Adhesive composition for the manufacture of waterproof, breathable objects

Description

Scope of the invention

[0001] The present invention relates to an adhesive composition, and the use of said adhesive composition for the preparation of self-adhesive articles. Technical background

[0002] A hot-melt pressure-sensitive adhesive (also known as a self-adhesive adhesive or HMPSA) is a composition that provides the substrate with immediate tack at room temperature. This tack allows for instant adhesion of the adhesive to a substrate under the effect of brief, light pressure. HMPSAs are widely used in the manufacture of self-adhesive articles, such as self-adhesive labels affixed to items for informational purposes (barcodes, names, prices, etc.) and / or for decorative purposes, whether for permanent or temporary bonding. HMPSAs are also used in the manufacture of self-adhesive tapes for a variety of applications.Besides transparent adhesive tape, which is widely used in everyday life, examples include: shaping and assembling cardboard packaging; protecting surfaces for painting work in construction; fixing and holding various elements such as panels, bricks, protruding objects, in the construction of buildings or structures; fixing and holding metal, plastic or glass parts, flat or with specific profiles, such as electrical cables, plastic films, windows, sheets, inscriptions, logos, seat parts, dashboards, plastic or textile walls, conduits or pipes for circulating fluids, particularly in the transport industry; and bonding carpets with double-sided adhesive tapes in the building sector.

[0003] Self-adhesive, waterproof-breathable articles can be used in medical applications such as bandages, dressings, electrodes, plasters, in clothing applications such as breathable clothing to cope with inclement weather or breathable dry clothing exposed to a humid environment, and in construction applications such as roofing or wall cladding, or watertight window frame systems that still need to be breathable so that moisture is released into the environment.

[0004] In particular, adhesive materials used in medical applications, such as medical tapes, wound care dressings, and consumer bandages, require a high Moisture Vapor Transmission Rate (MVTR) to allow the evaporation of moisture generated by the skin or wound exudate. A high MVTR of the adhesive prevents moisture from becoming trapped under the dressing, which could otherwise lead to skin maceration.

[0005] Thus, breathable articles must meet certain conditions such as a homogeneous appearance, wind resistance, high water vapor permeability, a certain elasticity, as well as the ability to adhere to different substrates.

[0006] Adhesive compositions suitable for the preparation of self-adhesive articles are already known.

[0007] For example, document WO 2013 / 136108 A1 relates in particular to an adhesive composition comprising at least one silylated polymer, at least one tackifying resin and at least one catalyst, and its use for manufacturing waterproof-breathable articles.

[0008] Document WO 2019 / 115952 A1 relates in particular to a multicomponent adhesive composition comprising a composition A comprising at least one silylated polymer, having at least one hydrolyzable alkoxysilane group, and at least one tackifying resin; and a composition B comprising at least one catalyst and at least one compound C. Compound C is chosen from a compound C1 having a number-average molecular weight ranging from 300 g / mol to 500,000 g / mol and a compound C2 having a vapor pressure at 20°C greater than or equal to 0.08 kPa.

[0009] Document WO 2019 / 186014 A1 relates in particular to an adhesive composition comprising at least one crosslinkable silylated polymer and a catalytic composition comprising a tertiary amine and an organometallic compound.

[0010] Document WO 03 / 087254 A2 relates in particular to a hydrophilic adhesive composition characterized in that it comprises a thermoplastic elastomer of the poly(styrene-olefin-styrene) sequence copolymer type, a tackifying product, a liquid plasticizer, water and an amphiphilic copolymer.

[0011] Document WO 2020 / 016581 A1 relates in particular to a composition comprising polymers including silylated groups functionalized by urea and amine groups and a tackifying resin, these compositions being used as pressure-sensitive hot melt adhesives.

[0012] Examples of compositions containing at least one silylated polymer, at least one crosslinking catalyst and at least one polyvinyl ether copolymer are described in JP S63 89559 A, JP H07 82492 A, JP 3 473049 B2, and JP H10 147723 A.

[0013] These various self-adhesive, waterproof, and breathable products, and the adhesive compositions they contain, exhibit satisfactory adhesive properties. However, these products and their compositions are not necessarily suitable for medical applications. In particular, these products and their compositions, such as medical tapes, bandages, and dressings, are not necessarily suitable for prolonged application to the skin or a wound. Indeed, prolonged application of these products can lead to maceration of the skin or wound, which can cause discomfort for the patient, slow healing, and other problems.

[0014] There is therefore a real need to provide an adhesive composition that allows the manufacture of self-adhesive articles suitable for medical use and exhibiting improved water vapor permeability, without compromising good adhesion properties. There is also a real need to provide an adhesive composition that allows the manufacture of self-adhesive articles—such as medical tapes, bandages, or dressings—suitable for prolonged application to the skin or wound. Furthermore, there is a real need to provide an adhesive composition that allows the manufacture of self-adhesive articles—such as medical tapes, bandages, or dressings—that limit or even prevent maceration of the skin or wound to which they are applied.There is also a real need for an adhesive composition that enables the manufacture of self-adhesive products—such as medical tapes, bandages, or dressings—that promote wound healing. There is also a real need for an adhesive composition that enables the manufacture of self-adhesive products suitable for the construction market, offering improved water vapor permeability without compromising good adhesion properties. Summary of the invention

[0015] The invention relates primarily to an adhesive composition comprising: at least one silylated polymer comprising at least one hydrolyzable alkoxisilane group; at least one polyvinyl ether compound; and at least one crosslinking catalyst, wherein the polyvinyl ether compound is a homopolymer selected from poly(methylvinyl ether), poly(ethylvinyl ether), poly(butylvinyl ether), poly(isobutylvinyl ether), poly(isopropylvinyl ether), poly(propylvinyl ether), poly(octylvinyl ether), and mixtures thereof.

[0016] In some embodiments, the silylated polymer is chosen from: a silylated polymer of general formula [Chem 2] a silylated polymer of general formula [Chem 3] a silylated polymer of general formula [Chem 4] a silylated polymer of general formula [Chem 5] in which: X1< and X2< represent, independently of each other, an oxygen atom or an -NH- group; R1< represents a divalent hydrocarbon radical comprising from 5 to 15 carbon atoms which may be aromatic or aliphatic, linear, branched or cyclic; R0< represents a linear or branched alkylene divalent radical comprising from 3 to 6 carbon atoms; R3< represents a linear or branched alkylene divalent radical comprising from 1 to 6 carbon atoms, preferably R3< representing methylene or n-propylene; R2< represents a polyether block -Rpe< -[ORpe< ] n- in which Rpe< represents a linear or branched alkylene divalent 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;R 6< represents a hydrogen atom, a phenyl radical, a linear, branched or cyclic alkyl radical comprising 1 to 6 carbon atoms, or a 2-succinate radical of general formula [Chem 6]; in which R7 is a linear or branched alkyl radical comprising from 1 to 6 carbon atoms; n is an integer such that the number-average molecular weight of the polyether block -[ORpe]n - ranges from 300 g / mol to 40,000 g / mol in the polymers of general formulas [Chem2], [Chem3], and [Chem4]; m1 is zero or an integer; m1 are such that the number-average molecular weight of the polymer of general formula [Chem3] ranges from 500 g / mol to 50,000 g / mol, preferably from 700 g / mol to 20,000 g / mol; m is a non-zero integer; m is such that the number-average molecular mass of the polymer of general formula [Chem 4] ranges from 500 g / mol to 50,000 g / mol, preferably from 700 g / mol to 20,000 g / mol; p is an integer equal to 0, 1 or 2, p being preferably 0 or 1; Ral represents a divalent hydrocarbon radical derived from a diol by replacement of each of the two hydroxyl groups by a free valence or represents the radical R2;R ac< represents a divalent hydrocarbon radical derived from a dicarboxylic acid by replacement of each of the two carboxyl groups COOH by a free valence; [Y] q represents a repeating motif of general formula [Chem 28]; t is a number such that the polyester diol of general formula [Chem 7] has a hydroxyl number IOH between 4 and 60 mg KOH / g; q is a non-zero integer; t and q are such that the number-average molecular weight of the polymer of general formula [Chem 5] is between 400 g / mol and 50,000 g / mol, said hydroxyl number IOH and said number-average molecular weight being determined according to ISO 14900:200

[0017] In some embodiments, the crosslinking catalyst is chosen from the group consisting of amines, organometallic compounds, acids and their derivatives, and mixtures thereof.

