EP3746517A1 - Ruban adhésif à matière adhesive dense et film adhésif à base d'un revêtement de silicone collant - Google Patents

Ruban adhésif à matière adhesive dense et film adhésif à base d'un revêtement de silicone collant

Info

Publication number
EP3746517A1
EP3746517A1 EP19700803.0A EP19700803A EP3746517A1 EP 3746517 A1 EP3746517 A1 EP 3746517A1 EP 19700803 A EP19700803 A EP 19700803A EP 3746517 A1 EP3746517 A1 EP 3746517A1
Authority
EP
European Patent Office
Prior art keywords
weight
silicone
layer
adhesive
mol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19700803.0A
Other languages
German (de)
English (en)
Inventor
Nikolay BELOV
Tobias Winkler
Birgit Sommer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tesa SE
Original Assignee
Tesa SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tesa SE filed Critical Tesa SE
Publication of EP3746517A1 publication Critical patent/EP3746517A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00—Presence of polysiloxane
    • C09J2483/005—Presence of polysiloxane in the release coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/14—Layer or component removable to expose adhesive
    • Y10T428/1452—Polymer derived only from ethylenically unsaturated monomer
    • Y10T428/1457—Silicon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/14—Layer or component removable to expose adhesive
    • Y10T428/1476—Release layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2839—Web or sheet containing structurally defined element or component and having an adhesive outermost layer with release or antistick coating

Definitions

  • the present invention relates to a layer composite, in particular an adhesive tape, containing a) a release liner with at least one carrier layer (TS) and at least one on this T carrier layer (TS) silicone coating applied (SB) of special addition-crosslinked or radically crosslinked Silikonhaftklebemasssen 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.
  • TS carrier layer
  • SB T carrier layer
  • S1 silicone coating applied
  • the present invention relates to the use of an assembly 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 or radically crosslinked Silikonhaftklebemasssen.
  • TS carrier layer
  • SB silicone coating
  • 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.
  • various procedures are known in the prior art.
  • adhesives can be used which have different degrees of adhesion and can therefore be detached from one another even after direct contact (see US Pat. No. 6,274,213 B1).
  • 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.
  • separating material also referred to as separating material
  • liners are also used to cover labels.
  • Adhesive tapes are also possible in which not two liners but a single double-sided separating equipped liner is worked. 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 thus u.a. as an aid for the storage of the adhesive tape or for further processing by 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.
  • the adhesive force of the PSA must not be significantly affected for later use.
  • the stability of the release coating on the liner, ie the adhesiveness, over long periods of time is 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.
  • 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.
  • the material of adhesive separating layer is preferably selected according to the prior art from the group consisting of silicones, fluorinated silicones, silicone copolymers, waxes, carbamates, fluoropolymers and polyolefins and mixtures of two or more of said substances.
  • 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.
  • 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.
  • 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.
  • an alkenylated polydiorganosiloxane especially alkenyl-terminated and vinyl-terminated linear polymers, and vinyl-terminated branched silicones
  • a polyorganohydrogensiloxane crosslinking agent especially alkenyl-terminated and vinyl-terminated linear polymers, and vinyl-terminated branched silicones
  • platinum or platinum compounds such as, for example, the Karstedt catalyst [a Pt (0) complex compound] and rhodium catalysts have become established.
  • photoactive catalysts known as photoinitiators
  • UV-curable cationically crosslinking siloxanes based on epoxide and / or vinyl ethers
  • UV-curable free-radical crosslinking siloxanes such as acrylate-modified siloxanes.
  • 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.
  • Organopolysiloxanmassen which crosslink by heating or irradiation. Called masses, as described for example in DE 600 01 779 T2, which crosslink by addition reaction, namely by temperature treatment of a mixture of an organopolysiloxane with hydrogen atoms bonded directly to the silicon atoms and an organopolysiloxane with directly bonded to the silicon atoms vinyl groups in the presence a hydrosilylation catalyst.
