WO2009147104A1

WO2009147104A1 - Adhesive made of isotactic 1-butene resin

Info

Publication number: WO2009147104A1
Application number: PCT/EP2009/056643
Authority: WO
Inventors: Dr. Bernhard Müssig
Original assignee: Tesa Se
Priority date: 2008-06-04
Filing date: 2009-05-29
Publication date: 2009-12-10
Also published as: DE112009001174A5; DE102008026670A1

Abstract

Adhesive made of an isotactic 1-butene resin having a density between 0.86 and 0.91 g/cm³, preferably between 0.86 and 0.89 g/cm³, particularly preferably between 0.87 and 0.89 g/cm³, and a crystallite melting point of at least 90°C, preferably at least 105°C, particularly preferably at least 110°C, and made from at least one adhesive resin, wherein the fraction of the adhesive resin is at least 20 phr, preferably at least 50 phr.

Description

description

Adhesive from isotactic 1-butane resin

The invention relates to an adhesive comprising an isotactic 1-butene resin and at least one tackifier resin and to the use of the adhesive in an adhesive tape. The adhesive and the adhesive tape are suitable, for example, for bonding to low-energy surfaces.

Low crystallinity polyolefins such as high VA containing EVA or copolymers of ethylene and propylene or ethylene and 1-butene are used in hot melt adhesives. Due to their low melting point of about 40 ⁰ C to 80 ⁰ C, such adhesives are not heat resistant.

Conventional partially crystalline polyolefins have no tackiness, in particular polypropylene polymers are much too hard. Special soft polyolefins of low crystallinity, such as some butyl or EPDM rubbers, are also non-tacky, that is, they have no significant bond strength. Very smooth layers of such soft polyolefins can easily adhere to very smooth surfaces such as glass or plastic lenses, they behave as smooth as layers of natural rubber, butyl rubber or highly plasticized PVC. Such materials can hold their own weight so that they do not fall off by themselves, but have virtually no resistance to peel stress because their glass transition temperature is far too low compared to that of a pressure-sensitive adhesive. In addition, such materials tend to coalesce upon storage because of insufficient crystallinity or are already delivered as a block (bale). In addition, they have no heat resistance due to lack of sufficiently high crystallite melting point. Conventional random copolymers with low comonomer content, as used for sealing layers, have a sufficiently high melting point but are too crystalline and therefore also too hard (flexural modulus about 1000 to 1300 MPa). Randomcopolymere with high comonomer content (also called plastomers) are offered as flexibilizers for hard polyolefins are soft, little crystalline and therefore sticky to adjust, but have a crystallite melting point depending on the type between 40 ⁰ C and 60 ⁰ C and therefore do not give heat-resistant adhesives or pressure sensitive adhesive. In addition, it has been found that when using a well-compatible adhesive resin, the melting peak of polyolefins having a melting point of well below 100 ⁰ C in an adhesive formulation is lost, that is, even at room temperature, no shear strength is given by crystalline crosslinking. Plasticizers have the same effect on melt peaks clearly below 100 ^° C. Soft random copolymers are therefore only suitable for resin-free or at least low-resin and plasticizer-free surface protection films in which there is no requirement for a significant bond strength (that is to say above 0.1 N / cm) and heat resistance.

Adhesive tapes contain at least one layer of (adhesive) adhesive, these are based on natural rubber, synthetic rubber (for example, polyisobutylene, styrene block copolymer, SBR) or acrylate and very rarely made of very expensive silicone. The conventional pressure-sensitive adhesives do not combine high adhesive properties, particularly low energy surfaces, thermal shear strength, solventless melt processability, high water resistance (as opposed to dispersion coatings), and high heat aging and UV stability.

Adhesive tapes for bonding to low-energy surfaces are usually produced with adhesives based on natural rubber, styrene block copolymer and acrylate. The natural rubber adhesives are solvent-containing and have a low aging and UV stability. Styrene block copolymer adhesives, usually based on styrene-isoprene-styrene block copolymers, are solvent-free processable, but also have a low aging and UV stability. Both types of rubber compounds have good adhesion to low-energy surfaces. Adhesives based on hydrogenated styrene block copolymers are very expensive, have low tack and adhesion and stick poorly on many substrates. They also soften already well below 100 ⁰ C. acrylate adhesives have good aging and UV stability, but adhere poorly to low-energy non-polar polymers such as polyolefins despite all previous efforts, which is why the surfaces to be bonded must be pretreated with solvent-containing primers. Silicone pressure-sensitive adhesives have good aging and UV stability as well as good adhesion to low-energy surfaces, but are extremely expensive and can not be covered with the usual siliconized liners (or not peel off again).