[0018] In some embodiments, the composition further comprises a tackifying resin; preferably a tackifying resin selected from terpene-phenolic resins, hydrocarbon resins, rosin resins; acrylic resins and mixtures thereof.

[0019] In embodiments, the polyvinyl ether compound has a K value of 40 to 120, and preferably of 40 to 70, said K value being measured according to ISO 1628-1.

[0020] In embodiments, the polyvinyl ether compound has a glass transition temperature of -60 to 0°C, and preferably of -50 to -5°C, said glass transition temperature being measured according to standard NF EN ISO 11357-2.

[0021] In embodiments, the polyvinyl ether compound has a content of 1 to 60% by weight, preferably 5 to 40% by weight and preferably 5 to 25% by weight relative to the total weight of the composition.

[0022] In some embodiments, the composition further comprises at least one silsesquioxane.

[0023] In some embodiments, said composition is a single-component composition.

[0024] In some embodiments, said composition is a two-component composition comprising: a part A comprising said at least one silylated polymer; and a part B comprising said at least one crosslinking catalyst said at least one polyvinyl ether compound being present in part A and / or in part B of the composition.

[0025] The invention also relates to the use of the composition described above as an adhesive.

[0026] The invention also relates to a self-adhesive article comprising at least one support layer and at least one layer of the composition described above.

[0027] In embodiments, said article is chosen from dressings, bandages and medical tapes.

[0028] The present invention addresses the needs expressed above. More specifically, it provides a composition that enables the manufacture of articles exhibiting improved water vapor permeability without compromising good adhesion properties.

[0029] This is achieved through the composition according to the invention. More specifically, the inventors have demonstrated, in a surprising manner, that the adhesive composition according to the invention—in particular, a composition comprising at least one silylated polymer, at least one polyvinyl ether compound, and at least one crosslinking catalyst—makes it possible to obtain self-adhesive articles exhibiting improved vapor permeability without compromising good adhesion properties to a substrate. Indeed, the presence of the polyvinyl ether compound ensures good compatibility with the other constituents of the composition, and more particularly with the chains of the silylated polymer (which already exhibit good water vapor permeability), resulting in improved water vapor permeability of the adhesive composition. By "good compatibility," we mean the stability of the composition during storage and over time. Detailed description

[0030] The invention is now described in more detail and in a non-limiting manner in the following description. Adhesive composition

[0031] In a first aspect, the present invention relates to an adhesive composition comprising at least one silylated polymer including at least one hydrolyzable alkoxysilane group, at least one polyvinyl ether compound, and at least one crosslinking catalyst. Various additives may also be present in the adhesive composition. Silyl polymer

[0032] The silylated polymer comprises at least one hydrolyzable alkoxysilane group, preferably terminal, and preferably at least two hydrolyzable alkoxysilane groups, preferably terminal.

[0033] The silylated polymer can be a polymer comprising at least one, preferably at least two groups, in particular terminal (aux), of general formula [Chem 1]-Si(R 4< ) p (OR 5< ) 3-p in which: R4< and R5<, whether identical or different, each represent a linear or branched alkyl radical comprising 1 to 4 carbon atoms; and p is an integer equal to 0, 1 or 2.

[0034] When p = 2, the R4< groups may be identical or different. When p = 1 or p = 0, the R5< groups may be identical or different. The silylated polymer comprising at least one hydrolyzable alkoxysilane group, preferably at least two, may have a main chain selected from the following main chains: polyether, polyester, polyester-polyether-polyester, polyether-polyester-polyether, polyolefin, polycaprolactone, polyacrylate, polycarbonate, poly(ether-carbonate), poly(ester-carbonate), polyacetal, polyesteramide, polythioether, polyurethane, polyester-polyurethane, polyether-polyurethane, polyether-polyester-polyurethane, polyolefin-polyurethane, polyether-polyolefin-polyurethane, polyurea, or poly(urethane-urea).

[0035] Preferably, silylated polymers comprising at least one hydrolyzable alkoxysilane group are selected from silylated polyether-polyurethanes, silylated polyethers, silylated polyesters, silylated polyester-polyurethanes, silylated polyether-polyester-polyurethanes, silylated polyureas, silylated poly(urethane-urea) and their mixtures.

[0036] The silylated polymer can have a number-average molecular weight (Mn) ranging from 500 to 50,000 g / mol, preferably ranging from 700 to 30,000 g / mol, advantageously from 1,000 to 25,000 g / mol, in particular from 1,000 to 21,000 g / mol.

[0037] The number-average molecular weight of silylated polymers can be measured by methods well known to those skilled in the art, for example by size-exclusion chromatography using polystyrene-type standards.

[0038] The silylated polymer having at least one hydrolyzable alkoxysilane group may be selected from the polymers of general formulas [Chem 2], [Chem 3], [Chem 4], or [Chem 5] as defined below, and their mixtures: [Chem 2] (R 5< O) 3-p (R 4< ) p Si-R 0< -OR 2< -OR 0< -Si(R 4< )p(OR 5< ) 3-p in which: X1< and X2< represent, independently of each other, an oxygen atom or an -NH- group; R1< represents a divalent hydrocarbon radical comprising 5 to 15 carbon atoms which may be aromatic or aliphatic, linear, branched or cyclic; R0 represents a linear or branched alkylene divalent radical comprising 3 to 6 carbon atoms; R3< represents a linear or branched alkylene divalent radical comprising 1 to 6 carbon atoms, preferably R3< representing methylene or n-propylene; R2< represents a polyether block -Rpe< -[ORpe< ] n - in which Rpe< represents a linear or branched alkylene divalent radical comprising 2 to 4 carbon atoms; n is an integer such that the number-average molecular mass of the polyether block -[OR pen]n - ranges from 300 g / mol to 40,000 g / mol in the polymers of general formulas [Chem 2], [Chem 3] and [Chem 4]; R4 and R5, being as defined above;R 6< represents a hydrogen atom, a phenyl radical, a linear, branched or cyclic alkyl radical comprising 1 to 6 carbon atoms, or a 2-succinate radical of general formula [Chem 6]; in which R 7< is a linear or branched alkyl radical comprising from 1 to 6 carbon atoms; m 1 is zero or an integer; m 1 is such that the number-average molecular mass of the polymer of general formula [Chem 3] ranges from 500 g / mol to 50,000 g / mol, preferably from 700 g / mol to 20,000 g / mol; m is a non-zero integer; m is such that the number-average molecular mass of the polymer of general formula [Chem 4] ranges from 500 g / mol to 50,000 g / mol, preferably from 700 g / mol to 20,000 g / mol; p is as defined above, p preferably being 0 or 1; R al< represents a divalent hydrocarbon radical derived from a diol by replacement of each of the two hydroxyl groups with a free valence or represents the radical R 2<; R ac< represents a divalent hydrocarbon radical derived from a dicarboxylic acid by replacement of each of the two carboxyl groups -COOH by a free valence; [Y] q represents a repeating motif of general formula [Chem 28] t is a number such that the polyester diol of formula [Chem 7] has a hydroxyl number (IOH) between 4 and 60 mg KOH / g; q is a non-zero integer; and t and q are such that the number-average molecular weight of the polymer with general formula [Chem 5] is between 400 g / mol and 50,000 g / mol. In some embodiments, X1< and X2< are both oxygen atoms.

[0039] Alternatively, X 1< and X 2< are both -NH- groups.

[0040] Alternatively, one of X 1< and X 2< can be an oxygen atom and the other of X 1< and X 2< can be an -NH- group.

[0041] Preferably, the radical R 1< of the general formulas [Chem 3], [Chem 4] and [Chem 5] is chosen from one of the following divalent radicals whose formulas below show the 2 free valences: the divalent radical derived from isophorone diisocyanate (IPDI) [Chem 8] the divalent radical derived from 4,4'- and 2,4'-dicyclohexylmethane diisocyanate (HMDI) of formula [Chem 9] or formula [Chem 10] the radical derived from 2,4- and 2,6-toluene diisocyanate (TDI) of formula [Chem 11] or formula [Chem 12] the radical derived from 4,4'- and 2,4'-diphenylmethane diisocyanate (MDI) of formula [Chem 13] or formula [Chem 14] the radical derived from m-xylylene diisocyanate (m-XDI) of formula [Chem 15] the radical derived from hexamethylene diisocyanate (HDI) with the formula [Chem 16]-(CH 2 ) 6-

[0042] Preferably, the radical R 1< of the general formulas [Chem 3], [Chem 4] and [Chem 5] is the divalent radical derived from isophorone diisocyanate or xylylene diisocyanate.