  • photopolymerizable organopolysiloxane compositions can be used. Mention may be made, for example, of masses which are synthesized directly by the reaction between organopolysiloxanes which are substituted by (meth) acrylate groups
  • 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 compositions are described for example in US 4,725,630 A1.
  • cationic-mechanism-curable organopolysiloxane compositions are materials having, for example, propenyloxysiloxane end groups.
  • 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 described in EP 2 025 07 B1 or WO 2010/022154 A2, and carbamates can furthermore be used as the release layer.
  • MQ resins are Silicone compounds containing structural units of the formulas (R3S1O1 / 2) (M unit) and (S1O4 / 2), (Q unit).
  • R here stands for an organic group, for example a substituted or unsubstituted monovalent hydrocarbon group.
  • the release value of the liner in addition to the silicone coating and the proportion of MQ resin in this coating depends on the pressure-sensitive adhesive used of the adhesive tape, especially with polyacrylate-based adhesives with tack-free or heat-activated adhesives bondable at room temperature, are not or only slightly tacky at room temperature , Adhesives even with the addition of very high amounts of MQ resin only very weak separation forces of less than 3 cN / cm achieved. These weak separation forces can cause the liner to unintentionally detach during production, storage or use.
  • 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 3 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.
  • 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:
  • 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, b) at least one alkenyl group-containing crosslinking agent
  • Organopolysiloxanes suitable compound containing at least two silicon-bonded hydrogen atoms
  • 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.
  • 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) comprising a free-radically crosslinked silicone pressure-sensitive adhesive which is obtainable by reaction:
  • 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.
  • S1 further layer
  • 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 previously described addition- or free-radically crosslinked silicone PSAs.
  • 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, due to their adhesive properties, this silicone coating is not used in pre-adhesive release liners but as a pressure-sensitive adhesive for bonding protective films for displays, window images and symbols.
  • Adhesives are known as "PSAs" which allow a permanent bond with the primer under relatively low pressure.
  • 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 ⁇ m, 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.
  • 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, 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 the adhesives for various applications.
  • 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.
  • 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 ), Polyesters - 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).
  • POPP oriented polypropylene
  • COC cyclic olefin copolymers
  • 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.
  • organic or inorganic coatings or layers This can be done by conventional methods such as painting, printing, evaporation, sputtering, co-extrusion or lamination.
  • oxides or nitrides of silicon and aluminum By way of example, but not limited to oxides or nitrides of silicon and aluminum, indium tin oxide (ITO) or sol-gel coatings.
  • the release liner A contains at least one carrier layer (TS).
  • TS carrier layer
  • 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).
  • 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 are particularly preferably used according to the invention as carrier layer (TS).
  • the carrier layer (TS) is a multilayer film structure (film laminate), for example in the form A-B-A or A-B-C, wherein A, B and C correspond to the above film materials.
  • film laminate film laminate
  • A, B and C correspond to the above film materials.
  • Polymer-coated papers or nonwovens can also be used.
  • the release liner A comprises at least one silicone coating (SB) which contains at least one addition- or free-radically crosslinked silicone PSA of polyorganosiloxanes and silicone resins. It has been found that even with a low coating thickness of the adhesive on the support, these silicone pressure-sensitive adhesives 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 3 cN / cm are achieved. Due to the very stable Si-O-Si bond, these silicone PSAs also have a high resistance to environmental influences, such as UV light and high temperatures, so that the layer composites of the invention have excellent storage stability.
  • the silicone coating (SB) comprises an addition-crosslinked silicone pressure-sensitive adhesive which is obtainable by reaction:
  • reaction of components a), b) and optionally c) is accelerated by a catalyst.
  • a specific molar ratio of the abovementioned 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.
  • the use of a molar ratio of silicon-bonded hydrogen atoms of component b) to the silicon-bonded alkenyl groups of component a) from 0.5 to 7 has proved to be advantageous in view of the required for the release force of at least 3 cN / cm cohesion ,
  • a silicone resin (component c)) can be added when the addition-crosslinked silicone PSA is prepared.
