EP3036100A1 - STANZLING INSBESONDERE ZUM DAUERHAFTEN VERSCHLIEßEN VON LÖCHERN - Google Patents

STANZLING INSBESONDERE ZUM DAUERHAFTEN VERSCHLIEßEN VON LÖCHERN

Info

Publication number
EP3036100A1
EP3036100A1 EP14747879.6A EP14747879A EP3036100A1 EP 3036100 A1 EP3036100 A1 EP 3036100A1 EP 14747879 A EP14747879 A EP 14747879A EP 3036100 A1 EP3036100 A1 EP 3036100A1
Authority
EP
European Patent Office
Prior art keywords
adhesive
diecut
acrylate
hole
previous
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.)
Pending
Application number
EP14747879.6A
Other languages
German (de)
English (en)
French (fr)
Inventor
Thomas Niemeyer
Rainer Stricker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tesa SE
Original Assignee
Tesa SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tesa SE filed Critical Tesa SE
Publication of EP3036100A1 publication Critical patent/EP3036100A1/de
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/06—Sealing strips
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
    • B29C73/04—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D using preformed elements
    • B29C73/10—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D using preformed elements using patches sealing on the surface of the article
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof

Definitions

  • the present invention relates to a stamped product, in particular for permanently sealing holes, which are preferably located in sheets or in plastic parts, as well as a method for permanently closing holes.
  • holes In the automotive industry, holes must be set or punched out at various points in the bodywork. As a rule, this is done during the stamping and forming process of the individual sheet metal or aluminum parts, and holes can also be drilled in plastic components. Subsequently, the individual metal parts are connected to each other by means of various joining processes, and the body shell is created.
  • the holes, openings or openings therein serve, among other things, as paint drainage holes (for example for cathodic dip paint), wax injection holes, wax drainage holes, holes for subsequent screwing in the assembly or for cable bushings. Many of these holes need to be resealed after drying the cathodic dip or even after the final clear coat process (then the pinhole would take place in the assembly process).
  • the holes or openings are closed by means of injection-molded parts (plugs) made of various plastics, which are manufactured according to the requirements.
  • plugs made of various plastics, which are manufactured according to the requirements.
  • plastics can be, for example, stoppers made of PET, ABS, PP, PVC, EPDM, PA and other common plastics on the market or even combinations of the materials mentioned and commercially customary plastic substrates not listed here.
  • stoppers made of PET, ABS, PP, PVC, EPDM, PA and other common plastics on the market or even combinations of the materials mentioned and commercially customary plastic substrates not listed here.
  • glass fibers Also conceivable are carbon fibers, which reinforce the plug against, for example to provide the puncture.
  • carbon fibers which reinforce the plug against, for example to provide the puncture.
  • all common plastic substrates are possible, as long as they offer certain parameters for paintability, temperature stability, dimensional stability under climatic conditions and also fulfill a certain economy in the production process of the plug.
  • plastic plugs are usually used for closing body holes, which are not sure to close the hole on the one hand in an individual case and on the other hand are comparatively complex and expensive to produce.
  • a special, adapted to the hole size plug is required. This means high logistical and administrative effort for the customer of the plug.
  • die-cuts are also suitable for the special perforated closure, which consist of a heat-resistant carrier at least partially self-adhesive base layer whose area is greater than the area of the hole to be closed and in particular is provided centrally on the adhesive side equipped with a first portion of a heat-activatable adhesive film whose area is greater than the area of the hole to be closed and smaller than the surface of the base layer.
  • the blank is applied over the hole to be closed so that the hole is substantially covered by the first portion.
  • the described heat-activatable adhesive films are well suited for sealing, but are relatively expensive.
  • these acoustically relevant hole closures are used in the assembly in order to achieve a foreclosed area in the passenger compartment, the vehicle interior.
  • a disturbing in the vehicle interior acoustics is generated for example by rolling noise of the tires or by rolling chips and small stones that are thrown against the Anlagenbeplankung and also against the vehicle carrier. Further wind noise, which may be due to aerodynamically unfavorable design, may be a cause of higher, undesirable noise level in the passenger compartment.
  • acoustically effective products must also be used outside the vehicle.
  • effective acoustic protection is to mask holes in the underbody or in the vehicle platform. Often holes, punched holes or holes in the longitudinal and transverse beams are introduced. Here, special care must be taken to ensure that every possible opening is carefully closed.
  • the object of the invention is to provide a stamped product which is suitable for permanently sealing holes, in particular in sheets or in plastic parts of automobile bodies, which closes said holes in such a way that a passage of moisture is eliminated, which improves the noise insulation and the the holes even with rockfall on the subfloor or mechanical stresses in the interior, especially in the bottom area, safely closes.
  • the invention relates to a stamped product, in particular for permanently sealing holes, in particular in sheets or in plastic parts with a carrier made of a laminate of at least two plastic films, wherein the lower film has a basis weight of at least 1, 5 kg / m 2 and on the upper Foil opposite side of the lower film, an adhesive, in particular curable or self-adhesive adhesive is applied.
  • the lower film has a basis weight between 1, 5 and 6 kg / m 2 , preferably between 1, 5 and 3.9 kg / m 2 between 1, 5 and 2.5 kg / m 2 .
  • the lower film is preferably a heavy film such as a polyolefin film filled in particular with mineral or an elastomer-modified bituminous film.
  • a heavy foil consists of a foil-like layer of any thickness, in particular from 0.015 mm to over 12 mm, wherein the heavy foil in particular of thermoplastic polymers, in particular PE (polyethylene), EPDM (ethylene-propylene-diene rubber) and / or EVA (ethylene-vinyl acetate ) and mineral fillers, in particular limestone powder or calcite (CaC0 3 ) and heavy spar (BaS0 4 ) composed. Furthermore, for filling talc, slate, graphite, mica or asbestos (the latter today rather less) can be used.
  • PE polyethylene
  • EPDM ethylene-propylene-diene rubber
  • EVA ethylene-vinyl acetate
  • mineral fillers in particular limestone powder or calcite (CaC0 3 ) and heavy spar (BaS0 4 ) composed.
  • talc slate, graphite, mica or asbestos (the latter today rather less) can be used.
  • the proportion of fillers is in particular 30 to 90 wt .-%, preferably 40 to 70 wt .-%.
  • the proportion is preferably from 30 to 60% by volume, more preferably from 45 to 55% by volume,
  • the heavy foil may additionally contain oil for swelling and for better absorption of the fillers.
  • the oil content can be between 8 vol.% To 20 vol.%.
  • a stampable aluminum sheet, a corrosion resistant steel sheet or an aluminum foil with a scrim for reinforcement or strength may be laminated on the lower sheet.
  • the top film may be any polymer, either alone or in admixture.
  • Suitable polymers are olefinic polymers such as homo- or copolymers of olefins such as ethylene, propylene or butylene (the term copolymer is to be understood as meaning herein terpolymers), polypropylene homopolymers or polypropylene copolymers including the block (impact) and random polymers.
  • polyesters such as in particular polyethylene terephthalate (PET), polyamides, polyurethanes, polyoxymethylene, polyvinyl chloride (PVC), polyethylene naphthalate (PEN), ethylene vinyl alcohol (EVOH), Polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polycarbonate (PC), polyamide (PA), polyethersulfone (PES), polyimide (PI), polyarylene sulfides and / or polyarylene oxides.
  • PET polyethylene terephthalate
  • PVC polyvinyl chloride
  • PEN polyethylene naphthalate
  • EVOH ethylene vinyl alcohol
  • PVDC Polyvinylidene chloride
  • PVDF polyvinylidene fluoride
  • PAN polyacrylonitrile
  • PC polycarbonate
  • PA polyamide
  • PA polyethersulfone
  • PI polyimide
