DE102018207182A1 - Adhesive tape with release liner based on a pressure sensitive silicone coating - Google Patents

Abstract

The present invention relates to a layer composite, in particular adhesive tape, which a) a Releaseliner of a carrier layer and a silicone coating of special addition-crosslinked silicone PSAs and b) at least one layer of polyacrylate-based adhesives with tack at room temperature Tack or heat activated bonded, not at room temperature or only weakly adhesive, adhesives. Furthermore, the present invention relates to the use of an assembly as a release liner, which contains a carrier layer and the above-mentioned silicone coating of special addition-crosslinked silicone PSAs. Finally, the present invention relates to the use of a silicone resin, which is functionalized with at least one alkenyl group, in silicone-containing release liners for reducing the silicone transfer from the release liner to the PSA of an adhesive tape

Description

The present invention relates to a layer composite, in particular an adhesive tape, comprising a) a release liner with at least one support layer (TS) and at least one on this carrier layer (TS) silicone coating applied (SB) of special addition-crosslinked silicone PSAs and b) at least one further layer (S1 ), comprising polyacrylate-based adhesives having at room temperature low tack or heat activated bondable, at room temperature, or only weakly tacky, adhesives. Furthermore, the present invention relates to the use of an arrangement as a release liner, wherein the arrangement comprises a carrier layer (TS) and on this carrier layer (TS) applied silicone coating (SB) of special addition-crosslinked silicone PSAs. Finally, the present invention relates to the use of a silicone resin functionalized with at least one alkenyl group in silicone-containing release liners for reducing the silicone transfer from the release liner to the PSA of an adhesive tape.

State of the art

Adhesive tapes, which are coated with adhesives on one or both sides, are usually wound into a roll in the form of an Archimedean spiral at the end of the production process. In order to prevent the adhesives from coming into contact with one another or sticking to the support, various procedures are known in the prior art. On the one hand, it is possible to use adhesives which have different degrees of adhesion and can therefore be detached from one another even after direct contact (cf. US Pat. No. 6,274,213 B1 ). On the other hand, the adhesive tapes can be applied to a covering material (also referred to as separating material) before winding, which is wound up together with the adhesive tape. The person skilled in such cover materials under the name Releaseliner or Liner are known. In addition to covering single- or double-sided adhesive tapes, liners are also used to cover labels. Adhesive tapes are also possible, which do not use two liners but a single double-sided separating liner. The adhesive tape web is then covered on its upper side with one side of a double-sided separating liner, its underside with the back of the double-sided separating liner equipped. This is the case in particular for an adjacent turn on a bale or a roll.

The liner (release paper, release film) is not part of an adhesive tape or label, but only an aid for its production, storage or for further processing by e.g. Punching. If a double-sided adhesive tape, which has been provided with a liner, is unrolled, it is normally stuck to the substrate with the open, ie liner-free, PSA side. Meanwhile, the other pressure-sensitive adhesive side still adheres sufficiently to the coated surface of the liner to allow handling of the adhesive tape. However, the liner must be peelable from the adhesive tape to allow adhesion to the second side of the double-sided adhesive tape. Therefore, in contrast to an adhesive tape carrier, the liner must not be firmly bonded to the adhesive layer of the adhesive tape or label. Furthermore, by the liner itself or by the removal of the liner, the adhesive force of the PSA must not be significantly affected for later use. At the same time, the stability of the release coating on the liner and its release properties, ie the adhesiveness, over long periods of time are important in order to ensure the function of this coating and the properties of the pressure-sensitive adhesive covered with the liner.

A prior art liner consists of at least one abhesive layer, also referred to as a "release layer", to reduce the adhesion tendency of adherend products to these surfaces (release function). This layer can be applied to a carrier material. As a carrier material of the liner, in particular papers or films can be used. Preferred films are those made of biaxially stretched polyethylene terephthalate, polybutene, polypropylene, polyethylene, monoaxially oriented polypropylene, biaxially oriented polypropylene or polyethylene, particularly preferably polyolefin films (polypropylene and polyethylene films) or polyester films. Polymer-coated papers or nonwovens are also to be found.

All the systems known to the person skilled in the art, in particular those which are mentioned in the "Handbook of Pressure Sensitive Adhesive Technology" by Donatas Satas (Satas & Associates, Warwick 1999), can be used as separating layer. The material of the adhesive separating layer is preferably selected from the group consisting of silicones, fluorinated silicones, silicone copolymers, waxes, carbamates, fluoropolymers and polyolefins and mixtures of two or more of the substances mentioned.

Frequently crosslinkable silicone systems are used as the release layer. These include mixtures of crosslinking catalysts and so-called thermally curable condensation, addition or free-radical crosslinking polysiloxanes. For condensation-crosslinking silicone systems, tin compounds, such as dibutyltin diacetate, are frequently present in the composition as crosslinking catalysts. Silicone-based release coatings on an addition-curing basis can be hardened by hydrosilylation. These release systems typically include the following components: an alkenylated polydiorganosiloxane (especially alkenyl-terminated and vinyl-terminated linear polymers, and vinyl-terminated branched silicones), a polyorganohydrogensiloxane crosslinking agent, and a hydrosilylation catalyst. Platinum or platinum compounds, such as, for example, the Karstedt catalyst [a Pt (0) complex compound] and rhodium catalysts, have become established as catalysts for addition-crosslinking silicone systems.

Furthermore, it is also possible to use photoactive catalysts, known as photoinitiators, in combination with UV-curable cationically crosslinking siloxanes based on epoxide and / or vinyl ethers or UV-curable free-radical crosslinking siloxanes, such as acrylate-modified siloxanes. Likewise, the use of electron beam curable silicone acrylates is possible. Corresponding systems may also contain further additives, depending on the intended use, such as stabilizers, pigments, antistatic additives or leveling agents. Also additives are used which improve the anchoring of the silicone layer on the substrate.

Furthermore, various types of Organopolysiloxanmassen are known which crosslink by heating or irradiation. Called masses, as they are for example in the DE 600 01 779 T2 which crosslink by addition reaction, namely by temperature treatment of a mixture of an organopolysiloxane having hydrogen atoms bonded directly to the silicon atoms and an organopolysiloxane having vinyl groups bonded directly to the silicon atoms in the presence of a hydrosilylation catalyst.

Also, photopolymerizable organopolysiloxane compositions can be used. Mention may be made, for example, of masses which are crosslinked by the reaction between organopolysiloxanes which are substituted by (meth) acrylate-substituted hydrocarbon radicals bonded directly to the silicon atoms and are crosslinked in the presence of a photosensitizer (cf. EP 0 168 713 B1 or DE 38 20 294 C1 ). Also useful are compositions in which the crosslinking reaction between organopolysiloxanes having hydrocarbyl substituted with mercapto groups bonded directly to the silicon atoms and organopolysiloxanes having vinyl groups attached directly to the silicon atoms is induced in the presence of a photosensitizer. Such masses are used for example in the US 4,725,630 A1 described.

When using the example in the DE 33 16 166 C1 The organopolysiloxane compositions containing epoxy groups substituted hydrocarbon radicals directly bonded to the silicon atoms are induced by the release of a catalytic amount of acid, which is obtained by photodecomposition of added onium salt catalysts. Other cationic-mechanism-curable organopolysiloxane compositions are materials having, for example, propenyloxysiloxane end groups.

Particular embodiments of the silicone systems are polysiloxane block copolymers, e.g. with urea block, as offered by the company Wacker under the trade name Geniomer, or separation systems of fluorosilicone, which are used in particular for adhesive tapes with silicone adhesives.

Waxes, fluorinated or partially fluorinated polymers or polyolefins, in particular polyethylene block copolymers, as used in US Pat EP 2 025 07 B1 or WO 2010/022154 A2 are described; as are carbamates and acrylic esters with hydrophobic substituents.

In order to prevent the liner from unintentionally detaching from the pressure-sensitive adhesive layer of the adhesive tape, release forces of at least 10 cN / cm are desirable. The adjustment of the separation forces to the required values can be achieved by the addition of so-called MQ resins, wherein the release value of the liner increases with the proportion of MQ resin in the silicone system. MQ resins are silicone compounds which contain structural units of the formulas (R ₃ SiO _1/2 ) (M unit) and (SiO _4/2 ), (Q unit). R here stands for an organic group, for example a substituted or unsubstituted monovalent hydrocarbon group. Since the release value of the liner in addition to the silicone coating and the proportion of MQ resin in this coating also depends on the pressure-sensitive adhesive used for the adhesive tape especially in the case of polyacrylate-based adhesives with adhesives that are tack-free or heat-activated at room temperature, adhesives that are not or only slightly tacky at room temperature, only very weak release forces of less than 10 cN / cm are achieved even with the addition of very high amounts of MQ resin. These weak separation forces can cause the liner to unintentionally detach during production, storage or use. Furthermore, when using silicone-containing release liners, a silicone transfer from the liner to the PSA of the adhesive tape occurs, which can lead to a reduction in the bond strength of the PSA.

Object of the invention

The object of the invention was thus to provide a layer composite, in particular an adhesive tape, which comprises polyacrylate-based adhesives having room tack with little tack or heat activated, adhesives that are not or only slightly tacky at room temperature, and a release liner, wherein the release liner has a sufficient release force of at least 10 cN / cm. In this way, an unwanted separation of the liner during the manufacturing or storage process and during the application of the liner provided with the adhesive tape is avoided. Another object of the invention was to reduce the silicone transfer from the silicone-containing release liner to the PSA of the layer composite. In this way, a reduction in the adhesive force of this PSA can be reduced or prevented.