There has long been a desire for an adhesive that combines the positive properties of various adhesives: solvent-free, high adhesion to low-energy surfaces and aging and UV stability such as acrylic adhesives.

The object of the invention is to provide an adhesive, in particular a pressure-sensitive adhesive for, for example, an adhesive tape, which does not have the disadvantages of the prior art.

The problem is solved by an adhesive, as laid down in the main claim. Advantageous developments of the subject invention as well as uses of the adhesive can be found in the dependent claims.

Accordingly, the invention relates to an adhesive of an isotactic 1-butene resin having a density between 0.86 and 0.91 g / cm ³ , preferably between 0.86 and 0.89 g / cm ³ , more preferably between 0.87 and 0 , 89 g / cm ³ , and a crystallite melting point of at least 90 ⁰ C, preferably at least 105 ⁰ C, more preferably at least 1 1 ^{0 0} C and at least one tackifier resin, wherein the proportion of the adhesive resin is at least 20 phr, preferably at least 50 phr , "Phr" denotes parts by weight based on 100 parts by weight of rubber or polymer (parts per hundred rubber or resin), which means here relative to 100 parts by weight of 1-butene resin.

The adhesive is preferably a pressure-sensitive adhesive. In the following, the terms pressure-sensitive adhesive and PSA are used interchangeably. A pressure-sensitive adhesive is a viscoelastic material which is dry at room temperature Condition is permanently sticky and sticky. The bonding takes place by light pressure immediately on all substrates with sufficient surface tension (thus silicone and Teflon are excluded).

Isotactic crystalline polyolefins have hitherto been regarded as unsuitable for the person skilled in the art for adhesives and in particular for PSAs. Common 1-Butene resins are hard and are processed into tubes or serve in peel packages as a release layer to polyethylene. Surprisingly, from 1 -Butenharzen with a density between 0.86 and 0.91 g / cm ³ and a crystallite melting point of at least 90 ⁰ C adhesives or PSAs with high bond strength, high tack and high shear strength can be produced, which on many substrates have excellent adhesion and especially on low-energy surfaces such as non-polar paints or olefin polymers.

The 1-butene resin according to the invention preferably has a melt index of 0.5 to 10 g / 10 min, more preferably 3 to 8 g / 10 min. The flexural modulus of the 1-butene resin is preferably less than 50 MPa, more preferably less than 26 MPa.

The 1-butene resin according to a further advantageous embodiment of the invention contains 1-butene and at least one further comonomer selected from the C ₂ to do olefins, preferably C ₂ to C ₁₀ α-olefins. Particularly suitable are copolymers of 1-butene and ethylene and especially copolymers of 1-butene and propylene and terpolymers of 1-butene, propylene and ethylene.

The 1-butene resin preferably contains predominantly 1-butene as monomer, that is to say the proportion of the 1-butene is at least more than 50% by weight, preferably at least more than 70% by weight. This means that the crystalline portion of the polymer is preferably determined by isotactic sequences.

The 1-butene resin may have been constructed in various ways, for example as a random polymer, but preferably as a block copolymer, as a graft polymer or as a heterophasic copolymer or as a terpolymer, for example as a so-called reactor blend analogous to the impact polypropylenes. The 1-butene resin is not a classical low melting point non-heterophasic random copolymer containing the monomers 1-butene and the further olefin (for example ethylene, propylene, 1-hexene or 1-octene) because these polymers have only low shear strengths , Adhesive forces and heat resistance can be achieved. The 1-butene resin is preferably a block copolymer, a graft polymer or a heterophasic polymer having a crystalline content which guarantees a melting point at the level of the invention. However, a heterophasic 1-butene resin may contain small amounts of a comonomer in the crystalline component, as long as the crystallite melting point is still in the range according to the invention.

The size of the crystals of the 1-butene resin is preferably less than 100 nm, whereby the adhesive has a high transparency. Such a 1-butene resin can be prepared with a metallocene catalyst. The 1-butene resin preferably has a Haze value, measured according to ASTM D 1003, of less than 8 (measured on 2 mm thick pressures in cyclohexanol).