  • polyarylene sulfides and
  • the upper film preferably consists of polyester (in particular of polyethylene terephthalate (PET)), polyurethane or PVC.
  • PET polyethylene terephthalate
  • PVC polyurethane
  • the polymers for forming the top film and the bottom film may be in pure form or in blends with additives such as antioxidants, sunscreens, antiblocking agents, lubricants and processing aids, fillers, dyes, pigments, blowing or nucleating agents.
  • the films have none of the additives mentioned.
  • the carrier may also have more than two foils.
  • the upper carrier foil can consist of an at least two-layer laminate of two or more foil layers of any desired material (for example polyethylene, polypropylene, polyester, PA and / or PVC).
  • a layered body is present in the carrier (between the upper and the lower film) or on the carrier, which consists of metal, of a metal foil, for example aluminum foil, or of a metal-containing film.
  • the thickness of the upper film between 15 and 350 ⁇ , preferably between 30 and 200 ⁇ , more preferably between 50 and 150 ⁇ .
  • the thickness of the lower film is between 600 and 3500 ⁇ , preferably between 1100 and 3500 ⁇ , more preferably between 1700 and 3500 ⁇ .
  • the thickness of the lower film is between 600 and 1100 ⁇ , between 1100 and 1700 ⁇ or between 1700 and 3500 ⁇ .
  • the upper and / or lower film are reinforced by integrated or attached fibers or filaments, so that their strength is particularly reinforced in the longitudinal direction.
  • a filament is understood to mean a bundle of parallel, straight individual fibers, often referred to in the literature as multifilament.
  • this fiber bundle can be solidified by twisting, then one speaks of spun or twisted filaments.
  • the fiber bundle can be solidified by swirling with compressed air or water jet.
  • the term filament is used for all these embodiments - as well as for the embodiment reinforced with fibers - generally only the term filament is used.
  • a film is reinforced only by longitudinally integrated / attached filaments, it is called monofilament adhesive tapes.
  • the upper film and / or the lower film are reinforced by an open filament fabric. In this case, it is called cross-filament tape.
  • the individual filaments are preferably continuous filaments and / or have a fineness between 4 and 8 dtex, preferably 5 dtex. In an advantageous embodiment, all filaments are endless filaments.
  • the filaments can consist of organic or inorganic materials, for example and preferably glass, carbon, combinations of both types of fibers, aramid fibers or special polyamides, drawn polymer fibers such as polyester fibers, polypropylene fibers, polyethylene fibers, furthermore, the reinforcing fibers may be at least partially colored be to make the substrate more visually appealing. In this way it is easily possible to visually differentiate the reinforced carrier. Dyed glass or polymer threads are particularly suitable for this purpose.
  • the film (s) are further preferably laminated with the filaments. The filaments should be firmly bonded to the film (s). This can be done by direct incorporation or incorporation of the fibers, threads or threads or mixed threads in the film (s), for example weaving in fabrics, knitting in knitted fabrics, embedding or insertion in the production process.
  • the filaments can also be subsequently connected to the film (s); for example, welding or lamination with a corresponding bonding layer may be mentioned.
  • the reinforcements are preferably inserted selectively in accordance with the direction of loading of the carrier, that is to say primarily in the longitudinal direction. However, they may also, if more appropriate, additionally in transverse or oblique direction or, for example, curved, spiral or zigzag-shaped or run randomly.
  • the curable adhesive used in an inventive variant is a structural adhesive (construction adhesive, assembly adhesive) (see Römpp, Georg Thieme Verlag, document identifier RD-19-04489, last update: September 2012).
  • structural adhesives are adhesives that form adhesive bonds that can maintain a specified strength in a microstructure for a predetermined, longer period of time (according to the ASTM definition: bonding agents used for transferring required loads between adherends exposed to service environments typical for the structure involved ”).
  • These are adhesives for bonds which are chemically and physically highly stressable and which, when cured, contribute to the bonding of bonded substrates and are used to produce structures made of metals, ceramics, concrete, wood or reinforced plastics
  • Structural adhesives according to the invention are based in particular on (thermosetting) reaction adhesives (phenolic resins, epoxy resins, polyimides, polyurethanes and others).
  • the curable adhesive may be elastic after curing to ensure a durable, insensitive to vibration and twisting closure.
  • the curable adhesive is self-adhesive, or at least partially a self-adhesive composition is applied to the curable adhesive.
  • Useful adhesive compositions include, in particular, reactive heat-activable adhesives.
  • thermosetting resins have a very good dimensional stability when the elastomeric component has a high elasticity.
  • the reactive resins require that a crosslinking reaction can occur, which significantly increases the bond strength.
  • heat-activatable adhesives based on nitrile rubbers and phenolic resins can be used, for example commercially available in product 8401 from tesa.
  • the adhesive consists at least of a) a polyamide having amino and / or acid end groups,
  • polyamide reacts at temperatures of at least 150 ° C with the epoxy resin and the ratio in parts by weight of a) and b) is between 50:50 to 99: 1.
  • the adhesive is made
  • thermoplastic polymer in a proportion of 30 to 89.9 wt .-%, ii) one or more tackifying resins in a proportion of 5 to 50 wt.% And / or
  • epoxy resins with hardeners, optionally also accelerators, in a proportion of 5 to 40 wt .-%.
  • This adhesive is a blend of reactive resins that crosslink at room temperature to form a three-dimensional, high-strength polymer network, and permanently elastic elastomers that resist embrittlement of the product.
  • the elastomer may preferably be selected from the group of polyolefins, polyesters, polyurethanes or polyamides or a modified rubber such as nitrile rubber.
  • thermoplastic polyurethanes are known as reaction products of polyester or polyether polyols and organic diisocyanates such as diphenylmethane diisocyanate. They are composed of predominantly linear macromolecules. Such products are usually commercially available in the form of elastic granules, for example from Bayer AG under the trade name "Desmocoll”.
  • the softening temperature of the adhesive can be lowered. In parallel, there is even an increase in adhesion.
  • suitable resins for example, certain rosin, hydrocarbon and coumarone resins have been found.
  • the reduction of the softening temperature of the adhesive can be achieved by combining TPU with selected epoxy resins based on bisphenol A and / or F and a latent curing agent.
  • An adhesive from such a system allows a post-curing of the bondline, either gradually at room temperature without any further external intervention or for a short time by a targeted tempering.
  • the addition of these reactive resin / hardener systems also leads to a lowering of the softening temperature of the above-mentioned polymers, which advantageously lowers their processing temperature and speed.
  • the suitable product is a self-adhesive product at room or slightly elevated temperatures. When the product is heated, it also reduces the viscosity in the short term, allowing the product to wet even rough surfaces.
  • compositions for the adhesive can be widely varied by changing the nature and content of the raw material.
  • further product properties such as color, thermal or electrical conductivity can be achieved by targeted additions of dyes, mineral or organic fillers and / or carbon or metal powders.
  • all acrylonitrile-butadiene copolymers having an acrylonitrile content of 15 can be used as nitrile rubbers in adhesives of the invention to 50% by weight.
  • copolymers of acrylonitrile, butadiene and isoprene can be used.
  • the proportion of 1, 2-linked butadiene is variable.
  • the aforementioned polymers can be hydrogenated to a different degree and fully hydrogenated polymers having a double bond content of less than 1% can be used.
  • All of these nitrile rubbers are carboxylated to a certain extent; the proportion of the acid groups is preferably from 2 to 15% by weight.
  • Commercially, such systems are available, for example, under the name Nipol 1072 or Nipol NX 775 from Zeon.
