DE102008025979A1 - Adhesive tape for use, e.g. as sticking plaster, cable wrapping or packaging material, comprises a support coated with adhesive containing a special olefin polymer and a tackifier resin - Google Patents

Abstract

Adhesive tape comprising a support coated on at least one side with adhesive material (I) consisting of (A) an olefin polymer with a density of 0.86-0.89 g/cm 3>and a crystallite melting point (CMP) of at least 105[deg] C and (B) a tackifier resin.

Description

The The invention relates to an adhesive tape, especially for outdoor applications with a textile carrier.

Fabric tapes, consisting of a woven textile as a carrier material and a one-side applied layer of a self-adhesive, belong to one of the oldest types of self-adhesive Systems as roll goods. First used in the medical field, they solved in the second half of the last century partially insulating tapes made of soft PVC during bandaging cable harnesses in automobiles. Because of the extraordinary Property combination of flexibility and conformability, high mechanical strength combined with simultaneous tearability By hand, the range of applications expanded greatly. fabric adhesive tapes can be used for bandaging, repairing, covering, fixing, Marking etc. can be used and can be done without scissors, knives or cut other tools to length by hand. they provide therefore universal adhesive tapes (so-called "Multi Purpose "or" General Purpose "tapes) representing on a variety of substrates, whether polar or nonpolar, rough or smooth, sticking and for just about everyone conceivable applications are used.

When Adhesive is almost exclusively based on recipes Natural or synthetic rubber used. Next to the historical aspect (natural rubber as the main constituent of the first industrially available self-adhesives) are in particular the adhesive properties, with regard to adhesion, Tack and cohesion balanced and for such Universal tapes are ideally suited. As carrier materials Dense woven textiles are preferably made of (modified) natural fibers such as cotton, rayon, viscose, etc. used.

Initially were fabric adhesive tapes made of uncoated fabric, as Raw fabric or dyed in yarn, with only one side Adhesive mass produced coated. Through the open fabric structure however, the rubber adhesive on the back is light vulnerable: oxygen, aggressive substances such as solvents, UV or solar radiation etc. have almost unhindered access.

• • Die hochwertigsten Produkte nutzen ein dichtes Gewebe mit einem Flächengewicht von überwiegend 70 bis 150 g/m² bei einer Meshzahl (Summe der Fäden in Kett- und Schussrichtung, jeweils pro inch) in der Größenordnung von 100 bis 250 inch^–2 mit einer meist farbigen Kunststoffbeschichtung aus PVC, Acrylat, Polyurethan oder ähnlichem, die aus Dispersionen oder Organosolen einseitig aufgebracht wird. Diese Produkte haben ihren Ursprung in Mitteleuropa und werden überwiegend auch dort hergestellt. Als Beispiel für ein derartiges „Premium Tape” sei hier tesa^® 4651 genannt.
• • Eher asiatischen Ursprungs sind Gewebeklebebänder mit einem leichteren, offenen, netzartigen Gewebe von 40 bis 100 mesh, auf das eine 50 bis 200 μm dicke PE-Folie aufextrudiert wird. Gewebe und Folie bilden zumeist einen stabilen, belastbaren Verbund. Wegen ihrer Positionierung bezüglich Preises und der Eigenschaften werden sie auch als „Midgrades” bezeichnet. Als Beispiel kann hier tesa^® 4688 gelten.
• • Ursprünglich aus Nordamerika kommend haben sich die so genannten „Duct Tapes” global verbreitet. Hierbei kommen sehr offene Gewebe, Gelege oder Gewirke mit 25 bis 40 mesh mit einem Flächengewicht von 15 bis 40 g/m² zum Einsatz, auf die mit einem Teil der Selbstklebemasse eine meist farbige, undurchsichtige PE-Folie auflaminiert wird. Die Dauerhaftigkeit des Trägerverbunds aus Folie und Textil wird allein durch die Klebkraft und Alterungsstabilität der Klebemasse bestimmt. Diese Art von Gewebebändern stellt preislich die unterste Kategorie dar und wird meist in der Farbe Silber verwendet. Beispielhaft aus der Vielzahl der kommerziellen Duct Tapes kann hier tesa^® 4662 genannt werden.

Therefore, and also to protect the fabric itself, plastic coatings were applied to the top of the tape. Three types of fabric adhesive tapes can be distinguished based on the product structure:

• • The highest quality products use a dense fabric with a basis weight of predominantly 70 to 150 g / m ² with a mesh count (sum of filaments in warp and weft direction, each per inch) in the order of 100 to 250 inch ^-2 with a mostly colored plastic coating of PVC, acrylate, polyurethane or the like, which is applied from dispersions or Organosolen one-sided. These products have their origins in Central Europe and are mainly produced there. An example of such a "premium tape" is ^tesa® 4651.
• • More Asian origin are fabric adhesive tapes with a lighter, open, net-like fabric of 40 to 100 mesh on which a 50 to 200 micron thick PE film is extruded. Fabric and film usually form a stable, load-bearing composite. Because of their positioning in terms of price and characteristics, they are also referred to as "midgrades". As an example, tesa ^® 4688 can be used here.
• • Originally coming from North America, the so-called "duct tapes" have spread globally. In this case, very open fabrics, scrims or knits with 25 to 40 mesh with a weight per unit area of 15 to 40 g / m ² are used, onto which a part of the self-adhesive is laminated, usually a colored, opaque PE film. The durability of the carrier composite of film and textile is determined solely by the bond strength and aging stability of the adhesive. This type of fabric tapes is the lowest category in terms of price and is usually used in the color silver. An example of the large number of commercial duct tapes is tesa ^® 4662.

such Adhesive tapes generally have a total thickness of 200 to 400 microns, wherein the adhesive layer about 50 to 250 microns contributes, and are structurally in principle designed for indoor applications.

• • Kautschukklebemassen mit Doppelbindungen in den Elastomeren werden durch UV-Licht, Sauerstoff und Ozon angegriffen und geschädigt und verlieren dadurch ihre ursprünglichen Klebeigenschaften.
• • Gewebe aus Baumwolle, Viskose, Zellwolle etc. werden durch Mikroorganismen angegriffen. Bei Anwesenheit von Feuchtigkeit, Wärme und Licht verrottet diese für die mechanischen Festigkeitseigenschaften des Klebebandes maßgebliche Komponente.
• • Wasseraufnahme im Gewebe durch die Saugfähigkeit der Garne führt durch Aufquellen zur Verbundschwächung sowie zu Festigkeitsverlusten.