Solution of the task

1. A mindestens einen Releaseliner, umfassend mindestens eine Trägerschicht (TS) sowie mindestens eine Silikonbeschichtung (SB), enthaltend eine additionsvernetzte Silikonhaftklebemasse, welche erhältlich ist durch Umsetzung:
   1. a) mindestens eines Organopolysiloxans mit einem gewichtsmittleren Molekulargewicht M_w von 30.000 bis 2.000.0000 g/mol, welches mindestens eine Diorganosiloxaneinheit und mindestens zwei Silizium-gebundenen Alkenylgruppen enthält, wobei das gewichtsmittlere Molekulargewicht M_w durch Gelpermeationschromatographie in Toluol bei 23 °C und einer Flussrate von 1,0 ml/min mittels eines modifizierten Styrol-Divinylbenzol-Copolymer-Netzwerkes als Säulenmaterial und Polydimethylsiloxan als internem Standard bestimmt wird,
   2. b) mindestens einer zur Vernetzung von Alkenylgruppen enthaltender Organopolysiloxane geeigneten Verbindung, welche mindestens zwei Silizium-gebundene Wasserstoffatome enthält,
   3. c) mindestens eines Silikonharzes mit einem gewichtsmittleren Molekulargewicht M_w von 500 bis 29.999 g/mol, welches mindestens eine Struktureinheit (R¹R²R³SiO_1/2), (R¹SiO_3/2) oder (R¹R²SiO_2/2), worin R¹, R² und R³ unabhängig voneinander für eine organische Gruppe stehen und mindestens einer der Reste R¹, R² oder R³ für eine Alkenylgruppe steht, enthält, wobei das gewichtsmittlere Molekulargewicht M_w durch Gelpermeationschromatographie in Toluol bei 23 °C und einer Flussrate von 1,0 ml/min mittels eines modifizierten Styrol-Divinylbenzol-Copolymer-Netzwerkes als Säulenmaterial und Polydimethylsiloxan als internem Standard bestimmt wird,
   wobei die Umsetzung der Komponenten a), b) und c) durch einen Katalysator beschleunigt wird,
2. B mindestens eine weitere Schicht (S1), umfassend eine Polyacrylat-basierte Klebemasse mit bei Raumtemperatur geringem Tack oder eine hitzeaktiviert verklebbare, bei Raumtemperatur nicht oder nur schwach haftklebrige, Klebemasse.

The object is achieved by a layer composite, in particular adhesive tape, containing:

1. A at least one release liner comprising at least one support layer (TS) and at least one silicone coating (SB), containing an addition-crosslinked silicone pressure-sensitive adhesive which is obtainable by reaction:
   1. a) at least one organopolysiloxane having a weight-average molecular weight M _{w of} from 30,000 to 2,000,000 g / mol, which contains at least one diorganosiloxane unit and at least two silicon-bonded alkenyl groups, wherein the weight-average molecular weight M _w by gel permeation chromatography in toluene at 23 ° C and a Flow rate of 1.0 ml / min using a modified styrene-divinylbenzene copolymer network as the column material and polydimethylsiloxane as the internal standard,
   2. b) at least one compound suitable for crosslinking alkenyl groups containing organopolysiloxanes, which contains at least two silicon-bonded hydrogen atoms,
   3. c) at least one silicone resin having a weight average molecular weight M _w of 500 to 29999 g / mol, which at least one structural unit (R ¹ R ² R ³ SiO _1/2 ), (R ¹ SiO _3/2 ) or (R ¹ R ² SiO _2/2 ), wherein R ¹ , R ² and R ^{3 are} independently an organic group and at least one of R ¹ , R ² or R ^{3 is} an alkenyl group, wherein the weight average molecular weight M _w by gel permeation chromatography in toluene at 23 ° C and a flow rate of 1.0 ml / min by means of a modified styrene-divinylbenzene copolymer network as column material and polydimethylsiloxane as internal standard,
   wherein the reaction of components a), b) and c) is accelerated by a catalyst,
2. B at least one further layer (S1), comprising a polyacrylate-based adhesive having a tack that is low at room temperature or a heat-activated, bondable adhesive which is not or only slightly tacky at room temperature.

Furthermore, the object is achieved by the use of an arrangement as a release liner, wherein the arrangement contains at least one carrier layer (TS) and at least one silicone coating (SB) of the above-described addition-crosslinked silicone PSA.

Finally, the object is achieved by the use of a silicone resin comprising at least one structural unit (R ¹ R ² R ³ SiO _1/2 ), (R ¹ SiO _3/2 ) or (R ¹ R ² SiO _2/2 ), wherein R ¹ , R ² and R ³ independently of one another are an organic group and at least one of R ¹ , R ² or R ^{3 is} an alkenyl group, in silicone-containing release liners for reducing the silicone transfer from the release liner to the PSA of an adhesive tape.

From the literature (eg Technology of Pressure-Sensitive Adhesives and Products, CRC Press, FL, edited by I. Benedek and MM Feldstein, pages 9-20, 2009; RG Schmidt, LR Badour, GV Gordon, Polymer Preprints, 42, 113, 2001, and T. Cosgrove, C. Roberts, Y. Choi, Langmuir, 18, pp. 10075-10079, 2002 ), it is known that non-functional MQ resins which can participate in the hydrosilylation reaction to crosslink the silicone-containing base polymer increase the release force of a silicone-containing release liner more than MQ resins having such functional groups. The invention is therefore based on the surprising finding that, despite the addition of alkenyl-functionalized MQ resins in the production of the addition-crosslinked silicone coating of the release liner, PSAs with room temperature tack or heat-activated bondable release adhesives which are not or only slightly tacky at room temperature have sufficient release forces of at least 10 cN / cm can be achieved. Surprisingly, the use of these functionalized MQ resins also reduces the silicone transfer from the silicone-containing release liner to the pressure-sensitive adhesive of the adhesive tape and in this way reduces or avoids a reduction in the bond strength of this pressure-sensitive adhesive.

The silicone coatings (SB) used in the release liner of the product according to the invention are already known from the prior art (see EP 2 524 954 A1 . US 2013/0316076 A1 . EP 1 652 899 A1 ). However, according to the disclosure of these documents, the alkenyl functionalized MQ resin is merely used to modify the viscosity of these resins. Furthermore, because of their adhesive properties, the silicone coatings disclosed in these documents are not used in release liners which can be removed before bonding, but are used as pressure-sensitive adhesives for bonding protective foils for displays, window images and symbols.

Surprisingly, it has thus been found that sufficient release values of at least 10 cN / cm can be obtained by using the silicone coatings known in the prior art if these silicone coatings are used in release liners for PSAs having a tack that is low at room temperature. In addition, it has surprisingly been found that by the addition of MQ resins functionalized with at least one alkenyl group during the production of the silicone coating, the silicone transfer from the release liner to the PSA of the adhesive reduces and in this way the reduction of the bond strength of this PSA can be reduced or prevented ,

Adhesive compositions are referred to as "pressure-sensitive adhesives" which, even under relatively slight pressure, permit a permanent bond with the primer and, after use, can be removed again from the primer without leaving any residue. For the purposes of the present invention, a pressure-sensitive adhesive has an adhesive force of at least 1 N / cm.

The bond strength is determined here on steel in accordance with ISO 29862: 2007 (Method 3) at 23 ° C. and 50% relative atmospheric humidity at a take-off speed of 300 mm / min and a take-off angle of 180 °. The reinforcing film used is an etched PET film having a thickness of 36 μm, as available from Coveme (Italy). The gluing of a 2 cm wide measuring strip is carried out by means of a 4 kg coiler at a temperature of 23 ° C. The tape is removed immediately after application. The measured value (in N / cm) is the average of three individual measurements.

Pressure-sensitive adhesives are permanently tacky at room temperature and therefore have a sufficiently low viscosity and high tack, so that they wet the surface of the respective adhesive base even at low pressure. The adhesiveness of the adhesives is based on their adhesive properties and the removability on their cohesive properties.

Detailed description of the invention

The layer composite according to the invention, in particular adhesive tape, can be designed without a carrier or else with at least one carrier material. If a carrier material is present, it may be provided on one side or preferably on both sides with the PSA B (layer (S1)) or may consist thereof. The carrier material comprises all flat structures, for example films or film sections which are expanded in two dimensions, tapes with an extended length and limited width, strip sections, Diecuts (for example in the form of borders or boundaries of an (opto) electronic arrangement), multilayer arrangements and the like. Different carriers such as films, fabrics, nonwovens and papers can be combined with the adhesives for various applications.

As carrier material, it is possible to use all flat structures, for example films or film sections expanded in two dimensions, strips of extended length and limited width, strip sections, diecuts (for example in the form of borders or boundaries of an (opto) electronic arrangement), multilayer arrangements and the like. Different carriers such as films, fabrics, nonwovens and papers can be combined with different adhesives for different applications.