The density of the 1-butene resin is determined according to ISO 1 183 and expressed in g / cm ³ . The melt index is tested according to ISO 1 133 with 2.16 kg and expressed in g / 10 min. The values referred to in this disclosure - as the skilled person is familiar - determined at different temperatures in function of the main monomer of the polymer, it is predominantly ethylene or 1-butene containing at 190 ⁰ C and with predominantly propylene-containing polymer at 230 ⁰ C. The flexural modulus should be determined according to ASTM D 790 (secant modulus at 2% elongation). The crystallite melting point (T _cr ) and the heat of fusion are determined with DSC (Mettler DSC 822) at a heating rate of 10 'O / min according to ISO 3146. When several melt peaks occur, the one with the highest temperature is selected because only the melt peaks above 100 ^° C. are retained and become effective in adhesive formulations, whereas melting peaks significantly below 90 ^° C. are not retained and have no effect on the product properties (heat resistance). The heat of fusion determines on the one hand the bond strength and tack of the formulation and on the other hand the shear strength especially in the heat (ie 70 ⁰ C and above). The heat of fusion of the 1-butene resin is therefore important for the optimum compromise of the adhesive properties, it is preferably between 3 and 18 J / g, more preferably between 5 and 12 J / g. The heat of fusion of the adhesive is therefore also important for the optimal compromise of the adhesive properties, it is preferably between 1 and 6 J / g, more preferably between 2 and 5 J / g.

The content of inventive 1-butene resin in the adhesive is preferably at least 15 wt .-%, more preferably at least 20 wt .-%. The content of inventive 1-butene resin in the adhesive is preferably below 40 wt .-%, more preferably below 35 wt .-% and most preferably below 30 wt .-%, whereby a particularly good tack (adhesiveness, tackiness) achieved in pressure-sensitive adhesives can be.

The 1-butene resin according to the invention can be combined with the elastomers known from rubber compounds, such as natural rubber or synthetic rubber. Preferably, unsaturated elastomers such as natural rubber, SBR, NBR or unsaturated styrenic block copolymers are only used in small amounts or particularly preferably not at all. Synthetic rubbers saturated in the main chain such as polyisobutylene, butyl rubber, EPM, HNBR, EPDM or hydrogenated styrenic block copolymers are preferred in the case of a desired modification.

It surprisingly turned out that the tack and bond strength of the polybutadiene-based adhesive of the invention are extremely dependent on the polydispersity of the resin, in contrast to conventional rubber compounds. Polydispersity is the ratio of weight average to number average molecular weight distribution and can be determined by gel permeation chromatography. As adhesive resin therefore those with a polydispersity of less than 2.1, preferably less than 1, 8, more preferably less than 1, 6 are used. The highest tack can be achieved with resins having a polydispersity of 1, 0 to 1, 4.

As adhesive resin for the adhesive according to the invention or in particular the pressure-sensitive adhesive according to the invention it has been found that resins based on

Rosin (for example gum rosin) or rosin derivatives (for example disproportionated, dimerized or esterified rosin), preferably partially or fully hydrogenated, are well suited. They show the highest tack of all adhesive resins (stickiness, tackiness), presumably because of the low polydispersity of 1, 0 to 1, 2. Terpene phenolic resins are also suitable, but lead to only moderate tack, but to very good shear strength and aging resistance.

Also preferred are hydrocarbon resins, which are probably well tolerated due to their polarity. These are, for example, aromatic resins, such as coumarone-indene resins or styrene-based or α-methylstyrene or cycloaliphatic hydrocarbon resins, from the polymerization of C ₅ monomers, such as piperylene, from C ₅ or C ₉ fractions of crackers or terpenes, such as Pinen 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.

Furthermore, resins based on polyterpenes, preferably partially or completely hydrogenated, can be used.

The amount of tackifier resin is preferably 130 to 350 phr, more preferably 200 to 240 phr.

The adhesive or the adhesive preferably contains a liquid plasticizer such as, for example, 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 rubber). , Butadiene or Polyisoprenkautschuke), liquid polymers of isobutene and / or butene, liquid and soft resins having a melting point below 40 ⁰ C based on the raw materials of adhesive resins, in particular the classes of adhesive resin listed above. Particular preference is given to liquid isobutene polymers such as isobutene homopolymer or isobutene-butene copolymer (butene = 1-butene) and esters of phthalic, trimellitic, citric or adipic acid, in particular their esters of branched octanols and nonanols. Mineral oils are very good at tackifying the 1-Butene resin, but can migrate to surfaces to be bonded. Therefore, the adhesive is preferably substantially free of mineral oils.

