SELF-ADHESIVE ARTICLE SUPPORTED ON FOAM

专利摘要:
The present invention relates to a self-adhesive article comprising a foam-type support layer or the like and an adhesive layer obtained by crosslinking an adhesive composition. The present invention also relates to a mixture of at least two polymers that can be used for the manufacture of the self-adhesive article and an adhesive composition comprising said mixture of at least two polymers according to the invention.
公开号:FR3015984A1
申请号:FR1363674
申请日:2013-12-30
公开日:2015-07-03
发明作者:David Goubard；Olivier Laferte；Herveline Troadec
申请人:Bostik SA；
IPC主号:

专利说明:

[0001] TECHNICAL FIELD The present invention relates to a self-adhesive article comprising a foam-type carrier layer or the like and an adhesive layer obtained by crosslinking an adhesive composition. The present invention also relates to a mixture of at least two polymers that can be used for the manufacture of the self-adhesive article and an adhesive composition comprising said mixture of at least two polymers according to the invention.
[0002] STATE OF THE ART Pressure-sensitive adhesives (also called self-adhesive adhesives or, in English, "Pressure Sensitive Adhesives" or PSA) are substances giving the support layer, also called a substrate which is coated with a sticky power, or tackiness, immediate at room temperature (often referred to as "tack"), which allows its instant adhesion to a substrate under the effect of a light and brief pressure. PSAs are widely used for the manufacture of labels or self-adhesive films which are affixed to articles for the purpose of presenting information (such as bar code, name, price) and / or for decorative purposes, which it is during final or temporary collages. PSAs are also used for the manufacture of self-adhesive tapes of various uses. For example, in addition to the transparent adhesive tape widely used in everyday life, there is the shaping and assembly of cardboard packaging; surface protection for painting work; the fixing and maintenance of various elements such as panels, bricks, protruding objects, in the construction of buildings or buildings; the fixing and maintenance of flat or profile-specific metal or plastic or glass parts, such as electrical cables, plastic films, windows, sheets, inscriptions, logos, parts of seats, dashboards plastic or textile walls, conduits or pipes for the circulation of fluids, especially in the transport industry; the gluing of the carpets by double-sided adhesive tapes. For the manufacture of self-adhesive labels and / or tapes, PSAs are often applied by continuous coating processes over the entire surface of a large (possibly printable) backing layer, in a quantity (usually expressed in g / m2) hereinafter referred to as "grammage". The support layer is made of paper or film or sheet or plate of a single or multi-layered polymeric material. The adhesive layer which covers the support layer may itself be covered with a protective release layer (often called the "release liner"), for example consisting of a silicone film. The multilayer system obtained is generally packaged by winding into large coils typically up to 2 m wide and 1 m in diameter, which can be stored and transported. These multilayer systems can be subsequently converted into end-user-applicable self-adhesive labels, by means of processing methods that include printing the desired informative and / or decorative elements on the printable face of the support layer, and then cutting to the shape and dimensions desired. The protective release layer can be easily removed without modification of the adhesive layer which remains attached to the support layer. After separation of its protective release layer, the label is applied to the article to be coated either manually or using labellers on automated packaging lines. These multilayer systems can also be converted into self-adhesive tapes by cutting and packaging rolls of width and length determined. The PSAs make it possible, because of their tackiness ("tack" in English) raised to ambient temperature, to rapidly grip or attach the self-adhesive label and / or tape to the substrate (or article) to be coated (for example , in the case of labels, on bottles or, in the case of ribbons, on packaging cartons to be shaped), suitable for obtaining significant industrial production rates. There is a field of application of the PSAs for which it is desirable that the adhesive strength of the labels and / or ribbons on the substrate is also maintained when the bonding adhesive seal is exposed (likewise, therefore, that the article coated with the label and / or ribbon) at a temperature likely to vary over a wide range. Examples include the placing of labels on certain bodies of automobiles (or other vehicles) located near the engine, or on packaging designed to receive during their conditioning a hot liquid, or on items (such as tires) which are hot labeled, out of the production lines. We can also mention the implementation of self-adhesive tapes for the assembly of parts for which a good thermal resistance is necessary as in the case, for example, of the interior trim of aircraft or other vehicles. It may also be useful to assemble surfaces that are not strictly parallel, or to stick a self-adhesive article on a surface that is not smooth, for example a surface with irregularities. A so-called "conformable" support layer makes it possible to erase the surface irregularities but also to bond two surfaces that are not strictly parallel to one another, for example by absorbing the differences in thickness, the deformations originating from the laying of the self-adhesive article or the use of the adhesive seal thus produced, the curved surfaces or the complex surfaces requiring a seal as adherent as possible, supporting the vibrations. The formed joint can also serve as a total or partial or temporary barrier to fluids more or less abundant and frequent. Self-adhesive articles including this type of support called "conformable" can be used in many areas of application, such as: - automotive: for the application of logos, lettering, interior soundproofing, dressing interior, the collages in the cockpit; - construction: for sound and heat insulation, window assembly; - Industry: for mounting (assembly-fixing), for the fixing of photopolymer plates for example, used by printers; - furniture: for fixing mirrors for example; the electronics, for fixing or superimposing the different constituent elements of the control or interface elements.
[0003] International application WO 2011/082094 discloses a self-adhesive article comprising a support layer in the form of a foam and a silyl-modified polyacrylate-based adhesive composition. The polymers used in this document are polymers in the solvent phase. This document does not describe the adhesive composition used for the manufacture of the self-adhesive article according to the invention. US Pat. No. 6,231,962 describes a self-adhesive article comprising a support layer in the form of a foam and an adhesive composition chosen from olefins, silicone glues, glues based on natural rubber, glues based on synthetic rubber and other glues based on elastomers. The adhesive compositions described herein exhibit high temperature strength problems and therefore do not exhibit satisfactory shear strength. This document does not describe the adhesive composition used for the manufacture of the self-adhesive article according to the invention.
[0004] The application WO 2009/106699 describes a self-adhesive article comprising an adhesive layer obtained from a polyurethane. EP 2336208 discloses a self-adhesive article comprising an adhesive layer obtained from a polyether. These two applications describe self-adhesive articles using rigid supports of polyethylene terephthalate (PET) type. These two applications do not disclose self-adhesive articles comprising a carrier as claimed, or the particular blend of at least two polymers as claimed. The conformable supports are stretchable and generally have a low density. Therefore, this type of support is deformable and can break easily. In particular, a foam has a cellular structure, for example a structure filled with air with thin membranes, which can therefore easily break. All adhesive compositions that allow the manufacture of a self-adhesive article comprising a PET type support do not allow the manufacture of a self-adhesive article comprising a conformable support and having properties satisfactory for the intended applications, such as high shear strength and high glue joint failure temperature. SUMMARY OF THE INVENTION A first object of the present invention is a self-adhesive article comprising a backing layer coated with an adhesive layer, said backing layer having an elongation at break ranging from 50 to 1200% and an apparent density ranging from from 25 to 1200 kg / m 3, said adhesive layer is obtained by crosslinking an adhesive composition comprising: a) at least one polymer of formula (Ib) or at least one polymer of formula (IIbis) or a mixture of at least two polymers chosen from polyurethanes and polyethers having one, two or three mono-, di- or tri-alkoxysilane end groups, said mixture comprising at least one polymer corresponding to one of the formulas (Ibis), (IIbis) , (IIIbis) and (IVbis), it being understood that: - when a polymer having two or three monoalkoxysilane end groups is present, said mixture comprises up to 15% by weight, relative to the total weight of the mel angel, said polymer, - when a polymer having a terminal group of mono-, di- or tri-alkoxysilane type is present, said mixture comprises up to 15% by weight, relative to the total weight of the mixture, of said polymer, b) at least one tackifying resin, and c) at least one crosslinking catalyst; wherein the polymer of formula (Ibis) is a polyurethane or a polyether comprising two or three hydrolyzable trialkoxysilane end groups having a silyl function quantity of 0.480 meq / g of polymer and corresponding to the following formula: ) the polymer of formula (IIbis) is a polyurethane or a polyether comprising two or three hydrolyzable dialkoxysilane end groups, having a silyl function quantity less than or equal to 0.480 meq / g of polymer and corresponding to the following formula: (IIbis ) the polymer of formula (IIIa) is a polyurethane or a polyether comprising two or three hydrolyzable monoalkoxysilane end groups having a silyl function quantity of 0.480 meq / g of polymer and corresponding to the following formula: is) the polymer of formula (IVbis) is a polyurethane or a polyether comprising a group ter hydrolysable mono-, di- and / or trialkoxysilane type having a silyl functional amount of less than or equal to 0.480 meq / g of polymer and corresponding to the following formula: (IVa) in formulas (Ibis), (IIa) (IIIbis) and (IVbis) above, B represents one of the two formulas below: ## STR1 ## where: ## STR2 ## OR 2 - where D and T represent a linear, branched, cyclic, alicyclic or aromatic, saturated or unsaturated hydrocarbon-based radical containing 2 to 66 carbon atoms, optionally comprising one or more heteroatoms, - R 1 represents a divalent hydrocarbon radical comprising of 5 to 15 carbon atoms which may be aromatic or aliphatic, linear, branched or cyclic, - R3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, - R2 represents a divalent linear or branched alkylene radical comprising from 2 to 4 carbon atoms, - R4 and R5, which may be identical or different, each represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, R4 possibly being engaged in a ring; R6 represents a hydrocarbon radical comprising from 1 to 22 carbon atoms, linear, branched; cyclic, alicyclic or aromatic, saturated or unsaturated, optionally containing one or more heteroatoms, - R7 represents a hydrogen atom, a phenyl radical or a linear, branched or cyclic alkyl radical comprising from 1 to 10 carbon atoms, - n is an integer such that the average molar mass of the polyether block of formula 40 R21 ranges from 300 g / mol to 40000 g / mol, m is an integer such that the average molar mass of the polymer is 600 g / mol at 100000 g / mol, - p is an integer equal to 0, 1 or 2, - f is an integer equal to 2 or 3. According to one embodiment, the mixture of at least two polymers comprises: least one respondent polymer t to one of the formulas (Ibis), (IIbis), (IIIbis) or (IVbis) described above, and - at least one polymer corresponding to one of the formulas (I), (II), (III ) or (IV) below: (I) ## STR2 ## wherein: ## STR1 ## wherein: when a polymer of formula (IIIa) and / or (III) is present, said mixture comprises up to 15% by weight of polymer of formula (IIIa) and / or (III), relative to the total weight of the mixture of polymers, - when a polymer of formula (IIIbis) and / or (III) is present, said mixture comprises up to 15% by weight of polymer of formula (IIIa) and / or (III), with respect to total weight of the polymer blend; in formulas (I), (II), (III), and (IV) above, - B represents one of the two formulas below: OR.2: - / [OR '- D or T - - OR2: n - {OR: 27n - 30 where D and T represent a linear, branched, cyclic, alicyclic or aromatic hydrocarbon radical containing 2 to 66 carbon atoms, saturated or unsaturated, optionally comprising one or more heteroatoms R 'represents a divalent hydrocarbon radical comprising from 5 to 15 carbon atoms which may be aromatic or aliphatic, linear, branched or cyclic, - R3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, R 6 ORI - R 2 represents a linear or branched divalent alkylene radical comprising from 2 to 4 carbon atoms, - R 4 and R 5, which are identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, R 4 possibly being to be engaged in a cycle, - R6 represents a hydrocarbon radical comprising 1 to 22 carbon atoms, linear, branched, cyclic, alicyclic or aromatic, saturated or unsaturated, optionally comprising one or more heteroatoms, n is an integer such that the average molar mass of the polyether block of formula PRI - is from 300 g / mol to 40000 g / mol, - m is an integer such that the average molar mass of the polymer ranges from 600 g / mol to 100000 g / mol, - p is an integer equal to 0 , 1 or 2, - f is an integer equal to 2 or 3.
[0005] Preferably, the support layer has a Young's modulus less than or equal to 300 MPa. According to one embodiment of the invention, the support layer is in the form of a foam.
[0006] According to one embodiment of the invention, the support layer is in the form of one or more polymeric layers. Preferably, the adhesive composition comprises: from 20% to 85% by weight, relative to the total weight of the adhesive composition, of at least one polymer or a mixture of polymers as defined in the invention; 80% by weight, relative to the total weight of the adhesive composition, of at least one tackifying resin, of 0.01 to 3% by weight, relative to the total weight of the adhesive composition, of at least one catalyst crosslinking.
[0007] Preferably, the tackifying resin has a number-average molar mass ranging from 100 Da to 5 kDa and is chosen from: (i) resins obtainable by polymerization of terpene hydrocarbons and phenols, in the presence of Friedel-Crafts, (ii) resins obtainable by polymerization of alpha-methyl styrene, (iii) rosins of natural origin or modified, (iv) resins obtained by hydrogenation, polymerization or copolymerization of mixtures of unsaturated aliphatic hydrocarbons having about 5, 9 or 10 carbon atoms from petroleum cuts, (v) terpene resins generally resulting from the polymerization of terpenic hydrocarbons in the presence of Friedel-Crafts catalysts, (vi) copolymers based on natural terpenes, and (vii) acrylic resins. Another subject of the present invention relates to a polymer mixture that can be used in the adhesive composition as defined above, said mixture comprising at least two polymers belonging to 2 different groups chosen from the groups P1, P2, P3 and P4, said mixture comprising at least one polymer corresponding to one of the formulas (Ibis), (IIbis), (IIIa) and (IVa) and having a silyl function quantity of less than or equal to 0.480 meq / g of polymer, being understood that: when a polymer of the P3 group is present, the mixture comprises up to 15% by weight, relative to the total weight of the mixture, of at least one polyurethane or at least one polyether of the P3 group; when a polymer of the P4 group is present, the mixture comprises up to 15% by weight, relative to the total weight of the polymer mixture, of at least one polyurethane or at least one polyether of the P4 group; P1 being a group consisting of polyurethanes and polyethers having two or three terminal groups of trialkoxysilane type; P2 being a group consisting of polyurethanes and polyethers having two or three end groups of dialkoxysilane type P3 being a group consisting of polyurethanes and polyethers having two or three end groups of monoalkoxysilane type; P4 being a group consisting of polyurethanes and polyethers having a terminal group of mono-, di- or tri-alkoxysilane type.