In the present case, polymer films, film composites or films or film composites provided with organic and / or inorganic layers are preferably used as support material of the layer composite. Such films / film composites may consist of all common plastics used for film production, but are not restrictive by way of example: polyethylene, polypropylene - in particular the oriented polypropylene (OPP) produced by mono- or biaxial stretching, cyclic olefin copolymers (COC), polyvinyl chloride (PVC Polyester, in particular polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), ethylene vinyl alcohol (EVOH), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polycarbonate (PC), polyamide (PA), polyethersulfone (PES) or Polyimide (PI).

The support may also be combined with organic or inorganic coatings or layers. This can be done by conventional methods such as painting, printing, evaporation, sputtering, co-extrusion or lamination. By way of example, but not by way of limitation, oxides or nitrides of silicon and of aluminum, indium-tin oxide (ITO) or sol-gel coatings may be mentioned here.

Support material (TS) of the release liner

According to the invention, the release liner A contains at least one carrier layer (TS). In principle, any carrier layer which is known to the person skilled in the art for use in layer composites, in particular adhesive tapes, can be used as carrier layer (TS). In particular, however, papers or films are used as carrier layer (TS). Preferred films are those made of polyethersulfones, polysulfones, polyolefins and polyesters, in particular of biaxially oriented polyethylene terephthalate, polybutene, polypropylene, polyethylene, monoaxially oriented polypropylene and biaxially oriented polypropylene or polyethylene. Polyolefin films (polypropylene and polyethylene films) or polyester films, in particular polyester films and very particularly preferably films of biaxially oriented polyethylene terephthalate, are used particularly preferably according to the invention as support layer (TS). Polymer-coated papers or nonwovens can also be used.

Silicone coating (SB) of release liner A

Furthermore, the release liner A comprises at least one silicone coating (SB) which contains at least one addition-crosslinked silicone PSA of polyorganosiloxanes and silicone resins functionalized with at least one alkenyl group. Despite the lack of inherent tack, it has been found that these silicone PSAs have a sufficiently high adhesion to pressure-sensitive adhesives having a tack that is low at room temperature, so that sufficient release forces of at least 10 cN / cm are achieved. In addition, the silicone transfer from the silicone PSA to the PSA of the further layer (S1) is reduced by adding the functionalized silicone resin when preparing the silicone PSA. In this way, a reduction in the adhesive force of this PSA is reduced or avoided due to the silicone transfer. In addition, as a result of the very stable Si-O-Si bond, these silicone PSAs exhibit high resistance to environmental influences, such as UV light and high temperatures, so that the layer composites according to the invention have outstanding storage stability.

1. a) mindestens eines Organopolysiloxans mit einem gewichtsmittleren Molekulargewicht M_w von 30.000 bis 2.000.0000 g/mol, welches mindestens eine Diorganosiloxaneinheit und mindestens zwei Silizium-gebundenen Alkenylgruppen enthält, wobei das gewichtsmittlere Molekulargewicht M_w durch Gelpermeationschromatographie in Toluol bei 23 °C und einer Flussrate von 1,0 ml/min mittels eines modifizierten Styrol-Divinylbenzol-Copolymer-Netzwerkes als Säulenmaterial und Polydimethylsiloxan als internem Standard bestimmt wird,
2. b) mindestens einer zur Vernetzung von Alkenylgruppen enthaltender Organopolysiloxane geeigneten Verbindung, welche mindestens zwei Silizium-gebundene Wasserstoffatome enthält,
3. c) mindestens eines Silikonharzes mit einem gewichtsmittleren Molekulargewicht M_w von 500 bis 29.999 g/mol, welches mindestens eine Struktureinheit (R¹R²R³SiO_1/2), (R¹SiO_3/2) oder (R¹R²SiO_2/2), worin R¹, R² und R³ unabhängig voneinander für eine organische Gruppe stehen und mindestens einer der Reste R¹, R² oder R³ für eine Alkenylgruppe steht, enthält, wobei das gewichtsmittlere Molekulargewicht M_w durch Gelpermeationschromatographie in Toluol bei 23 °C und einer Flussrate von 1,0 ml/min mittels eines modifizierten Styrol-Divinylbenzol-Copolymer-Netzwerkes als Säulenmaterial und Polydimethylsiloxan als internem Standard bestimmt wird,

wobei die Umsetzung der Komponenten a), b) und c) durch einen Katalysator beschleunigt wird,According to a preferred embodiment of the present invention, the silicone coating (SB) comprises an addition-crosslinked silicone pressure-sensitive adhesive which is obtainable by reaction:

1. a) at least one organopolysiloxane having a weight-average molecular weight M _{w of} from 30,000 to 2,000,000 g / mol, which contains at least one diorganosiloxane unit and at least two silicon-bonded alkenyl groups, wherein the weight-average molecular weight M _w by gel permeation chromatography in toluene at 23 ° C and a Flow rate of 1.0 ml / min using a modified styrene-divinylbenzene copolymer network as the column material and polydimethylsiloxane as the internal standard,
2. b) at least one compound suitable for crosslinking alkenyl groups containing organopolysiloxanes, which contains at least two silicon-bonded hydrogen atoms,
3. c) at least one silicone resin having a weight average molecular weight M _w of 500 to 29999 g / mol, which at least one structural unit (R ¹ R ² R ³ SiO _1/2 ), (R ¹ SiO _3/2 ) or (R ¹ R ² SiO _2/2 ), in which R ¹ , R ² and R ³ independently of one another represent an organic group and at least one of the radicals R ¹ , R ² or R ^{3 is} an alkenyl group, wherein the weight average molecular weight M _w by gel permeation chromatography in toluene at 23 ° C and a flow rate of 1.0 ml / min using a modified styrene-divinylbenzene copolymer network as column material and polydimethylsiloxane as an internal standard,

wherein the reaction of components a), b) and c) is accelerated by a catalyst,

As organopolysiloxanes a) it is possible to use linear, cyclic or branched polydialkylsiloxanes. Particular preference is given to using linear polydimethylsiloxanes and polydimethylsiloxanes which contain terminal and / or internal alkenyl groups as component a).

It has proved to be advantageous according to the invention if a specific molar ratio of the above-mentioned components a) and b) is used in the preparation of the addition-crosslinked silicone PSA. This allows the setting of a certain degree of crosslinking and thus the cohesion of the silicone PSA. In particular, the use of a molar ratio of silicon-bonded hydrogen atoms of component b) to the silicon-bonded alkenyl groups of component a) from 0.8 to 5 has proved to be advantageous in view of the required for the release force of at least 10 cN / cm cohesion ,

Furthermore, it is preferred according to the invention if the components a), b) and c) are used in specific total amounts. The component a) is therefore preferably in a total amount of 30 to 70, more preferably 35 to 65 parts by weight, the component b) preferably in a total amount of 7 to 12 parts by weight and the component c), preferably in a total amount of 20 to 60, stronger preferably from 25 to 55 parts by weight, based in each case on the sum of components a), b) and c) of 100 parts by weight.

The crosslinking of the abovementioned components a), b) and c) takes place by means of a hydrosilylation reaction between the alkenyl-functionalized organopolysiloxanes and the corresponding SiH-functionalizing organopolysiloxanes. This hydrosilylation reaction is accelerated by the use of catalysts according to the invention. In particular, platinum or rhodium catalysts are used as catalysts. With regard to the required for the separation force of at least 10 cN / cm cohesion, it has proved to be advantageous if the platinum or rhodium catalyst preferably in a total amount of 40 to 600 ppm, calculated as platinum or rhodium metal and based on the sum of Components a), b) and c) of 100 parts by weight is used. The crosslinking reaction is preferably carried out at elevated temperatures of 100 to 150 ° C.

On the one hand, to set the release values of the silicone coating (SB) of the release liner A to at least 10 cN / cm and, on the other hand, to prevent silicone transfer from the silicone coating (SB) to the PSA and thus a reduction in the bond strength of this PSA (adhesive depression, KKD), In the preparation of the addition-crosslinked silicone PSA, a special silicone resin (component c)) is added. These resins are polydisperse mixtures of possibly differently substituted, branched siloxane structures. Depending on the functionality of the silicon group (mono-, di-, tri- or tetrafunctional), the siloxane units are abbreviated by the symbols M, D, T and Q. M stands for a (R ¹ R ² R ³ SiO _1/2 ) unit, D for a (R ¹ R ² SiO _2/2 ) unit, T for a (R ¹ SiO _3/2 ) unit and Q for a SiO _4/2 unit. At least one of the radicals R ¹ , R ² or R ^{3 of} at least one of these units is in the silicone resin of the invention for an alkenyl group. As component c) silicone resins are preferably used, which are composed of MQ, MTQ, TQ, MT or MDT units. Particularly preferred as component c) MQ resins of the formula (R ¹ R ² R ³ SiO _1/2 ) (SiO _4/2 ) are used, wherein R ¹ , R ² and R ^{3 are} independently an organic group and at least one of the radicals R ¹ , R ² or R ^{3 is} at least one M unit for an alkenyl group. The ratio of M units to Q units is preferably in the range of 0.5 to 1.2. By adding such silicone resins, on the one hand, the release value of the silicone coating (SB) of the release liner A can be set to the required minimum value of 10 cN / cm. In addition, in this way the release value of the release liner A can be adapted individually to the respective application, without having to use different types of release coatings for the production of the release liner. In addition, a silicone transfer from the silicone coating (SB) is reduced or avoided by the addition of these special silicone resins on the PSA B of the composite layer and counteracted in this way a reduction in the adhesive force (adhesive depression, KKD).