As universal tapes, they are also used in outdoor applications. However, the effects of light, direct sunlight, moisture, heat, microorganisms, etc. then reveal weaknesses that can lead to damage to the adhesive tapes or their complete destruction:

• • Rubber adhesives with double bonds in the elastomers are attacked and damaged by UV light, oxygen and ozone, thereby losing their original adhesive properties.
• • Fabrics made of cotton, viscose, rayon etc. are attacked by microorganisms. At Anwe The humidity, heat and light of these components ravages this component which is decisive for the mechanical strength properties of the adhesive tape.
• • Water absorption in the fabric due to the absorbency of the yarns leads to swelling as well as to loss of strength due to swelling.

Previous Try to find suitable high-quality universal tissue tapes for longer-term outdoor applications as So-called "outdoor tapes" are to develop not been successful or only with restrictions.

A high-quality but expensive fabric adhesive tape with a dense 200 to 250 mesh viscose acetate fabric is used in US 3,853,598 A1 described. The fabric is provided with a polyacrylate primer layer to which synthetic and natural rubber adhesive is applied. Due to the very high mesh count fabric and polyacrylate primer fabric finish, the tape has good and very easy hand tearability. However, there are no indications of outdoor suitability. The selected adhesive and in particular the upper side unprotected fabric based on modified natural fibers speak against it. Explicit only medical, that is called indoor applications.

A technical tape, especially for the construction sector, is in EP 1 548 080 A1 described. Although a weather-stable adhesive is used with a UV-crosslinked acrylate adhesive on a band-shaped support, selecting supports with papers, films, fabrics or nonwovens made of PE, PP or PET does not reveal an orientation towards outdoor applications. An easy hand tearability, as required for general purpose tape, is not available. Furthermore, in the case of UV-crosslinkable acrylate adhesives, there is the latent risk that, under the action of sunlight, a crosslinking which is not completely set during production continues, and thus the adhesive properties change negatively in the course of the use time.

A special tape for long-term outdoor use, after 500 hours in the weathering test after ASTM G155 less than 10% of adhesive residue is in WO 03/097758 A1 described. Essential here is the multilayer PE plastic film on the top, which contains up to 35% sunscreen additives. For the other adhesive tape components such as a 10 to 90 mesh scrim and the self-adhesive, no special features are described. Therefore, it can be assumed that protection against (UV) light is achieved over a large area by the multilayer film on the surface, but access of oxygen, ozone, etc. at the edge can lead to undesired changes in the adhesive at the edges of the adhesive tape. In addition, in the described support structure of a 50 to 100 microns thick multilayer PE film and a clutch of 10 to 90 mesh with the typical Duct tapes, frayed tear edges to be expected, which are not accepted for a high-quality fabric adhesive tape. Furthermore, the high proportion of light protection additives and the multilayer film structure can be expected to result in correspondingly high production costs.

In EP 1 074 595 A1 describes a polyester fabric tape which is hand tearable by the selection of special yarns and defined fabric construction (maximum 2500 dtex / cm as the denier of the longitudinal yarns per unit length) as well as by the necessary fixation of the warp yarns by the adhesive coating. Thus, special conditions must be met in order to achieve at least a tear strength of less than 10 N in the transverse direction. The description of the yarn and fabric parameters has for those skilled in the lightweight fabric well below 100 g / m ² towards that only by reducing the grammage has been less strength not entirely surprising per se, but only in addition, through the adhesive layer the warp threads must be fixed in place, hand tearable. Furthermore, a tear propagation resistance of below 10 N is erroneously linked to the property of hand tearability. In practice, in addition to the tear propagation strength described above, the force for the initial tearing of the carrier is of great importance for easy hand tearability, but this is significantly influenced by further parameters such as the tensile-elongation behavior of the wearer, the cutting technology and good used, etc. on which no information can be found in the disclosure.

In DE 10 2005 044 942 A1 describes a cross-tearable adhesive tape with an uncoated textile fabric carrier based on polyester or polyamide, whereby the reduction of the fiber strength and thus the hand tearability by targeted damage to the yarn (in PET with alkalis, in polyamide with acids). By additional impregnation with slip solid chemicals such as silicates, the hand tearability is to be further improved. The alkalization of PET fabric, for example, is accompanied by a marked loss of strength, which is negatively affected by aging, thermal stress, bending and / or tensile loads, and with an increase in gas and vapor permeability. Letz terer in medical applications beneficial effect reverses in technical applications to the contrary, since oxygen, ozone and similar aggressive gases and liquids can penetrate unhindered to the adhesive and thus damage them more than untreated or even coated fabrics.

Even though there are a variety of fabric adhesive tapes in both the technical, medical and consumer sector is a hand-tearable weather-resistant universal fabric tape for longer-term Outdoor applications unknown.

• – leicht handeinreißbares Gewebeklebeband aufzufinden,
• – welches auf einer Vielzahl von im täglichen Gebrauch gängigen Untergründen sicher klebt und
• – auch bei längerer Anwendung von mindestens sechs Monaten im Außenbereich (Mitteleuropa) seine klebende Funktionalität nicht verliert.

Therefore, it is an object of the invention to eliminate the shortcomings of existing products here and a

• - easy to find tearable tissue tape,
• - which on a variety of common in everyday use surfaces safely sticks and
• - even with prolonged use of at least six months in the outdoor area (Central Europe) does not lose its adhesive functionality.

As a yardstick, a reduction of the relevant measured values by a maximum of 50% is used, for example for the maximum tensile strength and elongation at break in the longitudinal direction and the bond strength to steel according to AFERA 5001 , Also, changes in the appearance, such as clearly discernible destruction or tearing, marked disappearance or discoloration, detachment from the adhesive substrates, are to be avoided according to the invention.

Solved This task is performed by a tape, as stated in the main claim is laid down. The subject of the claims are advantageous developments of the invention.

Accordingly, the invention relates to an adhesive tape, in particular for outdoor use, with a textile support having a basis weight of 15 to 150 g / m ² , which is provided on the top with an additional layer, which is applied by extrusion coating, by dispersion coating or by film lamination, and which the underside is provided with an adhesive of an ethylene polymer having a density between 0.86 and 0.89 g / cm ³ and a crystallite melting point of at least 105 ° C and an adhesive resin.