  • Hydrogenated carboxylated nitrile rubbers are commercially available under the name Therban XT VP KA 8889 from Lanxess.
  • Epoxy resins are usually understood as meaning both monomeric and oligomeric compounds having more than one epoxide group per molecule. These may be reaction products of glycidic esters or epichlorohydrin with bisphenol A or bisphenol F or mixtures of these two. It is also possible to use epoxy novolak resins obtained by reaction of epichlorohydrin with the reaction product of phenols and formaldehyde. Also, monomeric compounds having multiple epoxide end groups used as thinners for epoxy resins are useful. Also elastically modified epoxy resins can be used.
  • epoxy resins examples include Araldite TM 6010, CY-281 TM, ECN TM 1273, ECN TM 1280, MY 720, RD-2 from Ciba Geigy, DER TM 331, 732, 736, DEN TM 432 from Dow Chemicals, Epon TM 812, 825, 826, 828, 830 etc. from Shell Chemicals, HPT TM 1071, 1079 also from Shell Chemicals, Bakelite TM EPR 161, 166, 172, 191, 194 etc. from Bakelite AG.
  • aliphatic epoxy resins are, for example, vinylcyclohexane dioxides such as ERL-4206, 4221, 4201, 4289 or 0400 from Union Carbide Corp.
  • Elastified epoxy resins are available from Noveon under the name Hycar.
  • Epoxy diluents monomeric compounds having a plurality of epoxide groups are, for example, Bakelite TM EPD KR, EPD Z8, EPD HD, EPD WF from Bakelite AG or Polypox TM R 9, R12, R 15, R 19, R 20 from UCCP. More preferably, the adhesive contains more than one epoxy resin.
  • novolac resins for example, Epi-Rez TM 5132 from Celanese, ESCN-001 from Sumitomo Chemical, CY-281 from Ciba Geigy, DEN TM 431, DEN TM 438, Quatrex 5010 from Dow Chemical, RE 305S from Nippon can be used Kayaku, Epiclon TM N673 from DaiNipon Ink Chemistry or Epicote TM 152 from Shell Chemical.
  • melamine resins such as Cymel TM 327 and 323 from Cytec can also be used as reactive resins.
  • reactive resins can also be used for terpene phenolic resins such as, for example, NI REZ TM 2019 from Arizona Chemical.
  • reactive resins and phenolic resins such as YP 50 from Toto Kasei, PKHC Union Carbide Corp. can be. and BKR 2620 from Showa Union Gosei Corp. deploy.
  • phenolic resole resins can also be used as reactive resins in combination with other phenolic resins.
  • adhesive-increasing (tackifying) resins are also added; very advantageous to a proportion of up to 30 wt .-%, based on the adhesive.
  • Non-hydrogenated, partially or completely hydrogenated resins based on indene, rosin and rosin derivatives, hydrogenated polymers of dicyclopentadiene, non-hydrogenated, partially, selectively or completely hydrogenated hydrocarbon resins based on C 5 -, C 5 / C 9 are particularly suitable, inter alia or Cg monomer streams, terpene phenolic resins, terpene resins based on ⁇ -pinene and / or ⁇ -pinene and / or ⁇ -limonene or hydrogenated polymers preferably pure C 8 and C 9 aromatics, aromatic resins such as cumarone-indene resins or resins of styrene or ⁇ -methylstyrene such as rosin and its derivatives such as disproportionated, dimerized or esterified resins, glycols, glycerol or pentaerythrito
  • elastomers can also be used.
  • unmodified elastomers for example polyvinyl alcohol, polyvinyl acetate, styrene block copolymers, polyvinyl formal, polyvinyl butyral or soluble polyesters.
  • copolymers with maleic anhydride for example a copolymer of polyvinyl methyl ether and maleic anhydride, for example available under the name Gantrez TM, marketed by ISP.
  • additives can typically be used:
  • Primary antioxidants such as sterically hindered phenols
  • UV absorbers such as UV absorbers or hindered amine processing aids
  • Fillers such as silica, glass (milled or in the form of spheres), aluminas, zinc oxides, calcium carbonates, titanium dioxides, carbon blacks, metal powders, etc.
  • Plasticizers which may be used are, for example, low molecular weight polyisoprenes, polybutadienes, polyisobutylenes or polyethylene glycols and polypropylene glycols or plasticizers based on polyethylene oxides, phosphate esters, aliphatic carboxylic acid esters and benzoic acid esters. Furthermore, it is also possible to use aromatic carboxylic esters, relatively high molecular weight diols, sulfonamides and adipic esters.
  • the adhesive does not escape from the adhesive joint during gluing and hot pressing. During this process, the epoxy resins crosslink with the elastomers, resulting in a three-dimensional network.
  • reaction rate By adding so-called accelerators, the reaction rate can be further increased.
  • Accelerators can be for example:
  • tertiary amines such as benzyldimethylamine, dimethylaminomethylphenol, tris (dimethylaminomethyl) phenol
  • imidazoles commercially available as 2M7, 2E4MN, 2PZ-CN, 2PZ-CNS, PO550, L07N from Shikoku Chem. Corp. are suitable as accelerators. or Curezol 2MZ from Air Products. Further suitable crosslinkers are HMTA (hexamethylenetetramine) additives.
  • optional fillers for example fibers, carbon black, zinc oxide, titanium dioxide, chalk, solid or hollow glass spheres, microspheres of other materials, silicic acid, silicates
  • nucleating agents for example fibers, carbon black, zinc oxide, titanium dioxide, chalk, solid or hollow glass spheres, microspheres of other materials, silicic acid, silicates
  • blowing agents for example adhesive-enhancing additives and thermoplastics, compounding agents and / or aging inhibitors, for example in Form of primary and secondary antioxidants or in the form of sunscreens.
  • further additives are added to the adhesive, for example polyvinylformal, polyacrylate rubbers, chloroprene Rubbers, ethylene-propylene-diene rubbers, methyl-vinyl-silicone rubbers, fluorosilicone rubbers, tetrafluoroethylene-propylene copolymer rubbers, butyl rubbers, styrene-butadiene rubbers.
  • polyvinylformal polyacrylate rubbers
  • chloroprene Rubbers ethylene-propylene-diene rubbers
  • methyl-vinyl-silicone rubbers methyl-vinyl-silicone rubbers
  • fluorosilicone rubbers tetrafluoroethylene-propylene copolymer rubbers
  • butyl rubbers styrene-butadiene rubbers.
  • Polyvinyl butyrals are available as Butvar TM from Solucia, under Pioloform TM from Wacker and under Mowital TM from Kuraray.
  • Polyacrylate rubbers are available under Nipol AR TM from Zeon.
  • Chloroprene rubbers are available under Baypren TM from Bayer.
  • Ethylene-propylene-diene rubbers are available under Keltan TM from DSM, under Vistalon TM from Exxon Mobile and under Buna EP TM from Bayer.
  • Methyl vinyl silicone rubbers are available from Silastic TM from Dow Corning and Silopren TM from GE Silicones. Fluo silicone rubbers are available as Silastic TM from GE Silicones.
  • Butyl rubbers are available on Esso Butyl TM from Exxon Mobile. Styrene-butadiene rubbers are available as Buna S TM from Bayer, and Europrene TM from Eni Chem and under Polysar S TM from Bayer.
  • Polyvinylformals are available on Formvar TM from Ladd Research.
  • thermoplastic materials from the group of the following polymers: polyurethanes, polystyrene, acrylonitrile-butadiene-styrene terpolymers, polyesters, hard polyvinyl chlorides, flexible polyvinyl chlorides, polyoxymethylenes, polybutylene terephthalates, Polycarbonates, fluorinated polymers such as polytetrafluoroethylene, polyamides, ethylene-vinyl acetates, polyvinyl acetates, polyimides, polyethers, copolyamides, copolyesters, polyolefins such as polyethylene, polypropylene, polybutene, polyisobutene and poly (meth) acrylates.
  • the bond strength of the heat-activatable adhesive can be counteracted by further targeted addition of additives.
  • polyimine or polyvinyl acetate copolymers can also be used as adhesion-promoting
  • the adhesive applied to the carrier is a pressure-sensitive adhesive, that is to say an adhesive which, even under relatively weak pressure, permits a lasting connection with almost all adhesive properties and can be removed from the primer again without leaving any residue after use.
  • a PSA is permanently tacky at room temperature, so it has a sufficiently low viscosity and high tack, so that it wets the surface of the respective Klebegrunds already at low pressure. The Adhesiveness of the adhesive is based on its adhesive properties and the removability on its cohesive properties.
  • silicone adhesives and also polyacrylate adhesives, preferably a low molecular weight acrylate hot melt pressure-sensitive adhesive.
  • the adhesive can be selected from the group of natural rubbers or synthetic rubbers or from any blend of natural rubbers and / or synthetic rubbers, the natural rubber or natural rubbers basically being made of all available qualities such as Crepe, RSS, ADS, TSR. or CV types, depending on the required level of purity and viscosity, and the synthetic rubber or synthetic rubbers from the group of random copolymerized styrene-butadiene rubbers (SBR), butadiene rubbers (BR), the synthetic polyisoprenes (IR), the Butyl rubbers (NR), the halogenated butyl rubbers (XI IR), the acrylate rubbers (ACM), the ethylene-vinyl acetate copolymers (EVA) and the polyurethanes and / or their blends can be selected.
