.
- EP 1 308 492 A1 describes a three-layered adhesive tape, wherein the middle layer is a crosslinked polyurethane support material and outer layer A is a heat-activatable adhesive.
- the disadvantage here is not for all applications unrestricted good anchoring between the heat-activatable outer layer A and the crosslinked polyurethane support material, especially after moist heat treatments.
- Heat activated adhesive tapes can be used to make composite articles.
- EP 1 262 532 A1 describes a corresponding composite article. The disadvantages arise from the disadvantages of the adhesive tape described above.
- EP 0 679 123 B1 discloses a composite profile consisting of an adhesive tape and a sealing profile. There, a foam carrier layer, which is part of an adhesive tape, is melted to form the composite. The disadvantage of this is that the foam thereby at least partially loses its foam structure and thus the adhesive tape loses its characteristic adhesive properties.
- the object of the invention is the satisfaction of the need for other heat-activated adhesive tapes that do not or not to the extent show the disadvantages of the prior art.
- the tape should have two different sides.
- One side should be tacky, the other side should be heat-activated.
- heat-activatable is meant that the side softens or melts at higher temperatures or at least partially melts should, in order to flow onto the substrate to be bonded, to melt to the substrate or to be able to fuse with the substrate.
- the bond strength between the layers of the adhesive tape should always be so good that there is never a delamination between the individual layers of the adhesive tape when the adhesive tape fails, but always a failure within one layer. This should also apply after a moist heat treatment of the adhesive tape. It should also be accessible to very high layer thicknesses and these should also be realized in a foamed or foamy form.
- Thick foam-like layers can greatly increase both the bond strength and the shear strength of an adhesive tape.
- the adhesive tape should also reliably withstand higher temperatures, which can typically occur in the interior of an automobile.
- the adhesive tape should be producible for economic reasons with a high coating speed.
- the adhesive tape should be suitable for the production of composite articles and for the bonding of EPDM profiles and other rubber-like profiles, in particular automotive gaskets.
- the invention relates to a double-sided adhesive tape having a first outer pressure-sensitively adhesive and a second outer heat-activatable side, comprising an at least two-layered product structure of the layers A and B,
- layer A is a chemically crosslinked by thermal initiation pressure-sensitive adhesive layer or a chemically crosslinked by thermal initiation pressure sensitive adhesive carrier layer,
- layer B is a layer based on a thermoplastic, wherein layer A and layer B are in direct contact with each other and
- layer A which is directly in contact with layer B, has been corona or plasma pretreated
- Layer A is a chemically crosslinked by thermal initiation pressure-sensitive adhesive layer or a chemically crosslinked by thermal initiation pressure sensitive adhesive backing layer.
- a pressure-sensitive adhesive layer or a pressure-sensitive adhesive layer is understood in this document as in general language a layer that - especially at room temperature - permanently sticky and sticky.
- This layer may be both an outer, tactile layer of an adhesive tape, as well as a middle layer and thus visible and palpable only at the outer edges. Characteristic of such a layer is that it can be applied by pressure to a substrate and adhere there, whereby the pressure to be applied and the duration of this pressure are not defined further. In some cases, depending on the precise nature of the pressure-sensitive adhesive, the temperature and humidity, and the substrate, the application of a short-term, minimum pressure that does not exceed a light touch for a brief moment to achieve the adhesion effect is sufficient in other cases may also be a longer-term exposure time of high pressure necessary. Pressure-sensitive adhesive layers or pressure-sensitive adhesive layers have special, characteristic viscoelastic properties, which lead to permanent tackiness and adhesiveness.
- Characteristic of them is that when they are mechanically deformed, it comes both to viscous flow processes as well as to build elastic restoring forces. Both processes are in a certain ratio with regard to their respective proportions, depending on the exact composition, the structure and the degree of crosslinking of the pressure-sensitive adhesive layer to be considered as well as on the speed and duration of the deformation and on the temperature.
- the proportional viscous flow is necessary to achieve adhesion. Only the viscous portions, caused by macromolecules with relatively high mobility, allow a good wetting and a good flow onto the substrate to be bonded. A high proportion of viscous flow leads to a high pressure tack (also referred to as tack or surface tack) and thus often to a high Adhesive force. Strongly crosslinked systems, crystalline or glassy solidified polymers are usually not or at least only slightly tacky due to lack of flowable components.
- the proportional elastic restoring forces are necessary to achieve cohesion. They are caused for example by very long-chained and strongly entangled as well as by physically or chemically crosslinked macromolecules and allow the transmission of forces acting on an adhesive bond forces. They result in an adhesive bond being able to withstand a sustained load acting on it, for example in the form of a permanent shearing load, to a sufficient extent over a relatively long period of time.
- G ' storage modulus
- G " loss modulus
- DMA dynamic mechanical analysis
- the sizes can be determined with the help of a rheometer.
- the layered material to be examined is exposed to a sinusoidally oscillating shear stress in a plate-and-plate arrangement, for example.
- shear stress controlled devices the deformation as a function of time and the time lag of this deformation are compared with the introduction of the shear stress measured. This time offset is referred to as the phase angle ⁇ .