In the context of the present invention, it has proven to be particularly preferable if certain radicals R ¹ , R ² or R ³ in the structural units (R ¹ R ² R ³ SiO _1/2 ), (R ¹ SiO _3/2 ) or ( R ¹ R ² SiO _2/2 ) of the silicone resin for to stand a particular group. It is therefore particularly preferred according to the invention if at least one of the radicals R ¹ , R ² or R ^{3 is} at least one of the abovementioned structural units for a vinyl group. Through the use of silicone resins c) which have at least one vinyl group, the silicone transfer from the silicone coating (SB) to the PSA can be reduced particularly effectively and thus the reduction of the bond strength of this PSA (adhesive depression, KKD) can be significantly counteracted. In addition, the use of such silicone resins also leads to the achievement of sufficient release values to prevent unwanted detachment of the release liner A during manufacture, storage and handling.

According to a further preferred embodiment of the first subject of the invention, silicone resins c), in particular the previously mentioned MQ resins, which have a weight-average molecular weight M _{w of} from 1,000 to 25,000 g / mol are used for the preparation of the addition-crosslinked silicone PSA. The data of the average molecular weight M _w in this document refer to the determination by gel permeation chromatography in toluene at 23 ° C and a flow rate of 1.0 ml / min using a modified styrene-divinylbenzene copolymer network as column material and polydimethylsiloxane as an internal standard , as described in the example section. The use of silicone resins c) with the previously mentioned molecular weight on the one hand allows a particularly good adaptation of the required release value even in conjunction with PSAs which have only a slight tack at room temperature. On the other hand, silicone resins c) with the above-mentioned molecular weight lead to an effective reduction of the silicone transfer from the silicone coating (SB) of the liner to the PSA B of the laminar composite, so that the adhesive depression resulting from the silicone transfer can be reduced.

The release values achieved with the silicone coating (SB) and the amount of silicon transfer from the silicone coating (SB) of the Relaseliner A can be adapted to the respective requirements by varying the proportion of the specific silicone resin c) during the preparation of the silicone pressure-sensitive adhesive. By increasing the proportion of special silicone resin c), the release value of the release liner A can be increased and the silicone transfer from the silicone coating (SB) to the PSA can be reduced. In this way, a simple adaptation of the Relaseliners A to the separation value and silicone transfer required for the respective application is possible. The silicone coating (SB) therefore preferably has a weight ratio of the organopolysiloxane a) to the silicone resin c) of from 90:10 to 10:90, in particular from 50:20 to 30:50.

• - Prozessstabilisatoren, wie Vinylsilane, Maleate oder Alkinole als Inhibitoren für den Platin- oder Rhodiumkatalysator,
• - Prozessbeschleuniger, wie Aminoorganyle,
• - Füllstoffe, wie Siliziumdioxid, Glas (gemahlen oder in Form von Kugeln), Aluminiumoxide und Zinkoxide,
• - Plastifizierungsmittel, wie Flüssigharze, Weichmacheröle oder niedermolekulare flüssige Polymere (niedermolekulare Silikonöle mit gewichtsmittleren Molekulargewichten M_w von kleiner 1.500 g/mol).

In addition to the resin modification, the silicone PSA (SB) may also contain other additives. In particular, these additives are chosen so that the release values of the coating do not deteriorate. As further additives can be used for example:

• Process stabilizers, such as vinylsilanes, maleates or alkynols, as inhibitors of the platinum or rhodium catalyst,
• - Process accelerators, such as Aminoorganyle,
• Fillers, such as silica, glass (ground or in the form of spheres), aluminum oxides and zinc oxides,
• - Plasticizers, such as liquid resins, processing oils or low molecular weight liquid polymers (low molecular weight silicone oils having weight average molecular weights M _w of less than 1500 g / mol).

Preferably, the silicone coating (SB) of the release liner is free of silicone oils. Silicone oils can move comparatively well through the silicone compound (SB) and thus increase the risk of silicone transfer into the PSA. Their absence thus contributes to reducing the risk of silicone transfer.

The silicone coating (SB) of the release liner is preferably applied in the form of a solution or dispersion to the release layer (TS) and then the solvent is removed at elevated temperatures. Preferably followed by a further increase in temperature to achieve the crosslinking of the organopolysiloxanes.

In order to enable the releasability of the release liner A from the PSA (S1), the silicone coating (SB) of the release liner A must have a low surface energy. Therefore, the release properties or the cohesion must be matched to the adhesive properties of the PSA (S1). The central factor that describes the release behavior is the release force or withdrawal force. On the one hand to achieve sufficient adhesion of the release liner during handling of the layer composite, in particular adhesive tape, separation forces of at least 10 cN / cm are required. Lower separation forces may result in unwanted detachment of the liner during manufacture, storage and handling. On the other hand, however, a simple detachment of the release liner of the To ensure pressure-sensitive adhesive, the release force must not be too high. According to a preferred embodiment of the first subject of the invention, the silicone coating (SB) therefore has a peel force of 10 to 80 cN / cm, preferably 10 to 70 cN / cm, in particular 10 to 60 cN / cm, the peel force on a PE Carrier plate by a tensile test (machine speed 300 mm / min, peel angle 180 °) is determined. The exact determination of the pull-off force by means of tensile testing is described in the example section. On the one hand, the abovementioned stripping or separating forces make it possible to ensure sufficient adhesion of the release liner A to the PSA (S1) during the production, handling and storage of the layer composite according to the invention, but on the other hand also allow easy removal of the liner after application of the PSA (S1). on the desired surface.

bestimmt wird. Bei der Referenzprobe handelt es sich um eine Haftklebemasse (S1), welche vor Bestimmung der Klebkraft mittels Zugprüfung nicht mit einer Silikonbeschichtung (SB) eines Releaseliners in Kontakt stand.For some applications of the layered composite according to the invention, it may be necessary to reduce the silicone transfer from the silicone coating (SB) of the release liner A to the PSA (S1), since the transfer of silicone leads to a reduction of the adhesive force of the PSA (S1) (bond strength). Depression). It is therefore particularly preferred according to the invention if the further layer (S1) has an adhesive depression (KKD) of 6 to 20%, preferably 5 to 20%, in particular 4 to 20%, the adhesive depression (KKD) on a steel surface compared to a reference sample by a tensile test (machine speed 300 mm / min, peel angle 180 °) using the formula below $$KKD=\frac{Klebkraf{t}_{Referenz}-Kelbkraf{t}_{PrObe}}{Kelbkraf{t}_{Referenz}}\cdot 100\%$$

is determined. The reference sample is a pressure-sensitive adhesive (S1) which, prior to the determination of the bond strength, was not in contact with a silicone coating (SB) of a release liner by means of a tensile test.

Surprisingly, it has been found that sufficient release forces with PSAs which have only a slight tack at room temperature are obtained even if the silicone coating (SB) itself is not tacky. Although the silicone coating (SB) comprises a silicone PSA. However, the thin application of this silicone pressure-sensitive adhesive causes the silicone coating (SB) of the release liner A to be non-sticky. According to a particularly preferred embodiment of the present invention, the silicone coating (SB) therefore has a thickness of 0.5 to 200 .mu.m, in particular from 1.0 to 100 .mu.m.

Pressure Sensitive Adhesive B (Layer S1)

As a layer (S1), the layer composite according to the invention contains at least one polyacrylate-based adhesive with tack that is low at room temperature or a heat-activated, tack-bondable adhesive which is not or only slightly tacky at room temperature.

As a polyacrylate-based PSA having a room temperature-low tack, random copolymers starting from unfunctionalized α, β-unsaturated acrylic acid or acrylates can be used. Preference is given to α, β-unsaturated carboxylic acids and their derivatives of the general structure CH ₂ = C (R ³ ) (COOR ⁴ ) (I) wherein R ³ = H or CH ₃ and R ⁴ = H or linear, branched or cyclic, saturated or unsaturated alkyl radicals having 1 to 30, in particular having 4 to 18 carbon atoms.

Monomers which are very preferably used in the context of the general structure (I) include acrylic and methacrylic acid esters having alkyl groups consisting of 4 to 18 C atoms. Specific examples of such compounds include but are not limited to n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, n-nonyl acrylate, lauryl acrylate, stearyl acrylate, stearyl methacrylate, their branched isomers, such as For example, 2-ethylhexyl acrylate and iso-octyl acrylate and cyclic monomers such. B. cyclohexyl or norbornyl acrylate and isobornyl acrylate.

Furthermore, vinyl monomers can be optionally used from the following groups: vinyl esters, vinyl ethers, vinyl halides, vinylidene halides, and vinyl compounds containing aromatic cycles or heterocycles in α-position. Examples of monomers which can be used according to the invention for the optionally usable vinyl monomers include: vinyl acetate, vinylformamide, vinylpyridine, ethylvinylether, 2-ethylhexylvinylether, butylvinylether, vinylchloride, vinylidenechloride, acrylonitrile, styrene and .alpha.-methylstyrene. Further monomers which can be used according to the invention are glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, acrylic acid, methacrylic acid, itaconic acid and its esters, crotonic acid and its esters, maleic acid and their esters, fumaric acid and its esters, maleic anhydride, methacrylamide and N-alkylated derivatives, acrylamide and N-alkylated derivatives, N-methylolmethacrylamide, N-methylolacrylamide, vinyl alcohol, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether and 4-hydroxybutyl vinyl ether.