Of the general term "adhesive tape" includes the meaning this invention all planar structures as in two dimensions extended bands with extended length and limited width, band sections and the like, ultimately Diecuts or labels.

According to a first advantageous embodiment of the invention, the adhesive tape comprises a textile backing made of a very open fabric, scrim or knitted fabric of 25 to 40 mesh and having a basis weight of 15 to 40 g / m ² . On the upper side there is a UV-stabilized PE film with a thickness of 50 to 200 μm, which is preferably not transparent and in particular UV-impermeable by fillers and dye pigments. Due to advantageous UV stabilizers and anti-aging agents additionally used in the PE film as well as by the UV-impermeability of the PE film, the adhesive below the carrier is additionally protected against photo-oxidative attacks.

at This embodiment is the actual carrier a laminate consisting of the textile and the PE film in particular in situ is generated in the adhesive coating process. A small one Part of the adhesive is forced through the open textile under pressure and acts as a laminating adhesive. The side of the textile carrier with the small amount of adhesive is laminated with the PE film. This creates a composite of foil, laminating adhesive and textile.

at The PE film may be required on the open side facing away from the adhesive Page previously inline or offline with a release, to ensure easy unrolling.

in principle performs the preliminary production of a laminate from a film, applied to the laminating adhesive and then Covered with the textile before the adhesive coating on the opposite side of the textile, to comparable products.

In the embodiment described herein is a support for the already above-mentioned category of duct tapes such as tesa ^® 4,662th

According to a further advantageous embodiment of the invention, the textile carrier of the adhesive tape consists of an open, net-like fabric of 40 to 100 mesh and with a basis weight of 20 to 60 g / m ² , on which a 50 to 200 .mu.m thick PE film is extruded , Fabric and foil mostly form a stable, strong composite. A suitable UV stabilization can also be done here as in the case of the Duct Tapes UV stabilizers, anti-aging agents and coloring. If required, release equipment can be applied to the open side of the PE film facing away from the adhesive.

In this type of carrier is already described above category of Midgrades such as tesa ^® 4688th

According to a further advantageous embodiment of the invention, the textile carrier of the adhesive tape consists of an 80 to 250 mesh PET fabric with a grammage of 50 to 150 g / m ² , on top of which a dispersion paste, in particular aqueous acrylate paste with an application weight of 15 to 75 g / m ^{2 is} applied.

The fabric with a grammage of 50 to 150 g / m ² , in particular 70 to 130 g / m ² , is selected so that by the special construction an at least moderate hand and tearability by hand in the transverse direction (as a weft direction or CD designated). This fabric is coated on one side with a colored, aqueous acrylate paste or similar with a coating weight of 15 to 75 g / m ² , in particular 25 to 50 g / m ² .

The tissue carrier is particularly advantageous if the coloring coating is applied in two lines in succession with two different formulations. The main portion is applied as a coloring base coat with 10 to 60 g / m ² directly on the fabric. By using an acrylate binder with a glass transition point of 0 ° C and less, a soft and elastic coating is obtained which has a positive effect on the flexibility and the grip of the wearer and promotes a smooth adhesion of the tissue adhesive tape.

On this sometimes slightly blocking (pressure-sticking) paint coating 5 to 20 g / m ^{2 of} a hard, resistant topcoat are applied in a second line. Thus, the resistance of the adhesive tape surface increases both against its own adhesive (direct contact during manufacture, transport and storage as a roll of adhesive tape) and in the subsequent application against all possible influences such as mechanical stress, visible, infrared or ultraviolet radiation, water , Chemicals etc.

Of the so-called topcoat is preferably selected from acrylate dispersions, in which hardening comonomers such as styrene, methacrylate, Acrylonitrile were polymerized.

Of the inventive carrier as a composite system from a PET fabric and the preferred acrylate coating not only very good resistance to the most diverse Stresses on how they are related to outdoor applications occur, but also a relation to the raw fabric improved Handling. There is an easy tear and tearability in the transverse direction without the use of cutting tools and a Flexibility for contour-matched bonds one.

This composite support a fabric tape of the premium class is obtained, as for example, represents tesa ^® 4,651th

By skillful choice of yarns, the fabric construction and the process steps, it is possible PET fabric in the desired grammage range of 50 to 150 g / m ² , in particular 70 to 130 g / m ² , with thicknesses of less than 100 to 250 microns with satisfactory To create hand and tearability. With the in DE 10 2005 044 942 A1 described methods for damaging the yarn, the strengths are deliberately reduced, so that a balance of remaining maximum tensile force in the warp direction and Querißzißbarkeit set.

alternative In addition, the fabric can be constructed so that the chain, the cut in the later tissue when Querdurchreißen must be chosen so that the individual warp threads allow this without undue effort.

Either the thread cross-section is reduced so that the tearing is possible without any problems, or by means of the choice of material for the chain, acceptable through-cutting behavior is set. In order to achieve sufficient overall machine direction (MD) in the subsequent fabric, the number of threads per unit length should be selected to achieve the desired maximum MD of at least 40 N / cm and a maximum of 100 N / cm. Ideally, it is desirable for the premium tissue adhesive tied a maximum tensile force MD of 60 to 80 N / cm. For example, PET yarn of 75 denier or finer denier is suitable for the warp, but also brittle materials which result in breakage of the warp when the energy is impulsively introduced during the breaking process: PET fibers with suitable comonomers or crystallization or else warp yarn based on PA6 ,. 6 In order to obtain in such chains a tissue with the desired feel and appearance, the weft threads must be correspondingly thicker and heavier. As a result, on the one hand the basis weight increases in the range of 70 g / m ² and more, on the other hand the desired thicknesses for the fabric of 100 to 250 μm are achieved; The fabric also has a high-quality finish, despite the thin warp threads, because the thicker weft threads determine the look. PET weft yarns from 150 den are possible, but a 300 denier PET yarn is particularly advantageous in terms of look and feel.

analog applies to the use of other synthetic polymers instead of PET as a material for the yarn such as other types of polyester (PBT, PEN), polyamide (PA), polyacrylates, polyimides, Polypropylene.