- a substance and the layer produced therefrom are generally considered to be tacky and are defined as tacky, if at room temperature, here by definition at 23 ° C, in the deformation frequency range of 10 ° to 10 1 rad / sec, G ' at least in part in the range of 10 3 to 10 7 Pa and if G "is also at least partly in this range, substances of this type are sometimes also referred to as viscoelastic substances and the layers produced therefrom as viscoelastic layers
- a chemically crosslinked pressure-sensitive adhesive layer or a chemically crosslinked pressure-sensitively adhesive carrier layer is present when the pressure-sensitive adhesive layer or pressure-sensitive adhesive carrier layer has reached a state by chemical reaction with a crosslinker which no longer fuses it and can no longer be dissolved in organic solvents. A liquefaction is then possible only by decomposition, which is irreversible.
- Suitable crosslinkers are all at least difunctional substances which can undergo chemical crosslinking reactions with the functional groups of the pressure-sensitive adhesive. Their selection depends on the functional groups of the pressure-sensitive adhesive.
- Carboxyl-bearing pressure-sensitive adhesives are typically crosslinked with di- or polyepoxides, possibly with additional catalysis, for example by tertiary amines, or with metal acetylacetonates, metal alkoxides and alkoxy-metal acetylacetonates.
- diisocyanates or polyisocyanates are suitable for crosslinking pressure-sensitive adhesives bearing hydroxyl groups.
- thermal initiation refers to the fact that the crosslinker or the crosslinker system consisting of crosslinker, accelerator and / or initiator initiates or initiates the chemical crosslinking reaction by the action of heat and not by the action of radiation Calculated systems in which the activation energy can already be overcome at room temperature or below without additional use of radiation, ie, which already occur at room temperature or below.
- crosslinking reactions in this invention are thus initiated neither by actinic nor by ionizing radiation such as UV, X-ray nor electron beams.
- additional crosslinks initiated by actinic or ionizing radiation are excluded because it has surprisingly been found that the bond strength between layers A and B of the adhesive tape can be degraded in some cases by additional exposure to actinic or ionizing radiation .
- layer A is produced in a hotmelt process, in particular an extrusion process.
- the pressure-sensitively adhesive material from which the pressure-sensitive adhesive layer chemically crosslinked by thermal initiation or the pressure-sensitive adhesive layer A chemically crosslinked by thermal initiation is introduced in the molten state into a continuously operating mixing unit, preferably an extruder.
- a continuously operating mixing unit preferably an extruder.
- the crosslinking system is further introduced, so that the crosslinking reaction is started. This is followed by the discharge of the still uncrosslinked melt from the mixing unit and the immediate coating and shaping of the layer A.
- the initiated crosslinking reaction progresses in the meantime, so that layer A has reached its crosslinked state a short time later.
- the main advantages of this method are that high coating speeds can be realized and that thicker layers can be produced than with a solvent-based method.
- layers (A) produced by such a method can be bonded to thermoplastic layers (B) according to the invention with high bond strength.
- layer A is foamed or has a foam-like consistency.
- the foam or the foam-like consistency may have been prepared by the introduction or by the chemical production of one or more gases in the polymer matrix or by the use of micro-glass beads, hollow glass microspheres and / or micro-plastic balls of all kinds. Mixtures of the substances mentioned can be used.
- the microplastic balls can be used pre-expanded or in an expandable form.
- microbeads also called microballoons
- microballoons are elastic hollow spheres which have a thermoplastic polymer shell; they are therefore also referred to as expandable polymeric microspheres. These balls are filled with low-boiling liquids or liquefied gas.
- low-boiling liquids or liquefied gas In particular, polyacrylonitrile, polyvinyldichloride (PVDC), polyvinyl chloride (PVC), polyamides or polyacrylates are used as the shell material.
- Hydrocarbons of the lower alkanes, for example isobutane or isopentane, which are enclosed in the polymer shell as a liquefied gas under pressure, are particularly suitable as the low-boiling liquid.
- the outer polymer shell By acting on the microballoons, in particular by a heat effect - in particular by heat supply or production, for example by ultrasound or microwave radiation - softens on the one hand, the outer polymer shell. At the same time, the liquid propellant gas in the casing changes into its gaseous state. At a certain pairing of pressure and temperature - referred to in this document as critical pairing - the microballoons expand irreversibly and expand in three dimensions. The expansion is completed when the internal and external pressures equalize. As the polymeric shell is preserved, this results in a closed-cell foam.
- microballoons are commercially available, such as Akzo Nobel's Expancel DU (dry unexpanded) grades, which essentially depend on their size (6 to 45 ⁇ m diameter in the unexpanded state) and their starting temperature needed for expansion ( 75 ° C to 220 ° C) differentiate.
- unexpanded microballoon types are also obtainable as an aqueous dispersion having a solids or microballoon fraction of about 40 to 45% by weight, and also as polymer-bound microballoons (masterbatches), for example in ethylvinyl acetate having a microballoon concentration of about 65% by weight.
- microballoon slurry systems are available in which the microballoons are present with a solids content of 60 to 80 wt .-% as an aqueous dispersion.
- microballoon dispersions, the microballoon slurries and the masterbatches are, like the DU types, suitable for foaming in accordance with the advantageous development of the invention.
- the foams made with microballoons have a higher gap bridging capability than those filled with non-expandable, non-polymeric hollow microspheres (such as glass or ceramic hollow spheres). Therefore, they are better suited to compensate for manufacturing tolerances, as they occur for example in injection molded parts. Furthermore, such a foam can better compensate for thermal stresses.
- the mechanical properties of the foam can be further influenced.