[0008] According to one embodiment of the invention, the polymer mixture comprises: up to 95% by weight, relative to the total weight of the mixture, of at least one polymer corresponding to the formula (Ibis), and at least one polymer corresponding to formula (IIa) as described in claim 1.
[0009] According to one embodiment of the invention, the polymer mixture comprises: from 10 to 85% by weight of at least one polymer corresponding to the formula (Ibis), and from 15 to 90% by weight of at least one polymer corresponding to the formula (IIbis), relative to the total weight of the mixture, of at least two polymers. According to one embodiment of the invention, the polymer mixture comprises: up to 15% by weight, relative to the total weight of the mixture, of at least one polymer corresponding to formula (IIIa), and at least one polymer corresponding to formula (IIa) as described in claim 1. According to one embodiment of the invention, the polymer mixture comprises: from 5 to 95% by weight of at least one polymer corresponding to the formula (Ibis), and from 5 to 15% by weight of at least one polymer corresponding to formula (IIIa), relative to the total weight of said mixture. According to one embodiment of the invention, the polymer mixture comprises: at least one polymer corresponding to one of the formulas (Ibis), (IIbis), (IIIa) or (IVa) described above, and at least one polymer corresponding to one of the formulas (I), (II), (III) or (IV) described above.
[0010] The present invention also relates to an adhesive composition that can be used for the manufacture of the self-adhesive article according to the invention, comprising: - the polymer mixture according to the invention, - at least one tackifying resin, and - at minus a crosslinking catalyst. Preferably, the adhesive composition according to the invention relates to: - from 20 to 85% by weight, relative to the total weight of the adhesive composition, of said polymer mixture, - from 15 to 80% by weight, relative to the total weight of the adhesive composition, of at least one tackifying resin, of 0.01 to 3% by weight, relative to the total weight of the adhesive composition, of at least one crosslinking catalyst.
[0011] The advantages of the present invention are as follows: the self-adhesive article according to the invention has excellent properties of adhesiveness and tack; the self-adhesive article according to the invention has a high shear strength; the self-adhesive article according to the invention is such that the adhesive bond resulting from its attachment to a substrate retains the required cohesion over a wide temperature range; the self-adhesive article according to the invention can be applied to many surfaces, such as concrete, plastic or metallic materials, automobile bodies and painted materials; the support layer present in the self-adhesive article according to the invention makes it possible to adhere the self-adhesive article to all types of surface, in particular the surfaces having irregularities; the self-adhesive article according to the invention makes it possible to erase surface irregularities, the lack of parallelism of two surfaces to be bonded; the self-adhesive article according to the invention can be applied to complex, curved surfaces; the self-adhesive article according to the invention makes it possible to ensure good thermal and sound insulation thanks to the properties of the support layer, in particular thanks to the support layer in the form of a foam.
[0012] DETAILED DESCRIPTION OF THE INVENTION Self Adhesive Article The present invention relates to a self-adhesive article comprising a support layer coated with an adhesive layer, said support layer having an elongation at break ranging from 50 to 1200% and an apparent density ranging from from 25 to 1200 kg / m 3, said adhesive layer is obtained by crosslinking an adhesive composition comprising: a) at least one polymer of formula (Ib) or at least one polymer of formula (IIbis) or a mixture of at least two polymers chosen from polyurethanes and polyethers having one, two or three mono-, di- or tri-alkoxysilane end groups, said mixture comprising at least one polymer corresponding to one of the formulas (Ibis), (IIbis) , (IIIbis) and (IVbis), it being understood that: - when a polymer having two or three monoalkoxysilane end groups is present, said mixture comprises up to 15% by weight, relative to the weight in the total mixture of said polymer, when a polymer having a mono-, di- or tri-alkoxysilane end group is present, said mixture comprises up to 15% by weight, relative to the total weight of the mixture, said polymer, b) at least one tackifying resin, and c) at least one crosslinking catalyst.
[0013] The polymer of formula (Ibis) is a polyurethane or a polyether comprising two or three hydrolyzable trialkoxysilane end groups having a silyl function quantity of 0.480 meq / g of polymer and corresponding to the following formula: The polymer of formula (IIbis) is a polyurethane or a polyether comprising two or three hydrolyzable dialkoxysilane end groups having a silyl function quantity of 0.480 meq / g of polymer and corresponding to the following formula: (IIbis) The polymer of formula (IIIbis) is a polyurethane or a polyether comprising two or three hydrolyzable monoalkoxysilane end groups having a silyl function quantity of 0.480 meq / g of polymer and corresponding to the following formula: ) The polymer of formula (IVbis) is a polyurethane or a polyether comprising a termina group 1 of hydrolyzable mono-, di- and / or trialkoxysilane type, having a silyl function quantity of less than or equal to 0.480 meq / g of polymer and corresponding to the following formula: (IVbis) in formulas (Ibis), (IIbis) , (IIIbis) and (IVbis) above, - B represents one of the two formulas below: fOR = Tù - [OR2in - D OR: or T - [OR: [OR - where D and T represent a hydrocarbon radical comprising 2 to 66 carbon atoms, linear, branched, cyclic, alicyclic or aromatic, saturated or unsaturated, optionally comprising one or more heteroatoms, - R1 represents a divalent hydrocarbon radical comprising from 5 to 15 carbon atoms which may be aromatic or aliphatic, linear, branched or cyclic, - R3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, - R2 represents a linear or branched divalent alkylene radical comprising from 2 to 4 carbon atoms, - R4 and R5, identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, R4 possibly being engaged in a ring, - R6 represents a hydrocarbon radical comprising from 1 to 22 carbon atoms, linear, branched, cyclic, alicyclic or aromatic, saturated or unsaturated, optionally containing one or more heteroatoms, - R7 represents a hydrogen atom, a phenyl radical or a linear, branched or cyclic alkyl radical comprising from 1 to 10 carbon atoms, - n is a number integer such that the average molar mass of the polyether block of formula 40 R21 ranges from 300 g / mole to 40000 g / mole, m is an integer such that the average molar mass of the polymer ranges from 600 g / mole to 100,000 g. / mole, - p is an integer equal to 0, 1 or 2, - f is an integer equal to 2 or 3.
[0014] In the case where the adhesive composition comprises at least two polymers of different formulas, each parameter defined above B, R2, R3, R4, R5, R6, n, m, p and f can be chosen independently in each of the formulas, that is to say that they are identical or different in each of the polymers.
[0015] By way of example, B may have the following structure (in this example f will then be equal to 2): CH2 - [OR2] '- CH2 - [OR2] - or the following structure (in this example f will then be equal to to 3): CH - [(DP, 2_11 - H3 CC - CH: n - CH2 - [OR2 - By way of example, R6 may be a methyl radical.R1 is preferably selected from one of the radicals following divalents whose formulas below show the 2 free valences: a) the divalent radical derived from isophorone: b) c) CH 2 OR - (CH 2) 6- (or hexamethylene radical). d) e) Support layer The support layer has an elongation at break of from 50% to 1200%, preferably from 100% to 1000%, more preferably from 200% to 700%, and an apparent density of from 25% to 100%. at 1200 kg / m 3, preferably from 25 to 1000 kg / m 3, more preferably from 25 to 900 kg / m 3, more preferably from 32 to 800 kg / m 3, more preferably from 50 to 600 kg / m 3, more preferably from 60 to 400 kg / m3. The elongation at break can be measured according to ISO 1926 at 23 ° C, in the direction of length or width. Preferably, the elongation is measured lengthwise. The apparent density can be measured according to the ISO 845 standard. Fillers can be added during the manufacture of the support layer in order to obtain a support layer having a bulk density greater than or equal to 1000 kg / m 3. One skilled in the art knows how to increase the apparent density of a material while maintaining the desired elongation properties at break. Preferably, the support layer has a Young's modulus less than or equal to 300 MPa, preferably ranging from 2 to 100 MPa, more preferably ranging from 5 to 50 MPa, more particularly ranging from 5 to 35 MPa. Preferably, the support layer has a thickness of from 0.01 to 50 mm, more preferably from 0.01 to 20.00 mm, preferably from 0.05 to 10.00 mm, more preferably from 0.05 to 1.00 mm, advantageously from 0.10 to 0.75 mm. Preferably, the support layer is in the form of a foam. For the purposes of the present invention, a foam is a polymeric material comprising cells filled with gas. The foam may be closed cell or open cell, the foam structure depending on the foaming process.
[0016] Preferably, the outer surface of the support layer in contact with the adhesive composition is closed, i.e. the cells present on the surface in contact with the adhesive composition are all closed cells. Preferably, the entire support layer is a closed cell foam. According to a first embodiment, the support layer is made of a material chosen from: polyolefins, such as polyethylene, including high density polyethylene, low density polyethylene, linear low density polyethylene and linear ultra low density polyethylene; polypropylene and polybutylenes, - polystyrene, - natural or synthetic rubber, - vinyl copolymers, such as plasticized or unplasticized polyvinyl chloride, and polyvinyl acetate, - olefinic copolymers, such as ethylene / methacrylate copolymers, ethylene / vinyl acetate copolymers, acrylonitrile / butadiene / styrene copolymers, and ethylene / propylene copolymers, acrylic polymers and copolymers, polyurethanes, polyethers, polyesters, and mixtures thereof. Preferably, the support layer comprises a mixture of elastomeric and / or plastic materials, such as polypropylene / polyethylene, polyurethane / polyolefins, polyurethane / polycarbonate, polyurethane / polyester. Preferably, the support layer is in the form of one or more layers of polymeric foam, preferably in the form of a polyolefin foam. Among the foams that can be used to form the support layer of the self-adhesive article according to the invention, mention may be made of: the TL SRZ® 1200.8 foam (available from Alveo) having a length elongation at break of 408.8 ± 53% at 23 ° C, a bulk density of about 96.62 kg / m3, a thickness of about 0.67 mm and a Young's modulus of 11.2 ± 0.5 MPa; the foam TEE® 0400.2 (available from Alveo) having a length elongation at break of 362.5 ± 85% at 23 ° C., an apparent density of approximately 293 kg / m3, a thickness of approximately 0, 17 mm and a Young's modulus of 18.3 ± 0.6 MPa; TMA SRZ® 0500.8 foam (available from Alveo) having a break length elongation of 717.5 ± 117% at 23 ° C, a bulk density of about 196.31 kg / m3, a thickness of about 0.72 mm and a Young's modulus of 6.7 ± 0.8 MPa; and TL SRZ® 0700.8 foam (available from Alveo) having a length elongation at break of 635.4 ± 76% at 23 ° C, a bulk density of about 148.15 kg / m 3, a thickness of approximately 0.76 mm and a Young's modulus of 12.9 ± 0.8 MPa.
[0017] According to one embodiment, the support layer is a syntactic foam. Syntactic foam technology is described, for example, in Klempner et al., Polymeric foam technology, second edition Hanser (2004), page 479.
[0018] The adhesive composition is applied to the support for the manufacture of a self-adhesive article. The support layer may be covered on one of its two faces, the rear face which is not coated with the adhesive layer, by a non-adherent protective layer, for example by a silicone film. In this way, the self-adhesive article can be wound on itself and unrolled without problems thanks to the absence of adhesion of the adhesive layer on the silicone face. The support layer according to the invention may also be treated by any type of surface treatment, such as a corona treatment in particular to increase the wettability. Adhesive Composition The adhesive layer is obtained by crosslinking the adhesive composition.
[0019] As indicated above, the support layer may also be obtained by expansion of a matrix comprising the adhesive composition according to the invention, for obtaining a so-called syntactic foam.
[0020] The adhesive composition used in the self-adhesive article of the invention comprises: a) a polymer or a mixture of polymers as described below for the self-adhesive article, b) at least one tackifying resin, c) at least one crosslinking catalyst. According to one embodiment, the adhesive composition used in the self-adhesive article of the invention consists essentially of: a) a polymer or a mixture of polymers as described below for the self-adhesive article, b) at least one tackifying resin, and c) at least one crosslinking catalyst.
[0021] The polymer may be a polymer of formula (Ib) or a polymer of formula (IIa). The mixture of at least two polymers present in the adhesive composition used for the manufacture of the self-adhesive article comprises at least two different polymers chosen from polyurethanes and polyethers having one, two or three mono- type end groups, di- or tri-alkoxysilane, said mixture comprising at least one polymer of formula (Ibis), (IIa), (IIIa) or (IVb is). When when a polymer having two or three monoalkoxysilane end groups is present in the mixture of at least two polymers, said mixture comprises up to 15% by weight of said polymer, relative to the total weight of the mixture. When a polymer having a mono-, di- or tri-alkoxysilane end group is present in the mixture of at least two polymers, said mixture comprises up to 15% by weight of said polymer, relative to the total weight of the polymer. mixed. The quantity of silyl functions is given by the suppliers or can be determined by analysis (NMR) or it can be determined according to the content (% by weight) and the nature (chemical structure and molar mass) of the aminosilanes used. for the synthesis of polymers (Ibis), (IIa), (IIIa) and (IVa).
[0022] The polymers corresponding to one of the formulas (Ibis), (IIa), (IIIa) and (IVa) can be obtained according to a process as described in the experimental part of the present invention with a possible total or partial substitution of the polyethers. diols by polyethers monols in polymers (IVbis).
[0023] Preferably, the polymer or the mixture of polymers used for the manufacture of the self-adhesive article according to the invention has a number-average molar mass ranging from 600 to 100000 g / mol, more preferably from 1000 to 50000 g / mol. mole, more preferably from 2000 to 20000 g / mole.
[0024] The number-average molar mass (Mn) expressed in g / mol is calculated from the amount of silyl functions (E (s)) expressed in meq / g and the functionality F of the polymer. The functionality F is equal to 2 or 3 for the polymers of formulas (Ibis), (IIbis) and (IIIbis). The functionality F is equal to 1 for the polymers of formula (IVbis). The number-average molar mass is calculated as follows: F × 1000 Mn = E (s) Among the polymers according to the invention corresponding to the formula (Ia), mention may be made of the Ex19 and Ex20 polymers described in the experimental part. . Among the polymers according to the invention corresponding to formula (IIbis), mention may be made of the polymer Ex8 and the polymer Ex6-18 described in the experimental part. Among the polymers according to the invention corresponding to formula (IIIa), mention may be made of the polymer Ex15 described in the experimental part.