The low tack room temperature polyacrylate-based adhesive may be a non-foamed or foamed pressure-sensitive adhesive, e.g. a microballoon foamed PSA. Such a pressure-sensitive adhesive may be present both on a foamed and on a non-foamed carrier.

Heat-activated adhesive compositions are not or only slightly tacky at room temperature and reach their full adhesive strength only after application of heat. Such adhesives are based, for example, on thermoplastic polyurethane, nylon, polyester or vinyl polymers. Other heat-activated adhesives which can be used are, for example, synthetic rubbers from the group consisting of the random copolymerized styrene-butadiene rubbers (SBR), the butadiene rubbers (BR), the synthetic polyisoprenes (IR), the butyl rubbers (NR), the halogenated butyl rubbers (US Pat. XIIR), the acrylate rubbers (ACM), the ethylene vinyl acetate copolymers (EVA) and the polyurethanes and / or their blends.

Structure of the layer composite

The layer composite according to the invention may be an adhesive tape with a carrier material in which the at least one further layer (S1), i. the pressure-sensitive adhesive to which the carrier layer (TS) facing away from the silicone coating (SB) of the liner adjacent. The silicone coating (SB) of the release liner A thus covers the PSA (S1) in this embodiment. Therefore, before using the adhesive tape, the release liner A must be removed.

According to a further embodiment of the present invention, the layer composite has at least one further acrylate-based pressure-sensitive adhesive (S2), which lies between the silicone coating (SB) and the further layer (S1) and / or on the side facing away from the silicone coating (SB) further layer (S1) is located. In this way, the bond strength of the layer (S1) can be adapted to the surface condition of the substrate to be bonded. Suitable acrylate-based adhesives are, for example, the abovementioned polyacrylate-based adhesives.

Furthermore, the layer composite according to the invention may also be a so-called "transfer adhesive tape", that is to say an adhesive tape without a support. In the case of this transfer adhesive tape, the pressure-sensitive adhesive (layer (S1)), which here corresponds to the adhesive tape, is applied between two flexible release liners A before application. For application, the first release liner is first removed, the pressure-sensitive adhesive (layer S1) is applied, and then the second release liner is removed. The adhesive can be used directly for connecting two surfaces. With such a carrierless transfer adhesive tape a very accurate in positioning and metering bonding is possible. In the context of this embodiment it can be provided that the first release liner has a different release force than the second release liner. In this way, an unintentional partial redetachment of the freshly bonded PSA during the detachment of the second release liner can be avoided.

In addition to the above-mentioned layer composites, those are also possible which do not have two release liners but a single release liner equipped on both sides. The layer composite is then covered on its upper side with the front of a double-sidedly equipped liner A, on its underside with the back of the double-sidedly equipped liner A. Such arrangements are particularly suitable for an adjacent turn on a bale or a roll. According to a preferred embodiment of the present invention, the carrier layer (TS) is therefore coated on both sides with the previously mentioned silicone coating (SB). In this way, a double-sided separating liner A is obtained.

The layer composite according to the invention preferably has a thickness of 100 to 3000 μm. The thickness of the layer composite is determined here in particular by the thickness of the release liner A and the thickness of the PSA B. Layer composites with larger thicknesses can be achieved in particular by the use of foamed PSAs B.

An inventive layer composite can be present as a so-called dish roll in the form of an Archimedean spiral. But it can also be wound into a coil, ie be spirally wound uniformly around a core, wherein the individual layers of windings are usually one above the other.

• A mindestens eine Trägerschicht (TS), sowie
• B mindestens eine Silikonbeschichtung (SB), umfassend mindestens eine additionsvernetzte Silikonhaftklebemasse, welche erhältlich ist durch Umsetzung:
  1. a) mindestens eines Organopolysiloxans mit einem gewichtsmittleren Molekulargewicht M_w von 30.000 bis 2.000.0000 g/mol, welches mindestens eine Diorganosiloxaneinheit und mindestens zwei Silizium-gebundenen Alkenylgruppen enthält, wobei das gewichtsmittlere Molekulargewicht M_w durch Gelpermeationschromatographie in Toluol bei 23 °C und einer Flussrate von 1,0 ml/min mittels eines modifizierten Styrol-Divinylbenzol-Copolymer-Netzwerkes als Säulenmaterial und Polydimethylsiloxan als internem Standard bestimmt wird,
  2. b) mindestens einer zur Vernetzung von Alkenylgruppen enthaltender Organopolysiloxane geeigneten Verbindung, welche mindestens zwei Silizium-gebundene Wasserstoffatome enthält,
  3. c) mindestens eines Silikonharzes mit einem gewichtsmittleren Molekulargewicht M_w von 500 bis 29.999 g/mol, welches mindestens eine Struktureinheit (R¹R²R³SiO_1/2), (R¹SiO_3/2) oder (R¹R²SiO_2/2), worin R¹, R² und R³ unabhängig voneinander für eine organische Gruppe stehen und mindestens einer der Reste R¹, R² oder R³ für eine Alkenylgruppe steht, enthält, wobei das gewichtsmittlere Molekulargewicht M_w durch Gelpermeationschromatographie in Toluol bei 23 °C und einer Flussrate von 1,0 ml/min mittels eines modifizierten Styrol-Divinylbenzol-Copolymer-Netzwerkes als Säulenmaterial und Polydimethylsiloxan als internem Standard bestimmt wird,
  wobei die Umsetzung der Komponenten a), b) und c) durch einen Katalysator beschleunigt wird.

Another object of the present invention is the use of an assembly as a release liner, the arrangement comprising:

• A at least one carrier layer (TS), as well
• B at least one silicone coating (SB) comprising at least one addition-crosslinked silicone pressure-sensitive adhesive which is obtainable by reaction:
  1. a) at least one organopolysiloxane having a weight-average molecular weight M _{w of} from 30,000 to 2,000,000 g / mol, which contains at least one diorganosiloxane unit and at least two silicon-bonded alkenyl groups, wherein the weight-average molecular weight M _w by gel permeation chromatography in toluene at 23 ° C and a Flow rate of 1.0 ml / min using a modified styrene-divinylbenzene copolymer network as the column material and polydimethylsiloxane as the internal standard,
  2. b) at least one compound suitable for crosslinking alkenyl groups containing organopolysiloxanes, which contains at least two silicon-bonded hydrogen atoms,
  3. c) at least one silicone resin having a weight average molecular weight M _w of 500 to 29999 g / mol, which at least one structural unit (R ¹ R ² R ³ SiO _1/2 ), (R ¹ SiO _3/2 ) or (R ¹ R ² SiO _2/2 ), wherein R ¹ , R ² and R ^{3 are} independently an organic group and at least one of R ¹ , R ² or R ^{3 is} an alkenyl group, wherein the weight average molecular weight M _w by gel permeation chromatography in toluene at 23 ° C and a flow rate of 1.0 ml / min by means of a modified styrene-divinylbenzene copolymer network as column material and polydimethylsiloxane as internal standard,
  wherein the reaction of components a), b) and c) is accelerated by a catalyst.

Regarding further preferred embodiments of the use according to the invention, in particular with regard to the addition-crosslinked silicone pressure-sensitive adhesive used in the arrangement, what has been said with respect to the layer composite according to the invention applies mutatis mutandis.

Finally, another object of the present invention is the use of a silicone resin comprising at least one structural unit (R ¹ R ² R ³ SiO _1/2 ), (R ¹ SiO _3/2 ) or (R ¹ R ² SiO _2/2 ), wherein R ¹ , R ² and R ^{3 are} independently an organic group and at least one of R ¹ , R ² or R ^{3 is} an alkenyl group, in silicone-containing release liners for reducing the silicone transfer from the release liner to the PSA of one tape. The reduction of the silicone transfer to the PSA leads to a higher bond strength of the PSA, since the bond strength of this PSA is reduced with increasing silicone transfer (bondage depression).

With regard to further preferred embodiments of the use according to the invention, in particular with regard to the silicone resin used, the statements made mutatis mutandis with regard to the layer composite according to the invention and the use according to the invention apply.