  • SBR random copolymerized styrene-butadiene rubbers
  • BR butadiene rubbers
  • IR synthetic polyisoprenes
  • NR Butyl rubbers
  • thermoplastic elastomers having a weight proportion of 10 to 50% by weight, based on the total elastomer content.
  • styrene-isoprene-styrene (SIS) and styrene-butadiene-styrene (SBS) types may be mentioned as examples.
  • Suitable elastomers for blending are also, for example, EPDM or EPM rubber, polyisobutylene, butyl rubber, ethylene-vinyl acetate, hydrogenated block copolymers of dienes (for example by hydrogenation of SBR, cSBR, BAN, NBR, SBS, SIS or IR, such polymers for example known as SEPS and SEBS) or acrylate copolymers such as ACM.
  • SIS styrene-isoprene-styrene
  • Crosslinking is advantageous for improving the redetachability of the adhesive tape after use and may be thermal or by exposure to UV light or electron beams.
  • thermally activatable chemical crosslinkers such as accelerated sulfur or sulfur donor systems, isocyanate systems, reactive melamine, formaldehyde and (optionally halogenated) phenol-formaldehyde resins or reactive phenolic or Diisocyanatvernetzungssysteme with the corresponding activators, epoxidized polyester - And acrylate resins and their combinations used.
  • the crosslinkers are preferably activated at temperatures above 50 ° C, in particular at temperatures of 100 ° C to 160 ° C, most preferably at temperatures of 1 10 ° C to 140 ° C.
  • the thermal excitation of the crosslinker can also be effected by IR radiation or high-energy alternating fields.
  • Suitable adhesives are solvent-based, water-based or even as a hot-melt system.
  • a composition based on acrylate hotmelt is also suitable, it being possible for it to have a K value of at least 20, in particular greater than 30, obtainable by concentrating a solution of such a composition into a system which can be processed as a hotmelt
  • the concentration can take place in suitably equipped boilers or extruders, in particular in the concomitant degassing a vented extruder is preferred.
  • self-adhesives used are copolymers of (meth) acrylic acid and their esters having 1 to 25 C atoms, maleic, fumaric and / or itaconic acid and / or their esters, substituted (meth) acrylamides, maleic anhydride and other vinyl compounds, such as vinyl esters, in particular vinyl acetate, vinyl alcohols and / or vinyl ethers used.
  • An adhesive which also shows to be suitable is a low molecular weight acrylate hot melt pressure-sensitive adhesive, such as that supplied by BASF under the name acResin UV or Acronal®, in particular Acronal® DS 3458 or AC Resin A 260UV. This adhesive with a low K value obtains its application-oriented properties through a final radiation-induced crosslinking.
  • the self-adhesive composition 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 or elastomers.
  • additives such as tackifiers (resins), plasticizers, fillers, pigments, UV absorbers, light stabilizers, aging inhibitors, crosslinking agents, crosslinking promoters or elastomers.
  • Tackifiers are the resins already described in detail.
  • Suitable fillers and pigments are, for example, carbon black, titanium dioxide, calcium carbonate, zinc carbonate, zinc oxide, silicates or silicic acid.
  • Suitable plasticizers are, for example, aliphatic, cycloaliphatic and aromatic mineral oils, di- or poly-esters of phthalic acid, trimellitic acid or adipic acid, liquid rubbers (for example nitrile or polyisoprene rubbers), liquid polymers of butene and / or isobutene, acrylic esters, polyvinyl ethers, liquid and soft resins based on the raw materials to adhesive resins, wool wax and other waxes or liquid silicones.
  • liquid rubbers for example nitrile or polyisoprene rubbers
  • liquid polymers of butene and / or isobutene acrylic esters
  • polyvinyl ethers polyvinyl ethers
  • liquid and soft resins based on the raw materials to adhesive resins, wool wax and other waxes or liquid silicones.
  • Crosslinking agents are, for example, phenolic resins or halogenated phenolic resins, melamine and formaldehyde resins.
  • Suitable crosslinking promoters are, for example, maleimides, allyl esters, such as triallyl cyanurate, polyfunctional esters of acrylic and methacrylic acid.
  • a "poly (meth) acrylate” is understood as meaning a polymer whose monomer base consists of at least 60% by weight of acrylic acid, methacrylic acid, acrylic acid esters and / or methacrylic acid esters, acrylic esters and / or methacrylates being at least partly, preferably at least 50% by weight.
  • poly (meth) acrylate means a polymer which is obtainable by radical polymerization of acrylic and / or methacrylic monomers and optionally other copolymerizable monomers
  • the poly (meth) acrylate or poly (meth) acrylates are from 30 to
  • the PSA according to the invention contains from 35 to 55% by weight, based on the total weight of the PSA, of at least one poly (meth) acrylate.
  • Meth) acrylate is preferably ⁇ 0 ° C, more preferably between -20 and -50 ° C.
  • the glass transition temperature of polymers or polymer blocks in block copolymers is determined in the context of this invention by means of dynamic scanning calorimetry (DSC).
  • the poly (meth) acrylates of the PSA of the invention are preferably obtainable by at least partial incorporation of functional monomers which are preferably crosslinkable with epoxide groups.
  • functional monomers which are preferably crosslinkable with epoxide groups.
  • monomers having acid groups especially carboxylic acid, sulfonic acid or phosphonic acid groups
  • acid groups especially carboxylic acid, sulfonic acid or phosphonic acid groups
  • monomers containing carboxylic acid groups especially carboxylic acid groups
  • the polyacrylate comprises copolymerized acrylic acid and / or methacrylic acid. All of these groups have a crosslinking ability with epoxide groups, whereby the polyacrylate is advantageously accessible to thermal crosslinking with incorporated epoxides.
  • poly (meth) acrylates in addition to acrylic acid and / or methacrylic acid esters having up to 30 carbon atoms per molecule, for example vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl aromatic compounds with up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols containing 1 to 10 carbon atoms, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds or mixtures of these monomers.
  • the properties of the relevant poly (meth) acrylate can be influenced in particular by varying the glass transition temperature of the polymer by different weight proportions of the individual monomers.
  • the poly (meth) acrylate (s) of the invention may preferably be recycled to the following monomer composition: a) acrylic acid esters and / or methacrylic acid esters of the following formula
  • R 1 H or CH 3 and R "is an alkyl radical having 4 to 14 C atoms,
  • component (a) optionally further acrylates and / or methacrylates and / or olefinically unsaturated monomers which are copolymerizable with component (a).
  • the proportions of the respective components (a), (b), and (c) are preferably selected so that the polymerization product has a glass transition temperature of ⁇ 0 ° C, more preferably between -20 and -50 ° C (DSC).
  • the monomers of component (a) in a proportion of 45 to 99 wt .-%, the monomers of component (b) in a proportion of 1 to 15 wt .-% and the monomers of component (c) in a proportion of 0 to 40 wt .-% are based on the monomer mixture for the "base polymer", ie without additives of any additives to the finished polymer, such as resins, etc.).
  • the monomers of component (a) are, in particular, plasticizing and / or nonpolar monomers.
  • Preferably used as monomers (a) are acrylic and methacrylic acid esters having alkyl groups consisting of 4 to 14 C atoms, particularly preferably 4 to 9 C atoms.
  • Examples of such monomers are n-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-amyl acrylate, n-hexyl acrylate, n-hexyl methacrylate, n-heptyl acrylate, n-octyl acrylate, n-octyl methacrylate, n-nonyl acrylate and their branched isomers such as isobutyl acrylate, isooctyl acrylate, isooctyl methacrylate, 2-ethylhexyl acrylate or 2-ethylhexyl methacrylate.
  • the monomers of component (b) are, in particular, olefinically unsaturated monomers having functional groups, in particular having functional groups capable of undergoing reaction with epoxide groups.
  • component (b) preference is given to using monomers having functional groups which are selected from the group comprising: hydroxyl, carboxy, sulfonic or phosphonic acid groups, acid anhydrides, epoxides, amines.