Instead of a liquid plasticizer can also be a very soft and hardly crystalline

Olefin polymer be used in addition to the 1-butene resin. This is preferably a copolymer or terpolymer of ethylene or propylene combined with ethylene, propylene, butene-1, hexene-1 or octene-1, which may be mentioned, for example, in U.S. Pat Trade names Exact®, Engager®, Versify® or Tafmer®, or a terpolymer of ethylene, propylene and butene-1, hexene-1 or octene-1, the flexural modulus preferably being less than 20 MPa and / or or the crystallite melting point is preferably below 60 ^° C. and / or the density is between 0.86 and 0.87 g / cm ³ . Another preferred olefin polymers are EPDM, ie terpolymers of ethylene and propylene and a diene such as ethylidene norbornene, preferably having an ethylene content of 40 to 70 wt .-%, a Mooney viscosity (conditions 1 +4, 125 ⁰ C) below 50 and / or a density below 0.88 g / cm ³ , more preferably below 0.87 g / cm ³ . Although such olefin polymers are very soft compared to a liquid plasticizer, the amount should be very high in relation to the inventive 1-butene resin, ie more than 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 1-butene resin according to the invention, this seems to be reversed. Adhesive resins with a high melting point of 105 ⁰ C to 140 ⁰ C are significantly less favorable than those below 90 ⁰ C, which the invention preferred. Resins with a melting point of less than 85 ⁰ C are little commercially available, since the flakes or pastilles cake during transport and storage. Therefore, a common adhesive resin is combined (for example, having a melting point in the range 85 ⁰ C to 105 ⁰ C) with a plasticizer to lower the fact resin melting point according to the invention preferably. 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 from 45 ^° C. to 95 ^° C.

Conventional adhesives based on natural rubber or unsaturated styrene block copolymers as the elastomer component usually contain a phenolic antioxidant to avoid the oxidative degradation of this elastomer component having double bonds in the polymer chain. However, the adhesive according to the invention contains a 1-butene resin without oxidation-sensitive double bonds and can therefore manage without an antioxidant.

To optimize the properties, however, the self-adhesive composition or the adhesive used can be mixed with other additives such as primary and secondary antioxidants, fillers, flame retardants, pigments, UV absorbers, antiozonants, metal deactivators, light stabilizers, flame retardants, photoinitiators, crosslinking agents or crosslinking promoters. Suitable fillers and pigments are, for example, carbon black, titanium dioxide, calcium carbonate, zinc carbonate, zinc oxide, silicates or silicic acid. Preference is given to hollow bodies of glass or polymers such as microballoons, in particular hollow spheres. For single-layer adhesive tapes, glass or polymer fibers are preferably added.

Preferably, a primary antioxidant, and more preferably a secondary antioxidant, are used. 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, more preferably 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 instead can also be combined in one 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 phenol 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. In particular, the combination of a primary antioxidant, preferably hindered phenol having a relative molecular weight greater 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 , preferably, wherein the phenolic, the sulfur-containing and the phosphitic functions need not be present in three different molecules, but also more than one function can be combined in one molecule.

The preparation and processing of the adhesive or of the PSA according to the invention can be carried out from solution as well as from the melt. Particularly advantageously, the adhesive can be produced solvent-free. Preferred production and processing methods are carried out from the melt. For the latter case, suitable manufacturing processes include both batch processes and continuous processes.

Particularly preferred is the continuous production of the PSA by means of an extruder and subsequent coating directly on the substrate to be coated correspondingly high temperature of the adhesive. As a coating method for PSAs, extrusion coating with slot dies and Kaiander coating and, for non-sticky hotmelt adhesives, slot dies, hot melt glue guns and nozzles for spinning adhesive threads are preferred.

The subject invention is preferably used in a single or double-sided adhesive tape. In the case of multi-layered construction of the adhesive tape, several layers can be brought together by coextrusion, lamination or coating. The coating can be done directly on the carrier or on a liner or on a process liner.

The (adhesive) adhesive composition can be present without a support and without further layers, without carriers having a further PSA layer, on one side on a support, on the other side of the support a non-inventive PSA, preferably based on polyacrylate, or one not sealing layer according to the invention is present, or be present on both sides on a support, wherein the two pressure-sensitive adhesives may have the same or different composition.

The adhesive tape is preferably covered on one or both sides with a liner. The liner for the product or process liner is, for example, a release paper or release liner, preferably with silicone coating. As a carrier of the liner, for example, films of polyester or polypropylene or calendered papers with or without dispersion or polyolefin coating in question.

The application rate (coating thickness) of a layer is preferably between 15 and 300 g / m ² , preferably between 20 and 75 g / m ² .