  • These resins are polydisperse mixtures of differently substituted siloxanes of various molecular weights.
  • the radicals on the silicon atom can be saturated with organic groups or other siloxane compounds, resulting in branched silicone resins.
  • the siloxane units are abbreviated by the symbols M, D, T and Q.
  • M stands for a RsSiO 1/2 unit, D for R 2 Si0 2/2 unit, T for a RSi0 3/2 unit, and Q represents a Si0 4/2 unit.
  • Each R is independently a substituted or unsubstituted monovalent hydrocarbon group.
  • component c) are preferably used silicone resins, which are composed of MQ, MTQ, TQ, MT or MDT units.
  • Particularly preferred as component c) MQ resins of the formula (R 1 3 Si0i / 2 ) x (Si04 / 2) y are used, wherein R 1 is in each case an organic group, in particular a substituted or unsubstituted monovalent hydrocarbon group.
  • the ratio of M units to Q units is preferably in the range of 0.5 to 1.2.
  • component a), b) and optionally c) are used in specific total amounts.
  • Component a) is therefore preferably used in a total amount of 20 to 60 parts by weight, component b) in a total amount of 3 to 10 parts by weight and component c) in a total amount of 30 to 75 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) and b) takes place by means of a hydrosilylation reaction between the alkenyl-functionalized organopolysiloxanes and the corresponding SiH-functionalized organopolysiloxanes.
  • This hydrosilylation reaction is accelerated by the use of catalysts according to the invention.
  • platinum or rhodium catalysts are used as catalysts.
  • the platinum or rhodium catalyst preferably in a total amount of 50 to 1, 000 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.
  • the silicone coating (SB) comprises a free-radically crosslinked silicone pressure-sensitive adhesive which is obtainable by reaction:
  • 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 optionally at least one hydroxyl group,
  • reaction product of the at least one organopolysiloxane a) and of the at least one silicone resin b) as the starting compound and then to further crosslink it by adding the radical generator.
  • 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 hydroxyl groups as component a).
  • the silicone resins used as component b) correspond to the silicone resins described in connection with the first preferred embodiment. Also in connection with this embodiment, it has proven to be advantageous in terms of increasing the release value, when used as silicone resin, the previously described as preferred MQ silicone resins.
  • the components a) and b) are used for producing the silicone pressure-sensitive adhesive in specific total amounts.
  • the component a) is therefore preferably used in a total amount of 25 to 55 parts by weight and the component b) in a total amount of 45 to 75 parts by weight, based in each case on the sum of the components a) and b) of 100 parts by weight.
  • components a) and b) are compounded with at least one free radical generator.
  • at least one free radical generator Particularly preferred are in this Related Peroxo initiators, in particular benzoyl peroxide (BPO), used.
  • BPO benzoyl peroxide
  • the radical generator In order to achieve the separation values of at least 3 cN / cm, it is preferred to use the radical generator in a certain amount range. It has therefore proved to be advantageous to use the at least one free-radical initiator, in particular benzoyl peroxide, in a total amount of 5 to 15 parts by weight, based on the sum of components a) and b) of 100 parts by weight.
  • the total quantities of the radical former given above permit the preparation of silicone PSAs which have sufficient cohesion to achieve release values of at least 3 cN / cm on PSAs having a low tack at room temperature.
  • the free-radical crosslinking takes place at elevated temperatures, in particular at 170 to 190 ° C.
  • silicone resins in particular the MQ resins mentioned above, 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- or free-radically crosslinked silicone PSA.
  • the data on the average molecular weight M w in this document relate to the determination by gel permeation chromatography.
  • silicone resins having the abovementioned molecular weight allows a particularly good adaptation of the required release value even in conjunction with pressure-sensitive adhesives which have only a slight tack at room temperature.