  • monomers of component (b) are acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, aconitic acid, dimethylacrylic acid, ⁇ -acryloyloxypropionic acid, trichloroacrylic acid, vinylacetic acid, vinylphosphonic acid, maleic anhydride, hydroxyethyl acrylate, in particular 2-hydroxyethyl acrylate, hydroxypropyl acrylate, in particular 3 Hydroxypropyl acrylate, hydroxybutyl acrylate, in particular 4-hydroxybutyl acrylate, hydroxyhexyl acrylate, in particular 6-hydroxyhexyl acrylate, hydroxyethyl methacrylate, in particular 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, in particular 3-
  • component (c) Hydroxybutyl methacrylate, hydroxyhexyl methacrylate, especially 6-hydroxyhexyl methacrylate, allyl alcohol, glycidyl acrylate, glycidyl methacrylate.
  • All vinylically functionalized compounds which are copolymerizable with component (a) and / or component (b) can be used as component (c).
  • the monomers of component (c) can serve to adjust the properties of the resulting PSA.
  • Exemplary monomers of component (c) are:
  • Monomers of component (c) may advantageously also be chosen such that they contain functional groups which promote a subsequent radiation-chemical crosslinking (for example by electron beams, UV).
  • Suitable copolymerizable photoinitiators are, for example, benzoin acrylate and acrylate-functionalized benzophenone derivatives.
  • Monomers which promote electron beam crosslinking are, for example, tetrahydrofurfuryl acrylate, N-he / f-butylacrylamide and allyl acrylate.
  • polyacrylates is understood in the context of the invention to be synonymous with “poly (meth) acrylates"
  • poly (meth) acrylates can be familiar to the person skilled in the art Processes are carried out, in particular advantageous by conventional free-radical polymerizations or controlled radical polymerizations.
  • the polyacrylates can be prepared by copolymerization of the monomeric components using the usual polymerization initiators and optionally regulators, being polymerized at the usual temperatures in bulk, in emulsion, for example in water or liquid hydrocarbons, or in solution.
  • the polyacrylates are prepared by polymerization of the monomers in solvents, in particular in solvents having a boiling range of 50 to 150 ° C, preferably from 60 to 120 ° C using the usual amounts of polymerization initiators, generally at 0.01 to 5, in particular at 0.1 to 2 wt .-%, based on the total weight of the monomers, are prepared.
  • radical sources are peroxides, hydroperoxides and azo compounds, for example dibenzoyl peroxide, cumene hydroperoxide, cyclohexanone peroxide, di-i-butyl peroxide, cyclohexylsulfonylacetyl peroxide, diisopropyl percarbonate, ⁇ -butyl peroctoate, benzpinacol.
  • the free-radical initiator used is 2,2'-azobis (2-methylbutyronitrile) (Vazo® 67 TM from DuPont) or 2,2'-azobis (2-methylpropionitrile) (2,2'-azobisisobutyronitrile; AIBN Vazo® 64 TM from DuPont).
  • Suitable solvents for the preparation of the poly (meth) acrylates are alcohols such as methanol, ethanol, n- and iso-propanol, n- and iso-butanol, preferably isopropanol and / or isobutanol, and hydrocarbons such as toluene and in particular gasoline having a boiling range of 60 up to 120 ° C in question.
  • alcohols such as methanol, ethanol, n- and iso-propanol, n- and iso-butanol, preferably isopropanol and / or isobutanol
  • hydrocarbons such as toluene and in particular gasoline having a boiling range of 60 up to 120 ° C in question.
  • ketones such as, preferably, acetone, methyl ethyl ketone, methyl isobutyl ketone and esters, such as ethyl acetate, and mixtures of solvents of the type mentioned, with mixtures containing isopropanol, in particular in amounts of from 2 to 15% by weight, preferably from 3 to 10% by weight. , based on the solvent mixture used, are preferred.
  • the concentration of the polymer can be done in the absence of crosslinker and accelerator substances. But it is also possible, one add these classes of compounds to the polymer before concentration, so that the concentration then takes place in the presence of this substance (s).
  • the weight-average molecular weights M w of the polyacrylates are preferably in a range from 20,000 to 2,000,000 g / mol; more preferably in a range of 100,000 to 1,500,000 g / mol, most preferably in a range of 150,000 to 1,000,000 g / mol.
  • the data of the average molecular weight M w and the polydispersity PD in this document relate to the determination by gel permeation chromatography.
  • suitable polymerization regulators such as thiols, halogen compounds and / or alcohols in order to set the desired average molecular weight.
  • the polyacrylates preferably have a K value of 30 to 90, particularly preferably 40 to 70, measured in toluene (1% solution, 21 ° C).
  • the K value according to Fikentscher is a measure of the molecular weight and the viscosity of the polymer.
  • polyacrylates which have a narrow molecular weight distribution (polydispersity PD ⁇ 4).
  • polydispersity PD ⁇ 4 a narrow molecular weight distribution
  • these compositions have a particularly good shear strength.
  • the lower polydispersity allows for easier melt processing, since the flow viscosity is lower compared to a more widely dispersed polyacrylate with largely similar application properties.
  • Narrowly distributed poly (meth) acrylates can be advantageously prepared by anionic polymerization or by controlled radical polymerization, the latter being particularly well suited. Also via / V-Oxyle can be produced corresponding polyacrylates.
  • ATRP atom transfer radical polymerization
  • the monomers for preparing the poly (meth) acrylates preferably contain proportionate functional groups which are suitable with epoxy groups linking reactions enter into. This advantageously allows thermal crosslinking of the polyacrylates by reaction with epoxides.
  • linking reactions are meant in particular addition and substitution reactions.
  • the epoxide group-containing substances are preferably multifunctional epoxides, ie those having at least two epoxide groups; Accordingly, it is preferable in total to an indirect linkage of the blocks carrying the functional groups.
  • the poly (meth) acrylates of the PSA of the invention are preferably crosslinked by linking reactions - in particular in the context of addition or substitution reactions - of functional groups contained in them with thermal crosslinkers. It is possible to use all thermal crosslinkers which ensure both a sufficiently long processing time, so that there is no gelling during the processing process, in particular the extrusion process, as well as a rapid post-crosslinking of the polymer to the desired degree of crosslinking at temperatures lower than the processing temperature , especially at room temperature, lead. For example, a combination of polymers containing carboxyl, amine and / or hydroxyl groups and isocyanates, in particular aliphatic or amine-deactivated trimerized isocyanates, as crosslinkers is possible.
  • Suitable isocyanates are in particular trimerized derivatives of MDI [4,4-methylene di (phenyl isocyanate)], HDI [hexamethylene diisocyanate, 1,6-hexylene diisocyanate] and / or IPDI [isophorone diisocyanate, 5-isocyanato-1-isocyanatomethyl-1, 3, 3-trimethylcyclohexane], for example the types Desmodur® N3600 and XP2410 (in each case BAYER AG: aliphatic polyisocyanates, low-viscosity HDI trimers). Also suitable is the surface-deactivated dispersion of micronized trimerized IPDI BUEJ 339®, now HF9® (BAYER AG).
  • isocyanates such as Desmodur VL 50 (polyisocyanates based on MDI, Bayer AG), Basonat F200WD (aliphatic Polyisocyanate, BASF AG), Basonat HW100 (water-emulsifiable polyfunctional isocyanate based on HDI, BASF AG), Basonat HA 300 (allophanate-modified polyisocyanate based on isocyanurate, HDI-based, BASF) or Bayhydur VPLS2150 / 1 (hydrophilic modified IPDI, Bayer AG ).
  • Desmodur VL 50 polyisocyanates based on MDI, Bayer AG
  • Basonat F200WD aliphatic Polyisocyanate, BASF AG
  • Basonat HW100 water-emulsifiable polyfunctional isocyanate based on HDI, BASF AG
  • Basonat HA 300 allophanate-modified polyisocyanate based on isocyanurate, HDI-based, BASF
  • thermal crosslinkers Preference is given to using thermal crosslinkers at from 0.1 to 5% by weight, in particular from 0.2 to 1% by weight, based on the total amount of the polymer to be crosslinked.
  • the poly (meth) acrylates of the PSA of the invention are preferably crosslinked by means of epoxide (s) or by means of one or more epoxide group-containing substance (s).
  • the epoxide group-containing substances are in particular multifunctional epoxides, ie those having at least two epoxide groups; Accordingly, there is an overall indirect linkage of the functional groups bearing blocks of poly (meth) acrylates.