The adhesive tape has on at least one side an adhesion to steel of at least 0.5 N / cm, preferably at least 2 N / cm, more preferably at least 6 N / cm and most preferably at least 8 N / cm. The bond strength to steel is determined at a deduction angle of 180 ° according to AFERA 4001 on a 15 mm wide test strip. Preferably, at least one layer in the adhesive tape, preferably the inventive crosslinked. This can be done by means of high-energy radiation, preferably electron beams, or by peroxide or silane crosslinking.

As support material, it is possible to use all known supports, for example scrims, woven fabrics, knitted fabrics, nonwovens, films, papers, tissues, foams and foamed films. Suitable films are of polypropylene, preferably oriented, polyester, hard and / or soft PVC. Preference is given to polyolefin, polyurethane, EPDM and chloroprene foam. By polyolefin is meant here polyethylene and polypropylene, polyethylene being preferred for softness. The term polyethylene includes LDPE, but also ethylene copolymers such as LLDPE and EVA. In particular, crosslinked polyethylene foams or viscoelastic supports are suitable. The latter are preferably made of polyacrylate, more preferably filled with hollow bodies of glass or polymers. The backings may be prepared by priming or physical pretreatment such as corona prior to contacting with the adhesive. Crosslinked polyethylene foams are treated for double-sided adhesive tapes in such a way that adhesion of acrylic PSAs to it is very poor and even with a treatment this adhesion is not very satisfactory since these carriers contain lubricants such as erucamide due to the manufacturing process. It is therefore completely surprising that the adhesives according to the invention adhere perfectly well to such foams even without treatment, that is, in the violent attempt to detach them, the foam is destroyed.

The term "adhesive tape" in the sense of this invention encompasses all flat structures such as films or film sections expanded in two dimensions, tapes of extended length and limited width, tape sections, diecuts, labels and the like not as a punching or label before.

The adhesive according to the invention in an adhesive tape is eminently suitable for bonding to nonpolar paints, printing plates or olefin polymers, particularly preferably for closing or strapping polyolefin bags or for fixing parts made of olefinic plastics or elastomers, in particular for fixing parts in motor vehicles. The pressure-sensitive adhesive of the invention is also suitable for double-sided adhesive tapes, in particular if they are used for bonding plastic parts made of non-polar materials such as polypropylene or EPDM (ethylene-propylene-elastomer) plastic profiles or for lamination to EPDM foams. Furthermore, the subject invention is ideal for labels of cosmetic packaging (for example, shampoo bottles), since it is highly transparent, adheres well to plastic bottles, waterproof and resistant to aging. For security labels such as magnetic alarm labels or data carriers such as Holospot® the subject invention solves the problem of poor adhesion of conventional adhesives on non-polar substrates. The adhesive according to the invention in an adhesive tape is furthermore suitable for bonding to human skin and on rough substrates in the construction sector, as a packaging adhesive tape, as a surface protection film (for example

Automobackackschutzfolie) and suitable for winding applications. Examples of applications on human skin are roll and single patches, diecuts for sticking colostomy bags and electrodes, drug plasters (transdermal patches) and bandages. Because of the adhesive properties, the adhesive offers the possibility of avoiding skin-irritating or otherwise chemically active substances. Therefore, the adhesives according to the invention are also suitable for the construction of hygiene products such as baby diapers or sanitary napkins, moreover they adhere particularly to the polyolefin films and nonwovens used therein and have lower costs and a higher heat resistance than conventional compositions of hydrogenated styrene block copolymers. In addition, adhesives of the invention are useful in hygiene products not only as constructive adhesives, but also for pressure-sensitive adhesive applications such as diaper closures or sanitary napkins. Examples of winding applications are electrical insulation and the manufacture of automobile wiring harnesses. In contrast to natural or synthetic rubber adhesives, the adhesives of the invention are compatible with PP, PE and PVC wire insulation even at high temperatures. In building applications as a plastering tape, for the bonding of roof insulation films and as a bitumen adhesive tape for sealing applications, a good adhesion in the cold is noted. The subject invention is further suitable for film applications, so for example for laminating films such as polyolefin or polyamide film with aluminum foil, and easier to handle as a solvent or UV laminating adhesive. Further film applications are adhesive tapes for endless gluing of printed or unprinted film webs. Other applications include stripable adhesive strips (pressure-sensitive adhesive strips) at least one layer, which can be detached again by stretching stretching substantially in the bonding plane residue and non-destructive) and on hook-and-loop fasteners, such as those offered on a large scale by the company Velcro®.