The invention particularly relates to the following embodiments:

• A mindestens einen Releaseliner, umfassend mindestens eine Trägerschicht (TS) sowie mindestens eine Silikonbeschichtung (SB), enthaltend eine additionsvernetzte Silikonhaftklebemasse, welche erhältlich ist durch Umsetzung:
  1. a) mindestens eines Organopolysiloxans mit einem gewichtsmittleren Molekulargewicht M_w von 30.000 bis 2.000.0000 g/mol, welches mindestens eine Diorganosiloxaneinheit und mindestens zwei Silizium-gebundenen Alkenylgruppen enthält, wobei das gewichtsmittlere Molekulargewicht M_w durch Gelpermeationschromatographie in Toluol bei 23 °C und einer Flussrate von 1,0 ml/min mittels eines modifizierten Styrol-Divinylbenzol-Copolymer-Netzwerkes als Säulenmaterial und Polydimethylsiloxan als internem Standard bestimmt wird,
  2. b) mindestens einer zur Vernetzung von Alkenylgruppen enthaltender Organopolysiloxane geeigneten Verbindung, welche mindestens zwei Silizium-gebundene Wasserstoffatome enthält,
  3. c) mindestens eines Silikonharzes mit einem gewichtsmittleren Molekulargewicht M_w von 500 bis 29.999 g/mol, welches mindestens eine Struktureinheit (R¹R²R³SiO_1/2), (R¹SiO_3/2) oder (R¹R²SiO_2/2), worin R¹, R² und R³ unabhängig voneinander für eine organische Gruppe stehen und mindestens einer der Reste R¹, R² oder R³ für eine Alkenylgruppe steht, enthält, wobei das gewichtsmittlere Molekulargewicht M_w durch Gelpermeationschromatographie in Toluol bei 23 °C und einer Flussrate von 1,0 ml/min mittels eines modifizierten Styrol-Divinylbenzol-Copolymer-Netzwerkes als Säulenmaterial und Polydimethylsiloxan als internem Standard bestimmt wird,
  wobei die Umsetzung der Komponenten a), b) und c) durch einen Katalysator beschleunigt wird,
• B mindestens eine weitere Schicht (S1), umfassend eine Polyacrylat-basierte Klebemasse mit bei Raumtemperatur geringem Tack oder eine hitzeaktiviert verklebbare, bei Raumtemperatur nicht oder nur schwach haftklebrige, Klebemasse.

According to a first embodiment, the present invention relates to a layer composite, in particular adhesive tape, containing:

• A at least one release liner comprising at least one support layer (TS) and at least one silicone coating (SB), containing an addition-crosslinked silicone pressure-sensitive adhesive which is obtainable by reaction:
  1. a) at least one organopolysiloxane having a weight-average molecular weight M _{w of} from 30,000 to 2,000,000 g / mol, which contains at least one diorganosiloxane unit and at least two silicon-bonded alkenyl groups, wherein the weight-average molecular weight M _w by gel permeation chromatography in toluene at 23 ° C and a Flow rate of 1.0 ml / min using a modified styrene-divinylbenzene copolymer network as the column material and polydimethylsiloxane as the internal standard,
  2. b) at least one compound suitable for crosslinking alkenyl groups containing organopolysiloxanes, which contains at least two silicon-bonded hydrogen atoms,
  3. c) at least one silicone resin having a weight average molecular weight M _w of 500 to 29999 g / mol, which at least one structural unit (R ¹ R ² R ³ SiO _1/2 ), (R ¹ SiO _3/2 ) or (R ¹ R ² SiO _2/2 ), wherein R ¹ , R ² and R ^{3 are} independently an organic group and at least one of R ¹ , R ² or R ^{3 is} an alkenyl group, wherein the weight average molecular weight M _w by gel permeation chromatography in toluene at 23 ° C and a flow rate of 1.0 ml / min by means of a modified styrene-divinylbenzene copolymer network as column material and polydimethylsiloxane as internal standard,
  wherein the reaction of components a), b) and c) is accelerated by a catalyst,
• B at least one further layer (S1), comprising a polyacrylate-based adhesive having a tack that is low at room temperature or a heat-activated, bondable adhesive which is not or only slightly tacky at room temperature.

According to a second embodiment, the present invention relates to a layer composite according to embodiment 1, characterized in that the molar ratio of silicon-bonded hydrogen atoms of component b) to the silicon-bonded alkenyl groups of component a) is 0.8 to 5.

According to a third embodiment, the present invention relates to a composite layer according to one of embodiments 1 or 2, characterized in that component a) in a total amount of 30 to 70 parts by weight, component b) in a total amount of 7 to 12 parts by weight and the component c) in a total amount of 20 to 60 parts by weight, in each case based on the sum of components a), b) and c) of 100 parts by weight is used.

According to a fourth embodiment, the present invention relates to a composite layer according to one of the preceding embodiments, characterized in that the catalyst is selected from platinum or rhodium catalysts, and preferably in a total amount of 40 to 600 ppm, calculated as platinum or rhodium metal and based on the Sum of components a), b) and c) of 100 parts by weight is used.

According to a fifth embodiment, the present invention relates to a layer composite according to one of the preceding embodiments, characterized in that at least one of the radicals R ¹ , R ² or R ^{3 is} a vinyl group.

According to a sixth embodiment, the present invention relates to a composite layer according to one of the preceding embodiments, characterized in that the silicone resin c) has a weight-average molecular weight M _w of 1,000 to 25,000 g / mol, wherein the weight-average molecular weight M _w by gel permeation chromatography in toluene at 23 ° C and a flow rate of 1.0 ml / min by means of a modified styrene-divinylbenzene copolymer network as column material and polydimethylsiloxane as internal standard.

According to a seventh embodiment, the present invention relates to a layer composite according to one of the preceding embodiments, characterized in that the silicone coating (SB) has a weight ratio of the organopolysiloxane a) to the silicone resin c) of 90:10 to 10:90, in particular 50:20 to 30: 50.

According to an eighth embodiment, the present invention relates to a layer composite according to one of the preceding embodiments, characterized in that the silicone coating (SB) has a peel force of 10 to 80 cN / cm, preferably 10 to 70 cN / cm, in particular 10 to 60 cN / cm, wherein the peel force on a PE carrier plate by a tensile test (machine speed 300 mm / min, peel angle 180 °) is determined.

bestimmt wird.According to a ninth embodiment, the present invention relates to a layer composite according to one of the preceding embodiments, characterized in that the further layer (S1) has a bond strength depression (KKD) of 6 to 20%, preferably 5 to 20%, in particular 4 to 20%, wherein the adhesive depression (KKD) on a steel surface compared to a reference sample by a tensile test (machine speed 300 mm / min, peel angle 180 °) using the following formula $$KKD=\frac{Klebkraf{t}_{Referenz}-Kelbkraf{t}_{PrObe}}{Kelbkraf{t}_{Referenz}}\cdot 100\%$$

is determined.

According to a tenth embodiment, the present invention relates to a layer composite according to one of the preceding embodiments, characterized in that the silicone coating (SB) has a thickness of 0.5 to 200 .mu.m, in particular from 1.0 to 100 .mu.m.

According to an eleventh embodiment, the present invention relates to a composite layer according to one of the preceding embodiments, characterized in that the carrier layer (TS) is coated on both sides with the silicone coating (SB).

According to a twelfth embodiment, the present invention relates to a layer composite according to one of the preceding embodiments, characterized in that the at least one further layer (S1) adjoins the side facing away from the carrier layer (TS) of the silicone coating (SB) of the liner.

According to a thirteenth embodiment, the present invention relates to a layer composite according to one of the preceding embodiments, characterized in that it has a thickness of 100 to 3000 μm.

• A mindestens eine Trägerschicht (TS), sowie
• B mindestens eine Silikonbeschichtung (SB), umfassend mindestens eine additionsvernetzte Silikonhaftklebemasse, welche erhältlich ist durch Umsetzung:
  1. a) mindestens eines Organopolysiloxans mit einem gewichtsmittleren Molekulargewicht M_w von 30.000 bis 2.000.0000 g/mol, welches mindestens eine Diorganosiloxaneinheit und mindestens zwei Silizium-gebundenen Alkenylgruppen enthält, wobei das gewichtsmittlere Molekulargewicht M_w durch Gelpermeationschromatographie in Toluol bei 23 °C und einer Flussrate von 1,0 ml/min mittels eines modifizierten Styrol-Divinylbenzol-Copolymer-Netzwerkes als Säulenmaterial und Polydimethylsiloxan als internem Standard bestimmt wird,
  2. b) mindestens einer zur Vernetzung von Alkenylgruppen enthaltender Organopolysiloxane geeigneten Verbindung, welche mindestens zwei Silizium-gebundene Wasserstoffatome enthält,
  3. c) mindestens eines Silikonharzes mit einem gewichtsmittleren Molekulargewicht M_w von 500 bis 29.999 g/mol, welches mindestens eine Struktureinheit (R¹R²R³SiO_1/2), (R¹SiO_3/2) oder (R¹R²SiO_2/2), worin R¹, R² und R³ unabhängig voneinander für eine organische Gruppe stehen und mindestens einer der Reste R¹, R² oder R³ für eine Alkenylgruppe steht, enthält, wobei das gewichtsmittlere Molekulargewicht M_w durch Gelpermeationschromatographie in Toluol bei 23 °C und einer Flussrate von 1,0 ml/min mittels eines modifizierten Styrol-Divinylbenzol-Copolymer-Netzwerkes als Säulenmaterial und Polydimethylsiloxan als internem Standard bestimmt wird,
  wobei die Umsetzung der Komponenten a), b) und c) durch einen Katalysator beschleunigt wird.