[0043] Polymers of general formula [Chem 3] can for example be obtained according to a process described in documents EP 2336208 A1 and WO 2009 / 106699 A2.

[0044] Examples of polymers conforming to the general formula [Chem 3] include: GENIOSIL ®< STP-E10 (available from WACKER): polyether comprising two [Chem 1] dimethoxy groups (m 1 equals 0, p equals 1 and R 4< and R 5< represent a methyl group) with a number-average molecular mass of approximately 8,889 g / mol where R3 represents a methylene group; GENIOSIL ®< STP-E30 (available from WACKER): polyether comprising two groups of general formula [Chem 1] dimethoxy type (m 1 equals 0, p equals 1 and R 4< and R 5< represent a methyl group) with a number-average molecular mass of approximately 14,493 g / mol where R 3< represents a methylene group; SPUR+ ®< 1050MM (available from MOMENTIVE): polyether-polyurethane comprising two groups of general formula [Chem 1] of trimethoxy type (m 1 different from 0, p equal to 0 and R 5< represents a methyl group) having a number average molecular mass of about 16,393 g / mol where R 3< represents an n-propylene group;SPUR+ ®< Y-19116 (available from MOMENTIVE): polyether-polyurethane comprising two groups of general formula [Chem 1] of the trimethoxy type (m 1 not equal to 0 and R 5< represents a methyl group) having a number-average molecular weight ranging from 15,000 to 17,000 g / mol where R 3< represents an n-propylene group; DESMOSEAL ®< S XP 2636 (available from BAYER): polyether comprising two groups of general formula [Chem 1] of the trimethoxy type (m 1 equal to 0, p equal to 0 and R 5< represents a methyl group) having a number-average molecular weight of approximately 15,038 g / mol where R 3< represents an n-propylene group.

[0045] Polymers of general formula [Chem 2] can be obtained by hydrosilylation of polyether diallylether according to a process described for example in document EP 1829928 A1.

[0046] Among the polymers conforming to the general formula [Chem 2], we can mention: MS POLYMER ™< S303H (available from KANEKA) corresponds to a polyether comprising two groups of general formula [Chem 1] of the dimethoxy type (p is equal to 1 and R 4< represents a methyl group) having a number average molecular mass of about 22,000 g / mol and a viscosity of 12.5 Pa.s at 23°C; and MS POLYMER ™< S227 (available from KANEKA) corresponds to a polyether comprising two groups of general formula [Chem 1] of the dimethoxy type (p is equal to 1, R 5< and R 4< each represent a methyl group) having a number average molecular mass of about 27,000 g / mol, and a viscosity of 34 Pa.s at 23°C.

[0047] Polymers of general formula [Chem 4] can be obtained according to the following process (in the case where the polymer of general formula [Chem 4] is a silylated polyurethane): reaction of a polyether polyol of general formula [Chem 17] HO-R2<-OH with a stoichiometric excess of diisocyanate of formula NCO-R1<-NCO to form a polyurethane-polyether block having at least two -NCO terminal groups, said block preferably comprising 1.5% to 1.9% by weight of -NCO group, and then reaction between a block obtained in the previous step with a stoichiometric amount or a slight excess of an α-, β- or γ-aminosilane having the general formula [Chem 18] (R5<O)3-p(R4<)pSi-R3<-NHR6<

[0048] Such a process is described for example in WO 2013 / 136108 A1.

[0049] Examples of polymers conforming to the general formula [Chem 4] include: SPUR+ 1015 LM (available from MOMENTIVE) corresponds to a polyether-polyurethane comprising two [Chem 1] groups of the trimethoxy type (p is equal to 0, R 5< represents a methyl group) having a molecular mass by number of approximately 25,000 g / mol and a viscosity of 50 Pa at 23°C.

[0050] Polymers of general formula [Chem 4] can be obtained according to the following process (in the case where the polymer of general formula [Chem 4] is a silylated polyurea): reaction of a diamine of general formula [Chem 19] H 2 NR 2< -NH 2 with a stoichiometric excess of diisocyanate of formula NCO-R 1< -NCO to form a polyurea-polyether block having at least two terminal -NCO groups, said block preferably comprising 1.5% to 1.9% by weight of -NCO group, and then reaction between a block obtained in the previous step with a stoichiometric amount or a slight deficiency of an α-, β- or γ-aminosilane having the general formula [Chem 18] (R 5< O) 3-p (R 4< ) p Si-R 3< -NHR 6<

[0051] Such a process is described for example in WO 2020 / 016581 A1.

[0052] The polymers of general formula [Chem 5] may be those described in application EP 2865694 A1. They may be prepared according to the process described in that application.

[0053] The polymer with general formula [Chem 5] can be a first specific polymer with general formula [Chem 5] in which: Ral represents a divalent hydrocarbon radical derived from a dimerized fatty alcohol by replacing each of the two hydroxyl groups with a free valence, said alcohol having a hydroxyl number IOH between 200 and 220 mg KOH / g; Rac represents a divalent hydrocarbon radical derived from a dimerized fatty acid by replacing each of the two carboxyl groups -COOH with a free valence, said acid having an acid number IA between 190 and 200 mg KOH / g: t is preferably a number such that the polyester diol has the general formula [Chem 7] has a hydroxyl index I OH between 45 and 55 mg KOH / g.

[0054] This first specific general formula polymer [Chem 5] can be obtained according to the process described in application EP 2865 728 A1 (in particular on pages 5 to 9).

[0055] Preferably, this first specific general formula [Chem 5] polymer has a number-average molecular mass ranging from 900 to 15,000 g / mol.

[0056] The polymer with general formula [Chem 5] may be a second polymer with specific general formula [Chem 5] in which: Ral represents a divalent hydrocarbon radical derived from a saturated diol, by replacement of each of the two hydroxyl groups by a free valence, said diol having a hydroxyl number IOH greater than 220 mg KOH / g; Rac represents a divalent hydrocarbon radical derived from a saturated dicarboxylic acid, by replacement of each of the two carboxyl groups -COOH by a free valence, said acid having an acid number IA greater than 200 mg KOH / g. The number is preferably such that the polyester diol has the general formula [Chem 7] has a hydroxyl index I OH between 4 and 24 mg KOH / g, in particular between 9 and 24 mg KOH / g.

[0057] The second specific polymer with general formula [Chem 5] can be obtained by a process that includes several sequential steps: The first step in the process of obtaining the second specific general formula polymer [Chem 5] consists of repairing a polyester of general formula [Chem 7] having a hydroxyl number I OH between 4 and 24 mg KOH / g. The polyester of general formula [Chem 7] can be prepared by a polycondensation reaction between: at least one saturated dicarboxylic acid having an acid number IA greater than 200 mg KOH / g; and at least one saturated diol having a hydroxyl number I OH greater than 220 mg KOH / g.

[0058] In this text: the acid number IA of a dicarboxylic acid is the number of carboxylic groups per gram of acid, said number being expressed as the equivalent in milligrams of KOH required to neutralize the acidity of 1 gram of acid, determined by titration, said number being related to the number-average molecular mass M of said acid by the following relation [Math 1] I A = 56 , 1 × 2 × 1000 / M The hydroxyl number (I₂OH) of a diol is the number of hydroxyl groups per gram of diol, expressed as the equivalent in milligrams of KOH used in the determination of hydroxyl groups, as determined by titration according to ISO 14900:2001. This number is related to the number-average molecular weight (M') of the diol by the following relationship: I OH = 56 , 1 × 2 × 1000 / M ′

[0059] Preferably, the saturated dicarboxylic acid(s) has / have an acid value (AV) greater than or equal to 300 mg KOH / g, preferably greater than or equal to 400 mg KOH / g, preferably greater than or equal to 500 mg KOH / g, in particular greater than or equal to 700 mg KOH / g, and advantageously greater than or equal to 800 mg KOH / g. Preferably, the saturated dicarboxylic acid(s) has / have an acid value (AV) equal to 555 mg KOH / g or equal to 768 mg KOH / g.

[0060] Dicarboxylic acid can be linear or branched, preferably linear, aliphatic or cycloaliphatic.

[0061] The dicarboxylic acid according to the invention can be selected from the group consisting of malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, 1,3- or 1,4-cyclohexane dicarboxylic acid, 3-methyl-1,5-pentanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, azelaic acid, sebacic acid and mixtures thereof.