- typical foam properties such as adaptability to rough substrates with a high cohesive strength can be combined for PSA foams.
- the polymer composition to be foamed is added up to 30% by weight of microballoons, in particular between 0.5% by weight and 10% by weight, based on the overall formulation of the polymer composition without microballoons, for the foaming.
- layer A is a layer based on a known, chemically crosslinked by thermal initiation polyacrylate pressure-sensitive adhesive.
- Suitable crosslinkers for polyacrylate pressure-sensitive adhesives are diisocyanates or polyisocyanates, in particular dimerized or trimerized isocyanates, di- or polyepoxide compounds, epoxide-amine crosslinking systems and, for coordinative crosslinking, metal acetylacetonates, metal alkoxides and alkoxy metal acetylacetonates, in each case in the presence of functional groups in the polymer. Macromolecules which react with isocyanate groups or epoxide groups and can form coordinative compounds with the metal compounds.
- the crosslinker or, in the case of crosslinker systems, at least one constituent of the crosslinker system is added to the melt late and mixed in very homogeneously (by an efficient mixing, for example in the extruder) by the residence time of the reactive system
- the essential part of the crosslinking reaction takes place only after the shaping of the polymer, in particular after it has been formed into a layer, and preferably at room temperature
- the procedure can be optimized two procedural aspects to each other, namely on the one hand as little as possible crosslinking reaction before shaping, unwanted and uncontrolled pre-crosslinking and the corresponding gelling (formation of more highly crosslinked areas - for example specks - within the polymer melt) go far nd, on the other hand, however, the highest possible mixing efficiency of the crosslinker or the crosslinker system components in the relatively short residence time in the polymer melt before coating, in order to guarantee a very homogeneously cross-linked final product.
- crosslinking of polyacrylate pressure-sensitive adhesives having functional groups which are suitable for entering into linking reactions with epoxide groups has been found to be a crosslinker-accelerator system comprising at least one epoxide group-containing substance as crosslinker and at least one at a temperature below the melting temperature of the polyacrylate for the linking reaction accelerating substance as accelerator.
- Suitable epoxide-containing substances are, for example, multifunctional epoxides, in particular bifunctional or trifunctional (ie those epoxies having two or three epoxide groups), but also higher-functional epoxides or mixtures of differently functional epoxides.
- accelerators may preferably amines (formally be considered as substitution products of ammonia), for example, primary and / or secondary amines; In particular, tertiary and / or multifunctional amines are used. It is also possible to use those amines which have a plurality of amine groups, where these amine groups may be primary and / or secondary and / or tertiary amine groups, in particular diamines, triamines and / or tetramines. In particular, those amines are selected which undergo no or only minor reactions with the polymer building blocks.
- an accelerator can continue to be used, for example, those based on phosphate, such as phosphines and / or phosphonium compounds.
- polymers based on acrylates and / or methacrylates can be both foamed and crosslinked, it being advantageous for at least some of the acrylic esters to contain the functional groups and / or comonomers which have the functional groups to be present.
- functional groups of the polymer to be crosslinked in particular on (meth) acrylate basis, are particularly acid groups (carboxylic acid, sulfonic acid and / or phosphonic acid groups) and / or hydroxyl groups and / or acid anhydride groups and / or epoxy groups and / or amine groups, selected and especially tailored to the respective crosslinker. It is particularly advantageous if the polymer contains copolymerized acrylic acid and / or methacrylic acid.
- layer A is a layer based on a known, chemically crosslinked by thermal initiation polyurethane Pressure-sensitive adhesive.
- Correspondingly crosslinked polyurethane pressure-sensitive adhesives are described, for example, in EP 1 469 024 A1, EP 1 469 055 B1, EP 184981 1 B1 or in EP 2 046 855 A1.
- Pressure-sensitive polyurethane hotmelt prepolymers which can be processed and crosslinked in an extrusion process are described in EP 2 276 784 A1.
- Particularly suitable crosslinkers for polyurethane pressure-sensitive adhesives are diisocyanates or polyisocyanates, in particular di-isomerized or trimerized isocyanates.
- a special crosslinking system is described in EP 2 325 220 A1.
- a process for producing a chemically crosslinked polyurethane film is described in EP 2,119,735 A1. The disclosure content of these documents is explicitly included in the disclosure content of this invention.
- Both the advantageous polyacrylate pressure-sensitive adhesives and the advantageous polyurethane pressure-sensitive adhesives may contain other formulation constituents such as, for example, fillers, resins, tackifying resins, plasticizers, flame retardants, antioxidants, light stabilizers, UV absorbers, rheological additives, and other auxiliaries. and additives.
- the outer surface of the layer B which is identical to the second outer side of the adhesive tape, is heat-activated.
- heat-activatable is meant that this outer surface softens or melts at higher temperatures or at least partially softens or melts in order to flow onto the substrate to be bonded, to melt onto the substrate or to fuse with the substrate.
- Layer B is a thermoplastic based layer and thus a thermoformable meltable and weldable layer where the processes of deformation, fusion and welding are reversible and repeatable.
- thermoplastics are polyamide, polyester, thermoplastic polyurethane and polyethylene vinyl acetate.
- Particularly preferred, in particular for the bonding of EPDM and other rubber profiles, are polyolefins or polyolefin copolymers or mixtures of the substances mentioned, in particular polypropylene copolymers.