In a fourteenth embodiment, the present invention relates to the use of an assembly as a release liner, the assembly comprising:

• A at least one carrier layer (TS), as well
• B at least one silicone coating (SB) comprising at least one addition-crosslinked silicone pressure-sensitive adhesive which is obtainable by reaction:
  1. a) at least one organopolysiloxane having a weight-average molecular weight M _{w of} from 30,000 to 2,000,000 g / mol, which contains at least one diorganosiloxane unit and at least two silicon-bonded alkenyl groups, wherein the weight-average molecular weight M _w by gel permeation chromatography in toluene at 23 ° C and a Flow rate of 1.0 ml / min using a modified styrene-divinylbenzene copolymer network as the column material and polydimethylsiloxane as the internal standard,
  2. b) at least one compound suitable for crosslinking alkenyl groups containing organopolysiloxanes, which contains at least two silicon-bonded hydrogen atoms,
  3. c) at least one silicone resin having a weight average molecular weight M _w of 500 to 29999 g / mol, which at least one structural unit (R ¹ R ² R ³ SiO _1/2 ), (R ¹ SiO _3/2 ) or (R ¹ R ² SiO _2/2 ), wherein R ¹ , R ² and R ^{3 are} independently an organic group and at least one of R ¹ , R ² or R ^{3 is} an alkenyl group, wherein the weight average molecular weight M _w by gel permeation chromatography in toluene at 23 ° C and a flow rate of 1.0 ml / min by means of a modified styrene-divinylbenzene copolymer network as column material and polydimethylsiloxane as internal standard,
  wherein the reaction of components a), b) and c) is accelerated by a catalyst.

According to a fifteenth embodiment, the present invention relates to the use of a silicone resin comprising at least one structural unit (R ¹ R ² R ³ SiO _1/2 ), (R ¹ SiO _3/2 ) or (R ¹ R ² SiO _2/2 ), wherein R ¹ , R ² and R ^{3 are} independently an organic group and at least one of R ¹ , R ² or R ^{3 is} an alkenyl group, in silicone-containing release liners for reducing the silicone transfer from the release liner to the PSA of one tape.

The present invention will be explained in more detail below with reference to exemplary embodiments.

Examples:

Production of release liners:

The silicone coatings (SB) given below were coated with a laboratory coater (Manual Lab Coater, Euclid Coating Systems, Inc.) to a thickness of 0.5 to 0.7 g / cm ² (0.5 to 0.7 μm) was applied to PET film (50 μm, JBF) and PP film (100 μm, MW). The tab samples thus prepared were hung for 30 seconds at 120 ° C in a convection oven to crosslink the silicone coating (SB). The silicone coat weight was determined by X-ray fluorescence measurement as described below.

Measurement of silicone application:

The coating weight of the silicone coatings (SB) was determined by X-ray fluorescence measurements (Lab-X3000, Oxford). The meter was calibrated with a range of PDMS coatings of known application weight prior to use. All measurements were carried out under helium atmosphere. To determine the coating weight, three samples with a diameter of 3.5 cm were cut out of a cloth sample with the aid of a circular cutter and measured. From the three individual values thus obtained, the mean value for the order weight was calculated.

Lining Removal Force (Liner Removal Force):

The peel force of the release liners was determined using the 2 cm wide, double-sided adhesive tape tesa 7812 (PV24).
Sample preparation: A 30 cm long strip of adhesive tape was stuck with the uncovered during rolling side on the coated with release agent side of the cloth pattern and pressed defined by rolling 10 times with a 150 g steel roll. The flap pattern was then cut into strips along the adhered strips of tape and the samples thus prepared were stored for one week at room temperature prior to measurement. Measurement: The liner from the non-bonded side of the adhesive tape on the release layer was removed and the sample was fixed with the exposed adhesive layer on a PE support plate. The fixation was done so that a short piece of the release coated liner protruded over the panel. The test plate was then, with the extended end of the covering facing down, clamped in the lower jaw of a tensile testing machine (BZ2.5 / TN1S, Zwick). The extended end of the cover material was clamped in the upper jaw and withdrawn at a machine speed of 300 mm / min at an angle of 180 °.

Measurement of adhesive depression (KKD):

Sample preparation: The adhesive depression of the samples was determined with the 2 cm wide, one-sided tape tesa 7475. A 30 cm long strip of the test tape was stripped of liner, adhered to the release-coated side of the flap pattern and painted by hand. Then the test tape strip was pulled by hand at an angle of 180 ° quickly (1 second). This procedure was repeated with the same tape strip four times at each fresh spot of the flap pattern.
Adhesive force measurement: After the last removal of the test strip, it was applied to a ground steel plate (material no. 1.4301, DIN EN10088-2 , Ra = 100-110 nm) and pressed by rolling 10 times in the longitudinal direction defined with a 4 kg steel roll (roll speed: 10 m / min) defined. Immediately after starting, the steel plate was clamped in the lower clamping jaw of the traction machine (BZ2.5 / TN1S, Zwick) and the lower part of the test strip was clamped in the upper jaw by means of an extension. Then, the test tape strip was withdrawn at a speed of 300 mm / min at an angle of 180 ° from the steel plate and detects the necessary force from the force measuring system of the traction engine. From the force value in Newton and the width of the test tape strip in cm, the bond strength in N / cm was then calculated (adhesive force _sample ).

Adhesion measurement was repeated with a test tape strip that was not in contact with the release liner to be tested. From this measurement followed the bond strength reference value (adhesive force _reference ).

The adhesive force depression (KKD) was then calculated using the equation: $$KKD=\frac{Klebkraf{t}_{Referenz}-Kelbkraf{t}_{PrObe}}{Kelbkraf{t}_{Referenz}}\cdot 100\%$$

Gel Permeation Chromatography (GPC):

By means of GPC, the weight-average molecular weights (M _w ) of the organopolysiloxanes and silicone resins used can be determined. The following settings were used for the determination: eluent toluene; Measuring temperature 23 ° C; Precolumn PSS-SDV, 5 μm, 10 ² Å (10 nm), ID 8.0 mm × 50 mm; Separation: Columns PSS-SDV, 5 μm, 10 ² Å (10 nm), and 10 ³ Å (100 nm), and 10 ⁶ Å (105 nm), each having ID 8.0 mm × 300 mm; Sample concentration 3 g / l, flow rate 1.0 ml per minute; Polydimethylsiloxane standards.

Raw materials used:

DC 7651 Dispersion of polydimethylmethylvinylsiloxane gum and resin in xylene and toluene (about 40% by weight silicone solids content) DC 7066 Dispersion of MQ silicone resin in toluene (60% by weight silicone solids content) Syl-Off 7678 Methylhydrogen Siloxane Crosslinker (100% by Weight Silicone Solid Content) Syl-Off 4000 Reactive organoplatinum complex (5,000 ppm platinum metal) dispersed in polysiloxane Syl-Off 7210 Dispersion of Vinyl-Functionalized Polysiloxane in Xylene and Ethylbenzene (60% by Weight Silicone Solid Content) Dehesive 915 Vinyl group-functionalized polydimethylsiloxane (100% by weight silicone solids content) CRA 17 Dispersion of a polydimethylsiloxane with vinyl groups in 1-dodecane (30% by weight silicone solids content) Syl-Off SB 7458 Dispersion of a reactive silioxane polymer in toluene (30% by weight silicone solids content)

Production of Layer Composites According to the Invention with a Silicone Coating (SB) Comprising Addition-Crosslinked Silicone PSAs, Determination of the Release Force (LRF) and Adhesive-Power Depression (KKD):

The amounts of silicone adhesive listed in Table 1 below (DC 7651, Dow Corning), MQ resin (Syl-Off 7210, Dow Corning), SiH crosslinker (Syl-Off 7678, Dow Corning), platinum Catalyst (Syl-Off 4000, Dow Corning) and gasoline were each mixed in a glass jar and homogenized for 30 minutes with the magnetic stirrer. The mixtures were then applied as a thin layer (0.5 to 0.7 g / m ² ) on the substrate (PET film, 50 microns, Fa. JBF) and crosslinked in a drying oven at 120 ° C for 30 seconds.

Subsequently, the release force of the release liners prepared was compared with the test adhesive ACX-plus # 7812 and the adhesive depression (KKD) with the test tape tesa 7475 determined by the methods described above. Table 1: Amounts used and retained release forces (LRF) and adhesive depression (KKD): layer composite Quantity DC 7651 Quantity Syl-Off 7210 Lot Syl-Off 7678 Quantity Syl-Off 4000 Amount of gasoline LRF ACX-plus # 7812, KKD tesa 7475, [G] [G] [G] [G] [G] [CN / cm] [%] #1 17.0 3.5 0.66 0.60 16.7 18 17 # 2 13.3 6.2 0.90 0.60 9.4 26 11 # 3 16.4 12.0 1.54 0.90 15.3 41 7

Despite the use of release liners with non-tacky addition-crosslinked silicone coatings, the layer composites according to the invention have a sufficient release force of at least 10 cN / cm on PSAs having a tack that is low at room temperature. This ensures that the release liner during the production, storage and application not unintentionally from the PSA solves. In addition, due to the reduced silicone transfer from the liner to the test adhesive ACX-plus # 7812, only a slight bond strength depression of at most 17% occurs due to the use of the release liners according to the invention. By increasing the level of MQ resin in the silicone coating, both the release performance of the liner can be increased and the adhesive depression reduced and thus the properties of the liner can be adapted to the respective application.

Production of non-inventive laminates, determination of the separation force and the adhesive depression:

The quantities of DC 7651, DC 7066, Syl-Off 7678 and Syl-Off 4000 and gasoline given in Table 2 below were each mixed in a glass vessel and homogenized for 30 minutes with the magnetic stirrer. The mixtures were then applied as a thin layer (0.5 to 0.7 g / m ² ) on the substrate (PET film, 50 microns, Fa. JBF) and crosslinked in a drying oven at 120 ° C for 30 seconds.