[0025] Preferably, all the polymers of the polymer mixture that can be used for the manufacture of the self-adhesive article according to the invention have a silyl function quantity of less than or equal to 0.480 meq / g of polymer, preferably less than or equal to 0.450 meq / g.
[0026] According to one embodiment, the mixture of at least two polymers comprises at least two polymers chosen from polymers of formula (Ibis), (IIbis), (IIIbis) and (IVbis).
[0027] According to another embodiment, the mixture of at least two polymers comprises at least one polyurethane or polyether having one, two or three end groups of mono-, di- or tri-alkoxysilane type, different from polyurethanes and polyethers of formula (Ibis), (IIbis), (IIIbis) or (IVbis). Preferably, the polyurethane or polyether having one, two or three mono-, di- or tri-alkoxysilane end groups other than polyurethanes and polyethers of formula (Ia), (IIa), (IIIa) or (IVa) is chosen from: a polyurethane or a polyether comprising two or three hydrolyzable dialkoxysilane end groups and corresponding to formula (II): a polyurethane or a polyether comprising two or three hydrolyzable trialkoxysilane end groups and having the formula (I): (I) - a polyurethane or a polyether comprising two or three terminal groups of hydrolysable monoalkoxysilane type and corresponding to formula (III): FT LL - a polyurethane or a polyether comprising a terminal group of mono-, di-type; and / or hydrolysable trialkoxysilane corresponding to formula (IV): ## STR2 ## ## STR2 ## ## STR2 ## In formulas (I) ), (II), (III), and (IV) c above, - B represents one of the two formulas below: OR LOR21n. where D and T represent a linear, branched, cyclic, alicyclic or aromatic, saturated or unsaturated hydrocarbon-based radical comprising 2 to 66 carbon atoms, optionally comprising one or more heteroatoms, such as oxygen, sulfur, nitrogen or halogen, R1 represents a divalent hydrocarbon radical comprising from 5 to 15 carbon atoms which may be aromatic or aliphatic, linear, branched or cyclic, - R3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, - R2 represents a divalent linear or branched alkylene radical comprising 2 to 4 carbon atoms, and preferably 3 carbon atoms, - R4 and R5, identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, R4 possibly being engaged in a cycle, - R6 represents a hydrocarbon radical comprising from 1 to 22 carbon atoms, linear, branched cyclic, alicyclic or aromatic, saturated or unsaturated, optionally comprising one or more heteroatoms, such as oxygen, sulfur, nitrogen or halogen, n is an integer such that the average molar mass of the polyether block of formula -PRI.- is from 300 g / mol to 40000 g / mol, - m is an integer such that the average molar mass of the polymer ranges from 600 g / mol to 100000 g / mol, - p is an integer equal to 0, 1 or 2 f is an integer equal to 2 or 3. The polymers corresponding to one of formulas (I), (II), (III) and (IV) can be obtained according to a process described in applications EP 2 336 208 and WO 2009/106699 with possible total substitution or partial substitution of polyether diols by polyether monols in the polymers of formula (IV).
[0028] According to one embodiment, the mixture of at least two polymers used for the manufacture of the self-adhesive article comprises: from 5 to 95% by weight, preferably from 10 to 90% by weight, of at least a polymer chosen from polymers of formula (Ibis), (IIa), (IIIa) or (IVa); and from 5 to 95% by weight, preferably from 10 to 90% by weight, of at least one other silylated polymer, preferably chosen from polymers of formula (I), (II), (III) or ( IV); relative to the total weight of the polymer blend. According to one embodiment, the tackifying resin has a number-average molar mass ranging from 100 Da to 5 kDa, preferably from 500 Da to 4 kDa. According to one embodiment, the tackifying resin is chosen from: (i) resins capable of being obtained by polymerization of terpene hydrocarbons and phenols, in the presence of Friedel-Crafts catalysts, (ii) resins capable of obtained by polymerization of alpha-methyl styrene, possibly by reaction with phenols, (iii) naturally occurring or modified rosins, such as rosin extracted from pine gum, wood rosin extracted from roots of and their hydrogenated derivatives, dimerized, polymerized or esterified with monoalcohols or polyols such as glycerol, (iv) resins obtained by hydrogenation, polymerization or copolymerization (with an aromatic hydrocarbon) of unsaturated aliphatic hydrocarbon mixtures having about 5 , 9 or 10 carbon atoms from petroleum cuts, (v) terpene resins generally resulting from the polymerization of hydro terpene carbides, such as mono-terpene (or pinene) in the presence of Friedel-Crafts catalysts, (vi) natural terpenes-based copolymers, for example styrene / terpene, alpha-methyl styrene / terpene and vinyl toluene / terpene, and (vii) acrylic resins. Such resins are commercially available and among those of type (i), (ii) and (iii) defined above, mention may be made of the following products: resins of type (i): Dertophenee 1510 available from DRT having a molar mass in number Mn of about 870 Da; Dertophene H150 available from the same company of molar mass Mn equal to about 630 Da; Sylvareze TP 95 available from the company Arizona Chemical having a number average molar mass Mn of about 1200 Da; resins of type (ii): Norsolene W100 available from Cray Valley, which is obtained by polymerization of alpha-methyl styrene without the action of phenols, with a number average molecular weight of 900 Da; Sylvareze 510 which is also available from the company Arizona Chemical with a number average molar mass Mn of about 1740 Da, the method of obtaining also comprises the addition of phenols; type (iii) resins: Sylvalitee RE 100 which is an ester of rosin and pentaerythritol available from Arizona Chemical and having a number average molar mass Mn of about 1700 Da. The number-average molar masses of the resins can be measured according to methods that are well known to those skilled in the art, for example by steric exclusion chromatography using a polystyrene type standard. According to one preferred variant, a tackifying resin is chosen from among those of type (i) or (ii).
[0029] According to another preferred variant, a resin of type (iii) and preferably a rosin ester is used as tackifying resin. The crosslinking catalyst used in the adhesive composition according to the invention may be any catalyst known to those skilled in the art for the silanol condensation. Examples of such catalysts are organic titanium derivatives such as titanium acetyl acetonate (commercially available under the name TYZORe AA75 from DuPont), aluminum such as aluminum chelate (commercially available under the name denomination K-KATe 5218 from King Industries), amines such as 1,8-diazobicyclo (5.4.0) undecene-7 or DBU. Preferably, the adhesive composition comprises less than 5% by weight of solvent, preferably less than 3% by weight, more preferably less than 1% by weight, ideally less than 0.5% by weight, relative to the total weight of the adhesive composition before crosslinking the silylated functional groups.
[0030] As an option, the composition according to the invention may also include, in combination with the polymer or the mixture of polymers described above, thermoplastic polymers often used in the preparation of HMPSA, such as Ethylene Vinyl Acetate (EVA). or styrenic block copolymers.
[0031] The adhesive composition may further comprise up to 3% by weight of a hydrolyzable alkoxysilane derivative, as a desiccant, and preferably a trimethoxysilane derivative. Such an agent advantageously prolongs the shelf life of the composition according to the invention during storage and transport, prior to its use. Mention may be made, for example, of gamma-methacryloxypropyltrimethoxysilane available under the trade name Silqueste A-174 from the company US Momentive Performance Materials Inc. The composition according to the invention may also include a plasticizer such as a phthalate or a benzoate, an oil paraffinic and naphthenic (such as Primole 352 from ESSO) or a wax of a polyethylene homopolymer (such as PA-Ce 617 from Honeywell), or a wax of a copolymer of polyethylene and vinyl acetate, or still pigments, dyes or fillers. Finally, an amount of 0.1 to 2% by weight of one or more stabilizers (or antioxidants) is preferably included in the composition according to the invention. These compounds are introduced to protect the composition from degradation resulting from a reaction with oxygen that is likely to be formed by the action of heat or light. These compounds may include primary antioxidants that trap free radicals and are especially substituted phenols such as CIBA Irganoxe 1076. The primary antioxidants may be used alone or in combination with other secondary antioxidants or UV stabilizers.
[0032] According to one embodiment, the adhesive composition comprises: a) from 20 to 85%, preferably from 40 to 65%, by weight of the polymer or mixture of polymers as described above, b) from 15% to 80% by weight; %, preferably from 25 to 70%, preferably from 35 to 60%, by weight of tackifying resin (s), and c) from 0.01 to 3% by weight of crosslinking catalyst (s), relative to the total weight of the adhesive composition. According to one embodiment, the adhesive composition consists essentially of: a) from 20 to 85%, preferably from 40 to 65%, by weight of the polymer or of the polymer mixture as described above, b) by 15% at 80%, preferably 25 to 70%, preferably 35 to 60%, by weight of tackifying resin (s), and c) 0.01 to 3% by weight of catalyst (s) of crosslinking, based on the total weight of the adhesive composition.
[0033] The heat-curable adhesive composition used in the manufacture of the self-adhesive article according to the invention may be prepared by a process which comprises: a step of mixing in the absence of air, preferably under an inert atmosphere, of the polymer or of the mixture of polymers with the tackifying resins, at a temperature of between 30 and 170 ° C., preferably between 100 and 170 ° C., and then a step of cooling said mixture at a temperature ranging from 30 to 90 ° C. C, and preferably about 70 ° C, then - a step of incorporating into the mixture obtained in the previous step of the crosslinking catalyst and, if necessary, the desiccant and other optional components. According to one embodiment of the invention, the adhesive layer, after at least partial crosslinking of the silylated functional groups, has a sticking power ("loop tack" in English) of at least 0.75 N / cm, preferably at least 0.80 N / cm, more preferably at least 0.90 N / cm, more preferably at least 1 N / cm, preferably without residues, measured on a glass plate. According to one embodiment of the invention, the adhesive layer as described above, may have a tackiness of at least 5 N / cm, preferably at least 6 N / cm, more preferably at least 7 N / cm, ideally at least 8 N / cm. According to one embodiment, the adhesive composition according to the invention may have a tackiness ranging from 0.75 to 8 N / cm, preferably from 0.80 to 7 N / cm, more preferably from 0.90 to 6 N / cm, ideally 1 to 5 N / cm. Said tack can be obtained immediately after the bonding of the article on a surface and / or a few hours after the bonding of the article on a surface and / or a few days after the bonding of the article on a surface. For the purposes of the present invention, the term "self-adhesive article" includes any article that can be adhered to a surface only by the action of pressure with the hand or equipment, without the use of additional adhesives or adhesives . The term "self-adhesive article" also includes the term "pressure sensitive adhesive article" or "PSA article" ("Pressure Sensitive Adhesive Article" in English). These articles are intended to be applied to a surface to be glued in order to approximate, maintain, fix, or simply to immobilize, to expose shapes, logos, images or information. These items can be used in many fields, such as the medical field, clothing, packaging, automotive or construction, thanks in particular to excellent thermal and sound insulation properties. They can be shaped according to their final application, for example in the form of ribbons, such as ribbons for industrial use, DIY ribbons or for use on building sites, single or double-sided ribbons, or in the form of labels, bandages, dressings, patches or graphic films. The self-adhesive article according to the invention can be applied to surfaces having irregularities, on curved or complex surfaces or on deformable or deformable surfaces. The article according to the invention can make it possible to glue two surfaces that are not strictly plane. In particular, the surface to be bonded may have properties comparable to the properties of the support layer. The surface to be bonded can be chosen from plastics, concrete, steel, glass, cardboard, skin, textiles, foam. The surface can be painted or unpainted.
[0034] According to one embodiment of the invention, the self-adhesive article further comprises a protective release layer ("release liner" in English). According to one embodiment, said release layer is applied to the adhesive layer, after crosslinking of the adhesive composition.
[0035] According to a first embodiment, the self-adhesive article according to the invention may be prepared by a process comprising the following steps: (a) conditioning the adhesive composition as defined above at a temperature ranging from 20 to 160 ° VS ; then (b) coating the adhesive composition obtained in step (a) with a carrier surface; then (c) crosslinking the coated adhesive composition by heating the coated carrier surface to a temperature of from 20 to 200 ° C; optionally (d) backing up or transferring the crosslinked adhesive layer onto a support layer or onto a non-stick protective film.
[0036] By "carrier surface" within the meaning of the present invention, it is necessary to understand either a belt conveyor covered with a release layer, a release liner or a support layer. In the case where the carrier surface is not a support layer, the method for obtaining the self-adhesive article according to the invention comprises the step (d) of transfer of the crosslinked adhesive layer on a support layer. In the case where the carrier surface is a support layer, the process for obtaining the self-adhesive article according to the invention may comprise the step (d) of bonding the adhesive layer on a non-stick protective film .
[0037] According to one embodiment, the method of manufacturing the self-adhesive article according to the invention further comprises a step (e) of coating a second layer of adhesive composition on the support layer followed by a step ( f) crosslinking the adhesive composition coated in step (e) by heating at a temperature ranging from 20 to 200 ° C. According to this embodiment, a double-sided self-adhesive article is obtained. The coating step (b) can be carried out by means of known coating devices, such as for example a lip or curtain-type nozzle, or else a roller. It uses an adhesive composition weight ranging from 3 to 2000 g / m 2, preferably from 5 to 500 g / m 2, more preferably from 10 to 250 g / m 2.