A Another possibility, an inventive Base fabric with an acceptable tear and tearability in the transverse direction is, in particular for the Chain yarns from a fiber blend to use, at least one of these types of fibers soluble and thus subsequently is removable. Thus, a yarn with sufficient Strength for the spinning and weaving process are present and only in a downstream process step a thinning and weakening done the desired property the Tearability for the tissue result Has. As fiber blends are many combinations conceivable, whereby the use of resistant Polymers as permanent warp yarn, such as PET fibers in combination with water-soluble or chemical or enzymatically degradable materials such as polyvinyl alcohol, polylactates and similar offers. Depending on the selected fiber combination the mixing proportions are to be chosen so that the final strength of the (warp) yarn comes to rest in the target area.

Although self-adhesive tapes can be made with such uncoated fabrics, a premium universal fabric tape requires a high quality, one-sided plastic coating to achieve a smooth, homogeneous surface and to close the fabric so as to keep aggressive chemicals away from the adhesive and the bonding substrate. Furthermore, there is a cost-effective and flexible color about this coating, since a dyeing of the fabric itself is more complex. Surprisingly, in addition to these known aspects, the color coating according to the invention has markedly improved the hand tearability of the raw tissue with suitable formulations, so that claims to the tissue itself can be reduced. In the case of the one-sided coating with a suitable color paste on the upper side, this coating penetrates into the tissue at least with half the thickness of the fabric due to the three-dimensionally structured surface. After drying or curing of the plastic layer, the warp and weft threads are geometrically fixed, much like it EP 1 074 595 A1 mandatory for the warp threads through the adhesive coating calls.

For the plastic coatings are in principle a variety possible of systems such as organosols, radiation-crosslinkable Prepolymer systems, non-stick hotmelts, polymer solutions etc. However, aqueous dispersions are preferred and well established for reasons of cost, availability and existing Standard application technologies in the textile sector.

When Materials may include, for example, polyurethanes, (ethylene) vinyl acetate, PVC, styrene-butadiene or acrylate systems can be selected. For reasons of ecology, costs, availability and regarding the requirement "outdoor use / weather resistance" Acrylates are to be preferred. These will vary depending on the existing coating technology thickened and dispersed with appropriate color pastes / pigments, to create the coloring one-sided coating.

When Particularly advantageous is a two-line coating has been found: For a good "grip" of the final fabric tape to reach, that is, pleasant touch, cuddly and flexible behavior, making the tape even on arched, uneven Surfaces can be well bonded, the color should be Bottom line to be soft and flexible; the glass transition temperature for the binder in the color paste should be below the Room temperature are, in particular in the range of 0 ° C. or deeper.

For a good resistance of the adhesive tape, however, a hard, chemically resistant topcoat is favorable. Such a topcoat not only protects the layers underneath, but, when properly selected, also acts as a barrier layer against the adhesive, which is in direct contact with the topcoat in the later adhesive tape roll. Interactions such as migration of components of the adhesive into the plastic coating or vice versa are undesirable because they lead to changes in the respective properties and in extreme cases, the defined interface between the adhesive and plastic surface is dissolved. The consequence of this would be a strong mounting of the adhesive and thus high unwinding forces. Topcoats, especially acrylate-based, with a glass transition temperature above room temperature, in particular from 30 to 50 ° C and above are suitable, as well as chemically or thermally crosslinking systems, if the final film properties are in the same range. However, the topcoat must not be too hard, so that no cracks occur during bonding around tight radii due to bending or bending in the topcoat, thus damaging the closed lacquer layer.

The coloring plastic coating is at 15 to 75 g / m ² , in particular 20 to 50 g / m ² , to apply overall, in order to achieve a good color, closed layer and a uniform surface structure. For reasons of low complexity, it has proved favorable to apply the base coat pigmented with 70 to 95% of the total amount as a coloring layer and the topcoat with 5 to 30% as unpigmented , transparent topcoat. With regard to formulation and process parameters, care must be taken that on the one hand the adhesion of the base coat to the raw fabric is high and, on the other hand, the bond between the base coat and the topcoat so that the subsequent adhesive tape does not tearing or peeling off the coloring plastic layer, for example during unrolling from the role.

at Demand if, for example, easy unwindability of the roll of adhesive tape is desired, the topcoat one or more Added release additives or on the side facing away from the adhesive, open side applied a separate release coating / -printing become.

The universal fabric tape according to the invention suitable for long-term outdoor applications is characterized by the following structure and manufacture, the description being considered as an example and can be used by a person skilled in modified form without thereby abandoning the scope of this application. On the carriers described above as being advantageous, 50 to 300 g / m ² , in particular 70 to 150 g / m ² , of a UV- and moisture-resistant self-adhesive are applied as adhesive layer on one side in order to ensure secure bonding in interior and exterior applications on smooth, structured and to ensure rough surfaces.

According to the invention used as adhesive adhesives of an ethylene polymer.

Ethylene polymers were not suitable for the person skilled in the art for high-quality PSAs. Nevertheless, surprisingly, from ethylene polymers having a density between 0.86 and 0.89 g / cm ³ , preferably between 0.86 and 0.88 g / cm ³ , particularly preferably between 0.86 and 0.87 g / cm ³ , and a crystallite melting point of at least 105 ° C, preferably at least 115 ° C, PSAs with high bond strength, Tack in the cold, UV and aging resistance and shear strength are produced, which for bonding to rough and dirty substrates such as sawn wood, concrete, brick or plaster are suitable.

The The ethylene polymer according to the invention preferably has a melt index of less than 6 g / 10 min, more preferred less than 1.5 g / 10 min. The flexural modulus of the ethylene polymer is preferably less than 26 MPa, more preferably less than 17 MPa.

The ethylene polymer preferably contains a C ₃ to C ₁₀ olefin, in particular 1-octene, as comonomer. The ethylene polymer preferably has a structure of crystalline polyoxyethylene blocks and substantially amorphous blocks of ethylene and a C ₃ to C ₁₀ olefin.

The density of the ethylene polymer is decreasing ISO 1183 determined and expressed in g / cm ³ . The melt index is decreasing ISO 1133 tested at 190 ° C and 2.16 kg and expressed in g / 10 min. The crystallite melting point (T _cr ) is detected by DSC at a heating rate of 10 ° C / min after ISO 3146 determined. The flexural modulus (flexural modulus) is after ASTM D 790 (Secant modulus at 2% strain).