  • the release values of the Relaseliners A achieved with the silicone coating (SB) can be adapted to the respective requirements by varying the proportion of the silicone resin during the preparation of the silicone pressure-sensitive adhesive. By increasing the proportion of silicone resin in this case the release value of the release liner A achieved can also be increased. In this way, a simple adaptation of the Relaseliners A to the required separation value for each application is possible.
  • the silicone coating (SB) has a weight ratio of the organopolysiloxane a) (component a) of the first and second embodiments) to the silicone resin (component c) of the first and component b) of the second embodiment) of 1: 1 to 1: 3, in particular from 2: 3 to 1: 2.
  • the silicone pressure-sensitive adhesives of the first and second embodiments of the present invention may also contain other additives.
  • these additives are chosen so that the release values of the Do not worsen the coating.
  • additives can be used for example:
  • Fillers such as silica, glass (ground or in the form of spheres), aluminas and zinc oxides.
  • 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.
  • the silicone coating (SB) of the release liner A 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 describing the detachment behavior is the release force or withdrawal force.
  • separation forces of at least 3 cN / cm are required. Lower separation forces may result in unwanted detachment of the liner during manufacture, storage and handling.
  • the release force On the other hand, however, to ensure easy detachment of the release liner from the PSA, the release force must not be too high.
  • the silicone coating (SB) has a peel force of 3.0 to 200 cN / m, preferably 4.0 to 190 cN / m, more preferably 5.0 to 180 cN / m the peel force is determined according to the measuring method defined herein.
  • 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.
  • the silicone coating (SB) comprises a silicone PSA.
  • the thin application of this silicone pressure-sensitive adhesive causes the silicone coating (SB) of the release liner A to be non-sticky.
  • the silicone coating (SB) therefore has a thickness of 0.5 to 200 ⁇ m, in particular from 1.0 to 100 ⁇ m.
  • 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.
  • random copolymers starting from unfunctionalized a, b-unsaturated acrylic acid or acrylates can be used. Preference is given to a, b-unsaturated carboxylic acids and their derivatives of the general structure
  • 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 carbon 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.
  • vinyl monomers, vinyl ethers, vinyl ethers, vinyl halides, vinylidene halides, as well as vinyl compounds containing aromatic cycles or heterocycles in the a position can optionally be used.
  • monomers which can be used according to the invention for the optionally usable vinyl monomers include vinyl acetate, vinylformamide, vinylpyridine, ethylvinyl ether, 2-ethylhexyl vinyl ether, butylvinyl ether, vinyl chloride, vinylidene chloride, acrylonitrile, styrene and ⁇ -methylstyrene.
  • 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.
  • 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.
  • Further 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 rubber. Rubbers (XI IR), acrylate rubbers (ACM), ethylene vinyl acetate copolymers (EVA) and polyurethanes and / or blends thereof.
  • SBR random copolymerized styrene-butadiene rubbers
  • BR butadiene rubbers
  • IR synthetic polyisoprenes
  • NR butyl rubbers
  • halogenated butyl rubber
  • 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), ie the pressure-sensitive adhesive, is applied on the side of the silicone coating (SB) of the liner facing away from the carrier layer (TS).
  • the silicone coating (SB) of the Releaselers A thus covers the PSA (S1) in this embodiment. Therefore, before using the adhesive tape, the release liner A must be removed.
  • 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.
  • S2 further acrylate-based pressure-sensitive adhesive
  • Suitable acrylate-based adhesives are, for example, the abovementioned polyacrylate-based adhesives.
  • 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.
  • the pressure-sensitive adhesive (layer (S1)) which here corresponds to the adhesive tape, is applied between two flexible release liners A before 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.
  • a carrierless transfer adhesive tape a very accurate in positioning and metering bonding is possible.
  • 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.
  • 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.
  • the carrier layer (TS) is therefore coated on both sides with the previously mentioned silicone coating (SB).