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:

NOTIO PN-0040: copolymer of propylene and butene (1) (possibly with small amounts of ethylene), melt index 4 g / 10min, density 0.868 g / cm ^3, flexural modulus 42 MPa, crystallite melting point 159 ⁰ C, heat of fusion

5.2 J / g

Borclear RD708CF: terpolymer of 1-butene, propylene and ethylene, melt index 8 g / 10 min, density 0.905 g / cm ^3, flexural modulus 950 MPa, crystallite melting point 142 ⁰ C PB 8640M: Copolymer of 1-butene and ethylene, melt index 1 g / 10 min .

Density 0.906 g / cm ³ , flexural modulus 300 MPa, crystallite melting point 1 13 ⁰ C

Tafcelen T3714: terpolymer of 1-butene, propylene and ethylene, melt index 3 g / 10 min, density 0.860 g / cm ³ , flexural modulus 1 MPa, no crystallite melting point discernible

PB 0300M: poly-1-butene homopolymer, melt index 4 g / 10min, density

0.915 g / cm ³ , flexural modulus 450 MPa, crystallite melting point 1 16 ⁰ C Versify 2400: copolymer of propylene and ethylene, melt index 2 g / 10 min

(230 ^° C.), density 0.86 g / cm ³ , flexural modulus 2 MPa, crystallite melting point 48 ^° C.

Exact 4053: Random copolymer of ethylene and butene (1), melt index

2.2 g / 10min (190 ⁰ C), density 0.888 g / cm ^3, flexural modulus 27 MPa, crystallite 70 ⁰ C Ondina 933: white oil (paraffinic-naphthenic mineral oil) Indopol H-100: polyisobutene-polybutene copolymer with a kinematic

Viscosity of 210 cSt at 100 ⁰ C according to ASTM D 445

Wingtack 10: liquid C ₅ hydrocarbon resin Regalite R1 100: hydrogenated aromatic hydrocarbon resin with a

Melting point of 100 ⁰ C and a polydispersity of 1, 6

Wingtack extra: aromatic-modified C ₅ -hydrocarbon resin, melting point

97 ⁰ C, polydispersity 1, 6

Foral 85: fully hydrogenated glycerol ester of rosin with a

Melting point of 85 ⁰ C and a polydispersity of 1, 2 Escorez 1310: non-hydrogenated C ₅ - hydrocarbon resin having a melting point of 94 ⁰ C and a polydispersity of 1, 5 Irganox 1726 phenolic antioxidant with sulfur-based function of a secondary antioxidant

Irganox 1076: phenolic antioxidant Tinuvin 622: HALS light stabilizer

example 1

The adhesive consists of the following components:

100 phr NOTIO PN-0040, 78.4 phr Wingtack 10, 212 phr Escorez 1310 and 8 phr Irganox 1726.

The adhesive is produced continuously in an extruder and applied by means of die coating from the melt on both sides with 70 g / m ² to a tissue of 25 g / m ² . The product is covered with a siliconized polyethylene-coated release paper.

The bond strengths are determined at a deduction angle of 180 ° according to AFERA 4001 on a 15 mm wide test strip. The non-bonded to steel or polypropylene side is laminated before the adhesion measurement with a 25 micron thick etched polyester film. The bond strength on steel of the open and on the covered side is 8.4 N / cm each. The bond strength on a polypropylene plate is> 10 N / cm in each case (polyester film separates from the adhesive tape). The heat of fusion of the pressure-sensitive adhesive is 1.6 J / g. Example 2

The adhesive consists of the following components: 100 phr Borclear RD708CF, 90 phr Ondina 933, 250 phr Wingtack extra and 8 phr Irganox 1726.

It is prepared as in Example 1 and applied at 90 g / m ² on a polyester fabric by means of die coating from the melt. The filament fabric has a basis weight of 130 g / m ² of polyester yarn of 167 dtex with 45 threads per cm in the warp direction and 25 threads per cm in the weft direction.

Adhesive force to steel 6.6 N / cm, adhesion to backside 2.8 N / cm.

Roller storage 1 month at 70 ⁰ C: The roller is slightly deformed and easy to unroll.

Compatibility testing: The finished adhesive tape is made according to LV 312-1 "Protection systems for wiring harnesses in motor vehicles, adhesive tapes; Test Guideline "(02/2008), common standard of the companies Daimler, Audi, BMW and Volkswagen, wrapped around a wire pair with different insulation materials and stored at appropriate temperature Six such test pieces are produced per insulation material Each one of the samples is checked every 500 hours , the tape is unwound and the cable wrapped around a mandrel of 10 mm diameter and one of 2 mm in diameter.It is examined whether the insulation is damaged and whether the adhesive exhibits a stickiness (test temperatures: on PVC at 105 ⁰ C and on crosslinked PE at 125 ^° C.) After 3000 hours, all wire insulation is still undamaged After 3,000 hours at 105 ^° C., the mass hardly penetrated into the support and still has good tack, after 3,000 hours at 125 ^° C. Mass partially penetrated into the carrier but is still sticky.