[0062] Preferably, the dicarboxylic acid is adipic acid or sebacic acid.

[0063] Preferably, the saturated diol(s) has a hydroxyl index I OH greater than or equal to 500 mg KOH / g, preferably greater than or equal to 700 mg KOH / g, even more preferably greater than or equal to 900 mg KOH / g.

[0064] The diol used can be aromatic or aliphatic (preferably aliphatic), linear or branched, preferably branched.

[0065] The diol according to the invention can be selected from the group consisting of ethylene glycol (CAS: 107-21-1), diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,6-hexanediol, 3-ethyl-2-methyl-1,5-pentanediol, 2-ethyl-3-propyl-1,5-pentanediol, 2,4-dimethyl-3-ethyl-1,5-pentanediol, 2-ethyl-4-methyl-3-propyl-1,5-pentadiol, 2,3-diethyl-4-methyl-1,5-pentanediol, 3-ethyl-2,2,4-trimethyl-1,5-pentadiol, 2,2-dimethyl-4-ethyl-3-propyl-1,5-pentanediol, 2-methyl-2-propyl-1,5-pentanediol, 2,4-dimethyl-3-ethyl-2-propyl-1,5-pentanediol, 2,3-dipropyl-4-ethyl-2-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,5-pentanediol, 2-butyl-2,3-diethyl-4-methyl-1,5-pentanediol, 2-butyl-2,4-diethyl-3-propyl-1,5-pentanediol, 3-butyl-2-propyl-1,5-pentanediol, 2-methyl-1,5-pentanediol (CAS: 42856-62-2), 3-methyl-1,5-pentanediol (MPD, CAS: 4457-71-0), 2,2-Dimethyl-1,3-pentanediol (CAS: 2157-31-5), 2,2-Dimethyl-1,5-pentanediol (CAS: 3121-82-2), 3,3-Dimethyl-1,5-pentanediol (CAS: 53120-74-4), 2,3-Dimethyl-1,5-pentanediol (CAS: 81554-20-3), 2,2-Dimethyl-1,3-propanediol (Neopentyl glycol - NPG, CAS: 126-30-7), 2,2-Diethyl-1,3-propanediol (CAS: 115-76-4), 2-Methyl-2-propyl-1,3-propanediol (CAS: 78-26-2), 2-Butyl-2-ethyl-1,3-propanediol (CAS: 115-84-4), 2-Methyl-1,3-propanediol (CAS: 2163-42-0), 2-Benzyloxy-1,3-propanediol (CAS: 14690-00-7), 2,2-Dibenzyl-1,3-propanediol (CAS: 31952-16-6), 2,2-Dibutyl-1,3-propanediol (CAS: 24765-57-9), 2,2-Diisobutyl-1,3-propanediol, 2,4-Diethyl-1,5-pentanediol, 2-Ethyl-1,6-hexanediol (CAS: 15208-19-2), 2,5-Dimethyl-1,6-hexanediol (CAS: 15208-19-2) : 49623-11-2), 5-methyl-2-(1-methylethyl)-1,3-hexanediol (CAS: 80220-07-1), 1,4-dimethyl-1,4-butanediol, 1,5-hexanediol (CAS: 928-40-5), 3-methyl-1,6-hexanediol (CAS: 4089-71-8), 3-tert-butyl-1,6-Hexanediol (CAS: 82111-97-5), 1,3-Heptanediol (CAS: 23433-04-7), 1,2-Octanediol (CAS: 1117-86-8), 1,3-Octanediol (CAS: 23433-05-8), 2,2,7,7-Tetramethyl-1,8-Octanediol (CAS: 27143-31-3), 2-Methyl-1,8-Octanediol (CAS: 109359-36-6), 2,6-Dimethyl-1,8-Octanediol (CAS: 75656-41-6), 1,7-Octanediol (CAS: 3207-95-2), 4,4,5,5-tetramethyl-3,6-dioxa-1,8-octanediol (CAS: 76779-60-7), 2,2,8,8-tetramethyl-1,9-nonanediol (CAS: 85018-58-2), 1,2-nonanediol (CAS: 42789-13-9), 2,8-dimethyl-1,9-nonanediol (CAS: 40326-00-9), 1,5-nonanediol (CAS: 13686-96-9), 2,9-dimethyl-2,9-dipropyl-1,10-decanediol (CAS: 85018-64-0), 2,9-dibutyl-2,9-dimethyl-1,10-decanediol (CAS: 85018-65-1), 2,9-dimethyl-2,9-dipropyl-1,10-decanediol (CAS: 85018-64-0), 2,9-diethyl-2,9-dimethyl-1,10-decanediol (CAS: 85018-63-9), 2,2,9,9-tetramethyl-1,10-decanediol (CAS: 35449-36-6), 2-nonyl-1,10-decanediol (CAS: 48074-20-0), 1,9-decanediol (CAS: 128705-94-2),of 2,2,6,6,10,10-hexamethyl-4,8-dioxa-1,11-undecanediol (CAS: 112548-49-9), of 1-phenyl-1,11-undecanediol (CAS: 109217-58-5), of 2-octyl-1,11-undecanediol (CAS: 48074-21-1), of 2,10-diethyl-2,10-dimethyl-1,11-undecanediol (CAS: 85018-66-2), of 2,2,10,10-tetramethyl-1,11-undecanediol (CAS: 35449-37-7), of 1-phenyl-1,11-undecanediol (CAS: 109217-58-5), of 1,2-undecanediol (CAS: 13006-29-6), 1,2-dodecanediol (CAS: 1119-87-5), 2,11-dodecanediol (CAS: 33666-71-6), 2,11-diethyl-2,11-dimethyl-1,12-dodecanediol (CAS: 85018-68-4), 2,11-dimethyl-2,11-dipropyl-1,12-dodecanediol (CAS: 85018-69-5), 2,11-dibutyl-2,11-dimethyl-1,12-dodecanediol (CAS: 85018-70-8), 2,2,11,11-tetramethyl-1,12-dodecanediol (CAS: 5658-47-9), 1,11-dodecanediol (CAS: 80158-99-2), 11-methyl-1,7-dodecanediol (CAS: 62870-49-9), 1,4-dodecanediol (CAS: 38146-95-1), 1,3-dodecanediol (CAS: 39516-24-0), 1,10-dodecanediol (CAS: 39516-27-3), 2,11-dimethyl-2,11-dodecanediol (CAS: 22092-59-7), 1,5-dodecanediol (CAS: 20999-41-1), 6,7-dodecanediol (CAS: 91635-53-9), and mixtures thereof.

[0066] Preferably, the diol is chosen from the group consisting of ethylene glycol (CAS: 107-21-1), 1,6-hexanediol, 3-methyl-1,5-pentanediol (MPD, CAS: 4457-71-0), 2,2-dimethyl-1,3-propanediol (Neopentyl glycol - NPG, CAS: 126-30-7), and mixtures thereof.

[0067] Preferably, the polyester of general formula [Chem 7] is obtained by polycondensation reaction between: adipic acid; and a mixture of neopentyl glycol, ethylene glycol, and 1,6-hexanediol; or between: adipic acid; and 3-methyl-1,5-pentanediol.

[0068] Preferably, the polyester diol of general formula [Chem 7] has a hydroxyl value (I₂OH) of between 4 and 24 mg KOH / g, preferably between 7 and 24 mg KOH / g, preferably between 7 and 20 mg KOH / g, and in particular between 9 and 19 mg KOH / g. Preferably, the hydroxyl value (I₂OH) is between 9 and 24 mg KOH / g.

[0069] The polyester diol of general formula [Chem 7] may have a glass transition temperature Tg less than 0°C, preferably less than or equal to -20°C, preferably less than or equal to -40°C, preferably less than or equal to -50°C, in particular less than or equal to -60°C, for example less than or equal to -64°C.

[0070] The polyester diol of general formula [Chem 7] may have a number-average molecular mass greater than or equal to 5,500 g / mol, preferably greater than or equal to 6,000 g / mol, in particular strictly greater than 6,000 g / mol, preferably greater than or equal to 8,000 g / mol, in particular greater than or equal to 9,000 g / mol, for example greater than or equal to 10,000 g / mol, advantageously greater than or equal to 12,000 g / mol, and in particular greater than or equal to 18,000 g / mol.