  • SB silicone coating
  • the layer composite according to the invention preferably has a thickness of 100 to 3,000 mhh. 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.
  • Another object of the present invention is the use of an assembly as a release liner, the arrangement comprising:
  • B at least one silicone coating (SB), comprising at least one addition-crosslinked or free-radically crosslinked silicone PSA,
  • addition-crosslinked silicone pressure-sensitive adhesive is obtainable by reaction: a) at least one organopolysiloxane having a weight average
  • Organopolysiloxanes suitable compound containing at least two silicon-bonded hydrogen atoms
  • 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 optionally at least one hydroxyl group,
  • reaction of components a) and b) is initiated by a free radical generator.
  • the 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) comprising an addition-crosslinked silicone pressure-sensitive adhesive which is obtainable by reacting: a) at least one organopolysiloxane having a weight-average
  • Organopolysiloxanes suitable compound containing at least two silicon-bonded hydrogen atoms
  • 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.
  • the 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 0.5 to 7.
  • the invention relates to a layer composite according to one of embodiments 1 or 2, characterized in that component a) in a total amount of 20 to 60 parts by weight, component b) in a total amount of 3 to 10 parts by weight and component c ) in a total amount of 30 to 75 parts by weight, in each case based on the sum of components a), b) and c) of 100 parts by weight is used.
  • the invention relates to a layer composite 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 50 to 1, 000 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 catalyst is selected from platinum or rhodium catalysts, and preferably in a total amount of 50 to 1, 000 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 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) comprising a free-radically crosslinked silicone pressure-sensitive adhesive which is obtainable by reaction:
  • 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.
  • the invention relates to a layer composite according to embodiment 5, characterized in that component a) in a total amount of 25 to 55 parts by weight and component b) in a total amount of 45 to 75 parts by weight, in each case based on the sum of the components a) and b) of 100 parts by weight is used.
  • the invention relates to a layer composite according to embodiment 5 or 6, characterized in that the radical generator is selected from peroxo initiators, in particular from benzoyl peroxide, and preferably in a total amount of 5 to 15 parts by weight, based on the sum of the components a ) and b) of 100 parts by weight.
  • the radical generator is selected from peroxo initiators, in particular from benzoyl peroxide, and preferably in a total amount of 5 to 15 parts by weight, based on the sum of the components a ) and b) of 100 parts by weight.
  • the invention relates to a layer composite according to one of the preceding embodiments, characterized in that the silicone resin has a weight-average molecular weight M w of from 1,000 to 25,000 g / mol.
  • the 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 of 1: 1 to 1: 3, in particular 2: 3 to 1: 2 has.
  • the 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 3.0 to 200 cN / m, preferably 4.0 to 190 cN / m, in particular 5 , 0 to 180 cN / m, the peel force being determined according to the measuring method defined herein.
  • the 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 pm, in particular from 1, 0 to 100 pm.
  • the invention relates to a layer composite according to one of the preceding embodiments, characterized in that the carrier layer (TS) is coated on both sides with the silicone coating (SB).
  • TS carrier layer
  • SB silicone coating
  • the invention relates to a layer composite according to one of the preceding embodiments, characterized in that the at least one further layer (S1) on the carrier layer (TS) facing away from the silicone coating (SB) of the liner is applied.
  • the invention relates to a layer composite according to one of the preceding embodiments, characterized in that it has a thickness of 100 to 3000 pm.
  • the invention relates to the use of an assembly as a release liner, the assembly comprising:
  • B at least one silicone coating (SB) comprising at least one addition-crosslinked or free-radically crosslinked silicone PSA, wherein the addition-crosslinked silicone PSA is obtainable by reaction:
  • R 1 is an organic group, in particular a substituted or unsubstituted monovalent hydrocarbon group, wherein the reaction of components a) and b) is initiated by a radical generator.
  • the peel force of the liner was determined using the respective test adhesive tapes.