[0038] Preferably, the coating is continuous or substantially continuous. According to one embodiment, the coated adhesive composition is further subjected, during step (c) to a treatment in a humid atmosphere characterized by its moisture level. Preferably, the humid atmosphere is an atmosphere in which from 2 to 100% of the molecules are water molecules, preferably from 4 to 50%, more preferably from 5 to 10% of the molecules are water molecules. . The moisture content is expressed as a percentage of water per unit volume, which is the number of water molecules divided by the total number of molecules in a unit volume. Due to the linear nature of this scale, the moisture content is easily measured and controlled using, for example, P.I.D ("Proportional-Integral-Derivative") type monitors. The percentage by weight can be calculated by multiplying the percentage of the number of water molecules with respect to the total number of molecules by a factor of 0.622. General information on moisture content in various environments is described by W. Wagner et al., In "International Steam Tables - Properties of Water and Steam Based on Industrial Formulation IAPWS-IF97". The time required for the crosslinking of step (c) can vary within wide limits, for example between 1 second and 10 minutes, depending on the weight of adhesive composition deposited on the carrier surface, the heating temperature, and moisture. This step of thermal crosslinking has the effect of creating - between the polymer chains of the polymer or the mixture of polymers as described above and under the action of moisture - siloxane type bonds which lead to the formation of a three-dimensional polymeric network. The thus crosslinked adhesive composition is a pressure-sensitive adhesive which provides the coated carrier layer with the desired adhesive strength and tack. Preferably, the coating is carried out uniformly on the support layer or on the non-stick protective layer, but the coating may also be adapted to the desired shape of the final self-adhesive article. According to one embodiment, the coating by the adhesive composition is performed on at least a portion of the two faces of the support layer. If both sides of the support layer are coated, the adhesive composition may be the same or different on both sides, and the basis weight may be the same or different on both sides. According to one embodiment of the invention, the self-adhesive article comprises an adhesive layer on at least a part of one or both sides of the support layer, said adhesive layer or layers being optionally coated with a layer non-stick protector. According to one embodiment, the self-adhesive article comprises two non-stick protective layers on each of the two adhesive layers. In this case, the two protective layers may be identical or different materials and / or they may have the same or different thickness.
[0039] The self-adhesive article according to the invention may be used in a gluing method comprising the following steps: a) removing the release liner, when such a film is present; b) apply the article on a surface; and c) applying pressure to said article. According to one embodiment in which the self-adhesive article is a double-sided article, the gluing method further comprises a step in which either a second surface is applied to the glued article on the first surface or the glued article on the first surface is applied on a second surface.
[0040] Mixture of at Least Two Polymers The present invention also relates to a mixture of at least two polymers, capable of being incorporated in the adhesive composition used for the manufacture of the self-adhesive article according to the invention. The mixture of at least two polymers according to the invention comprises at least two polymers belonging to 2 different groups chosen from the groups P1, P2, P3 and P4, it being understood that at least one of the two polymers of the mixture corresponds to one of the formulas (Ibis), (IIa), (IIIa) or (IVa).
[0041] As indicated above for the self-adhesive article, the polymers of formulas (Ibis), (IIbis), (IIIbis) and (IVbis) according to the invention have a silyl function quantity of less than or equal to 0.480 meq / g of polymer, preferably less than or equal to 0.450 meq / g of polymer.
[0042] Preferably, all the polymers of the mixture of at least two polymers have a silyl function amount of less than or equal to 0.480 meq / g of polymer, preferably less than or equal to 0.450 meq / g of polymer. Preferably, the mixture of polymers according to the invention has an average molar mass ranging from 600 to 100000 g / mol, more preferably from 1000 to 50000 g / mol, more preferably from 2000 to 20000 g / mol. The groups are defined as follows: Group P1: polyurethane or polyether having two or three terminal groups of trialkoxysilane type; examples: polymer corresponding to formula (Ibis) or (I), o Group P2: polyurethane or polyether having two or three terminal groups of dialkoxysilane type; Example: polymer corresponding to formula (IIbis) or (II), o Group P3: polyurethane or polyether having two or three terminal groups of monoalkoxysilane type; example: polymer corresponding to formula (IIIa) or (III), o Group P4: polyurethane or polyether having a terminal group of mono-, di- or tri-alkoxysilane type; example: polymer corresponding to formula (IVa) or (IV).
[0043] When a polymer belonging to the group P1 is present in the mixture of at least two polymers according to the invention, said mixture comprises up to 99% by weight, relative to the total weight of said mixture, of one or more polymers of Pi group.
[0044] When a polymer belonging to the group P2 is present in the mixture of at least two polymers according to the invention, said mixture comprises up to 99% by weight, relative to the total weight of said mixture, of one or more polymers of the P2 group.
[0045] When a polymer belonging to the group P3 is present in the mixture of at least two polymers according to the invention, said mixture comprises up to 15% by weight, relative to the total weight of said mixture, of one or more polymers of the group P3.
[0046] When a polymer belonging to the group P4 is present in the mixture of at least two polymers according to the invention, said mixture comprises up to 15% by weight, relative to the total weight of said mixture, of one or more polymers of the group P4.
[0047] Preferably, the mixture of at least two polymers essentially comprises polymers of groups P1, P2, P3 and P4. Preferably, the mixture of at least two polymers according to the invention does not comprise polymers other than those belonging to the groups P1, P2, P3 and P4.
[0048] According to a first embodiment of the invention, the mixture of at least two polymers comprises: up to 95% by weight, relative to the total weight of the polymer mixture, of at least one polymer belonging to the group P 1 and at least one polymer belonging to the group P2.
[0049] According to this embodiment, preferably the mixture of at least two polymers comprises: from 10 to 95% by weight, preferably from 20 to 90% by weight, more preferably from 25% to 85% by weight, preferably from 30 to 75% by weight, of at least one polymer belonging to the group P1, and from 5 to 90% by weight, preferably from 10 to 80% by weight, more preferably from 15 to 75% by weight, preferably from 25 to 70% by weight, of at least one polymer belonging to the P2 group, relative to the total weight of the mixture of at least two polymers. According to this embodiment of the invention, preferably the mixture of at least two polymers consists essentially of: up to 95% by weight, relative to the total weight of the polymer mixture, of at least one polymer belonging to to the group P1, and - at least one polymer belonging to the group P2. According to this embodiment, preferably, the mixture of at least two polymers consists essentially of: from 10 to 95% by weight, preferably from 20 to 90% by weight, more preferably from 25% to 85% by weight; preferably from 30 to 75% by weight of at least one polymer belonging to the group P1 and from 5 to 90% by weight, preferably from 10 to 80% by weight, more preferably from 15 to 75% by weight, by weight, advantageously from 25 to 70% by weight, of at least one polymer belonging to the P2 group, relative to the total weight of the mixture of at least two polymers. According to a second embodiment of the invention, the mixture of at least two polymers comprises: up to 95% by weight, relative to the total weight of the polymer mixture, of at least one polymer belonging to the group Pl and up to 15% by weight, based on the total weight of the polymer mixture, of at least one polymer belonging to the P3 group. According to this embodiment, preferably the mixture of at least two polymers comprises: from 10 to 95% by weight, preferably from 20 to 90% by weight, more preferably from 25% to 85% by weight, preferably from 30 to 75% by weight, of at least one polymer belonging to the group P1, and from 5 to 15% by weight, preferably from 7 to 15% by weight, more preferably from 9 to 12% by weight. of at least one polymer belonging to the group P3, relative to the total weight of the mixture of at least two polymers. According to this embodiment of the invention, preferably the mixture of at least two polymers consists essentially of: up to 95% by weight, relative to the total weight of the polymer mixture, of at least one polymer belonging to to the group P1 and up to 15% by weight, based on the total weight of the polymer mixture, of at least one polymer belonging to the P3 group.
[0050] According to this embodiment, preferably, the mixture of at least two polymers consists essentially of: from 10 to 95% by weight, preferably from 20 to 90% by weight, more preferably from 25% to 85% by weight; weight, advantageously from 30 to 75% by weight, of at least one polymer belonging to the P1 group, and from 5 to 15% by weight, preferably from 7 to 15% by weight, more preferably from 9 to 12% by weight, by weight, at least one polymer belonging to the group P3, relative to the total weight of the mixture of at least two polymers.
[0051] According to a third embodiment of the invention, the mixture of at least two polymers comprises: at least one polymer belonging to the P2 group, and up to 15% by weight, relative to the total weight of the polymer mixture of at least one polymer belonging to the group P3.
[0052] According to this embodiment, preferably, the mixture of at least two polymers comprises: from 85 to 99% by weight, preferably from 87 to 97% by weight, more preferably from 90% to 95% by weight; at least one polymer belonging to the group P2, and from 1 to 15% by weight, preferably from 3 to 13% by weight, more preferably from 5 to 10% by weight, of at least one polymer belonging to the group P3 group, based on the total weight of the mixture of at least two polymers. According to this embodiment of the invention, preferably the mixture of at least two polymers consists essentially of: at least one polymer belonging to the P2 group, and - up to 15% by weight, relative to the total weight of the mixture of polymers, at least one polymer belonging to the group P3. According to this embodiment, preferably, the mixture of at least two polymers consists essentially of: from 85 to 99% by weight, preferably from 87 to 97% by weight, more preferably from 90% to 95% by weight, the weight of at least one polymer belonging to the group P2, and from 1 to 15% by weight, preferably from 3 to 13% by weight, more preferably from 5 to 10% by weight, of at least one polymer. belonging to the group P3, relative to the total weight of the mixture of at least two polymers.
[0053] According to a fourth embodiment of the invention, the mixture of at least two polymers comprises: up to 95% by weight, relative to the total weight of the polymer mixture, of at least one polymer belonging to the group P 1 and up to 15% by weight, based on the total weight of the polymer mixture, of at least one polymer belonging to the P4 group. According to this embodiment, preferably the mixture of at least two polymers comprises: from 10 to 95% by weight, preferably from 20 to 90% by weight, more preferably from 25% to 85% by weight, preferably from 30 to 75% by weight, of at least one polymer belonging to the group P1, and from 5 to 15% by weight, preferably from 7 to 15% by weight, more preferably from 9 to 12% by weight. of at least one polymer belonging to the group P4, relative to the total weight of the mixture of at least two polymers.
[0054] According to this embodiment of the invention, preferably the mixture of at least two polymers consists essentially of: up to 95% by weight, relative to the total weight of the polymer mixture, of at least one polymer belonging to to the P1 group, and - up to 15% by weight, based on the total weight of the polymer mixture, of at least one polymer belonging to the P4 group. According to this embodiment, preferably, the mixture of at least two polymers consists essentially of: from 10 to 95% by weight, preferably from 20 to 90% by weight, more preferably from 25% to 85% by weight; weight, advantageously from 30 to 75% by weight, of at least one polymer belonging to the P1 group, and from 5 to 15% by weight, preferably from 7 to 15% by weight, more preferably from 9 to 12% by weight, by weight, at least one polymer belonging to the group P4, relative to the total weight of the mixture of at least two polymers.
[0055] According to a fifth embodiment of the invention, the mixture of at least two polymers comprises: at least one polymer belonging to the P2 group, and up to 15% by weight, relative to the total weight of the polymer mixture at least one polymer belonging to the group P4.
[0056] According to this embodiment, preferably, the mixture of at least two polymers comprises: from 85 to 99% by weight, preferably from 87 to 97% by weight, more preferably from 90% to 95% by weight; at least one polymer belonging to the group P2, and from 1 to 15% by weight, preferably from 3 to 13% by weight, more preferably from 5 to 10% by weight, of at least one polymer belonging to the group P4 group, based on the total weight of the mixture of at least two polymers. According to this embodiment of the invention, preferably the mixture of at least two polymers consists essentially of: at least one polymer belonging to the P2 group, and up to 15% by weight, relative to the total weight of the mixture of polymers, at least one polymer belonging to the group P4. According to this embodiment, preferably, the mixture of at least two polymers consists essentially of: from 85 to 99% by weight, preferably from 87 to 97% by weight, more preferably from 90% to 95% by weight, the weight of at least one polymer belonging to the group P2, and from 1 to 15% by weight, preferably from 3 to 13% by weight, more preferably from 5 to 10% by weight, of at least one polymer. belonging to the group P4, relative to the total weight of the mixture of at least two polymers.
[0057] According to one embodiment of the invention, the mixture of at least two polymers comprises: up to 95% by weight, based on the total weight of the polymer mixture, of at least one polymer corresponding to the formula ( Ibis), and - at least one polymer of formula (IIbis). According to this embodiment, preferably the mixture of at least two polymers comprises - from 10 to 95% by weight, preferably from 20 to 90% by weight, more preferably from 25% to 85% by weight, preferably from 30 to 75% by weight, of at least one polymer corresponding to the formula (Ibis), and from 5 to 90% by weight, preferably from 10 to 80% by weight, more preferably from 15 to 75% by weight. % by weight, advantageously from 25 to 70% by weight, of at least one polymer corresponding to formula (IIbis), relative to the total weight of the mixture of at least two polymers. According to this embodiment of the invention, preferably the mixture of at least two polymers consists essentially of: up to 95% by weight, relative to the total weight of the polymer mixture, of at least one polymer to the formula (Ibis), and - at least one polymer corresponding to the formula (IIbis). According to this embodiment of the invention, preferably the mixture of at least two polymers consists essentially of: from 10 to 95% by weight, preferably from 20 to 90% by weight, more preferably by 25% at 85% by weight, advantageously from 30 to 75% by weight, of at least one polymer corresponding to the formula (Ib), and from 5 to 90% by weight, preferably from 10 to 80% by weight, of more preferably from 15 to 75% by weight, advantageously from 25 to 70% by weight, of at least one polymer corresponding to formula (IIbis), relative to the total weight of the mixture of at least two polymers.