Subsequently, the release force of the release liners prepared was compared with the test adhesive ACX-plus # 7812 and the adhesive depression (KKD) with the test tape tesa 7475 determined by the methods described above. Table 2: Amounts used and separation forces (LRF) and adhesive depression (KKD): layer composite Quantity DC 7651 Quantity DC 7066 Lot Syl-Off 7678 Quantity Syl-Off 4000 Amount of gasoline LRF ACX-plus # 7812, KKD tesa 7475, [G] [G] [G] [G] [G] [CN / cm] [%] # 4 21.9 - 0.37 0.60 23.4 14 25 # 5 15.0 1.25 0.18 0.46 10.8 23 25 # 6 15.1 2.81 0.24 0.52 12.9 41 36 # 7 15.1 3.69 0.36 0.59 14.1 70 32

The non-inventive layer composites # 4 to # 7, in which for the preparation of the silicone coating (SB) MQ resins were used without vinyl groups, although have a sufficient release force of at least 10 cN / cm on PSAs having a low Tack at room temperature, but is due to the higher silicone transfer a stronger bond strength depression than in the inventive layer assemblies # 1 to # 3.

In addition, the release force of the release liners indicated in Table 3 was determined in relation to the test adhesive ACX-plus # 7812. layer composite liner material silicon system base polymer MQ resin Proportion of MQ resin [%] LRF ACX-plus # 7812, [cN / cm] #8th glassine solventless DEHESIVE 915 CRA 17 20 2 # 9 glassine solventless DEHESIVE 915 CRA 17 40 2 # 10 glassine solventless DEHESIVE 915 CRA 17 50 2 # 11 PP contains solvents Syl-Off SB 7458 Syl-Off 7210 30 2 # 12 PP contains solvents Syl-Off SB 7458 Syl-Off 7210 50 8th

The non-inventive layer composites # 8 to # 12, which contain different types of silicone-based polymers, do not have a sufficient release force of at least 10 cN / cm on PSAs having a low tack at room temperature.

QUOTES INCLUDE IN THE DESCRIPTION

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

Cited patent literature

• US Pat. No. 6274213 B1
• DE 60001779 T2 [0008]
• EP 0168713 B1 [0009]
• DE 3820294 C1 [0009]
• US 4725630 A1 [0009]
• DE 3316166 C1 [0010]
• EP 202507 B1 [0012]
• WO 2010/022154 A2 [0012]
• EP 2524954 A1 [0019]
• US 2013/0316076 A1 [0019]
• EP 1652899 A1 [0019]

Cited non-patent literature

• I. Benedek and M.M. Feldstein, page 9-20, 2009; R.G Schmidt, L.R. Badour, G.V. Gordon, Polymer Preprints, 42, 113, 2001, and T. Cosgrove, C. Roberts, Y. Choi, Langmuir, 18, pp. 10075-10079, 2002. [0018]
• DIN EN10088-2 [0081]

Claims (15)

Layer composite, in particular adhesive tape, containing: A at least one release liner comprising at least one support layer (TS) and at least one silicone coating (SB) containing an addition-crosslinked silicone pressure-sensitive adhesive which is obtainable by reacting: a) at least one organopolysiloxane having a weight-average molecular weight M _w of 30,000 to 2,000,000 g / mol, which contains at least one diorganosiloxane unit and at least two silicon-bonded alkenyl groups, wherein the weight-average molecular weight M _w by gel permeation chromatography in toluene at 23 ° C and a flow rate of 1.0 ml / min using a modified styrene Divinylbenzene copolymer network as column material and polydimethylsiloxane as internal standard, b) at least one compound suitable for crosslinking alkenyl-containing organopolysiloxanes containing at least two silicon-bonded hydrogen atoms, c) at least one Si silicone resin having a weight-average molecular weight M _w of 500 to 29999 g / mol, which has at least one structural unit (R ¹ R ² R ³ SiO _1/2 ), (R ¹ SiO _3/2 ) or (R ¹ R ² SiO _2/2 ), wherein R ¹ , R ² and R ^{3 are} independently an organic group and at least one of R ¹ , R ² or R ^{3 is} an alkenyl group, wherein the weight average molecular weight M _w by gel permeation chromatography in toluene at 23 ° C and a flow rate of 1.0 ml / min by means of a modified styrene-divinylbenzene copolymer network as column material and polydimethylsiloxane as internal standard, wherein the reaction of components a), b) and c) is accelerated by a catalyst B at least one further layer (S1), comprising a polyacrylate-based adhesive with tack that is low at room temperature or a heat-activated bondable adhesive which is not or only slightly tacky at room temperature, adhesive. Laminate after Claim 1 , characterized in that the molar ratio of silicon-bonded hydrogen atoms of component b) to the silicon-bonded alkenyl groups of component a) is 0.8 to 5. Layer composite according to one of Claims 1 or 2 , characterized in that component a) in a total amount of 30 to 70 parts by weight, component b) in a total amount of 7 to 12 parts by weight and component c) in a total amount of 20 to 60 parts by weight, in each case based on the sum of Components a), b) and c) of 100 parts by weight is used. Laminate according to one of the preceding claims, characterized in that the catalyst is selected from platinum or rhodium catalysts and preferably in a total amount of 40 to 600 ppm, calculated as platinum or rhodium metal and based on the sum of components a), b) and c) of 100 parts by weight is used. Laminate according to one of the preceding claims, characterized in that at least one of the radicals R ¹ , R ² or R ^{3 is} a vinyl group. Laminate according to one of the preceding claims, characterized in that the silicone resin c) has a weight-average molecular weight M _w of 1,000 to 25,000 g / mol, wherein the weight-average molecular weight M _w by gel permeation chromatography in toluene at 23 ° C and a flow rate of 1, 0 ml / min by means of a modified styrene-divinylbenzene copolymer network as column material and polydimethylsiloxane as internal standard. Laminate according to one of the preceding claims, characterized in that the silicone coating (SB) has a weight ratio of the organopolysiloxane a) to the silicone resin c) from 90: 10 to 10:90, in particular from 50: 20 to 30: 50. Laminate according to one of the preceding claims, characterized in that the silicone coating (SB) has a peel force of 10 to 80 cN / cm, preferably from 10 to 70 cN / cm, in particular from 10 to 60 cN / cm, wherein the peel force on a PE carrier plate by a tensile test (machine speed 300 mm / min, peel angle 180 °) is determined. Laminate according to one of the preceding claims, characterized in that the further layer (S1) has a bond strength depression (KKD) of 6 to 20%, preferably from 5 to 20%, in particular from 4 to 20%, wherein the adhesive depression (KKD) on a steel surface opposite one Reference test by a tensile test (machine speed 300 mm / min, peel angle 180 °) using the following formula $$KKD=\frac{Klebkraf{t}_{Referenz}-Kelbkraf{t}_{PrObe}}{Kelbkraf{t}_{Referenz}}\cdot 100\%$$

is determined. Laminate according to one of the preceding claims, characterized in that the silicone coating (SB) has a thickness of 0.5 to 200 .mu.m, in particular from 1.0 to 100 .mu.m. Laminate according to one of the preceding claims, characterized in that the carrier layer (TS) is coated on both sides with the silicone coating (SB). Laminate according to one of the preceding claims, characterized in that the at least one further layer (S1) adjacent to the carrier layer (TS) side facing away from the silicone coating (SB) of the liner. Laminate according to one of the preceding claims, characterized in that it has a thickness of 100 to 3000 microns. Use of an arrangement as a release liner, the assembly comprising: A at least one carrier layer (TS), and B at least one silicone coating (SB) comprising at least one addition-crosslinked silicone pressure-sensitive adhesive which is obtainable by reaction: a) at least one organopolysiloxane having a weight-average molecular weight M _w from 30,000 to 2,000,000 g / mol, which contains at least one diorganosiloxane unit and at least two silicon-bonded alkenyl groups, wherein the weight-average molecular weight M _w by gel permeation chromatography in toluene at 23 ° C and a flow rate of 1.0 ml / min b) at least one compound suitable for crosslinking alkenyl groups containing organopolysiloxanes, which contains at least two silicon-bonded hydrogen atoms, c) at least one silicone resin having a weight-average molecular weight M _w of 500 to 29999 g / mol, which has at least one structural unit (R ¹ R ² R ³ SiO _1/2 ), (R ¹ SiO _3/2 ) or (R ¹ R ² SiO _2/2 ), wherein R ¹ , R ² and R ^{3 are} independently an organic group and at least one of R ¹ , R ² or R ^{3 is} an alkenyl group, wherein the weight average molecular weight M _w by gel permeation chromatography in toluene at 23 ° C and a flow rate of 1.0 ml / min by means of a modified styrene-divinylbenzene copolymer network as column material and polydimethylsiloxane as internal standard, wherein the reaction of components a), b) and c) is accelerated by a catalyst , Use of a silicone resin comprising at least one structural unit (R ¹ R ² R ³ SiO _1/2 ), (R ¹ SiO _3/2 ) or (R ¹ R ² SiO _2/2 ), wherein R ¹ , R ² and R ³ independently of one another are an organic group and at least one of the radicals R ¹ , R ² or R ^{3 is} an alkenyl group, in silicone-containing release liners for reducing the silicone transfer from the release liner to the PSA of an adhesive tape.