  • a 30 cm long strip of the adhesive tape was glued with the uncovered during rolling side on the provided with the silicone coating (SB) side of the liner and pressed defined by rolling 10 times with a 150 g steel roll. The sample was then cut into strips along the adhered strips of tape and the samples so prepared stored for one week at room temperature prior to measurement. Measurement:
  • the liner on the non-bonded side of the adhesive tape on the liner to be examined 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 liner to be examined protruded beyond the plate.
  • the test plate was then, with the extended end of the liner to be examined facing down, clamped in the lower jaw of a tensile tester (BZ2.5 / TN1 S, Zwick). The extended end of the liner to be tested was clamped in the upper jaw and withdrawn at a machine speed of 300 mm / min at an angle of 180 °.
  • 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 pm, 10 2 ⁇ (10 nm), ID 8.0 mm x 50 mm; Separation: Columns PSS-SDV, 5 pm, 10 2 ⁇ (10 nm), and 10 3 ⁇ (100 nm), and 10 6 ⁇ (105 nm), each having ID 8.0 mm ⁇ 300 mm; Sample concentration 3 g / l, flow rate 1, 0 ml per minute; Polydimethylsiloxane standards.
  • the resulting release liners were adhered with two adhesive tapes having acrylate-based PSAs having room temperature low tack. Strips of the test tapes tesa ACX-plus # 7812 and tesa ACX-plus # 6812 were used for this purpose. Subsequently, the peel force was determined by the above method.
  • the layer composites of the invention have a sufficient release force of at least 3 cN / cm. This ensures that the release liner does not unintentionally detach from the PSA during manufacture, storage and use. By increasing the proportion of MQ resin in the silicone coating, the release performance of the linear can be increased and thus adapted to the particular application.
  • the layer composites of the invention have a sufficient release force of at least 3 cN / cm. This ensures that the release liner does not unintentionally detach from the PSA during manufacture, storage and use. By increasing the proportion of MQ resin, the separation performance of the liner can be increased and thus adapted to the particular application.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un composite à couches, en particulier un ruban adhésif, qui comporte a) un film antiadhésif formé d'une couche de support et d'un revêtement de silicone non collant formé de matières de silicone adhésives spéciales réticulées par addition ou de manière radicalaire, et b) au moins une couche de matières adhésives à base de polyacrylate ayant un pouvoir faiblement collant à la température ambiante ou comportant des matières adhésives liées thermiquement et ayant un pouvoir non collant ou seulement faiblement collant à la température ambiante. En outre, la présente invention concerne l'utilisation d'un ensemble, servant de film antiadhésif, qui contient une couche de support et le revêtement de silicone susmentionné formé de matières de silicone adhésives spéciales réticulées par addition ou de manière radicalaire.
EP19700803.0A 2018-01-29 2019-01-15 Ruban adhésif à matière adhesive dense et film adhésif à base d'un revêtement de silicone collant Pending EP3746517A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102018201328 2018-01-29
PCT/EP2019/050982 WO2019145194A1 (fr) 2018-01-29 2019-01-15 Ruban adhésif à matière adhesive dense et film adhésif à base d'un revêtement de silicone collant

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EP3746517A1 true EP3746517A1 (fr) 2020-12-09

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EP (1) EP3746517A1 (fr)
CN (1) CN111630127B (fr)
WO (1) WO2019145194A1 (fr)

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KR20210039412A (ko) * 2018-08-01 2021-04-09 신에쓰 가가꾸 고교 가부시끼가이샤 실리콘 점착제 조성물 및 이것을 사용한 점착 테이프 또는 점착 필름
DE102021205464B4 (de) * 2021-05-28 2023-05-11 Tesa Se Klebeband mit unvernetzter Silikon-Haftklebmasse und Verwendung

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CN111630127A (zh) 2020-09-04
CN111630127B (zh) 2023-01-10
WO2019145194A1 (fr) 2019-08-01
US20210032508A1 (en) 2021-02-04

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