- Particularly preferred are ethylene-propylene copolymers or blends of ethylene-propylene copolymers and other polyolefins.
- An especially preferred for the production of a composite of the inventive adhesive tape and a profile of EPDM or other rubbery material by hot sealing the heat-activatable side of the adhesive tape on the profile ethylene-propylene copolymer has a DSC determined melting temperature between 140 ° C and including 180 ° C, preferably between and including 150 ° C and including 170 ° C.
- the abbreviation DSC stands for the known thermoanalytical method "Differential Scanning Calorimetry", DIN 53765.
- the surface of the layer A ie, the chemically crosslinked by thermal initiation pressure-sensitive adhesive layer or the chemically crosslinked by thermal initiation pressure-sensitively adhesive backing layer, which is directly in contact with layer B, has been corona or plasma pretreated prior to the preparation of this contact, the corona or Plasma pretreatment in an atmosphere of nitrogen, carbon dioxide or a noble gas or a mixture of at least two of these gases is carried out.
- a corona pretreatment is a filamentary discharge surface treatment produced by high alternating voltage between two electrodes, the discrete discharge channels meeting the substrate surface to be treated.
- the term "corona” is usually understood to mean a “dielectric barrier discharge” (DBD).
- DBD dielectric barrier discharge
- At least one of the electrodes consists of a dielectric, ie an insulator, or is coated or coated with such a dielectric.
- the corona pretreatment is well-known as a method for surface pretreatment (see also Wagner et al., Vacuum, 71 (2003), 417-436) and is widely used industrially. Without further qualification, ambient air is assumed to be the process gas, which is not the case in this invention.
- process gases other than air such as nitrogen, carbon dioxide or noble gases, is also known in the art.
- the substrate is placed or passed in the discharge space between an electrode and a counter electrode, which is defined as a direct physical treatment. Web-shaped substrates are typically carried out between an electrode and a grounded roller. By a suitably high web tension, the substrate is pressed onto the counter electrode designed as a roller in order to prevent air pockets.
- the treatment distance is typically about 1 to 2 mm.
- a fundamental disadvantage of such a two-electrode geometry with a treatment in the space between electrode and counter electrode is the possible backside treatment.
- the backside treatment With the smallest air or gas inclusions on the back, for example, if the web tension is too low in a roll-to-roll treatment, there is a mostly unwanted corona treatment of the back.
- corona treatment in air is a technique in which plasma plays a role
- a plasma treatment at atmospheric pressure is usually understood to mean a narrower definition.
- a corona treatment at atmospheric pressure in the narrower sense is a homogeneous and discharge-free treatment.
- noble gases partly with admixtures, such a homogeneous plasma can be produced.
- the treatment takes place in a two-dimensional reaction chamber homogeneously filled with plasma.
- the reactive plasma contains radicals and free electrons, which can react quickly with many chemical groups in the substrate surface. This leads to the formation of gaseous reaction products and highly reactive, free radicals in the surface. These free radicals can rapidly react by secondary reactions with other gases and form various chemical functional groups on the substrate surface. As with all plasma techniques, the generation of functional groups is in competition with material degradation.
- the substrate to be treated instead of the reaction space of a two-electrode geometry, can also be exposed only to the discharge-free plasma ("indirect” plasma) .
- the plasma is usually also potential-free, the plasma being mostly by a gas flow from the discharge zone
- the lifetime (and hence the usable distance) of the reactive plasma, often called “afterglow”, is determined by the exact details of the recombination reactions and the plasma chemistry. Most will be one exponential decay of reactivity with distance from the discharge source observed.
- the nozzle can be round or linear, partially worked with rotary nozzles, without wishing to make a restriction here.
- a nozzle principle is advantageous because of its flexibility and its inherently one-sided treatment.
- Such nozzles for example the company Plasmatreat GmbH (Germany), are widely used industrially for the pretreatment of substrates before bonding. Disadvantages are the indirect and less efficient since discharge-free treatment, and thus the reduced web speeds.
- the usual design of a round die is particularly well suited to handle narrow webs, such as an adhesive tape with a width of a few cm.
- plasma generators on the market that differ in plasma generation technology, nozzle geometry, and gas atmosphere.
- a plasma treatment may take place in various atmospheres, with nitrogen, carbon dioxide or a noble gas or a mixture of at least two of these gases being found as the suitable atmosphere in this invention.
- Plasma pretreatment in this document is a
- atmospheric pressure plasma pretreatment Meant atmospheric pressure plasma pretreatment.
- atmospheric pressure plasma in this document an electrically activated, homogeneous, reactive gas is defined, which is not in the thermal equilibrium, with a pressure close to the ambient pressure.
- the electrical discharges and ionization processes in the electric field activate the gas and generate highly excited states in the gas constituents.
- the gas or gas mixture used is called process gas.
- the plasma atmosphere can also be mixed with coating or polymerizing constituents as gas or aerosol.
- the term “homogeneous” indicates that discrete, inhomogeneous discharge channels do not strike the surface of the substrate to be treated (even though they may be present in the production space.)
- the limitation “not in thermal equilibrium” means that the temperature of the ions is different from that of Electron temperature can differ. For a thermally generated plasma, they would be in equilibrium (see, for example, Akishev et al., Plasmas and Polymers, Vol. 7, No. 3, Sept. 2002).