  • the epoxide group-containing substances can be both aromatic and aliphatic compounds.
  • Highly suitable multifunctional epoxides are oligomers of epichlorohydrin, polyether polyhydric alcohols (especially ethylene, propylene and butylene glycols, polyglycols, thiodiglycols, glycerol, pentaerythritol, sorbitol, polyvinyl alcohol, polyallylalcohol and the like), epoxy ethers of polyhydric phenols [especially resorcinol, hydroquinone, bis - (4-hydroxyphenyl) -methane, bis (4-hydroxy-3-methylphenyl) -methane, bis (4-hydroxy-3,5-dibromophenyl) -methane, bis (4-hydroxy-3,5- difluorophenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) -propane, 2 , 2-bis- (4-
  • Very suitable ethers are, for example, 1,4-butanediol diglycidyl ether, polyglycerol-3-glycidyl ether, cyclohexanedimethanol diglycidyl ether, glycerol triglycidyl ether, neopentylglycol diglycidyl ether, pentaerythritol tetraglycidyl ether, 1,6-hexanediol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, bisphenol A diglycidyl ether and bisphenol F diglycidyl ether.
  • crosslinking system a crosslinking accelerator system
  • the crosslinker-accelerator system comprises at least one substance containing epoxide groups as crosslinker and at least one substance accelerating at a temperature below the melting temperature of the polymer to be crosslinked for crosslinking reactions by means of compounds containing epoxide groups as accelerator.
  • amines (formally as substitution products of ammonia, in the following formulas these substituents are represented by "R" and include in particular alkyl and / or aryl radicals and / or other organic radicals), particularly preferably such amines, which undergo no or only minor reactions with the building blocks of the polymers to be crosslinked.
  • accelerators In principle, it is possible to select both primary (NRH 2 ), secondary (NR 2 H) and tertiary amines (NR 3 ) as accelerators, of course also those which have a plurality of primary and / or secondary and / or tertiary amine groups.
  • particularly preferred accelerators are tertiary amines such as triethylamine, triethylenediamine, benzyldimethylamine, dimethylamino-methylphenol, 2,4,6-tris- (N, N-dimethylaminomethyl) -phenol, N, N'-bis (3- (dimethyl-amino ) propyl) urea.
  • accelerators may also be advantageous multifunctional amines such as diamines, triamines and / or tetramines are used. For example, diethylenetriamine, triethylenetetramine, trimethylhexamethylenediamine are excellent.
  • amino alcohols are preferably used as accelerators.
  • Secondary and / or tertiary amino alcohols are particularly preferably used, wherein in the case of several amine functionalities per molecule, preferably at least one, preferably all amine functionalities are secondary and / or tertiary.
  • Preferred amino alcohol accelerators may be triethanolamine, N, N-bis (2-hydroxypropyl) ethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, 2-aminocyclohexanol, bis (2-hydroxycyclohexyl) methylamine, 2- (diisopropylamino) ethanol, 2- Dibutylamino) ethanol, N-butyldiethanolamine, N-butylethanolamine, 2- [bis (2-hydroxyethyl) amino] -2- (hydroxymethyl) -1, 3-propanediol, 1 - [bis (2-hydroxyethyl) amino] -2- propanol, triisopropanolamine, 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, 2- (2-dimethylaminoethoxy) ethanol, N, N, N'-trimethyl-N'-hydroxyethyl bisaminoethyl ether, ⁇ ,
  • Trimethylaminopropylethanolamin be used.
  • accelerators are pyridine, imidazoles (such as 2-methylimidazole) and 1,8-diazabicyclo [5.4.0] undec-7-ene. Cycloaliphatic polyamines can also be used as accelerators. Also suitable are phosphate-based accelerators, such as phosphines and / or phosphonium compounds, for example triphenylphosphine or tetraphenylphosphonium tetraphenylborate.
  • Acrylic PSAs are typically radically polymerized copolymers of alkyl acrylates or alkyl methacrylates of C1 to C20 alcohols such as methyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2 Ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate,
  • esters of ethylenically unsaturated di- and tricarboxylic acids and anhydrides such as ethyl maleate, dimethyl fumarate and ethyl methyl itaconate.
  • vinylaromatic monomers such as styrene, vinyltoluene, methylstyrene, n-butylstyrene, decylstyrene, among others.
  • vinyl esters of carboxylic acids containing up to 20 carbon atoms such as vinyl acetate or vinyl laurate, vinyl ethers of alcohols containing up to 10 carbon atoms such as vinyl methyl ether or vinyl isobutyl ether, vinyl halides such as vinyl chloride or vinylidene dichloride, nitriles such as acrylonitrile or methacrylonitrile, acid amides such as acrylamide or methacrylamide and unsaturated hydrocarbons with 2 to 8 carbon atoms such as ethylene, propene, butadiene, isoprene, 1-hexene or 1-octene.
  • carboxylic acids containing up to 20 carbon atoms such as vinyl acetate or vinyl laurate
  • vinyl ethers of alcohols containing up to 10 carbon atoms such as vinyl methyl ether or vinyl isobutyl ether
  • vinyl halides such as vinyl chloride or vinylidene dichloride
  • nitriles such as acrylonitrile
  • polyfunctional ethylenically unsaturated monomers are suitable as crosslinking monomers.
  • examples include divinylbenzene, alkyl diacrylates such as 1, 2-ethylene glycol diacrylate, 1, 4-butanediol diacrylate, 1, 6 hexanediol diacrylate, 1, 8-octanediol diacrylate or 1, 12-dodecanediol diacrylate, triacrylates such as trimethylolpropane triacrylate and tetraacrylates such as pentaerythritol tetraacrylate.
  • the group of polyfunctional monomers also includes UV-crosslinkable monomers, such as (meth) acrylate-functionalized derivatives of benzophenone or benzoin.
  • Another group of monomers are those which create a latent crosslinking potential in the polymer and after the drying of the adhesive spontaneously (often catalysed) lead to a network structure.
  • a monomer is, for example, glycidyl methacrylate whose oxirane ring with hydroxyl or in particular carboxylate functions leads to a covalent bond under ring opening. This reaction occurs more rapidly in the presence of zinc ions or, especially in the presence of carboxyl functions, amines.
  • the processing temperature of the adhesive must be above its glass transition temperature to have viscoelastic properties.
  • the activatable adhesives in a particularly preferred embodiment then consist of a base polymer a) consisting of
  • a2) from 5 to 30% by weight of a copolymerizable vinyl monomer having at least one carboxylic acid and / or sulfonic acid and / or phosphonic acid group a3) from 1 to 10% by weight of a copolymerizable vinyl monomer having at least one epoxy group or one acid anhydride function
  • the polymer a) may comprise an activatable pressure-sensitive adhesive which becomes tacky under the action of temperature and optional pressure and builds up a high bond strength after bonding and cooling as a result of the solidification.
  • these activatable PSAs have different static glass transition temperatures T G, A or a melting point T S, A.
  • acrylic monomers are used for the monomers a1) which comprise acrylic and methacrylic acid esters having alkyl groups consisting of 4 to 14 C atoms, preferably 4 to 9 C atoms.
  • alkyl groups consisting of 4 to 14 C atoms, preferably 4 to 9 C atoms.
  • Specific examples are n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, n-nonyl acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate, and their branched isomers such as, for example 2-ethylhexyl acrylate.
  • Further classes of compounds which can also be added in small amounts under c1) are methyl methacrylates, cyclohexyl methacrylates, isobornyl acrylate and isobornyl methacrylates.
  • the monomers a2) used are itaconic acid, acrylic acid, methacrylic acid, vinylacetic acid, fumaric acid, crotonic acid, aconitic acid, dimethylacrylic acid, ⁇ -acryloyloxypropionic acid, trichloroacrylic acid, vinylphosphonic acid, vinylsulfonic acid and vinylsulfonic acid.
  • the monomers a3) used are glycidyl methacrylate, maleic anhydride and itaconic anhydride.
  • monomers a4) use vinyl esters, vinyl ethers, vinyl halides, vinylidene halides, vinyl compounds having aromatic rings and heterocycles in the ⁇ -position.
  • monomers having the following functional groups are used: hydroxyl, acid amide, isocyanato or amino groups.
  • component a4) are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate,
  • aromatic vinyl compounds are used for the component a4), wherein preferably the aromatic rings selected from C 4 to C 8 exist and may also contain heteroatoms.
  • Particularly preferred examples are styrene, 4-vinylpyridine, N-vinylphthalimide, methylstyrene, 3,4-dimethoxystyrene, 4-vinylbenzoic acid, although this list is not exhaustive.