[0058] According to another embodiment of the invention, the mixture of at least two polymers comprises: up to 95% by weight, relative to the total weight of the polymer mixture, of at least one polymer corresponding to the formula (Ibis), and - up to 15% by weight, relative to the total weight of the polymer mixture, of at least one polymer corresponding to formula (IIIa). According to this embodiment of the invention, preferably the mixture of at least two polymers comprises: from 10 to 95% by weight, preferably from 20 to 90% by weight, more preferably from 25% to 85% by weight; % by weight, advantageously from 30 to 75% by weight, of at least one polymer corresponding to the formula (Ibis), and from 5 to 15% by weight, preferably from 7 to 15% by weight, more preferably from 9 to 12% by weight, of at least one polymer corresponding to formula (IIIa), relative to the total weight of the mixture of at least two polymers.
[0059] According to this embodiment of the invention, preferably the mixture of at least two polymers consists essentially of: up to 95% by weight, relative to the total weight of the polymer mixture, of at least one polymer to the formula (Ibis), and up to 15% by weight, relative to the total weight of the polymer mixture, of at least one polymer corresponding to the formula (IIIa). According to this embodiment of the invention, preferably the mixture of at least two polymers consists essentially of: from 10 to 95% by weight, preferably from 20 to 90% by weight, more preferably by 25% at 85% by weight, advantageously from 30 to 75% by weight, of at least one polymer corresponding to the formula (Ib), and from 5 to 15% by weight, preferably from 7 to 15% by weight, of more preferably from 9 to 12% by weight, of at least one polymer corresponding to formula (IIIa), relative to the total weight of the mixture of at least two polymers. According to another embodiment of the invention, the mixture of at least two polymers comprises: at least one polymer corresponding to formula (IIbis), and up to 15% by weight, relative to the total weight of the polymer mixture of at least one polymer corresponding to formula (IIIa). According to this embodiment of the invention, preferably, the mixture of at least two polymers comprises: from 85 to 99% by weight, preferably from 87 to 97% by weight, more preferably from 90% to 95% by weight; % by weight, of at least one polymer corresponding to formula (IIa), and from 1 to 15% by weight, preferably from 3 to 13% by weight, more preferably from 5 to 10% by weight, at least one polymer corresponding to formula (IIIa), relative to the total weight of the mixture of at least two polymers. According to this embodiment of the invention, preferably the mixture of at least two polymers consists essentially of: at least one polymer corresponding to formula (IIa), and up to 15% by weight, with respect to total weight of the polymer mixture, of at least one polymer corresponding to formula (IIIa).
[0060] According to this embodiment of the invention, preferably, the mixture of at least two polymers consists essentially of: from 85 to 99% by weight, preferably from 87 to 97% by weight, more preferably by 90% at 95% by weight, of at least one polymer corresponding to formula (IIa), and from 1 to 15% by weight, preferably from 3 to 13% by weight, more preferably from 5 to 10% by weight of at least one polymer corresponding to formula (IIIa), relative to the total weight of the mixture of at least two polymers.
[0061] According to another embodiment of the invention, the mixture of at least two polymers comprises: up to 95% by weight, based on the total weight of the polymer mixture, of at least one polymer corresponding to the formula (Ibis), and - up to 15% by weight, relative to the total weight of the polymer mixture, of at least one polymer corresponding to formula (IVa). According to this embodiment of the invention, preferably, the mixture of at least two polymers comprises: from 10 to 95% by weight, preferably from 20 to 90% by weight, more preferably from 25% to 85% by weight; % by weight, advantageously from 30 to 75% by weight, of at least one polymer corresponding to the formula (Ibis), and from 5 to 15% by weight, preferably from 7 to 15% by weight, more preferably from 9 to 12% by weight, of at least one polymer corresponding to formula (IVa), relative to the total weight of the mixture of at least two polymers. According to this embodiment of the invention, preferably the mixture of at least two polymers consists essentially of: up to 95% by weight, based on the total weight of the polymer mixture, of at least one polymer to the formula (Ibis), and up to 15% by weight, based on the total weight of the polymer mixture, of at least one polymer corresponding to the formula (IVa).
[0062] According to this embodiment of the invention, preferably the mixture of at least two polymers consists essentially of: from 10 to 95% by weight, preferably from 20 to 90% by weight, more preferably by 25% at 85% by weight, advantageously from 30 to 75% by weight, of at least one polymer corresponding to the formula (Ibis), and from 5 to 15% by weight, preferably from 7 to 15% by weight, of more preferably from 9 to 12% by weight, of at least one polymer corresponding to formula (IVa), relative to the total weight of the mixture of at least two polymers.
[0063] According to another embodiment of the invention, the mixture of at least two polymers comprises: at least one polymer corresponding to formula (IIbis), and up to 15% by weight, relative to the total weight of the polymer mixture of at least one polymer corresponding to formula (IVa).
[0064] According to this embodiment of the invention, preferably, the mixture of at least two polymers comprises: from 85 to 99% by weight, preferably from 87 to 97% by weight, more preferably from 90% to 95% by weight; % by weight, of at least one polymer corresponding to formula (IIa), and from 1 to 15% by weight, preferably from 3 to 13% by weight, more preferably from 5 to 10% by weight, at least one polymer corresponding to the formula (IVa), relative to the total weight of the mixture of at least two polymers. According to this embodiment of the invention, preferably the mixture of at least two polymers consists essentially of: at least one polymer corresponding to formula (IIa), and up to 15% by weight, with respect to total weight of the polymer mixture, of at least one polymer corresponding to formula (IVa). According to this embodiment of the invention, preferably, the mixture of at least two polymers consists essentially of: from 85 to 99% by weight, preferably from 87 to 97% by weight, more preferably by 90% at 95% by weight, of at least one polymer corresponding to formula (IIa), and from 1 to 15% by weight, preferably from 3 to 13% by weight, more preferably from 5 to 10% by weight of at least one polymer corresponding to formula (IVa), relative to the total weight of the mixture of at least two polymers.
[0065] According to one embodiment, the mixture of at least two polymers essentially comprises polymers corresponding to formulas (Ibis), (IIa), (IIIa) and (IVa) described above. Preferably, the mixture of at least two polymers according to the invention does not comprise polymers other than those corresponding to formulas (Ibis), (Ilbis), (IIIbis) and (IVbis) described above. According to another embodiment, the mixture of at least two polymers comprises: at least one polymer corresponding to one of the formulas (Ibis), (IIa), (IIIa) and (IVa), and at least one another silylated polymer belonging to one of the groups P1, P2, P3 and P4, it being understood that the other silylated polymer does not belong to the same group as the polymer of formula (Ib), (IIbis), (IIIa) or (IVa). By "other silylated polymer" is meant a polymer different from the polymers of formulas (Ibis), (IIbis), (IIIa) and (IVa) and comprising at least one silylated function corresponding to the general formula: -Si (le) p (OR4) 3_p where R5, R4 and p have the same meaning as above. Preferably, the other one or more silylated polymers are chosen from: a polyurethane or a polyether, belonging to the group P2, comprising two or three terminal groups of dialkoxysilane type hydrolyzable and corresponding to formula (II): a polyurethane or a polyether, belonging to the group P1, comprising two or three hydrolyzable trialkoxysilane end groups of formula (I): (I) - a polyurethane or a polyether, belonging to the group P3, comprising two or three terminal groups of the type hydrolyzable monoalkoxysilane and corresponding to formula (III): LL - a polyurethane or a polyether, belonging to the group P4, comprising a terminal group of the mono-, di- and / or trialkoxysilane hydrolysable type and corresponding to formula (IV): C-NH R1-NH CEDRI II ## STR2 ## R (R5) P (R4) 3 -P (IV) R6 n alone or in admixture. In formulas (I), (II), (III), and (IV) above, 20 - B represents one of the two formulas below: where D and T represent a hydrocarbon radical comprising from 2 at 66 carbon atoms, linear, branched, cyclic, alicyclic or aromatic, saturated or unsaturated, optionally comprising one or more heteroatoms, such as oxygen, sulfur, nitrogen or halogen, R 1 represents a divalent hydrocarbon radical comprising from 5 to 15 carbon atoms; carbon atoms which may be aromatic or aliphatic, linear, branched or cyclic, - R3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, - R2 represents a linear or branched divalent alkylene radical comprising from 2 to 4 carbon atoms, and preferably 3 carbon atoms, - R4 and R5, identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, R4 may optionally be in a ring, R 6 represents a linear, branched, cyclic, alicyclic or aromatic, saturated or unsaturated, hydrocarbon-based radical containing 1 to 22 carbon atoms, optionally comprising one or more heteroatoms, such as oxygen, sulfur, nitrogen or halogen; n is an integer such that the average molar mass of the polyether block of formula -PRI is from 300 g / mol to 40000 g / mol, m is an integer such that the average molar mass of the polymer ranges from 600 g / mol to 100000 g / mol, - p is an integer equal to 0, 1 or 2, - f is an integer equal to 2 or 3.
[0066] The polymers corresponding to one of formulas (I), (II), (III) and (IV) can be obtained according to a process described in the applications EP 2 336 208 and WO 2009/106699 with possibly a total substitution or a partial substitution of polyether diols by polyether monols in the polymers of formula (IV).
[0067] Preferably, the mixture of at least two polymers according to the invention comprises: from 5 to 95% by weight, preferably from 10 to 90% by weight, of at least one polymer corresponding to one of the formulas ( Ibis), (Ilbis), (IIIbis) and (IVbis); and from 5 to 95% by weight, preferably from 10 to 90% by weight, of at least one other silylated polymer, preferably chosen from polymers of formula (I), (II), (III) or ( IV), relative to the total weight of the mixture of at least two polymers, it being understood that the mixture comprises at least two polymers belonging to 2 different groups chosen from the groups P1, P2, P3 and P4.
[0068] The present invention also relates to an adhesive composition that can be used for the manufacture of the self-adhesive article according to the invention. The adhesive composition according to the invention comprises: a) the mixture of at least two polymers according to the invention, b) at least one tackifying resin, and c) at least one crosslinking catalyst. According to one embodiment, the adhesive composition according to the invention comprises a) from 20 to 85% by weight, preferably from 40 to 65% by weight, of the mixture of at least two polymers according to the invention, b) 15 to 80% by weight, preferably 25 to 70% by weight, more preferably 35 to 60% by weight, tackifying resin (s), c) 0.01 to 3% by weight of crosslinking catalyst (s), based on the total weight of the adhesive composition. According to one embodiment, the adhesive composition according to the invention consists essentially of: a) from 20 to 85% by weight, preferably from 40 to 65% by weight, of the mixture of at least two polymers according to the invention, b) from 15 to 80% by weight, preferably from 25 to 70% by weight, more preferably from 35 to 60% by weight, of tackifying resin (s), c) from 0.01 to 3% by weight of crosslinking catalyst (s), relative to the total weight of the adhesive composition.
[0069] Preferably, the tackifying resin is as described above for the self-adhesive article according to the invention. Preferably, the crosslinking catalyst is as described above for the self-adhesive article according to the invention. According to one embodiment, the adhesive composition according to the invention further comprises one or more additives chosen from desiccants, plasticizers, stabilizers (or antioxidants). Preferably, these additives are as described above for the self-adhesive article according to the invention. The adhesive composition according to the invention may be prepared by a process comprising: - a step of mixing, in an air-free manner, preferably under an inert atmosphere, the mixture of at least two polymers with the tackifying resins or resins, at a temperature between 30 and 170 ° C, preferably between 100 and 170 ° C, then a cooling step of said mixture at a temperature ranging from 30 to 90 ° C, and preferably about 70 ° C, then - a step of incorporating into the mixture obtained in the previous step of the crosslinking catalyst and, where appropriate, the desiccant and other optional components.
[0070] The adhesive composition according to the invention is not described in the prior art. The adhesive composition according to the invention can be used with a support different from the support layer described above for the self-adhesive article according to the invention. The adhesive composition according to the invention can be used for the manufacture of a self-adhesive article, comprising a temporary or permanent support and an adhesive layer, said adhesive layer being obtained by crosslinking the adhesive composition. The support of the self-adhesive article obtained from the adhesive composition according to the invention may be a temporary or permanent support.
[0071] In the case where the support is a temporary support, the support is preferably a release liner ("release liner" in English). In this case, once the article is glued to a surface, the glued article comprises only an adhesive layer, the temporary medium being intended to be removed.
[0072] In the case where the support is a permanent support, the support may be based on any materials that can be used for the manufacture of pressure-sensitive articles or PSA articles, such as polypropylene, polyethylene and paper. The support may be in fibrous or plastic strips, fabric, metal fiber or fiberglass.
[0073] According to one embodiment, the support is based on polyethylene terephthalate (PET), polypropylene (PP) or polyurethane (PU). According to one embodiment of the invention, the support is in the form of a grid or a mesh or a non-woven material. In this case, the adhesive layer may be present on only one side of the support, but may also penetrate inside the support during the application of the adhesive composition due to the porous nature of the support, so that the fibers of the support medium are fully coated with the adhesive composition. In this case, a non-stick protective film is preferably present on the adhesive layer or adhesive composition.
[0074] According to one embodiment, the self-adhesive article obtained from the adhesive composition according to the invention comprises a permanent support coated with an adhesive layer. Preferably, the adhesive layer is further coated with a non-stick protective film, preferably a silicone film. As an alternative to the non-stick protective film, the back side of the permanent support which is not coated with the adhesive layer, may have an anti-adherent surface, for example a silicone protective layer. The two embodiments described above enable the self-adhesive article to be wound up and then unrolled without problem of transfer of adhesive between the adhesive layer and the permanent support.
[0075] According to one embodiment, the permanent support is coated on both sides with an adhesive composition, which may be identical or different, at least one of the two adhesive compositions being according to the invention. Supports may be prepared from the following materials: - Estane TM 58309NAT022 polyurethane materials (BF Goodrich, Cleveland, Ohio), - RucothaneTM polyurethane or HytreFM 4056 elastomeric polyester (DuPont, Wilmington, Del.), - PebaxTM 2533 polyether block amide or 3533 (Arkema, Paris, France).