- nitrogen, carbon dioxide or a noble gas or a mixture of at least two of these gases it must be ensured that there are no or at least only very small amounts of residual oxygen in this atmosphere. It is desirable to have oxygen contents of not more than 1000 ppm, preferably not more than 100 ppm, more preferably not more than 10 ppm.
- the corona pretreatment is preferably carried out at a dose of 1 to 150 W * min / m 2. Particularly preferred is a dose of 10 to 100 W * min / m 2 and in particular a dose of 20 to 80 W * min / m 2 .
- the corona or plasma pretreatment of the surface of layer A, which is in contact with layer B, preferably takes place in the already chemically crosslinked state of layer A, that is, at a time when the crosslinking reaction proceeding by thermal initiation has already progressed so far that layer A is no longer meltable.
- networking does not have to be complete at this time, but it can be.
- the anchoring between the layers A and B is then particularly well and varied claims, if the corona or plasma pretreatment has taken place after reaching the crosslinked state.
- layer A and layer B are in direct contact with each other.
- direct contact involves no additional adhesive, pressure-sensitive adhesive, adhesion-promoting or other substance between layer A and layer B or brought into it.
- the direct contact between layer A and layer B is made by a conventional laminating or laminating process, preferably at room temperature.
- the laminating or lamination process is preferably carried out directly after the corona or plasma pretreatment of the surface of the layer A, without layer A being previously covered with a release liner and without layer A, if present in sheet form, being covered with a release liner and wound up , Ideally, only a few seconds pass between the corona or plasma pretreatment of the surface of layer A and the laminating or laminating process.
- the surface of the layer B that is to say the layer based on a thermoplastic, which is in direct contact with layer A, can be pretreated by air corona before the contact is made.
- the surface of layer A which is not directly in contact with layer B, may be used to provide optimized adhesion to difficult-to-bond surfaces, such as low-energy surfaces, such as polyethylene or polypropylene, or on certain painted surfaces, such as certain clearcoat surfaces.
- Varieties with a further layer (layer C, Figure 2) or with a further layer sequence (layer sequence D, Figure 3) are in direct contact, wherein the outer layer of the layer sequence is a pressure-sensitive adhesive layer (layer E, Figure 3), which then for the special use is designed.
- a layer sequence (D) may be necessary to Example, to achieve an optimal anchoring between the outer pressure-sensitive adhesive layer (E) and the layer A according to the invention in order to suppress migration phenomena or to produce the most level as possible pressure-sensitively adhesive surface.
- Individual layers in the layer sequence can accordingly be, for example, adhesion-promoting layers, barrier layers or smoothing layers.
- the outer tacky surface of the adhesive tape may also be corona or plasma treated to achieve optimized adhesion to difficult to bond substrates.
- the double-sided adhesive tape according to the invention with a first outer pressure-sensitively adhesive and a second outer heat-activatable side comprising at least two-layered product structure of the layers A and B as shown in Figure 1, wherein layer A is a chemically crosslinked by thermal initiation pressure-sensitive adhesive layer or a chemically crosslinked by thermal initiation adhesive-tacky carrier layer is, and layer B is a layer based on a thermoplastic material, wherein layer A and layer B are in direct contact with each other and wherein the surface of the layer A, which is directly in contact with layer B, corona or plasma has been pretreated , characterized in that the corona or plasma pretreatment is carried out in an atmosphere of nitrogen, carbon dioxide or a noble gas or a mixture of at least two of these gases, shows a combination of outstanding product properties, which also for those skilled in such a g were not foreseen.
- the adhesive tape has a high internal bond strength, ie a high bond strength between the layers A and B.
- the bond strength is so high that it does not usually cause a splitting between destructive loads of the adhesive tape, for example during peel tests or shear tests
- the layers A and B comes. Instead, as a rule, a material break occurs within the layer A or, depending on the bonded substrate and the pressure-sensitive adhesive used, an adhesive failure between the adhesive tape and the bonded substrate. This also applies if the adhesive tape was hot laminated to a substrate as intended, for example at temperatures of 150 ° C to 200 ° C. The bond strength between layers A and B is not adversely affected thereby.
- the high bond strength is maintained, as well after a two-week climate change storage with the cycles 4 hours -40 ° C, 4 hours heating / cooling, 4 hours 80 ° C / 80% relative Humidity. Furthermore, the bond strength is maintained even when the destructive tests are performed at elevated temperatures, for example at 70 ° C. The prerequisite is that the test temperature does not exceed the melting temperature of the layer B.
- the double-sided adhesive tape according to the invention can be produced in such a way that the polymerization of the pressure-sensitive adhesive or the adhesive-tacky carrier layer and their crosslinking take place decoupled from the coating.
- very economical production processes with high coating speeds can be represented.
- the double-sided adhesive tape of the invention is advantageously produced in very thick layers and with a foamed layer.
- the adhesive tape for example, perceive gap-bridging sealing functions or contributions to noise reduction.
- composite articles can be produced from this adhesive tape and an article made from a thermoplastic, from EPDM or from another rubber-like material.
- the double-sided adhesive tape according to the invention is suitable for bonding profiles made of EPDM or another rubber-like material.
- the peel force was determined according to PSTC-101. The determination was carried out at a test climate of 23 ° C +/- 1 ° C temperature and 50% +/- 5% rel. Humidity.
- a composite was produced from the adhesive tape of the invention and a test substrate, which was selected in accordance with the thermoplastic material of the layer B used.