  • the monomers are in turn chosen so that the resulting polymers can be used as industrially useful adhesives or PSAs, in particular such that the resulting polymers adhesive or pressure-sensitive adhesive properties according to the "Handbook of Pressure Sensitive Sensitive Adhesive Technology" by Donatas Satas (van Nostrand).
  • control of the desired glass transition temperature can be achieved by the application of Fox's equation (G1) in the composition of the monomer mixture that underlies the polymerization PSAs, the static glass transition temperature of the resulting polymer is advantageously below 15 ° C.
  • the monomers are very preferably selected and the quantitative composition of the monomer mixture advantageously selected such that according to the Fox Equation (G1) (see TG Fox, Bull. Am. Phys Soc., 1 (1956) 123) gives the desired T G, A value for the polymer.
  • G1 Fox Equation
  • n the number of runs via the monomers used
  • w n the mass fraction of the respective monomer n (wt .-%) and T G, n the respective glass transition temperature of the homopolymer of the respective monomers n in K.
  • radical sources are peroxides, hydroperoxides and azo compounds
  • typical free-radical initiators are potassium peroxodisulfate, dibenzoyl peroxide, cumene hydroperoxide, cyclohexanone peroxide, di-t-butyl peroxide, Azodiisoklarebutyronitril, Cyclohexylsulfonylacetylperoxid, diisopropyl percarbonate, t-butyl peroctoate, Benzpinacol.
  • the free-radical initiator used is 1, 1'-azobis (cyclohexanecarbonitrile) (Vazo 88 TM from DuPont).
  • the average molecular weights M n of the PSAs formed in the free-radical polymerization are very preferably selected such that they are in a range from 20,000 to 2,000,000 g / mol; PSAs having average molecular weights M n of 100,000 to 500,000 g / mol are produced especially for further use as hotmelt PSAs.
  • the polymerization may be carried out neat, in the presence of one or more organic solvents, in the presence of water or in mixtures of organic solvents and water.
  • the aim is to keep the amount of solvent used as low as possible.
  • the polymerization time is - depending on the conversion and temperature - between 4 and 72 hours.
  • the film may be subjected to a corona treatment.
  • an etching of the film is advantageous in order to be able to anchor the adhesive.
  • a primer is present between lower film and adhesive to improve the adhesion of the adhesive to the film.
  • the upper and lower foils in the blank have the same shape and size and are congruently arranged.
  • a typical size for the diecut, with which many of the smaller holes can be closed represents a (circular) disc with a diameter of 10 to 60 mm, in particular 30 to 40 mm.
  • the lower film is coated over its entire surface with the adhesive.
  • the inventive method for closing a hole, in particular in a body with a punched product according to the invention is characterized by the following steps:
  • the punched product also withstands temperatures of, for example, 190 ° C. or more for a few minutes, for example if there is a plant breakdown and the (automobile) bodies are left in the drying ovens for longer.
  • the curing of the adhesive preferably takes place by supplying heat during the customary finishing process of the body shell, in particular during the painting, underbody protection or CDP drying. In this way, no additional operation is required.
  • the stamped body is applied concentrically over the hole to be closed.
  • the contours of the blank correspond to the contour of the hole to be closed. This results in a symmetrical projection of the individual layers of the stamped product.
  • the supernatant is preferably between 1 and 20 mm, more preferably between 5 and 10 mm.
  • the stamped product according to the invention is superior to the known from the prior art solutions, especially at elevated mechanical stress. The same is true when considering the noise attenuation.
  • the noise damping and the Strength are massively improved by the use of a carrier laminate with a heavy foil.
  • a single embodiment of the stamped product can cover a plurality of holes of different sizes.
  • the puncture resistance is determined by closing a hole with a punched product and piercing it in a targeted manner.
  • a mandrel is clamped in a tensile testing machine, which moves at a constant speed to the horizontally positioned, closed hole and pierces it by 30 mm. The force to be expended is measured.
  • the diecut has puncture strengths of 200 to 2000 N.
  • the surface of the stamped part offers an appealing and smooth surface in the points optics and haptics
  • the measurements are (unless otherwise stated) at a test climate of 23 ⁇ 1 ° C and 50 ⁇ 5% rel. Humidity carried out.
  • the statements of the number-average molar mass Mn and the weight-average molar mass Mw in this document refer to the determination by gel permeation chromatography (GPC). The determination is carried out on 100 ⁇ clear filtered sample (sample concentration 4 g / l). The eluent used is tetrahydrofuran with 0.1% by volume of trifluoroacetic acid. The measurement takes place at 25 ° C.
  • a combination of the columns of the type PSS-SDV, 5 [Jim, 10 3 ⁇ and 10 5 ⁇ and 10 6 ⁇ , each with 8.0 mm * 300 mm used (columns from Polymer Standards Service; Detection by means of a differential refractometer Shodex RI71)
  • the flow rate is 1, 0 ml per minute
  • the calibration is carried out with polyacrylates against PMMA standards (polymethyl methacrylate calibration) and otherwise (resins, elastomers) against PS standards (polystyrene calibration).
  • the polyacrylates preferably have a K value of 30 to 90, particularly preferably 40 to 70, measured in toluene (1% solution, 21 ° C).
  • the K value according to Fikentscher is a measure of the molecular weight and the viscosity of the polymer.
  • the principle of the method is based on the capillary-viscometric determination of the relative solution viscosity.
  • the test substance is dissolved in toluene by shaking for 30 minutes, so that a 1% solution is obtained.
  • the flow time is measured at 25 ° C and determined therefrom in relation to the viscosity of the pure solvent, the relative viscosity of the sample solution.
  • the glass transition temperature is determined by dynamic scanning calorimetry (DSC). For this purpose, 5 mg of an untreated polymer sample are weighed into an aluminum crucible (volume 25 ⁇ ) and closed with a perforated lid. For measurement, a DSC 204 F1 from Netzsch is used. It will for inerting under nitrogen. The sample is first cooled to -150 ° C, then heated at a heating rate of 10 K / min to +150 ° C and again cooled to - 150 ° C. The subsequent second heating curve is driven again at 10 K / min and recorded the change in heat capacity. Glass transitions are recognized as steps in the thermogram.
  • DSC dynamic scanning calorimetry
  • the glass transition temperature is evaluated as follows (see FIG. 2):
  • a tangent is applied to the baseline of the thermogram before ⁇ and after ⁇ of the step.
  • a straight line ⁇ parallel to the ordinate is placed so that it intersects the two tangents in such a way that two faces ⁇ and ⁇ (between the one tangent, the equalization line and the trace) of the same content are created.
  • the intersection of the thus positioned regression line with the trace gives the glass transition temperature
  • the punched article is intended to be explained in more detail with reference to a figure for the permanent closing of holes, in particular in metal sheets or in plastic parts of automobile bodies, without being intended to be limiting in any way. It shows
  • FIG. 1 shows a hole in a body, which is to be closed, and the state after the hole to be closed is closed by the action of heat.
  • a hole 6 is structurally present, it applies to be closed.
  • the surface of the stamped product 1 is larger than the area of the hole 6 to be closed.
  • the stamped product 1 is permanently connected to the body 5 by briefly acting on the stamped high temperatures that lead to the activation of the adhesive 4.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Body Structure For Vehicles (AREA)
  • Sealing Material Composition (AREA)
  • Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
  • Adhesive Tapes (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Transportation (AREA)
  • Perforating, Stamping-Out Or Severing By Means Other Than Cutting (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
EP14747879.6A 2013-08-23 2014-07-23 STANZLING INSBESONDERE ZUM DAUERHAFTEN VERSCHLIEßEN VON LÖCHERN Pending EP3036100A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201310216778 DE102013216778A1 (de) 2013-08-23 2013-08-23 Stanzling insbesondere zum dauerhaften Verschließen von Löchern
PCT/EP2014/065807 WO2015024725A1 (de) 2013-08-23 2014-07-23 STANZLING INSBESONDERE ZUM DAUERHAFTEN VERSCHLIEßEN VON LÖCHERN