[0076] The self-adhesive article obtained from the adhesive composition according to the invention may be manufactured according to a method as described above for the self-adhesive article according to the invention.
[0077] The self-adhesive article may be used in a bonding method comprising the following steps: a) removing the release liner, when such a film is present; b) apply the article on a surface; and c) applying pressure to said article.
[0078] According to an embodiment wherein the self-adhesive article is a double-sided article, the bonding method further comprises a step of applying the bonded article to the first surface on a second surface.
[0079] EXAMPLES Various adhesive compositions were tested on two different types of support layer: a PET support and a foam support according to the invention.
[0080] The following polymers were used: - GENIOSILe STP-E 15 (available from Wacker): polyether of group P1 corresponding to formula (I) having two trimethoxysilane end groups, an average molar mass of about 10,000 g / mol a polydispersity of about 1.6 and a silyl function amount of 0.200 milliequivalents per gram of polymer; GENIOSILe STP-E (available from Wacker): polyether of group P2 corresponding to formula (II) having two end groups of dimethoxysilane type, an average molar mass of approximately 14493 g / mol, a polydispersity of approximately 1 , 6 and a silyl function amount of 0.138 milliequivalents per gram of polymer; Polyurethane A as described in the international application WO 2009/106699: polyurethane of the P1 group corresponding to formula (I) having two trimethoxysilane end groups, an average molar mass of about 16393 g / mol, a polydispersity of about 1.7 and a silyl function amount of 0.122 milliequivalents per gram of polymer; SPUR + e 1050MM (available from Momentive): polyurethane of group P1 corresponding to formula (I) having two end groups of trimethoxysilane type, an average molar mass of approximately 16393 g / mol, a polydispersity of approximately 1, 7 and an amount of silyl functions of 0.122 milliequivalents per gram of polymer; MS Polymer SAT 145 (available from Kaneka): polymer having a dimethoxysilane type end group, an average molar mass of approximately 3497 g / mol, a polydispersity of approximately 2.1 and a silyl function quantity of 0.286 milliequivalent per gram of polymer; Polymer Ex8: polyether of group P2 corresponding to formula (IIbis) having two end groups of diethoxysilane type, an average molecular weight of approximately 5376 g / mol and a silyl function quantity of 0.372 meq / g; Polymer Ex15: polyether of the P3 group corresponding to the formula (IIIbis) having 2 end groups of monoethoxysilane type, an average molecular weight of approximately 5263 g / mol and a silyl function quantity of 0.380 meq / g; Polymer Ex6-18: polyether of group P2 corresponding to formula (IIbis) having 3 end groups of diethoxysilane type, an average molecular weight of approximately 7160 g / mol and a silyl function quantity of 0.419 meq / g; Polymer Ex19: polyether of the P1 group corresponding to the formula (Ibis) having 3 trimethoxysilane end groups, an average molecular weight of approximately 6818 g / mol and a silyl function quantity of 0.440 meq / g; Ex20 polymer: polyether of the P1 group corresponding to the formula (Ibis) having 2 trimethoxysilane end groups, an average molar mass of approximately 5376 g / mol and a silyl function quantity of 0.372 meq / g; ExC6 polymer: P1 group polyether having 2 trimethoxysilane end groups, an average molecular weight of about 4000 g / mol and a silyl function quantity of 0.500 meq / g.
[0081] The polymer Ex8 is prepared according to the following procedure: - Introduce 84.1 g of ACCLAIM 8200 polyol (available from Bayer) in a glass synthesis apparatus, under a nitrogen atmosphere and under vacuum, heated to about 85-90. ° C; then - Introduce 0.1 g of BORCHI KATe VP 0244 catalyst (bismuth and zinc neodecanoate available from Borchers); then - Hold the apparatus for about 1 hour under vacuum at 85-90 ° C; then - Introduce 6.4 g of isophorone diisocyanate; - Maintain at 85-90 ° C under nitrogen for about 2 hours until an NCO rate of functions between 1.5 and 1.9% (rate measured by assayed sampling); then - Cool the apparatus to 65-70 ° C; then - Introduce 9.01 g of GENIO sit® XL924 (N-cyclohexylaminomethyl-methyldiethoxysilane available from Wacker); - Maintain at 70 ° C under a nitrogen atmosphere for about 1 hour until the total disappearance of the NCO functions. The polymer Ex15 is prepared according to the following procedure: Introduce 87.3 g of ACCLAIM 8200 polyol (available from Bayer) in a glass synthesis apparatus, under a nitrogen atmosphere and under vacuum, heated to about 85-90.degree. ° C; then - Introduce 0.1 g of BORCHI KATe VP 0244 catalyst (bismuth and zinc neodecanoate available from Borchers); then - Hold the apparatus for about 1 hour under vacuum at 85-90 ° C; then - Introduce 6.6 g of isophorone diisocyanate; - Maintain at 85-90 ° C under nitrogen for about 2 hours until an NCO rate of functions between 1.5 and 1.9% (rate measured by assayed sampling); then - Cool the apparatus to 65-70 ° C; then - Introduce 6.14 g of 3-aminopropyldimethyl-ethoxysilane; then - Maintain at 70 ° C under nitrogen for about 1 hour until the complete disappearance of the NCO functions. The polymer Ex19 is prepared according to the following procedure: Introduce 82.18 g of ACCLAIMe 6300 polyol (available from Bayer) in a glass synthesis apparatus, under a nitrogen atmosphere and under vacuum, heated to about 85-90.degree. ° C; then - Introduce 0.04 g of catalyst BORCHI KATe VP 0244 (bismuth and zinc neodecanoate available from Borchers); then - Hold the apparatus for about 1 hour under vacuum at 85-90 ° C; then - Introduce 9.44 g of isophorone diisocyanate; - Maintain at 85-90 ° C under nitrogen for about 2 hours until an NCO function rate of between 1.8 and 2.2% (rate measured by assayed sampling); then - Cool the apparatus to 65-70 ° C; then - Introduce 7.84 g of Silanee A1110 (gammaaminopropyltrimethoxysilane available from the Momentive Company); then - Maintain at 70 ° C under nitrogen for about 1 hour until the complete disappearance of the NCO functions. The polymer Ex6-18 is prepared according to the following procedure: - Introduce 82.03 g of ACCLAIMe 6300 polyol (available from Bayer) in a glass synthesis apparatus, under a nitrogen atmosphere and under vacuum, heated to about 85.degree. -90 ° C; then - Introduce 0.04 g of catalyst BORCHI KATe VP 0244 (bismuth and zinc neodecanoate available from Borchers); then - Hold the apparatus for about 1 hour under vacuum at 85-90 ° C; then - Introduce 9.45 g of isophorone diisocyanate; - Maintain at 85-90 ° C under nitrogen for about 2 hours until an NCO function rate of between 1.8 and 2.2% (rate measured by assayed sampling); then - Cool the apparatus to 65-70 ° C; then - Introduce 7.98 g of 3-aminopropylmethyl-diethoxysilane; then - Maintain at 70 ° C under nitrogen for about 1 hour until the complete disappearance of the NCO functions.
[0082] The polymer Ex20 is prepared according to the following procedure: - Introduce 84.71 g of ACCLAIM 8200 polyol (available from Bayer) in a glass synthesis apparatus, under a nitrogen atmosphere and under vacuum, heated to about 85-90.degree. ° C; then - Introduce 0.04 g of catalyst BORCHI KATe VP 0244; then - Hold the apparatus for about 1 hour under vacuum at 85-90 ° C; then - Introduce 6.5 g of isophorone diisocyanate; - Maintain at 85-90 ° C under nitrogen for about 2 hours until an NCO function rate of between 1.7 and 2.2% (rate measured by assay sampling); then - Cool the apparatus to 65-70 ° C; then - Introduce 8.23 g of N-ethyl-3-trimethoxysilyl-2-methylpropanamine and then - Maintain at 70 ° C. under nitrogen for about 1 hour until the total disappearance of the NCO functions.
[0083] The ExC6 polymer is prepared according to the following procedure: Introduce 80.3 g of ACCLAIM 8200 polyol (available from Bayer) in a glass synthesis apparatus, under a nitrogen atmosphere and under vacuum, heated to about 85 ° -90 ° C. VS ; then - Introduce 0.07 g of catalyst BORCHI KATe VP 0244; then - Hold the apparatus for about 1 hour under vacuum at 85-90 ° C; then - Introduce 8.1 g of isophorone diisocyanate; - Maintain at 85-90 ° C under nitrogen for about 2 hours until an NCO function rate of between 1.7 and 2.2% (rate measured by assay sampling); then - Cool the apparatus to 65-70 ° C; then - Introduce 11.2 g of N-ethyl-3-trimethoxysilyl-2-methylpropanamine and then - Maintain at 70 ° C under nitrogen for about 1 hour until the total disappearance of the NCO functions. The following products have also been used: - DERTOPHENEe H 150: tackifying resin phenolic terpene type; IRGANOXe 1010 and IRGANOXe 245: stabilizing agents; K-KATe 5218: crosslinking catalyst; - Vinyl glycoxysilane: agent capable of absorbing water ("waterscavenger" in English).
[0084] Tables 1 and ibis indicate the components of the adhesive compositions that have been tested. The amounts of each component are indicated as a percentage by mass. Adhesive compositions C1, C2, C3, C4, C5 and C6 correspond to comparative adhesive compositions. Compositions 6, 8, 15, 18, 19 and 20 correspond to adhesive compositions according to the invention.
[0085] Table 1: Adhesive compositions (% by weight) Cl C2 C3 C4 C5 C6 GENIOSILO STPE15 51.10 38.90 GENIOSILO STPE30 12.90 Polyurethane A 51.70 41.00 W02009 / 106699 SPUR + 0 1050MM 51.70 MS Polymer0 SAT 145 10.10 Polymer Ex8 Polymer Ex15 Polymer Ex6-18 Polymer Ex19 Polymer ExC6 51.70 DERTOPHENEO H150 46.70 46.70 46.18 46.20 46.70 46.10 IRGANOXO 1010 0.47 0.47 0.47 0.45 0.45 0.45 IRGANOXO 245 0.25 0.25 0.25 0.25 0.25 0.25 K-KATC) 5218 0.50 0.50 2.00 2.00 1.00 2 , 00 Vinylglycoxysilane 0.38 0.38 Table ibis: Adhesive compositions (% by weight) (continued) 6 8 15 18 19 20 GENIOSILO STPE15 GENIOSILO STPE30 38.90 38.90 Polyurethane A from 45.90 W02009 / 106699 SPUR + 0 1050MM MS Polymer0 SAT 145 Polymer Ex8 51.70 Polymer Ex15 5.80 Polymer Ex6-18 51.70 12.90 Polymer Ex19 12.90 Polymer Ex20 51.70 DERTOPHENEO H150 46.70 46.70 46.70 46.70 46, 70 46.10 IRGANOXO 1010 0.45 0.47 0.45 0.45 0.45 0.45 IRGANOXO 245 0.25 0.25 0.25 0.25 0.25 0.25 K-KATC) 5218 1 , 00 0,50 1,00 1,00 1,00 2.00 Vinylgl The properties of the self-adhesive article according to the invention (with a carrier layer in the form of a foam) were evaluated and compared with the properties of a comparative self-adhesive article (with a layer). PET support). The support layer in the form of a foam which was used for the tests is a TL SRZ® 1200.8 foam available from Alveo having the following characteristics: - elongation in breaking length at 23 ° C. of 408.3 ± 53%, - An elongation in breaking width at 23 ° C of 390.3%, - An apparent density of about 96.92 kg / m3, - A thickness of about 0.67 mm, - A module of Young of 11.2 ± 0.5 MPa. The PET backing layer which was used for the tests has a thickness of 50 μm.
[0086] The compositions shown in Table 1 were applied to the two carrier layers described above with a basis weight of about 50 g / m 2 to obtain a self-adhesive article. Process for obtaining self-adhesive articles tested: Each The adhesive composition is preheated to a temperature of about 100 ° C and introduced into a cartridge from which a bead is extruded and deposited near the edge of the support layer parallel to its width. The adhesive composition contained in this bead is then spread over the entire surface of a silicone support (non-stick protective film), so as to obtain a uniform layer of substantially constant thickness, using an applicator (" coater "in English) with a lip nozzle which is moved from one side of the support layer to the opposite side. A layer of composition is thus deposited and corresponds to a basis weight of approximately 50 g / m 2 (thickness of approximately 50 μm). The support layer thus coated with the adhesive composition is then placed in a furnace at a temperature of about 120 ° C supplied with water vapor so that the amount of water is about 50 g / m 3 with a distribution of homogeneous. The passage time in the oven is about 5 minutes, allowing crosslinking of the adhesive composition to obtain an adhesive layer. Finally, once out of the oven, the crosslinked adhesive layer is then laminated to the desired support layer (Alveoe TLSRZe 1200.8 foam or PET 50 am support). Time of resistance of the glue joint to the static shear: The maintenance at high temperature of the adhesive power of the support layer coated with the crosslinked composition is evaluated at the latest within 5 hours of its obtaining by a test which determines the resistance time of the static shear glue joint at 90 ° C on PET and at 70 ° C on foam. For this test reference is made to the FINAT method n ° 8. The principle is the following. A test piece in the form of a rectangular strip (25 mm × 75 mm) is cut in the PET support layer or in the foam support layer coated with the crosslinked composition prepared previously, at most 5 hours after its preparation. After removing all of the protective release layer, a 25 mm square portion at the end of the adhesive strip is attached to a glass plate.
[0087] The test plate thus obtained is introduced, by means of a suitable support, in a substantially vertical position in an oven at 90 ° C for the PET article and 70 ° C for the foam article, the unglued portion 50 mm length band below the plate. After thermal equilibration, the remaining free portion of the strip is connected to a mass of 1 kg, the entire device still remaining during the test held in the oven at 90 ° C and 70 ° C respectively for the support in PET and the foam support.
[0088] Under the effect of this mass, the adhesive joint which ensures the fixing of the strip on the plate is subjected to shear stress. To better control this stress, the test plate is actually placed at an angle of 2 ° to the vertical. The time is recorded at the end of which the strip is detached from the plate as a result of the rupture of the adhesive joint under the effect of this constraint. This time is shown in Tables 2 and 2bis. Table 2: Properties of self-adhesive articles Cl C2 C3 C4 C5 C6 PET backing layer Shear strength at 90 ° C> 24h> 24h> 24h> 24h> 24h> 24h Support layer in the form of Alveo TL SRZO foam 1200.8 Shear strength at 70 ° C 0.1h 0.2h 0.1h lh 5h lh Table 2a: properties of self-adhesive articles (continued) 6 8 15 18 19 20 PET backing layer Shear strength at 90 ° C> 24h> 24h> 24h> 24h> 24h> 24h Support layer in the form of a foam Alveo TL SRZO 1200.8 Shear strength at 70 ° C> 24h> 24h 12h> 24h> 24h> 24h The comparative examples Cl, C2, C3, C4, C5 and C6 show that self-adhesive articles comprising an identical adhesive composition do not have the same properties depending on the support layer used. Indeed, these examples give good results with respect to the shear strength with a PET carrier (resistance greater than 24 hours), but these comparative examples do not give satisfactory results of shear strength with a support in the form of a foam (resistance of 0.1h, 0.2h, lh or 5h). These tests illustrate that all adhesive compositions of the prior art which have satisfactory properties on PET support do not have satisfactory properties on conformable foam-type support, as claimed. In contrast, Example 8 according to the invention, in which the adhesive composition comprises a single polymer of formula (IIa), give good results with a carrier in the form of a foam.
[0089] Similarly, Example 18 wherein the adhesive composition comprises a polymer of formula (IIbis) and a polymer of formula (II) gives good results with a carrier in the form of a foam. Example 20 comprises a polymer of formula (Ia) having a silyl function amount of 0.372 meq / g in the claimed range and shows good results with a carrier in the form of a foam. In contrast, Comparative Example C6 comprises a polymer of formula (Ib) having a silyl function amount of 0.500 meq / g, outside the claimed range. This example C6 does not give satisfactory results of shear strength with a carrier in the form of a foam. Examples 15 and 19, in which the composition comprises mixing two polymers belonging to two different groups among P1, P2, P3 and P4, give satisfactory results in terms of shear strength.
[0090] Of course, the present invention is not limited to the examples and to the embodiment described and shown, but it is capable of numerous variants accessible to those skilled in the art.