The The ethylene polymer of the present invention can be used with the Rubber compounds known elastomers such as natural rubber or synthetic rubbers be combined. Preferably, unsaturated elastomers such as natural rubber, SBR, NBR or unsaturated styrenic block copolymers only in small amounts or particularly preferably not used at all. In the main chain saturated synthetic rubbers such as polyisobutylene, Butyl rubber, EPM, HNBR, EPDM or hydrogenated styrenic block copolymers be in the case of a desired modification prefers.

It surprisingly, it turned out that stickiness (Tack) and adhesion in the new polyethylene-based adhesive in contrast to conventional rubber compositions of polydispersity of the resin are extremely dependent. The polydispersity is the ratio of weight average to number average molecular weight distribution and can be determined by gel permeation chromatography. When Adhesive resins are therefore those having a polydispersity of less than 2.1, preferably less than 1.8, more preferably less used as 1.6. The highest tack is with resins to achieve a polydispersity of 1.0 to 1.4.

When Adhesive resin has been found to be resins based on rosin (for example gum rosin) or rosin derivatives (for example disproportionated, dimerized or esterified rosin), preferably partially or fully hydrogenated, well suited are. They show the highest tack of all adhesive resins (Stickiness, aptitude). Probably that is at the low polydispersity of 1.0 to 1.2. Terpene phenolic resins are characterized as the hydrogenated resins by a particularly high Aging resistance.

Also preferred are hydrocarbon resins, which are probably well tolerated due to their polarity. These are, for example, aromatic resins such as cumarone-indene resins or styrene-based or α-methylstyrene or cycloaliphatic hydrocarbon resins from the polymerization of C ₅ monomers such as piperylene or C ₅ or C ₉ fractions of crackers or terpenes such as β -one or δ-limonene or combinations thereof, preferably partially or completely hydrogenated, and hydrocarbon resins obtained by hydrogenation of aromatic-containing hydrocarbon resins or cyclopentadiene polymers.

The Amount of adhesive resin is preferably 130 to 350 phr, more preferably 200 to 240 phr (phr means parts by weight based on 100 parts by weight of rubber, that is here Ethylene polymer).

The Adhesive preferably contains a liquid Plasticizers such as aliphatic (paraffinic or branched), cycloaliphatic (naphthenic) and aromatic mineral oils, Esters of phthalic, trimellitic, citric or adipic acid, Wool wax, liquid rubbers (for example, low-molecular weight nitrile, Butadiene or Polyisoprenkautschuke), liquid polymers from isobutene homopolymer and / or isobutene-butene copolymer, liquid and soft resins with a melting point below 40 ° C based the raw materials of adhesive resins, in particular those listed above Classes of adhesive resin. Particular preference is given to liquid Polymers of isobutene and / or butene and esters of phthalic, Trimellit, citric or adipic acid in particular their Esters of branched octanols and nonanols.

Instead of a liquid plasticizer, it is also possible to use a very soft and hardly crystalline ethylene polymer. This is preferably a copolymer of ethylene and butene (1), hexene (1) or octene (1), for example under the trade names Exact ^®, Engage ^{®, ®} or Versify Tafmer ^® known, or a terpolymer of ethylene, Propylene and butene (1), hexene (1) or octene (1), wherein the flexural modulus is preferably below 10 MPa and the crystallite melting point preferably below 50 ° C. Further preferred ethylene polymers are oil-free EPM or EPDM, ie copolymers or terpolymers of ethylene and propylene and optionally a diene such as ethylidenenorbornene, preferably having an ethylene content of 40 to 70% by weight, a Mooney viscosity (conditions 1 + 4, 125 ° C) below 50 and / or a density below 0.88 g / cm ³ , more preferably below 0.87 g / cm ³ . Although such ethylene polymers are very soft compared to a liquid plasticizer, the amount in relation to the ethylene polymer of the invention should be very high, well above 100 phr.

The melting point of the adhesive resin (determination according to DIN ISO 4625 ) is also important. The bond strength of a rubber compound (based on natural or synthetic rubber) usually increases with the melting point of the adhesive resin. In the case of the ethylene polymer according to the invention, this seems to be reversed. Adhesive resins with a high melting point of 115 ° C to 140 ° C are much less favorable than those having a melting point below 105 ° C, which are preferred. Resins with a melting point below 85 ° C are not widely available on the market as the flakes or pastilles cake together during transport and storage. Therefore, according to the present invention, a common adhesive resin (for example having a melting point in the range of 85 ° C to 105 ° C) is preferably combined with a plasticizer to actually lower the resin melting point. The Mischschmelzpunkt is determined on a homogenized mixture of adhesive resin and plasticizer, wherein the two components are present in the same ratio as in the adhesive. It is preferably in the range of 45 ° C to 95 ° C.

Conventional adhesives based on natural rubber or unsaturated styrene block copolymers as elastomer component usually contain a phenolic antioxidant to avoid the oxidative Degradation of this elastomer component with double bonds in the polymer chain. However, the adhesive according to the invention contains an ethylene polymer without oxidation-sensitive double bonds and therefore could do without an antioxidant. For a high long-term stability, it is preferable to use a primary antioxidant, and more preferably a secondary antioxidant. The adhesives of the invention contain in the preferred embodiments at least 2 phr, more preferably 6 phr of primary antioxidant or preferably at least 2 phr, especially at least 6 phr of a combination of primary and secondary antioxidant, where the primary and secondary antioxidant function need not be in different molecules, but also can be united in a molecule. The amount of secondary antioxidant is preferably up to 5 phr, more preferably 0.5 to 1 phr. It has surprisingly been found that a combination of primary antioxidants (for example sterically hindered phenols or C radical scavengers such as CAS 181314-48-7) and secondary antioxidants (for example sulfur compounds, phosphites or sterically hindered amines) gives improved compatibility. Above all, preference is given to the combination of a primary antioxidant, preferably sterically hindered phenols having a relative molecular weight of more than 500 daltons, with a secondary antioxidant from the class of sulfur compounds or from the class of phosphites preferably having a relative molecular weight of more than 500 daltons in which the phenolic, sulfur and phosphite functions need not be present in three different molecules, but may also be more than one function in a molecule.

at longer outdoor applications and / or Under UV radiation, a light stabilizer is in the adhesive, prefers a HALS such as Tinuvin III, a UV absorber such as Tinuvin P or opaque pigment used.

to Optimization of the properties may be the self-adhesive used with other additives such as fillers, flame retardants, Pigments, antiozonants, photoinitiators, flame retardants or crosslinkers or crosslinking promoters. Suitable fillers and pigments are, for example, carbon black, titanium dioxide, calcium carbonate, Zinc carbonate, zinc oxide, silicates or silica.