Example 3

The adhesive consists of the following components:

100 phr PB 8640M, 90 phr Indopol H-100, 200 phr Regalite R1 100, 5 phr Tinuvin 622 and

8 phr Irganox 1726.

It is prepared as in Example 1 and applied at 18 g / m ² on the base layer of a carrier film. This consists of a 50 μm thick base layer of 59.7 Parts by weight of PP homopolymer, 30 parts by weight LLDPE, 10 parts by weight of inorganic coated titanium dioxide and 0.3 parts by weight of a HALS stabilizer (Tinuvin 622). and a 15 micron thick top layer of 30 parts by weight of PP homopolymer and 70 parts by weight LDPE. The topcoat is provided with a release varnish based on polyvinyl stearyl carbamate prior to the adhesive composition coating.

The resulting product is bonded to a sheet with 2-component PU paint as usual for automobiles and subjected to UV aging (1750 hours of Xenotest 150 corresponding to 97 kLy). After the subsequent peeling off, no adhesive residues occurred.

Example 4

A melt pressure-sensitive adhesive composition of the following composition is prepared in a kneader: 100 phr Tafcelen T3714, 50 phr Ondina 933, 212 phr Regalite FM 100 and 3 phr Irganox 1076.

This is then applied by means of a hotmelt applicator from Nordson (CWEO-M2RCXE) spirally with a coating of 10 g / m ² onto a PE diaper film 25 μm and immediately laminated with a PP diaper fleece. The mass results in such a high bond strength that the fleece is destroyed during separation. The heat of fusion of the pressure-sensitive adhesive is 3.0 J / g.

Comparative Example 1

The execution takes place as described in example 1, but with PB 0300M instead of NOTIO PN-0040. The coating is not pressure-sensitive but hard with oily surface.

Comparative Example 2

The execution takes place as described in example 1, but with Versify 2400 instead of NOTIO PN-0040. The coating is very soft and sticky. An adhesion measurement is not possible due to cohesive failure. Comparative Example 3

The carrier film is Radil ™ 35 μm (biaxially stretched polypropylene homopolymer film). It is coated on the corona-treated side with polyvinyl stearyl carbamate from toluene solution and coated on the front with 28 g / m ^{2 of} a hotmelt PSA composition of the following composition: 100 phr NOTIO PN-0040, 78.4 phr Ondina 933 and 3 phr Irganox 1076. The sample adheres light on glass, the bond strength to glass and steel is less than 0.1 N / cm.

Comparative Example 4

The procedure is as described in Comparative Example 3, but with the following formulation: 100 phr NOTIO PN-0040 and 3 phr Irganox 1076. The sample adheres easily to glass, the bond strength to glass and steel is less than 0.1 N / cm.

Comparative Example 5

The execution takes place as described in Comparative Example 3, but with the following formulation:

100 phr (45% by weight) NOTIO PN-0040, 1 1 1 phr (50% by weight) Exact 4053 and 1 1 phr (5% by weight) Regalite R1 100.

The bond strengths on steel are 0.02 N / cm, on polycarbonate and Plexiglas (acrylate, PMMA) each 0.05 N / cm. The sample does not adhere to kraft paper.

Claims

claims

1 . An isotactic 1-butene resin adhesive having a density between 0.86 and 0.91 g / cm ³ , preferably between 0.86 and 0.89 g / cm ³ , more preferably between 0.87 and 0.89 g / cm ³ , and a crystallite melting point of at least

90 ⁰ C, preferably at least 105 ⁰ C, more preferably at least 1 10 ⁰ C and at least one tackifier resin, wherein the proportion of the adhesive resin is at least 20 phr, preferably at least 50 phr.

2. An adhesive according to claim 1, characterized in that the 1-butene resin

- has a melt index of 0.5 to 10 g / 10 min, preferably 3 to 8 g / 10 min and / or - has a flexural modulus of less than 50 MPa, preferably less than 26 MPa.

3. The adhesive of claim 1 or 2, characterized in that the 1-butene resin as a block copolymer, as a graft polymer or as a heterophasic

Copolymer or terpolymer is present.

4. An adhesive according to at least one of the preceding claims 1 to 3, characterized in that the heat of fusion of the 1-butene resin is between 3 and 18 J / g, preferably between 5 and 12 J / g.