权利要求:
Claims (15)
[0001]
REVENDICATIONS1. Self-adhesive article comprising a support layer coated with an adhesive layer, said support layer having an elongation at break of 50 to 1200% and an apparent density of 25 to 1200 kg / m3, said adhesive layer is obtained by crosslinking an adhesive composition comprising: a) at least one polymer of formula (Ib) or at least one polymer of formula (IIa) or a mixture of at least two polymers selected from polyurethanes and polyethers having one, two or three mono-, di- or tri-alkoxysilane end groups, said mixture comprising at least one polymer corresponding to one of the formulas (Ibis), (IIbis), (IIIa) and (IVa), it being understood that: - when a polymer having two or three monoalkoxysilane end groups is present, said mixture comprises up to 15% by weight, relative to the total weight of the mixture, of said polymer, when a polymer having a final grouping 1 of mono-, di- or tri-alkoxysilane type is present, said mixture comprises up to 15% by weight, relative to the total weight of the mixture, of said polymer, b) at least one tackifying resin, and c) at least a crosslinking catalyst; wherein the polymer of formula (Ibis) is a polyurethane or a polyether comprising two or three hydrolyzable trialkoxysilane end groups having a silyl function quantity of 0.480 meq / g of polymer and corresponding to the following formula: ) the polymer of formula (IIbis) is a polyurethane or a polyether comprising two or three hydrolyzable dialkoxysilane end groups, having a silyl function quantity of less than or equal to 0.480 meq / g of polymer and corresponding to the following formula: (IIb) is) the polymer of formula (IIIbis) is a polyurethane or a polyether comprising two or three hydrolyzable monoalkoxysilane end groups, having a silyl function amount of less than or equal to 0.480 meq / g of polymer and corresponding to the following formula: (Ilibi s) the polymer of formula (IVbis) is a polyurethane or a polyether comprising a group hydrolysable monomer, di- and / or trialkoxysilane type having a silyl function of less than or equal to 0.480 meq / g of polymer and corresponding to the following formula: (IVa) in formulas (Ibis), (IIa) (IIIbis) and (IVbis) above, B represents one of the two formulas below: OR2 II - // - D OR T - Le.DRZn- O.R27.; N. - [OR] - where D and T represent a linear, branched, cyclic, alicyclic or aromatic, saturated or unsaturated hydrocarbon-based radical containing 2 to 66 carbon atoms, optionally comprising one or more heteroatoms, - R 1 represents a divalent hydrocarbon radical comprising of 5 to 15 carbon atoms which may be aromatic or aliphatic, linear, branched or cyclic, - R3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, - R2 represents a divalent linear or branched alkylene radical comprising of 2 to 4 carbon atoms, - R4 and R5, identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, R4 may optionally be engaged in a ring, - R6 represents a hydrocarbon radical comprising 1 to 22 carbon atoms, linear, branched, cyclic, alicyclic or aromatic, saturated or unsaturated, including R7 represents a hydrogen atom, a phenyl radical or a linear, branched or cyclic alkyl radical comprising from 1 to 10 carbon atoms, n is an integer such that the average molar mass of the block polyether of formula -PRI is from 300 g / mol to 40000 g / mol, m is an integer such that the average molar mass of the polymer ranges from 600 g / mol to 100000 g / mol, p is a number integer equal to 0, 1 or 2, - f is an integer equal to 2 or 3. 15
[0002]
2. Self-adhesive article according to claim 1, in which the mixture of at least two polymers comprises: at least one polymer corresponding to one of the formulas (Ibis), (IIa), (IIIa) or (IVa) ) described in claim 1, and - at least one polymer corresponding to one of the formulas (I), (II), (III) or (IV) below: ## STR2 ## -N H CER1 0 CN HR
[0003]
Wherein it is understood that: - when a polymer of formula (IIIa) and / or (III) is present, said mixture comprises up to 15% by weight of polymer of formula (IIIa) and / or (III), relative to the total weight of the polymer mixture, when a polymer of formula (IIIa) and / or (III) is present, said mixture comprises up to 15% by weight of polymer of formula (IIIbis) and / or (III), relative to the total weight of the polymer mixture; in formulas (I), (II), (III), and (IV) above, - B represents one of the two formulas below: OR2: n - OR / R2-11 - / 0 ORii T - [ORn. Where D and T represent a hydrocarbon radical comprising 2 to 66 carbon atoms, linear, branched, cyclic, alicyclic or aromatic, saturated or unsaturated, optionally containing one or more heteroatoms, R 1 represents a divalent hydrocarbon radical comprising from 5 to 5 carbon atoms; at 15 carbon atoms which may be aromatic or aliphatic, linear, branched or cyclic, - R3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, - R2 represents a linear or branched divalent alkylene radical comprising from 2 to with 4 carbon atoms, - R4 and R5, identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, R4 possibly being engaged in a ring, - R6 represents a hydrocarbon radical comprising from 1 to to 22 carbon atoms, linear, branched, cyclic, alicyclic or aromatic, saturated or unsaturated, optionally containing one or more heteroatoms; n is an integer such that the average molar mass of the polyether block of formula 40 R21 ranges from 300 g / mole to 40000 g / mole, m is an integer such that the average molecular weight the polymer ranges from 600 g / mol to 100000 g / mol, - p is an integer equal to 0, 1 or 2, - f is an integer equal to 2 or 3.3. A self-adhesive article according to claim 1 or claim 2, wherein the support layer has a Young's modulus less than or equal to 300 MPa.
[0004]
Self-adhesive article according to any one of claims 1 to 3, wherein the support layer is in the form of a foam.
[0005]
Self-adhesive article according to any one of claims 1 to 4, wherein the support layer is in the form of one or more polymeric layers.
[0006]
Self-adhesive article according to any of claims 1 to 5, wherein the adhesive composition comprises: from 20 to 85% by weight, based on the total weight of the adhesive composition, of at least one polymer or a mixture of polymers as defined in claim 1 or 2, from 15 to 80% by weight, relative to the total weight of the adhesive composition, of at least one tackifying resin, from 0.01 to 3% by weight; weight, based on the total weight of the adhesive composition, of at least one crosslinking catalyst.
[0007]
Self-adhesive article according to any of claims 1 to 6, wherein the tackifying resin has a number average molecular weight ranging from 100 Da to 5 kDa and is selected from: (i) resins capable of being obtained by polymerization of terpene hydrocarbons and phenols, in the presence of Friedel-Crafts catalysts, (ii) resins obtainable by polymerization of alpha-methyl styrene, (iii) rosins of natural origin or modified (iv) resins obtained by hydrogenation, polymerization or copolymerization of unsaturated aliphatic hydrocarbon mixtures having about 5, 9 or 10 carbon atoms from petroleum cuts, (v) terpene resins generally resulting from the polymerization of terpene hydrocarbons in the presence of Friedel-Crafts catalysts, (vi) copolymers based on natural terpenes, and (vii) acrylic resins.
[0008]
8. Mixture of polymers that may be used in the adhesive composition as defined in claim 1 or 2, said mixture comprising at least two polymers belonging to 2 different groups chosen from the groups P1, P2, P3 and P4, said mixture comprising at least one polymer corresponding to one of the formulas (Ibis), (IIbis), (IIIa) and (IVa) and having a silyl function quantity of less than or equal to 0.480 meq / g of polymer, it being understood that: when a polymer of the P3 group is present, the mixture comprises up to 15% by weight, relative to the total weight of the mixture, of at least one polyurethane or at least one polyether of the P3 group; when a polymer of the P4 group is present, the mixture comprises up to 15% by weight, relative to the total weight of the polymer mixture, of at least one polyurethane or at least one polyether of the P4 group; P1 being a group consisting of polyurethanes and polyethers having two or three terminal groups of trialkoxysilane type; P2 being a group consisting of polyurethanes and polyethers having two or three terminal groups of dialkoxysilane type P3 being a group consisting of polyurethanes and polyethers having two or three terminal groups of monoalkoxysilane type; P4 being a group consisting of polyurethanes and polyethers having a terminal group of mono-, di- or tri-alkoxysilane type.
[0009]
9. Mixture of polymers according to claim 8, comprising: up to 95% by weight, relative to the total weight of the mixture, of at least one polymer corresponding to the formula (Ibis), and at least one polymer to formula (IIbis) as described in claim 1.
[0010]
Polymer blend according to Claim 8 or Claim 9, comprising: from 10 to 85% by weight of at least one polymer corresponding to the formula (Ibis), and from 15 to 90% by weight of at least one polymer corresponding to the formula (IIbis), relative to the total weight of the mixture, of at least two polymers.
[0011]
11. Polymer blend according to claim 8, comprising: up to 15% by weight, relative to the total weight of the mixture, of at least one polymer corresponding to formula (IIIa), and at least one polymer to formula (IIbis) as described in claim 1.
[0012]
The polymer blend of claim 8 comprising: from 5 to 95% by weight of at least one polymer of the formula (Ib), and from 5 to 15% by weight of at least one polymer in formula (IIIa), based on the total weight of said mixture.
[0013]
13. Polymer blend according to claim 8, comprising: at least one polymer corresponding to one of the formulas (Ibis), (IIa), (IIIa) or (IVa) described in claim 1, and at least one polymer corresponding to one of the formulas (I), (II), (III) or (IV) described in claim 2.
[0014]
An adhesive composition suitable for use in the manufacture of the self-adhesive article according to any one of claims 1 to 7, comprising: - the polymer blend according to any one of claims 8 to 13, - less a tackifying resin, and - at least one crosslinking catalyst. 20
[0015]
An adhesive composition according to claim 14, comprising: from 20 to 85% by weight, based on the total weight of the adhesive composition, of said polymer blend, from 15 to 80% by weight, based on the total weight of the adhesive composition of at least one tackifying resin; 0.01 to 3% by weight, based on the total weight of the adhesive composition, of at least one crosslinking catalyst.