- the test substrates were always made of the same Selected plastic type as they corresponded to the particular thermoplastic used in layer B. If, for example, the thermoplastic material of layer B was a polyurethane, a thermoplastic polyurethane test substrate was also selected. In the case of polypropylene types, commercially available EPDM profiles of different Shore A hardness were additionally used by Meteor Mattwerke as test substrate.
- the composite was prepared by hot lamination of the inventive adhesive tape with its layer B on the test substrate.
- the necessary temperature was generated with a hot air dryer and was based on the thermoplastic used in the layer B.
- an aluminum strip was attached on layer A.
- the adhesive tape of the invention was cut close to the substrate with a scalpel and then clamped together with the aluminum strip in the jaws of a tensile tester.
- the tearing or peeling was done using rubber-like substrates in a geometry that resembled a lying "T" when viewed from the side, and when using rigid rigid substrates, the peel was at an angle of 90 °.
- the aim was to determine whether there is a composite weakness between layers A and B or whether the failure occurs within a layer and how high the failure force is.
- test samples were prepared in such a way that in each case two adhesive tape strips according to the invention were welded to one another via their layers D by hot lamination by means of a hot air blower, so that a pressure-sensitive adhesive tape pattern was produced on both sides.
- This double-sided pressure-sensitive adhesive tape sample was bonded between two steel plates (ASTM A 666 stainless steel 302, 50 mm x 125 mm x 1, 1 mm, glossy annealed surface, surface roughness 50 ⁇ 25 nm arithmetic mean deviation from baseline) four times with a 2 kg weight pressed and then permanently exposed to a constant shear stress, which was chosen so that it comes after a long time to the failure of the adhesive tape pattern. It has been determined if there is a composite weakness between layers A and B, or if the failure occurs within a shift and how long the hold time is in minutes.
- the bond area was 13 ⁇ 20 mm 2 in each case.
- the shear stress of this bond area was 2 kg.
- the measurement was carried out at room temperature (23 ° C) and in some cases also at 70 ° C.
- the composites of the adhesive tape according to the invention and a substrate, as prepared for measuring the peel force, were subjected to storage at selected climatic conditions in order to determine the aging behavior.
- the determination of the static glass transition temperature via differential scanning calorimetry according to DIN 53765 The information on the glass transition temperature T g refer to the glass transition temperature T g according to DIN 53765: 1994-03, unless otherwise indicated in individual cases.
- the determination of the average molecular weight M w or of the average molecular weight M N and the polydispersity D was carried out by means of gel permeation chromatography (GPC).
- the eluent used was THF containing 0.1% by volume of trifluoroacetic acid. The measurement was carried out at 25 ° C.
- the precolumn used was PSS-SDV, 5 ⁇ m, 103 ⁇ (10-7 m), ID 8.0 mm ⁇ 50 mm.
- the columns PSS-SDV, 5 [Ji m, 103 ⁇ (10-7 m), 105 ⁇ (10-5 m) and 106 ⁇ (10-4 m) each having ID 8.0 mm 300 mm were used ,
- the sample concentration was 4 g / l, the flow rate 1, 0 ml per minute. It was measured against PMMA standards.
- Pentaerythritol tetraglycidyl ether Polypox R16 UPPC AG 3126-63-4
- the expandability of the microballoons can be described by determining the TMA density [kg / m 3 ] (Stare Thermal Analysis System from Mettler Toledo, heating rate 20 ° C / min).
- the TMA density is the minimum achievable density at a certain temperature T max under normal pressure before the microballoons collapse.
- An exemplary polyacrylate pressure-sensitive adhesive 1 (abbreviated designation in the examples: AC 1) was prepared as follows: A reactor conventional for radical polymerizations was reacted with 54.4 kg of 2-ethylhexyl acrylate, 20.0 kg of methyl acrylate, 5.6 kg of acrylic acid and 53 , 3 kg of acetone / isopropanol (94: 6). After passing nitrogen gas through with stirring for 45 minutes, the reactor was heated to 58 ° C. and 40 g of Vazo 67, dissolved in 400 g of acetone, added. Subsequently, the outer heating bath was heated to 75 ° C and the reaction was carried out constantly at this external temperature. After 1 h, 40 g of Vazo 67 dissolved in 400 g of acetone were again added, and after 4 h, the mixture was diluted with 10 kg of acetone / isopropanol mixture (94: 6).
- This base polymer was melted in a feed extruder (single screw extruder from TROESTER GmbH & Co KG, Germany) and conveyed with this as polymer melt through a heatable hose into a planetary roller extruder from Entex (Bochum).
- the molten resin Dertophene T 1 10 was then added via a metering orifice, resulting in a concentration of the resin in the melt of 28.3% by weight.
- the crosslinker Polypox R16 was added. Its concentration in the melt was 0.14 wt .-%. All components were mixed to a homogeneous polymer melt.
- the polymer melt was transferred to a twin-screw extruder (Berstorff). There the accelerator Epikure 925 was added. Its concentration in the melt was 0.14 wt .-%. Subsequently, the entire polymer mixture was freed in a Vakuumdom at a pressure of 175 mbar of all gas inclusions. Following the vacuum zone, the microballoons were metered in and incorporated homogeneously into the polymer mixture by means of a mixing element. Its concentration in the melt was 0.7 wt .-%. The resulting melt mixture was transferred to a nozzle.