5. An adhesive according to at least one of the preceding claims, characterized in that the 1-butene resin 1-butene and at least one other comonomer selected the

C ₂ - to C ₁₀ -olefins, preferably C ₂ - to C ₁₀ -α-olefins, wherein copolymers of 1-butene and ethylene and especially copolymers of 1-butene and propylene and terpolymers of 1-butene, propylene and ethylene particularly preferred.

6. An adhesive according to at least one of the preceding claims, characterized in that the 1-butene resin contains predominantly 1-butene, that is, the proportion of 1-butene is at least over 50 wt .-%, preferably at least over 70 wt. -%.

7. An adhesive according to at least one of the preceding claims, characterized in that the content of 1-butene resin in the adhesive is at least 15 wt .-%, preferably at least 20 wt .-%.

8. An adhesive according to at least one of the preceding claims, characterized in that the content of 1-butene resin in the adhesive is below 40 wt .-%, preferably below 35 wt .-% and particularly preferably below 30 wt .-%.

9. An adhesive according to at least one of the preceding claims, characterized in that the heat of fusion of the adhesive is between 1 and 6 J / g, preferably between 2 and 5 J / g.

10. An adhesive according to at least one of the preceding claims, characterized in that the adhesive resin 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 has.

1 1. adhesive according to at least one of the preceding claims, characterized in that the adhesive resin is selected from the group - the resins based on rosin or Kolophoniumderivaten preferably partially or fully hydrogenated,

the hydrocarbon resins based on C ₅ monomers, preferably partially or completely hydrogenated,

- the hydrocarbon resins from hydrogenation of aromatic-containing carbon-hydrogen resins, - The hydrocarbon resins based on hydrogenated cyclopentadiene polymers and / or

- The resins based on polyterpenes, preferably partially or completely hydrogenated, wherein the amount of adhesive resin in the adhesive is preferably 130 to 350 phr, more preferably 200 to 240 phr.

12. An adhesive according to at least one of the preceding claims, characterized in that the adhesive contains a plasticizer, preferably selected from the group of

Mineral oils, the liquid polymers such as isobutene homopolymer and / or isobutene-butene copolymer and the esters of phthalic, trimellitic, citric or adipic acid, in particular their esters of branched octanols and nonanols.

13. An adhesive according to at least one of the preceding claims, characterized in that the adhesive is a further copolymer of ethylene or propylene, 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 preferably below 20 MPa and / or the crystallite melting point preferably below

60 ⁰ C and / or the density between 0.86 and 0.87 g / cm ³ , or contains an EPDM, preferably having an ethylene content of 40 to 70 wt .-% and / or a density below 0.88 g / cm ³ , more preferably below 0.87 g / cm ³ , wherein the amount of copolymer or terpolymer is preferably above 100 phr.

14. An adhesive according to at least one of the preceding claims, characterized in that the adhesive contains a primary antioxidant, preferably in an amount of at least 2 phr, more preferably at least 6 phr and / or a secondary antioxidant in an amount of 0 to 5 phr, preferably in an amount of 0.5 to 1 phr, wherein the primary antioxidant preferably has a hindered phenolic group and / or a relative molecular weight greater than 500 daltons.

15. An adhesive according to at least one of the preceding claims, characterized in that the adhesive is a pressure-sensitive adhesive.

16. Use of the adhesive according to at least one of the preceding claims in a one- or double-sided adhesive tape.

17. Use of the adhesive according to at least one of the preceding claims in a single- or double-sided adhesive tape, wherein the adhesive tape on at least one side adhesion to steel of at least 0.5 N / cm, preferably at least 2 N / cm, particularly preferred at least 6 N / cm, most preferably at least 9 N / cm.

18. Use of the adhesive according to at least one of the preceding claims in a single- or double-sided adhesive tape, wherein the order of the

Adhesive in a layer between 15 and 300 g / m ² , preferably between 20 and 75 g / m ² .

19. Use of the adhesive according to at least one of the preceding claims in a single- or double-sided adhesive tape, wherein the carrier is a nonwoven, a

Tissue, a film or a foam, preferably a cross-linked polyethylene foam or a viscoelastic carrier in particular a selbiger of polyacrylate optionally filled with hollow bodies made of glass or polymers.

20. Use of the adhesive according to at least one of the preceding claims in a single- or double-sided adhesive tape which is used for bonding to low-energy surfaces, films, human skin or rough substrates in the construction sector, in stripe-adhesive tape or for winding applications such as automotive wiring harness manufacture.