[0071] The number-average molecular mass of the polyester diol with general formula [Chem 7] can be determined from its I OH and its functionality.

[0072] Among the amorphous diol polyesters of general formula [Chem 7], we can cite for example DYNACOLL ®< 7250 marketed by EVONIK (polyester polyol having a viscosity of 180 Pa.s at 23°C, a number average molecular mass Mn equal to 5,500 g / mol, and a T g equal to - 50°C), KURARAY ®< P-6010 marketed by KURARAY (polyester polyol having a viscosity of 68 Pa.s at 23°C, a number average molecular mass equal to 6,000 g / mol, and a T g equal to -64°C), or KURARAY ®< P-10010 marketed by KURARAY (polyester polyol having a viscosity of 687 Pa.s at 23°C, a number average molecular mass equal to 10,000 g / mol).

[0073] The second step in the process of obtaining the second specific general formula polymer [Chem 5] consists of preparing the general formula polymer [Chem 5].

[0074] According to a first variant, the aforementioned polyester(s) of general formula [Chem 7] can be reacted with isocyanatosilane of general formula [Chem 20] NCO-R 3< -Si(R 4< ) p (OR 5< ) 3-p in an amount corresponding to an equivalent molar ratio of the number of NCO / OH functions between 0.90 and 1.05 and preferably equal to about 1.

[0075] This step is carried out under anhydrous conditions to avoid hydrolysis of the alkoxysilane groups. A typical temperature range for this reaction step is 30°C to 120°C, and more specifically 60°C to 105°C.

[0076] The isocyanatosilanes of the general formula [Chem 20] mentioned above are widely available commercially. Examples include SILQUEST®< A-LINK 35 (3-isocyanatopropyl)trimethoxysilane) available from MOMENTIVE, SILQUEST®< A-LINK 25 (3-isocyanatopropyl)triethoxysilane) available from MOMENTIVE, (3-isocyanatopropyl)methyldimethoxysilane available from GELEST, GENIOSIL®< XL 42 (3-isocyanatomethyl)methyldimethoxysilane available from WACKER), and GENIOSIL®< XL 43 (3-isocyanatomethyl)trimethoxysilane available from WACKER. According to a second variant, the silylated polymer can be obtained in two steps by: reaction of polyester polyol(s) of general formula [Chem 7] with a diisocyanate of formula NCO-R 1< -NCO in quantities corresponding to an equivalent molar ratio of the number of NCO / OH functions between 0.3 and 0.7 and preferably equal to about 0.5, to form a polyester-polyurethane block; reaction between a block obtained in the previous step with isocyanatosilane of formula [Chem 20], in an amount corresponding to an equivalent molar ratio of the number of NCO / OH functions between 0.90 and 1.05 and preferably equal to about 1.

[0077] Isocyanatosilanes can be those mentioned above.

[0078] Preferably, the silylated polymer according to the invention is a polymer of general formula [Chem 3] in which: m 1 is an integer equal to 0; p = 1 ; R 4< and R 5< each represent a methyl radical; R 3< represents a divalent methylene radical; the number-average molecular mass of said polymer ranges from 5,000 to 30,000 g / mol, preferably from 10,000 to 20,000 g / mol, in particular from 14,000 g / mol to 15,000 g / mol.

[0079] Preferably, the silylated polymer according to the invention is a polymer of general formula [Chem 3] in which: m 1 is an integer other than 0; p = 0 ; R 3< represents a divalent propylene radical; R 5< represents a methyl radical; the number-average molecular mass of said polymer ranges from 5,000 to 30,000 g / mol, preferably from 10,000 to 30,000 g / mol, in particular from 15,000 to 25,000 g / mol.

[0080] Preferably, the silylated polymer according to the invention is a polymer of general formula [Chem 5] in which: q is an integer other than 0; p = 0 ; R 3< represents a divalent propylene radical; R 5< represents a methyl radical; the number-average molecular mass of said polymer ranges from 5,000 to 30,000 g / mol, preferably from 10,000 to 30,000 g / mol, in particular from 15,000 to 25,000 g / mol.

[0081] The adhesive composition may comprise a single polymer as described above.

[0082] Alternatively, the adhesive composition may comprise more than one silylated polymer, for example two, or three, or four, or five, or more than five silylated polymers.

[0083] The adhesive composition according to the invention may comprise from 20 to 90%, preferably from 30 to 70% by weight of silylated polymer, relative to the total weight of the adhesive composition. Polyvinyl ether compound

[0084] The polyvinyl ether compound according to the invention is a homopolymer selected from poly(methylvinyl ether), poly(ethylvinyl ether), poly(butylvinyl ether), poly(isobutylvinyl ether), poly(isopropylvinyl ether), poly(propylvinyl ether), poly(octylvinyl ether) and mixtures thereof.

[0085] The polyvinyl ether compound according to the invention can have a K value of 30 to 120, and preferably from 40 to 70. By " value K "This refers to a measurement of the average degree of polymerization. The K value is measured according to ISO 1628-1."

[0086] The polyvinyl ether compound according to the invention can further exhibit a glass transition temperature of -60 to 0°C, and preferably of -50 to -5°C. The glass transition temperature was measured by differential scanning calorimetry (DSC). The glass transition temperature can be measured according to standard NF EN ISO 11357-2.

[0087] Commercial polyvinyl ether compounds may include Lutonal ®< M 40, Lutonal ®< A 25, Lutonal ®< A 50, Lutonal ®< A 100, Lutonal ®< I 30, Lutonal ®< I 60, Lutonal ®< I 60 D, Lutonal ®< I 65 D available from BASF and Gantrez ®< M available from the company GAF.

[0088] The adhesive composition according to the invention may comprise from 1 to 60%, preferably from 5 to 40% and even more preferably from 5 to 25% by weight of polyvinyl ether compound, relative to the total weight of the adhesive composition. Crosslinking catalyst

[0089] The catalyst for the adhesive composition can be chosen from the group consisting of amines, organometallic compounds, acids and their derivatives, and mixtures thereof. It can be a mixture of catalysts from the same family (for example, a mixture of several amines), or a mixture of catalysts from different families (for example, a mixture of an amine and an organometallic compound).

[0090] In the context of the invention, the term " organometallic compounds compounds comprising an organic radical and at least one metal.

[0091] In the context of the invention, the term " organic radical", a radical comprising at least one carbon atom.

[0092] Organometallic compounds may include organometallic compounds (compounds comprising at least one metal-carbon covalent bond), metal alkoxides, metal carboxylates, and metal coordination complexes with one or more organic ligands.

[0093] Examples of organic ligands include acetylacetonate and oximes.

[0094] The metal atom in organometallic compounds can be any metal atom known to a person skilled in the art, and in particular can be chosen from tin, aluminum, zinc, cobalt, iron, nickel, bismuth, titanium, or zirconium. Organometallic compounds may, moreover, comprise several metal atoms.

[0095] Organometallic compounds (compounds containing at least one metal-carbon covalent bond) can be carboxylates of organometallic compounds.

[0096] Organometallic compounds may be selected from the group consisting of dibutyl tin dilaurate (DBTL), dibutyl tin diacetate, dibutyl tin diethylhexanoate, dioctyl tin dineodecanoate (for example, available under the name TIB KAT ®< 223 from TIB CHEMICALS), dibutyl tin dioleate, dibutyl tin benzylmaleate, diphenyl tin diacetate, and mixtures thereof.

[0097] Metal alkoxides can be selected from the group consisting of titanium tetrabutanolate, titanium tetraisopropylate, zirconium tetrabutanolate, zirconium tetraisopropylate, and mixtures thereof.

[0098] Metal carboxylates may be selected from the group consisting of zinc 2-ethylcaproate, zinc diacetate, zinc dineodecanoate, zinc diundecenoate, zinc dimethacrylate, cobalt acetylacetonate, cobalt diacetate, iron acetylacetonate, iron diacetate, nickel acetylacetonate, nickel diacetate, bismuth acetate, bismuth trioctanoate, bismuth dineodecanoate, zinc and bismuth dineodecanoate, and mixtures thereof.

[0099] Metal coordination complexes with one or more organic ligands may be chosen from the group consisting of zinc acetylacetonate, titanium acetylacetonate (for example, commercially available under the name TYZOR ®< AA75 from DORF KETAL), titanium tetraacetylacetonate, aluminum trisacetylacetonate, aluminum chelates such as, for example, bis(ethylacetoacetate) monoacetylacetonate (for example, commercially available under the name K-KAT ®< 5218 from KING INDUSTRIES), zirconium tetraacetylacetonate, diisopropoxybis(ethylacetonato)titanium, and mixtures thereof.