The Production and processing of the PSAs can be made from solution as well as from the melt. Preferred manufacturing and processing methods take place from the melt. For the latter case include suitable manufacturing processes both batch and continuous Method. Particularly preferred is the continuous production the PSA with the aid of an extruder and subsequent coating directly on the substrate to be coated at a correspondingly high Temperature of the adhesive. As coating methods are extrusion coating preferred with slot dies and calender coating.

The application (coating thickness) is preferably between 50 and 300 g / m ² , more preferably between 70 and 150 g / m ² .

Out Handling reasons and because of the high bond strengths it is in the universal fabric tapes according to the invention the rule, the klebmassenabgewandte top of the carrier to be provided with an anti-adhesive release system. As As is known to those skilled in the art, silicone systems offer the option for a light to very light unwind force, while fatty acid derivatives such as polyvinyl stearyl carbamate rather moderate unwinding forces of a few N / cm. As with fabric tapes medium Unrolling forces of 2 to 8 N / cm have been established is preferred a surface finish or print with a release agent such as polyvinyl stearyl carbamate or a reaction product of stearyl isocyanate and polyethyleneimine.

With this product structure according to the invention Get tissue tapes on the different ones Stick adhesive surfaces well and safely. On steel as standard underlay for polar substrates, a bond strength in the fresh state (maximum one week after production) of minimum 5 N / cm and up Polyethylene as a non-polar substrate an adhesive force in the fresh state reached at least 4 N / cm, which as required at least 50% over stay for six months.

by virtue of high adhesive strength and strong pulling up both polar as well as nonpolar surfaces adheres the inventive Adhesive tape already after a short time so strong that it afterwards and understandably especially after up to six months of use no longer residue-free to remove. The liability and other functionality as a self-adhesive tape is not or only slightly influenced. For this reason, such adhesive tapes are particularly suitable for long-term Permanentverklebungen in the outdoor area at.

invention Universal fabric tapes can be easily and with a Cut straight edges without fraying by hand in the transverse direction. In the machine direction, however, the fabric tape has sufficient strengths and thus can be used for many bandaging and fixation applications are used, where it depends on tensile strength. Most of time becomes a slightly increased initial force for tearing the edge is needed, with the further tearing then easily and evenly. These slightly increased tearing force protects advantageous the fabric tape against unintentional tearing during handling as well as in the final application.

• • ausreichende Festigkeit für mechanische Beanspruchungen,
• • Erhalt der Integrität des mehrlagigen Aufbaus des Klebebandes,
• • gute dauerhafte Haftung auf dem Substrat.

In outdoor applications, the universal tissue adhesive tape according to the invention proves to be extremely stable and suitable for long-term use of at least six months. While in particular the previously known duct tapes consistently decay into their constituents after a few weeks under the direct action of sunlight and rain, the functionality and product integrity remain in the fabric band according to the invention:

• Sufficient strength for mechanical stresses,
• Preserving the integrity of the multilayer construction of the adhesive tape,
• • good permanent adhesion to the substrate.

This is in the known natural rubber and Synthesekauschuk fabric tapes not given, because of the attack on the double bonds the framework elastomer is destroyed and partially also the carrier component noticeably irreversibly damaged becomes.

Next the suitability for outdoor applications, where previously known fabric tapes have significant weaknesses, are the adhesive tapes according to the invention as a universal tapes, of course, too suitable for indoor use, which is obvious to a person skilled in the art does not need to be mentioned separately.

Almost independent of the type of adhesive used, a universal fabric tape according to the invention requires a certain layer thickness for the adhesive in order to securely adhere even to rough or structured adhesive substrates such as wood, stone, concrete, etc. With a mass application of 50 to 300 g / m ² , in particular 70 to 150 g / m ² , the desired adhesive behavior is achieved; The absolute amount of adhesive layer thickness depends inter alia on the structure of the fabric. Depending on the roughness of the side to be coated, quantities of up to 50 g / m ^{2 are} needed, just to fill in the depressions in the tissue, without this part of the adhesive projecting beyond the "peaks of the fabric mountain" and being available for bonding. As a rough guide for the mass requirement in the desired adhesive behavior is an "effective" layer thickness of 50 to 150 microns mentioned.

On the coating side (coating side) can be the surfaces the carrier will be equipped adhesive friendly, for example via an anchoring line or physically pretreated such as by corona irradiation. Normally but offers the rough structure of the tissue as well as the affinity sufficient anchoring of the surface of the adhesive so that it is possible to dispense with separate process steps.

In Dependence on the recipe and viscosity of the Adhesive is to choose the coating technology. Here can on known systems such as squeegees, rollers, nozzles etc. are used. The appropriate choice can be made by a skilled person without problems. While in many cases the combination adhesive / coating technology to a sufficient penetration of the adhesive in the wells of the fabric and thus for a good anchorage of the adhesive layer on the carrier, in cases, in which an adhesive layer as a film, for example, from the nozzle undressed and only hung up, by additional use of pressure and temperature for a more intense and lasting Contact formation between the two layers should be taken care of. This can by a downstream pressure and Anpressvorgang such as a calender station can be reached. Alternatively leaves However, this also by a pretreatment pretension for example, by an additional primer stroke, the adhesion and anchoring of the adhesive on the support physically / chemically reinforced.

The adhesive tape is formed in that the adhesive is applied to the backing partially or completely, preferably on one side or optionally on both sides. The coating can also take the form of one or more strips in the longitudinal direction (machine direction), optionally in the transverse direction, but in particular it is full-surface. Furthermore, the adhesives can be applied in the form of a grid dot by means of screen printing, wherein the dots of adhesive can also be distributed differently and / or differently, by webs connected in the longitudinal and transverse direction by gravure printing, by screen printing or by intaglio printing. The adhesive may be in dome form (produced by screen printing) or in a different pattern such as grid, stripes, zigzag lines. Furthermore, it can also be sprayed on, for example, which results in a more or less irregular application pattern.

drying, Crosslinking, curing of the adhesive layer close as needed and are as state of the art known.