- the incorporated microballoons expanded, whereby the pressure drop resulted in a shear-free cooling of the polymer mass.
- the result was a foamed polyacrylate pressure-sensitive adhesive, which was then formed by means of a roll calender web-shaped in a thickness of 0.8 mm and covered with a double-sided siliconized release film (50 ⁇ polyester), during which the chemical crosslinking reaction progressed.
- a double-sided siliconized release film 50 ⁇ polyester
- An exemplary polyacrylate pressure sensitive adhesive 2 (abbreviated designation in the examples: AC2) was prepared as follows:
- a conventional 100 L glass reactor for free-radical polymerizations was charged with 4.8 kg of acrylic acid, 11.6 kg of butyl acrylate, 23.6 kg of 2-ethylhexyl acrylate and 26.7 kg of acetone / gasoline 60/95 (1: 1). After passing nitrogen gas with stirring for 45 minutes, the reactor was heated to 58 ° C and 30 g of AIBN was added. Subsequently, the outer heating bath was heated to 75 ° C and the reaction was carried out constantly at this external temperature. After 1 h of reaction time, 30 g of AIBN were again added. After 4 and 8 h, each was diluted with 10.0 kg of acetone / gasoline 60/95 (1: 1) mixture.
- PU 1 An exemplary polyurethane pressure-sensitive adhesive (abbreviated designation in the examples: PU 1) was prepared as follows:
- a pressure-sensitive adhesive hydroxyl-functionalized polyurethane hotmelt prepolymer was prepared by homogeneous mixing and thus chemical reaction of the following starting materials in the stated proportions:
- the NCO / OH ratio was 0.90.
- the theoretical gel point is calculated to be 0.91.
- the resulting prepolymer was solid at room temperature and rubbery in texture and tacky (tacky).
- the complex viscosity ⁇ * was 18,000 Pas at room temperature (23 ° C) and 210 Pas at 70 ° C.
- the weight average molecular weight M w was 120000 g / mol, the number average molecular weight M N 17600 g / mol.
- the resulting prepolymer was meltable.
- the prepolymer was preheated to 80 ° C.
- Twin-screw extruder supplied continuously.
- the crosslinker was added continuously and simultaneously to the twin-screw extruder at the same time.
- the crosslinker used was Desmodur W (dicyclohexylmethane diisocyanate).
- the time to exit the extrudate from the extruder was about two minutes.
- the extrudate was fed directly to a two-roll applicator and there coated between two tapered, double-sided siliconized polyester films and thus formed into a film.
- the thickness of the film was 0.8 mm.
- the film was coiled to room temperature after cooling, after previously removing one of the two siliconized polyester films.
- the wound film was stored at room temperature for at least two weeks before being further used for the tape production of the present invention.
- G 'at 1 rad / sec and 23 ° C was 120000 Pa
- G "at 1 rad / sec and 23 ° C was 90000 Pa
- G' at 10 rad / sec and 23 ° C was 360000 Pa
- G" at 10 rad / sec and 23 ° C was 200000 Pa.
- thermoplastics for the production of layer B were used:
- the corresponding physical pretreatments of the layer A could also be carried out with a homogeneous, indirect atmospheric pressure plasma, at least in a nitrogen atmosphere.
- a laboratory system FG5001 of the company Plasmatreat GmbH (Steinhagen) could be used with a rotating nozzle RD1004, at a speed of the passage of layer A (web speed) of 5m / min at 10mm distance to the surface of layer A. No significant differences were found ,
- the prepared cross-linked pressure-sensitive adhesive layers and the thermoplastic synthetic layers were combined in the following manner and brought into contact with each other immediately after physical pretreatment of the pressure-sensitive adhesive layers under process gas atmosphere by laminating at room temperature.
- Example 5 AC 1 TP 1 Argon 35
- Example 6 AC 1 TP 1 Argon 70
- Peel force In the peel force test, a cohesive failure within layer A was always determined in Examples 1 to 18. In Example 7, individual patterns resulted in a predominantly cohesive failure with low (approximately 10%) adhesive failure rates between Layer A and B. In Examples 1-14, the force that led to the cohesive failure of Layer A was the Splitting power, 25 to 30 N / cm. In Examples 15 to 18, the nip force was 38 to 42 N / cm.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201280033428.5A CN103649250B (zh) | 2011-05-06 | 2012-05-04 | 包含第一外部压敏粘合剂面、和可热活化的第二外部面的双面胶带 |
| US14/115,135 US9493680B2 (en) | 2011-05-06 | 2012-05-04 | Double-sided adhesive tape comprising a first outer, pressure-sensitive adhesive side, and a second outer side which can be thermally-activated |
| KR1020137032507A KR101877884B1 (ko) | 2011-05-06 | 2012-05-04 | 제 1 감압 접착제 외면, 및 제 2 열-활성화가능한 외면을 포함하는 양면 접착 테이프 |