[0100] Amines can be primary amines, secondary amines, or tertiary amines.

[0101] The amines can be aminosilanes, such as for example aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, bis(gamma-trimethoxysilylpropyl)amine, N-ethyl-gamma-aminoisobutyltrimethoxysilane, or N-phenylgamma-aminopropyltrimethoxysilane.

[0102] Preferably, the catalyst is not an aminosilane.

[0103] Preferably, the amines are chosen from the group consisting of triethylamine, tributylamine, tetramethylguanidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene, N,N-bis(N,N-dimethyl-2-aminoethyl)methylamine, N,N-dimethylcyclohexaylamine, N,N-dimethylphenylamine, N-ethylmorpholine, and mixtures thereof.

[0104] Acid catalysts can be chosen from organic acid catalysts, inorganic acid catalysts, and mixtures thereof.

[0105] Examples of inorganic acid catalysts include phosphoric or orthophosphoric acid, phosphorous acid, hypophosphorous acid, and sulfuric acid.

[0106] Preferably, the organic acid catalysts have a pKa less than or equal to 6, preferably less than or equal to 4, advantageously less than or equal to 2, advantageously less than or equal to 0.

[0107] Organic acid catalysts can be selected from sulfonic acids, carboxylic acids, acid organophosphates, acid organophosphonates, phosphonic acids, and mixtures thereof. Sulfonic acids can be aliphatic or aromatic, possibly substituted (for example, substituted with at least one substituent selected from halogens (such as fluorine), hydroxyl groups, alkyl groups, amines, and mixtures thereof), and can be mono- or disulfonic.

[0108] Sulfonic acids can be chosen from among N-alkylaminoalkylsulfonic acids and N,N-dialkylaminoalkylsulfonic acids (zwitterions), such as, for example, 2-(N-morpholino)ethanesulfonic acid, 3-(N-morpholino)propanesulfonic acid, 4-[N-morpholino]butanesulfonic acid, 1,4-piperazinediethanesulfonic acid, N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid, 2-(N-morpholino)ethanesulfonic acid, N-morpholinomethanesulfonic acid, N-(2-hydroxyethyl)piperazine-N'-methanesulfonic acid, piperazine-N,N'-bis(methanesulfonic) acid, cyclohexylaminomethanesulfonic acid, N-[tris(hydroxymethyl)methyl]aminomethanesulfonic acid, N,N-bis(2-hydroxyethyl)aminomethanesulfonic acid; para-toluenesulfonic acid; benzenesulfonic acid; methanesulfonic acid; dodecylbenzene disulfonic acid; dodecylbenzene sulfonic acid; dinonylnaphthalene disulfonic acid; dinonylnaphthalene sulfonic acid;trifluoromethylsulfonic acid; and mixtures thereof.

[0109] In particular, sulfonic acids are selected from para-toluene sulfonic acid, benzene sulfonic acid, methanesulfonic acid, dodecylbenzene sulfonic acid, dodecylbenzene disulfonic acid, dinonylnaphthalene disulfonic acid, dinonylnaphthalene sulfonic acid, trifluoromethylsulfonic acid, and mixtures thereof.

[0110] Examples of carboxylic acid catalysts include malonic acid, succinic acid, maleic acid, oxalic acid, acetic acid, lactic acid, benzoic acid, citric acid, glycolic acid, and mixtures thereof.

[0111] In the context of the invention, and unless otherwise stated, the term " acid organophosphate", an ester of phosphoric acid comprising at least one -OH radical. For example, methyl phosphate is an acidic organophosphate comprising two -OH radicals and of general formula [Chem 22]

[0112] In particular, acid organophosphates have the general formula [Chem 23] (R 10< O) g -(P=O)-(OH) h in which: R 10< is an organic radical, in particular a radical chosen from among the linear or branched C1-C22 alkyls, cycloalkyls, aryls, and mixtures thereof (said alkyl, cycloalkyl and aryl groups being optionally substituted); and g and h are integers, with g + h = 3 and h = 1 or 2.

[0113] Acid organophosphates, for example, may be chosen from the group consisting of mono- or dialkyl acid phosphates in C1-C22 and mixtures thereof, such as butyl phosphate, dibutyl phosphate, di-(2-ethylhexyl) phosphate, 2-ethylhexyl phosphate and mixtures thereof; mono- or diaryl phosphates and mixtures thereof, such as monophenyl phosphate, diphenyl phosphate and mixtures thereof; alkyl-phenyl phosphates; and mixtures thereof.

[0114] In the context of the invention, and unless otherwise stated, "acid organophosphonate" means a phosphorus compound having the general formula [Chem 24] R 11< -(P=O)-(OH)(OR 12< ) in which R 11< and R 12< are organic radicals, preferably chosen independently of each other, from linear or branched C1-C22 alkyls, cycloalkyls, aryls, and mixtures thereof (said alkyl, cycloalkyl and aryl groups being optionally substituted).

[0115] Examples of acid organophosphonates include C1-C22 acid monoalkyl phosphonates.

[0116] In the context of the invention, and unless otherwise stated, "phosphonic acid" means a phosphorus compound having the general formula [Chem 25] R 13< -(P=O)-(OH) 2 in which R 13< is an organic radical, preferably selected from linear or branched C1-C22 alkyls, cycloalkyls, aryls, and mixtures thereof (said alkyl, cycloalkyl and aryl groups being optionally substituted).

[0117] Examples of phosphonic acids include N-alkylaminoalkylphosphonic acids (zwitterions), N,N-dialkylaminoalkylphosphonic acids (zwitterions), C1-C20 alkylphosphonics such as methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, t-butylphosphonic acid, isobutylphosphonic acid, hexylphosphonic acid, ethyl-2-hexylphosphonic acid and higher linear or branched homologues, benzylphosphonic acid, phenylphosphonic acid, toluylphosphonic acid, and xylylphosphonic acid.Examples of organic acid catalysts include NACURE®< 155 (dinonylnaphthalene disulfonic acid, 55% active ingredient in isobutanol) marketed by KING INDUSTRIES, NACURE®< 1051 (dinonylnaphthalene sulfonic acid, 50% active ingredient in 2-butoxyethanol) marketed by KING INDUSTRIES, NACURE®< 5076 (dodecylbenzene sulfonic acid, 70% active ingredient in isopropanol) marketed by KING INDUSTRIES, K-CURE®< 1040 (para-toluene sulfonic acid, 40% active ingredient in isopropanol) marketed by KING INDUSTRIES, and NACURE®< 4000 (mixture of mono- and dialkyl acid phosphates, 100% active ingredient) marketed by KING INDUSTRIES. INDUSTRIES.

[0118] The acid derivatives according to the invention can be acid anhydrides, acid esters, ammonium salts of acid, the acid being as described above.

[0119] Acid derivatives are, in particular, so-called "acids" blocked or even latent " which advantageously allow the acid to be released by thermal activation (for example at a temperature ranging from 70°C to 170°C, preferably at a temperature ranging from 90°C to 120°C) or by hydrolysis, or by photoactivation, preferably by thermal activation.

[0120] The blocked acid advantageously allows the release of the acid that is the entity with catalytic activity. For example, the ammonium salt formed between aminomethyl propanol and para-toluenesulfonic acid is a blocked acid (acid derivative) that, upon thermal activation, releases para-toluenesulfonic acid.

[0121] Acid derivatives can be prepared by any method known to those skilled in the art from the corresponding acid, for example, by using typical acid-base reactions. For instance, the process for making an ester typically involves the condensation of an acidic compound with a compound containing a hydroxyl group, such as an alcohol, or with an oxirane-type compound. Ammonium salts can be prepared from any of the aforementioned acids, with ammonia, or with a primary, secondary, or tertiary amine. Amines may optionally include at least one functional group, such as a hydroxyl group (alkanolamines) or a C1-C4 alkyl group.Ammonium salts (zwitterions) can also be prepared by modifying the pH of a solution containing, for example, N-alkylaminoalkylphosphonic acids, N,N-dialkylaminoalkylphosphonic acids, N-alkylaminoalkylsulfonic acids or N,N-dialkylaminoalkylsulfonic acids.