Test Methods

adhesive power

The determination of the bond strength was based on AFERA 5001 carried out as follows. As a defined primer, a steel surface, a polyethylene surface (PE) and a 150 grit sandpaper were used. The glued surface element to be examined was cut to a width of 20 mm and a length of about 25 cm, provided with a handling section and immediately thereafter pressed five times with a steel roller of 4 kg at a feed rate of 10 m / min on the selected primer. Immediately thereafter, the glued surface element was removed at an angle of 180 ° from the primer with a tensile tester (Zwick) and measured the force required for this at room temperature. The measured value (in N / cm) was the average of three individual measurements.

UV test

to Measurement of UV stability were the patterns in 20 mm width and 25 cm in length on a glass plate with a thickness glued by 4 mm and rolled five times with a 2 kg roll.

The samples were stored with the glass side up in a UV chamber with xenon lamp at an irradiance of 300 W / m ² . Each day, a new strip was removed from each UV chamber per sample and removed from the glass plate after conditioning to room temperature for 1 hour.

there the liability was assessed as well as registered, whether there were noticeable changes, Tear or glue residue on the Glass plate gave.

weathering test:

As a quick test instead of the protracted outdoor weathering was the so-called "Suntest" in reference to the ISO 4892-2 (2006) carried out according to method A. For this purpose, samples were bonded to rigid PVC, glass and PE and subjected to a combination of UV irradiation by means of a 765 Watt xenon lamp and temporary irrigation. In the two-hour cycles, after 18 minutes of a combination of irrigation and irradiation, there is a period of 102 minutes irradiation without irrigation.

To the weathering time, the strips were after reconditioning visually assessed at room temperature, then below Subtracted 90 ° and 180 °. According to the manufacturer (for example, company Atlas) corresponds to a week Suntester about 3 Months weathering in Central Europe.

So far the withdrawn test strips allow it, this is the bond strength determined after storage.

Sporadically carried out permanent tests under real outdoor conditions (Outdoor weathering) took place in Hamburg on the same detention grounds on a building roof with south exposure below an inclination angle of 45 °. The results were comparable to the above quick tests.

In the following, the invention is explained in more detail by means of a few examples, without wishing to restrict the invention thereby. Raw materials of the examples: IN FOOT 9107: Copolymer of ethylene and octene (1), melt index 1 g / 10 min, density 0.866 g / cm ³ , flexural modulus 15.5 MPa, crystallite melting point 121 ° C IN FOOT 9507: Copolymer of ethylene and octene (1), melt index 5 g / 10 min, density 0.866 g / cm ³ , flexural modulus 13.9 MPa, crystallite melting point 119 ° C Ondina 933: White oil (paraffinic-naphthenic mineral oil) Oppanol 610: liquid polyisobutylene Regalite R1100: hydrogenated aromatic hydrocarbon resin, melting point 100 ° C, polydispersity 1.9 Foral 85: fully hydrogenated glycerol ester of rosin with a melting point of 85 ° C and a polydispersity of 1.2 Irganox 1076: phenolic antioxidant Tinuvin 111: HALS light stabilizer

example 1

A black plain weave PET fabric having a thread count of 31 cm ^-1 in the warp, 22 cm ^-1 in the weft, with the yarn in the warp, and the yarn in the weft, indicates after continuous alkalization according to DE 10 2005 044 942 A1 at a basis weight of 100 g / m ^2, a maximum tensile force in the warp direction of 70 N / cm. On one side, a black-pigmented acrylate dispersion is coated with an application of 35 g / m ² . The coating, which is soft due to its low T _G value and has a tendency to block, is then immediately covered with a transparent topcoat based on a hard acrylate dispersion with an application of 10 g / m ² and dried so that the self-crosslinking topcoat is cured.

The Tearability and in particular tearability in the weft direction from the edge are through this coating clearly improved. The carrier material is "hand-tearable".

The adhesive is produced continuously in an extruder and applied at 80 g / m ² to the carrier by means of die coating from the melt. Instead of the release coating, the adhesive for the production and testing of laboratory samples is covered with siliconized release paper. Adhesive composition with the following recipe: 100 phr IN FOOT 9107, 78.4 phr Ondina 933, 212 phr Foral 85 2 phr Irganox 1076 5 phr Tinuvin 111.

The Adhesion to steel is 9.8 N / cm. From PE leaves after one to two hours of mounting the fabric tape only remove under partial rewinding of the adhesive.

In the UV test after 7d and in SunTest after 2 weeks are minor to recognize visual changes, but the glued Adhesive tape shows little evidence of decomposition and detachment on and continues to stick securely and firmly.

Example 2

The carrier selected is a PE-extruded fabric. The support is finished equipped with polyvinyl stearyl carbamate paint from Japan. It is a 0.18 mm thick composite support made from a 55 mesh VIS / PET blend (30 x 25 in. 2) with a 65 g / m ² black LDPE coating firmly bonded thereto.

The adhesive composition and coating is carried out analogously to Example 1 with the following recipe: 100 phr IN FOOT 9507, 140 phr Oppanol B10, 250 phr Regalite R1100 2 phr Irganox 1076 5 phr Tinuvin 111.

The bond strength to steel is 9.0 N / cm at a mass application of 70 g / m ² . Aufziehverhalten, UV and weathering tests are described and carried out as described in Example 1, with a slight damage to the carrier tends to be recognized. Here is a slightly stronger UV stabilization of the PE film useful and implement for the expert without problems. The adhesive itself has no evidence of damage.

Counterexample 3

counterexample 3 corresponds to a commercial fabric tape made of rayon with a Standard natural rubber adhesive.

A 150 mesh viscose fabric (about 110 g / m ² gray fabric; symmetrical plain weave with Nm50 yarns in warp and weft) with upper, pigmented acrylate (60 g / m ²⁾ and rear-side natural rubber coating (110 g / m ^2, no special UV -Stabilisierung) can be easily torn, sticks well on different surfaces, but has serious shortcomings in the UV and weathering tests after a short exposure time. Significant signs of detachment from the substrate and decomposition of the adhesive can be seen especially in the Suntester. Because of its composition, the tape is easily attacked and destroyed by microorganisms, making it unsuitable for outdoor use.