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同族专利:

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公开号 | 公开日

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EP2889348A1|2015-07-01|

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CN110205045B|2021-11-30|

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FR3015984B1|2016-02-05|

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JP6552819B2|2019-07-31|

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JP2015129280A|2015-07-16|

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US9493690B2|2016-11-15|

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CN110205045A|2019-09-06|

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US20170058166A1|2017-03-02|

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EP2889348B1|2019-01-30|

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US20150184043A1|2015-07-02|

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CN104745113A|2015-07-01|

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US9976066B2|2018-05-22|

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法律状态:
2015-11-10| PLFP| Fee payment|Year of fee payment: 3 |

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2016-11-11| PLFP| Fee payment|Year of fee payment: 4 |

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2017-11-13| PLFP| Fee payment|Year of fee payment: 5 |

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2019-11-14| PLFP| Fee payment|Year of fee payment: 7 |

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2020-02-28| CA| Change of address|Effective date: 20200122 |

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2020-11-12| PLFP| Fee payment|Year of fee payment: 8 |

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2021-11-15| PLFP| Fee payment|Year of fee payment: 9 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1363674A|FR3015984B1|2013-12-30|2013-12-30|SELF-ADHESIVE ARTICLE SUPPORTED ON FOAM|FR1363674A| FR3015984B1|2013-12-30|2013-12-30|SELF-ADHESIVE ARTICLE SUPPORTED ON FOAM|

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US14/580,699| US9493690B2|2013-12-30|2014-12-23|Self-adhesive article with foam support|

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EP14200280.7A| EP2889348B1|2013-12-30|2014-12-24|Self-adhesive article with foam support|

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ES14200280T| ES2713433T3|2013-12-30|2014-12-24|Self-adhesive foam support article|

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JP2014263774A| JP6552819B2|2013-12-30|2014-12-26|Self-adhesive article having a foam support|

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CN201910480645.2A| CN110205045B|2013-12-30|2014-12-30|Self-adhesive article with foam carrier|

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CN201410838590.5A| CN104745113B|2013-12-30|2014-12-30|Self-adhesive article with foam carrier|

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US15/348,739| US9976066B2|2013-12-30|2016-11-10|Self-adhesive article with foam support|