[0122] Preferably, the catalyst is an ammonium salt of a sulfonic acid (the sulfonic acid being as described above), an ammonium salt of a phosphonic acid (the phosphonic acid being as described above), an ammonium salt of an acid organophosphonate (the acid organophosphonate being as described above), or an ammonium salt of an acid organophosphate (the acid organophosphate being as described above).

[0123] Examples of amines used in the preparation of ammonium salts include 2-amino-2-methyl-1-propanol, triethylamine, aniline, pyridine, dimethylaminoethanol, alkylpyridines, diisopropanolamine, dimethylethanolamine, triethanolamine, oxazolidines, bicyclic oxazolidines, amidines, diazabicyclooctanes, guanidines, N-alkylmorpholines, aminopyridines, aminoalkylpyridines, aminopyrrolidines, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholines, and mixtures thereof. Preferably, the amines are tertiary amines.

[0124] Examples of acid derivatives include NACURE® 3327 or NACURE® 3525 (amine-blocked dinonylnaphthalene sulfonic acid, with 25% active ingredient in isopropanol and isobutanol) marketed by KING INDUSTRIES; NACURE® 1557 or NACURE® 1953 (amine-blocked dinonylnaphthalene sulfonic acid, with 25% active ingredient in a butanol and 2-butoxyethanol mixture) marketed by KING INDUSTRIES; NACURE® 5225 or NACURE® 5528 or NACURE® 5925 (amine-blocked dodecylbenzene sulfonic acid, with 25% active ingredient in isopropanol) marketed by KING INDUSTRIES; and NACURE® 2107 or NACURE ®< 2500 (amine-blocked para-toluenesulfonic acid, with 25% or 26% active ingredient in isopropanol) marketed by KING INDUSTRIES, NACURE ®< 2501 or NACURE ®< 2530 (amine-blocked para-toluenesulfonic acid,NACURE®< 4167 (dialkyl phosphate blocked by an organic amine, with 25% active ingredient in an isopropanol and isobutanol mixture) marketed by KING INDUSTRIES, and NACURE®< 4575 (acid phosphate blocked by an amine, with 25% active ingredient in a methanol and butanol mixture) marketed by KING INDUSTRIES.

[0125] Preferably, the catalyst is selected from the group consisting of organometallic compounds (in particular aluminum-based coordination complexes), orthophosphoric acid, acid organophosphates (preferably C1-C22 mono- or dialkyl acid phosphates and mixtures thereof), ammonium salts (in particular sulfonic acid or acid organophosphate), and mixtures thereof. Even more preferably, the catalyst is selected from the group consisting of orthophosphoric acid, acid organophosphates (preferably C1-C22 mono- or dialkyl acid phosphates and mixtures thereof), and ammonium salts (in particular sulfonic acid or acid organophosphate). The adhesive composition according to the invention may comprise from 0.1 to 4%, preferably from 0.2 to 2%, and even more preferably from 0.3 to 2% by weight of crosslinking catalyst, relative to the total weight of the adhesive composition.

[0126] In the case where the composition according to the invention is a single-component composition, it is preferable to use one of the catalysts mentioned above other than inorganic acids and their salts, and also other than carboxylic acids.

[0127] In the case where the composition according to the invention is a two-component composition (as detailed below), the crosslinking catalyst can be mixed in a reactive or non-reactive diluent. A "non-reactive diluent" is understood to be a diluent that does not react in the presence of the catalyst. Thus, a "reactive diluent" is understood to be a diluent that reacts in the presence of the catalyst. The diluent can be chosen from among weakly reactive monosilanes (Geniosil XM25, MS RD359), water scavengers (XL33), and silsesquioxane resins.

[0128] Non-reactive: polyols, tackifying resins, rheological modifiers (listed under other additives), ...

[0129] This diluent can have a number molecular weight (Mn) ranging from 300 to 50,000 g / mol, and preferably from 1,000 to 20,000 g / mol. This prevents the diluent from migrating into the crosslinked adhesive.

[0130] This diluent can also have a viscosity ranging from 10 to 100,000 mPa.s at 23°C and even more preferably from 500 to 15,000 mPa.s at 23°C. This viscosity is measured with a Brookfield viscometer (flat cone, CAP2000+). Other additives

[0131] The composition according to the present invention may include at least one other additive, for example selected from the group consisting of tackifying resins, silsequioxanes, plasticizers, solvents, pigments, dyes, adhesion promoters, moisture absorbers, UV stabilizers, antioxidants, glitter, fluorescent materials, rheological additives, fillers, flame retardants, waxes, and mixtures thereof. Tackifying resin

[0132] The adhesive composition according to the invention may further comprise at least one tackifying resin.

[0133] The resin(s) used in the context of the invention may be any resin(s) compatible with the silylated polymer(s).

[0134] By " compatible tackifying resin "A tackifying resin is understood to be one which, when mixed in a 50 / 50 by weight ratio with the silylated polymer(s), gives a substantially homogeneous mixture (no phase separation observed visually). In the context of the invention, the tackifying resin is different from the polyvinyl ether compound."

[0135] Tackifying resins are advantageously chosen from among: terpene-phenolic resins; hydrocarbon resins; rosin resins; and acrylic resins.

[0136] Terpene-phenolic resins can have a softening point of 85 to 150°C. Hydrocarbon resins can have a softening point of 15 to 140°C. Rosin resins can have a softening point of 15 to 115°C. The softening point can be measured according to the ASTM E28 standard.

[0137] Terpene-phenolic resins can be obtained by polymerization of terpene hydrocarbons and phenols, in the presence of Friedel-Crafts catalyst(s).

[0138] Hydrocarbon resins can be selected from: resins obtained by a process including the polymerization of alpha-methyl styrene, and possibly in the presence of phenols; resins obtained by hydrogenation, preferably partial hydrogenation, polymerization or copolymerization (with an aromatic hydrocarbon) of a mixture of unsaturated aliphatic hydrocarbons having about 5, 9 or 10 carbon atoms derived from petroleum fractions, optionally grafted with maleic anhydride; terpene resins; generally resulting from the polymerization of terpene hydrocarbons such as, for example, monoterpene (or pinene) in the presence of Friedel-Crafts catalyst(s); copolymers based on natural terpenes, such as, for example, styrene / terpene, alpha-methyl styrene / terpene and vinyl toluene / terpene; and mixtures thereof.

[0139] Rosin resins can be chosen from natural or modified rosins (such as, for example, rosin extracted from pine gum, wood rosin extracted from tree roots) and their hydrogenated, dimerized, polymerized or esterified derivatives with monoalcohols or polyols (such as, for example, glycerol or pentaerythritol).

[0140] An acrylic resin is defined as a polymer or oligomer constructed with a significant amount of (meth)acrylic and / or (meth)acrylate monomers, preferably at least 5% w / w, more preferably at least 10% w / w, even more preferably at least 20% w / w, even more preferably at least 30% w / w in the polymer chain.

[0141] The (meth)acrylic monomers can be selected from: acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-heptyl acrylate, n-heptyl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl methacrylate, alkyl crotonates, vinyl acetate, di-n-butyl maleate, di-octylmaleate, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, methacrylate acetoacetoxypropyl, acetoacetoxypropyl acrylate, diacetone acrylamide, acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, allyl methacrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, n-hexyl acrylate,n-hexyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, isodecyl methacrylate, isodecyl acrylate, 2-methoxy acrylate, 2-methoxy methacrylate, 2-(2-ethoxyethoxy)ethylacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, caprolactone acrylate, caprolactone methacrylate, polypropylene glycol monomethacrylate, polypropylene glycol monoacrylate, polyethylene glycol acrylate (400), polypropylene glycol methacrylate (400), benzyl acrylate, benzyl methacrylate, N-vinyl pyrrolidone or N-vinyl lactam.

[0142] Preferably, the (meth)acrylic monomers have up to 20 carbon atoms, more preferably, the (meth)acrylic monomers are chosen from acrylic acid, methacrylic acid, butyl acrylate, 2-ethylhexyl acrylate and hydroxyethyl acrylate.

[0143] Acrylic resins can be selected from polymers containing at least one (meth)acrylic chain function or portion and at least one hydrocarbon chain portion, said polymers being able to be in the form of copolymers, grafted or reacted or sequenced.

[0144] Acrylic resins preferably have a viscosity at 100°C of less than 100 Pa.s and less than or equal to 100 Pa.s at 150°C.

[0145] Acrylic resins may comprise repeating units of at least one hydrocarbon monomer and at least one acrylate monomer.