Counterexample 4

counterexample Figure 4 corresponds to a commercial duct tape with a standard natural rubber adhesive.

A 30 mesh PETNIS-knitted fabric (20 x 10 inch ^-2) and a silver 50 microns PE film are the carrier components is to be ² equipped a very soft and tackig set natural rubber adhesive composition with a total of 160 g / m, with about 5 to 10 g / m ² act as laminating adhesive.

The Duct Tape adheres well to different substrates (for example on steel 5 N / cm, on PE 2.5 N / cm); after 1 to 2 weeks Weathering occur first massive decomposition phenomena, after 2 months, the carrier is almost completely delaminated and the adhesive lacks, that is no self-adhesive properties more. In the UV and weathering tests, these effects occur accordingly sooner after short test intervals, first strong wrinkling, then partial detachment of PE film of the knitted fabric or only low bond strength.

such Duct tapes are for longer-lasting outdoor applications not suitable.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - US 3853598 A1 [0009]
• EP 1548080 A1 [0010]
• WO 03/097758 A1 [0011]
• EP 1074595 A1 [0012, 0039]
• - DE 102005044942 A1 [0013, 0034, 0086]

Cited non-patent literature

• ASTM G155 [0011]
• AFERA 5001 [0016]
• - ISO 1183 [0051]
• - ISO 1133 [0051]
• - ISO 3146 [0051]
• ASTM D 790 [0051]
• - DIN ISO 4625 [0059]
• AFERA 5001 [0077]
• - ISO 4892-2 (2006) [0081]

Claims (14)

Adhesive tape, in particular for outdoor use, having a textile support with a basis weight of 15 to 150 g / m ² , which is provided on the top with an additional layer which is applied by extrusion coating, by dispersion coating or by film lamination, and which on the underside with an adhesive is made of an ethylene polymer having a density between 0.86 and 0.89 g / cm ³ and a crystallite melting point of at least 105 ° C and is made of an adhesive resin. Adhesive tape according to Claim 1, characterized in that the backing is a woven fabric, preferably having a mesh number of 80 to 250 inches ^-2 , on the upper side of which a dispersion paste with a coating weight of 15 to 75 g / m ² is more preferably applied. which particularly preferably contains an acrylate binder. Adhesive tape according to claim 1, characterized in that the carrier is a woven, knitted fabric or scrim with a mesh number of 20 to 80 inch ^-2 , on its upper side more preferably a PE coating with a coating weight of 30 to 200 g / m ^{2 is} applied, which is particularly preferably made of LDPE and / or applied by extrusion or lamination. Adhesive tape according to at least one of the preceding claims, characterized in that the yarn for the textile Polyester or cotton, rayon, viscose, polyamide or Mixtures thereof. Adhesive tape according to at least one of the preceding claims, characterized in that facing away from the adhesive Side of the additional layer an anti-adhesive release coating is applied, preferably with substances based on silicone or fatty acid derivatives. Adhesive tape according to at least one of the preceding claims, characterized in that the adhesive has an order of 50 to 300, preferably 70 to 150 g / m ² , wherein the adhesive is coated in particular from the melt. Adhesive tape according to at least one of the preceding claims, characterized in that the properties tear strength and elongation at break and adhesion to steel AFERA 5001 of the adhesive tape after 2 weeks Suntest according to ISO 4892-2, Method A, (2006) to a minimum of 50% of the initial value. Adhesive tape according to at least one of the preceding claims, characterized in that the density of the ethylene polymer is between 0.86 and 0.88 g / cm ³ , preferably between 0.86 and 0.87 g / cm ³ , and / or the ethylene polymer has a crystallite melting point of at least 115 ° C. Adhesive tape according to at least one of the preceding claims, characterized in that the ethylene polymer has a melt index of less than 6 g / 10 min, preferably less than 1.5 g / 10 min, a flexural modulus of less than 26 MPa, preferably less than 17 MPa and / or contains a C ₃ - to C ₁₀ -olefin, preferably 1-octene. Adhesive tape according to at least one of the preceding claims, thereby marked that contains the adhesive - one primary antioxidant, preferably in an amount of at least 2 phr, more preferably at least 6 phr and / or - one secondary antioxidant in an amount of 0 to 5 phr, preferably in an amount of 0.5 to 1 phr and / or - one Light stabilizer preferably a HALS and / or - one UV absorbers Adhesive tape according to at least one of the preceding claims, characterized in that the adhesive contains an adhesive resin, which preferably has a polydispersity of less than 2.1, preferably less than 1.8, more preferably less than 1.6, most preferably between 1.0 and 1.4. Adhesive tape according to at least one of the preceding claims, characterized in that the adhesive resin is a hydrocarbon, preferably selected from the group of resins based on rosin or Kolophoniumderivaten preferably partially or fully hydrogenated, the hydrocarbon resins based on C ₅ monomers, preferably partially or fully hydrogenated, the hydrocarbon resins from hydrogenation of aromatic hydrocarbon resins, the hydrocarbon resins based on hydrogenated cyclopentadiene polymers, and / or the resins based on polyterpenes, preferably partially or fully hydrogenated and / or the terpene phenolic resins, wherein the amount of tackifier resin in the adhesive is preferably from 130 to 350 phr, more preferably from 200 to 240 phr , in each case based on the total amount of polyethylene. Adhesive tape according to at least one of the preceding claims, characterized in that the adhesive contains a plasticizer selected from the group of mineral oils, the liquid Polymers of isobutene homopolymer and / or isobutene-butene copolymer and the ester of phthalic, trimellitic, citric or adipic acid. Adhesive tape according to at least one of the preceding claims, characterized in that the adhesive comprises a copolymer of ethylene and butene (1), hexene (1) or octene (1) or a terpolymer of ethylene, propylene and butene (1), Hexene (1) or octene (1), wherein the flexural modulus of the copolymer or terpolymer is preferably below 10 MPa and the crystallite melting point is preferably below 50 ° C, or contains an EPM or EPDM, preferably having an ethylene content of 40 to 70 Wt .-% and / or a density below 0.88, more preferably below 0.87 g / cm ³ , wherein the amount of copolymer or terpolymer is preferably above 100 phr.