| EP12718679.9A EP2705101B1 (de) | 2011-05-06 | 2012-05-04 | Doppelseitiges klebeband mit einer ersten äusseren haftklebrigen und einer zweiten äusseren hitzeaktivierbaren seite |
| DE112012002001.4T DE112012002001A5 (de) | 2011-05-06 | 2012-05-04 | Doppelseitiges Klebeband mit einer ersten äußeren haftklebrigen und einer zweiten äußeren hitzeaktivierbaren Seite |
| MX2013012736A MX349050B (es) | 2011-05-06 | 2012-05-04 | Cinta adhesiva de doble lado que comprende un primer lado adhesivo sensible a la presion, externo, y un segundo lado externo que puede ser termicamente activado. |
| CA2835046A CA2835046A1 (en) | 2011-05-06 | 2012-05-04 | Double-sided adhesive tape comprising a first outer, pressure-sensitive adhesive side, and a second outer side which can be thermally-activated |
| JP2014508836A JP6210974B2 (ja) | 2011-05-06 | 2012-05-04 | 第1の外側の感圧接着性の面および第2の外側の熱活性化性の面を備えた両面接着テープ |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011075470.9 | 2011-05-06 | ||
| DE201110075470 DE102011075470A1 (de) | 2011-05-06 | 2011-05-06 | Klebeband, bevorzugt Selbstklebeband, bestehend aus mindestens zwei direkt aufeinander laminierten Schichten A und B, wobei mindestens eine oder beide Schichten A oder B eine Klebmasse ist |
| DE102011075468 | 2011-05-06 | ||
| DE102011075468.7 | 2011-05-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2012152713A1 true WO2012152713A1 (de) | 2012-11-15 |
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| PCT/EP2012/058285 Ceased WO2012152713A1 (de) | 2011-05-06 | 2012-05-04 | Doppelseitiges klebeband mit einer ersten äusseren haftklebrigen und einer zweiten äusseren hitzeaktivierbaren seite |
| PCT/EP2012/058286 Ceased WO2012152714A1 (de) | 2011-05-06 | 2012-05-04 | Verfahren zur erhöhung der adhäsiven eigenschaften von haftklebemassen auf untergründen mittels plasmabehandlung |
| PCT/EP2012/058287 Ceased WO2012152715A1 (de) | 2011-05-06 | 2012-05-04 | Verfahren zur erhöhung der adhäsiven eigenschaften von haftklebemassen auf untergründen mittels plasmabehandlung |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
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| PCT/EP2012/058286 Ceased WO2012152714A1 (de) | 2011-05-06 | 2012-05-04 | Verfahren zur erhöhung der adhäsiven eigenschaften von haftklebemassen auf untergründen mittels plasmabehandlung |
| PCT/EP2012/058287 Ceased WO2012152715A1 (de) | 2011-05-06 | 2012-05-04 | Verfahren zur erhöhung der adhäsiven eigenschaften von haftklebemassen auf untergründen mittels plasmabehandlung |
Country Status (11)
| Country | Link |
|---|---|
| US (2) | US9493680B2 (enExample) |
| EP (2) | EP2705101B1 (enExample) |
| JP (2) | JP6210974B2 (enExample) |
| KR (2) | KR101877884B1 (enExample) |
| CN (2) | CN103649250B (enExample) |
| CA (2) | CA2835051A1 (enExample) |
| DE (2) | DE112012001999A5 (enExample) |
| ES (1) | ES2700519T3 (enExample) |
| MX (2) | MX349050B (enExample) |
| TW (3) | TWI532810B (enExample) |
| WO (3) | WO2012152713A1 (enExample) |
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- 2012-05-04 MX MX2013012736A patent/MX349050B/es active IP Right Grant
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- 2012-05-04 KR KR1020137032504A patent/KR101981695B1/ko active Active
- 2012-05-04 CA CA2835051A patent/CA2835051A1/en not_active Abandoned
- 2012-05-04 DE DE112012001999.7T patent/DE112012001999A5/de not_active Withdrawn
- 2012-05-04 EP EP12718679.9A patent/EP2705101B1/de active Active
- 2012-05-04 JP JP2014508837A patent/JP6063452B2/ja not_active Expired - Fee Related
- 2012-05-04 ES ES12720142T patent/ES2700519T3/es active Active
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- 2012-05-04 CA CA2835046A patent/CA2835046A1/en not_active Abandoned
- 2012-05-04 DE DE112012002001.4T patent/DE112012002001A5/de not_active Withdrawn
- 2012-05-04 EP EP12720142.4A patent/EP2705103B1/de active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013178462A1 (de) * | 2012-05-30 | 2013-12-05 | Tesa Se | Doppelseitiges klebeband mit einer ersten äusseren haftklebrigen und einer zweiten äusseren hitzeaktivierbaren seite |
| US9920223B2 (en) | 2012-05-30 | 2018-03-20 | Tesa Se | Double-sided adhesive tape having a first outer impact-adhesive side and a second outer side that can be heat activated |
| US20170114250A1 (en) * | 2014-04-01 | 2017-04-27 | Tesa Se | Method for plasma-initiated adhesive bonding |
| US10899947B2 (en) * | 2014-04-01 | 2021-01-26 | Tesa Se | Method for plasma-initiated adhesive bonding |
| WO2016146498A1 (de) * | 2015-03-17 | 2016-09-22 | Tesa Se | Niedertemperatur-plasma-behandlung |
| DE102015115717A1 (de) | 2015-09-17 | 2017-03-23 | Lohmann Gmbh & Co. Kg | Asymmetrische Klebefolie mit einer Kraftentkopplungsfunktion |
| DE102015115717B4 (de) | 2015-09-17 | 2022-12-08 | Lohmann Gmbh & Co. Kg | Asymmetrische Klebefolie mit einer Kraftentkopplungsfunktion und Verwendung |
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