Publications (1)

Publication Number Publication Date
EP3036100A1 true EP3036100A1 (de) 2016-06-29

Family

ID=51292928

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14747879.6A Pending EP3036100A1 (de) 2013-08-23 2014-07-23 STANZLING INSBESONDERE ZUM DAUERHAFTEN VERSCHLIEßEN VON LÖCHERN

Country Status (10)

Country Link
US (1) US10828841B2 (zh)
EP (1) EP3036100A1 (zh)
JP (1) JP6480937B2 (zh)
KR (1) KR20160045842A (zh)
CN (1) CN105492203B (zh)
BR (1) BR112016002940A2 (zh)
CA (1) CA2919922A1 (zh)
DE (1) DE102013216778A1 (zh)
MX (1) MX2016002074A (zh)
WO (1) WO2015024725A1 (zh)

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EP3569406A1 (de) 2018-05-18 2019-11-20 tesa SE Stanzling insbesondere zum dauerhaften verschliessen von löchern
EP3943283A1 (de) 2020-07-23 2022-01-26 tesa SE Stanzling insbesondere zum dauerhaften verschliessen von löchern
DE102020212530A1 (de) 2020-10-05 2022-04-07 Tesa Se Stanzling insbesondere zum dauerhaften Verschließen von Löchern
DE102021208046A1 (de) 2021-07-26 2023-01-26 Tesa Se Stanzling insbesondere zum dauerhaften Verschließen von Löchern
DE102021130344A1 (de) 2021-11-19 2023-05-25 Bayerische Motoren Werke Aktiengesellschaft Stanzling insbesondere zum dauerhaften Verschließen von Löchern

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US10480656B2 (en) * 2016-08-22 2019-11-19 Tesa Se Bridge tape with directed foam expansion and method for sealing holes in sheet metal or plastic parts of automobile bodies
DE102017216070A1 (de) * 2017-09-12 2019-03-14 Tesa Se Versiegelungsklebeband für Karosserien
EP3643496A1 (en) 2018-10-22 2020-04-29 Nitto Belgium N.V Multilayered patches for sealing applications and related methods
US11511610B2 (en) 2018-11-12 2022-11-29 Shape Corp. Vehicle door carrier with integrated edge seal and method of manufacture
DE102019101494B4 (de) 2019-01-22 2021-03-25 Dr. Ing. H.C. F. Porsche Aktiengesellschaft Montagehilfsmittel, Verwendung eines Montagehilfsmittels und Karosserieteil mit Montagehilfsmittel
DE102021101908A1 (de) 2021-01-28 2022-07-28 Dr. Ing. H.C. F. Porsche Aktiengesellschaft Schutzdeckel einer Kraftfahrzeugkarosserie
DE102021122381A1 (de) 2021-08-30 2023-03-02 Audi Aktiengesellschaft Karosseriestruktur für ein Fahrzeug

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EP3569406A1 (de) 2018-05-18 2019-11-20 tesa SE Stanzling insbesondere zum dauerhaften verschliessen von löchern
DE102018207850B4 (de) 2018-05-18 2020-06-18 Tesa Se Stanzling zum dauerhaften Verschließen von Löchern
US10946629B2 (en) 2018-05-18 2021-03-16 Tesa Se Diecut, in particular for permanently closing holes
EP3943283A1 (de) 2020-07-23 2022-01-26 tesa SE Stanzling insbesondere zum dauerhaften verschliessen von löchern
DE102020209289A1 (de) 2020-07-23 2022-01-27 Tesa Se Stanzling insbesondere zum dauerhaften Verschließen von Löchern
DE102020212530A1 (de) 2020-10-05 2022-04-07 Tesa Se Stanzling insbesondere zum dauerhaften Verschließen von Löchern
EP3992259A1 (de) 2020-10-05 2022-05-04 tesa SE Stanzling insbesondere zum dauerhaften verschliessen von löchern
DE102020212530B4 (de) 2020-10-05 2022-08-11 Tesa Se Stanzling insbesondere zum dauerhaften Verschließen von Löchern
US11939500B2 (en) 2020-10-05 2024-03-26 Tesa Se Diecut especially for permanently closing holes
DE102021208046A1 (de) 2021-07-26 2023-01-26 Tesa Se Stanzling insbesondere zum dauerhaften Verschließen von Löchern
WO2023006578A1 (de) 2021-07-26 2023-02-02 Tesa Se STANZLING INSBESONDERE ZUM DAUERHAFTEN VERSCHLIEßEN VON LÖCHERN
DE102021130344A1 (de) 2021-11-19 2023-05-25 Bayerische Motoren Werke Aktiengesellschaft Stanzling insbesondere zum dauerhaften Verschließen von Löchern

Also Published As

Publication number Publication date
CN105492203B (zh) 2018-08-24
JP6480937B2 (ja) 2019-03-13
US10828841B2 (en) 2020-11-10
WO2015024725A1 (de) 2015-02-26
KR20160045842A (ko) 2016-04-27
US20160271866A1 (en) 2016-09-22
JP2016536171A (ja) 2016-11-24
MX2016002074A (es) 2016-05-26
DE102013216778A1 (de) 2015-02-26
BR112016002940A2 (pt) 2017-08-01
CA2919922A1 (en) 2015-02-26
CN105492203A (zh) 2016-04-13

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