[0146] The hydrocarbon monomers are selected from the group consisting of styrene, alpha-methylstyrene, vinyl toluene, indene, methylindene, divinylbenzene, dicyclopentadiene, and methyl-dicyclopentadiene, and from polymerizable monomers found in the C5-pyrylene, C5-isoprene, and C9-aromatic petrochemical streams. These hydrocarbon monomers are usually polymerized together in various ratios by cationic polymerization using Lewis acid catalysts.

[0147] The acrylate monomers are selected from methyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, ethylhexyl, ethylhexyl methacrylate, n-heptyl acrylate, heptyl methacrylate, 2-methyl (meth)heptyl acrylate, octyl acrylate, octyl methacrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl acrylate, isodecyl methacrylate, dodecyl (meth)acrylate, isobornyl (meth)acrylate, lauryl methacrylate, lauryl acrylate, tridecyl acrylate, tridecyl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl methacrylate, alkyl crotonates,vinyl acetate, di-n-butylmaleate, di-octylmaleate, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxypropyl acrylate, diacetone acrylamide, acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, allyl methacrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, isodecyl methacrylate, isodecyl acrylate, acrylate 2-methoxy, 2-methoxy methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, caprolactone acrylate, caprolactone methacrylate, polypropylene glycol monoacrylate,polypropylene glycol monomethacrylate, polyethylene glycol acrylate (400), polypropylene glycol methacrylate (400), benzyl acrylate, benzyl methacrylate, sodium 1-allyloxy-2-hydroylpropyl sulfonate, acrylonitrile and mixtures thereof.

[0148] Preferably, hydrocarbon monomers are selected from the group of aromatic monomers or polymerizable monomers of the C9 aromatic stream from petrochemical sources; dicyclopentadiene or polymerizable monomers from the C5-pyperylene or C5-isoprene stream from petrochemical sources.

[0149] Preferably, the acrylate monomers are chosen from acrylic acid, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methacrylic acid, butyl acrylate.

[0150] The softening point of these acrylic resins is preferably from room temperature up to 180°C, preferably less than or equal to 150°C, more preferably less than or equal to 120°C, and even more preferably from 70 to 120°C. The softening point can be measured according to the ASTM E28 standard.

[0151] Such resins are commercially available, and examples include the following products: For resins obtained by polymerization of terpene hydrocarbons and phenols, in the presence of Friedel-Crafts catalyst(s): DERTOPHENE ®< 1510 available from DRT with a number average molecular mass M n of approximately 870 Da; DERTOPHENE ®< H150 available from DRT with a number average molecular mass M n of approximately 630 Da; DERTOPHENE ®< T available from DRT with a number average molecular mass M n of approximately 500 Da; SYLVAREZ ®< TP 95 available from ARIZONA CHEMICAL with a number average molecular mass of approximately 1200 Da.

[0152] For resins obtained by a process including the polymerization of alpha-methyl styrene, and possibly in the presence of phenols: CLEARTACK ®< W100 available from CRAY VALLEY, obtained by polymerization of alpha-methyl styrene without the action of phenols, having a number average molecular mass of 900 Da; SYLVAREZ ®< 510 which is available from ARIZONA CHEMICAL having a number average molecular mass of about 1740 Da, the process of obtaining which includes the addition of phenols.

[0153] For natural or modified rosins: SYLVALITE ®< RE 100 which is a rosin and pentaerythritol ester available from ARIZONA CHEMICAL, and whose average number molecular mass is about 1700 Da.

[0154] According to a preferred embodiment, the tackifying resin is chosen from resins obtained by polymerization of terpene hydrocarbons and phenols, in the presence of Friedel-Crafts catalyst(s).

[0155] The tackifying resin preferably has a number average molecular mass ranging from 100 to 6,000 g / mol, preferably from 300 to 4,000 g / mol, preferably from 500 to 2,000 g / mol.

[0156] The number-average molecular weights of tackifying resins can be measured using methods well known to those skilled in the art, for example by size-exclusion chromatography using a polystyrene-type standard.

[0157] The tackifying resin may have a hydroxyl value (I₂OH) ranging from 10 to 300 mg KOH / g, preferably from 100 to 200 mg KOH / g, preferably from 140 to 160 mg KOH / g. In particular, the tackifying resin has a hydroxyl value of 145 mg KOH / g.

[0158] The hydroxyl index of the tackifying resin represents the number of hydroxyl functions per gram of tackifying resin, and is expressed as the equivalent number of milligrams of potassium per gram of tackifying resin (mg KOH / g) for the determination of hydroxyl functions.

[0159] The acid value of rosin ester-type tackifying resin can range from 0 to 10 mg KOH / g, and preferably from 0 to 5 mg KOH / g. The acid value of the tackifying resin represents the number of acidic functional groups per gram of tackifying resin and is expressed as the equivalent number of milligrams of potassium hydroxide per gram of tackifying resin (mg KOH / g) for the determination of acidic functional groups.

[0160] The adhesive composition according to the invention may comprise from 0.1 to 80%, preferably from 20 to 70%, and even more preferably from 30 to 60% by weight of tackifying resin, relative to the total weight of the adhesive composition. In the case where the composition according to the invention comprises at least one tackifying resin, the mass ratio of polyvinyl ether compound to tackifying resin may be from 3 to 100%.

[0161] According to some embodiments, the adhesive composition comprises a single tackifying resin.

[0162] According to alternative embodiments, the adhesive composition comprises different tackifying resins, for example two or three or four or five different tackifying resins. Silsesquioxanes

[0163] Silsesquioxanes are typically silicon-organic compounds that can adopt a polyhedral or polymeric structure, with Si-O-Si bonds. They typically have the general formula [Chem 26] [R'SiO 3 / 2]t, where R', of the same or different nature, represents an organic radical, and t is an integer ranging from 6 to 12, preferably t equal to 6, 8, 10, or 12.

[0164] According to one embodiment, silsesquioxane has a polyhedral structure (or POSS for "Polyhedral Oligomeric Silsesquioxane" in English).

[0165] Preferably, silsesquioxane conforms to the general formula [Chem 27] in which each from R' 1< to R' 8< represents, independently of each other, a group chosen from: a hydrogen atom; a radical chosen from the group consisting of a linear or branched C1-C4 alkoxy radical, a linear or branched alkyl radical comprising 1 to 30 carbon atoms, an alkenyl radical comprising 2 to 30 carbon atoms, an aromatic radical comprising 6 to 30 carbon atoms, an allyl radical comprising 3 to 30 carbon atoms, an aliphatic cyclic radical comprising 3 to 30 carbon atoms, an acyl radical comprising 1 to 30 carbon atoms; and a group -OSiR' 9< R' 10< in which R' 9< and R' 10< each represent, independently of each other, a hydrogen atom or a radical chosen from the group consisting of linear or branched C1-C4 alkyls, linear or branched C1-C4 alkoxys, C2-C4 alkenyls, a phenyl, a C3-C6 allyl radical, a C3-C8 cyclic aliphatic radical, and a C1-C4 acyl radical;provided that: at least one radical among the radicals R' 1< to R' 8< is a C1-C4 alkoxy radical; and at least one radical among the radicals R' 1< to R' 8< is a phenyl radical. Silsesquioxanes are known compounds which are described in particular in application WO 2008 / 107331 A1. Some are also commercially available, such as the DOW product marketed under the names: DOW CORNING ®< 3074 and DOW CORNING ®< 3037 (CAS number = 68957-04-0).

[0166] The adhesive composition according to the invention may comprise from 0 to 40%, preferably from 0 to 20%, and even more preferably from 0 to 10% by weight of silsesquioxane, relative to the total weight of the adhesive composition. Charges

[0167] The filler can be chosen from organic fillers, inorganic fillers, and mixtures thereof.

[0168] As organic filler(s), any organic filler(s), and in particular polymeric filler(s), typically used in the field of adhesives, can be used. Examples of materials that can be used include polyvinyl chloride (PVC), polyolefin(s), rubber, ethylene vinyl acetate (EVA), aramid fibers such as KEVLAR®, expandable or non-expandable thermoplastic polymer hollow microspheres (such as vinylidene chloride / acrylonitrile hollow microspheres), thermoplastic polymer(s) selected from those used in the preparation of HMPSA, such as ethylene vinyl acetate (EVA), or styrenic block copolymers (such as SIS, SBS, SIBS, SEBS, SEPS, and their derivatives grafted with, for example, maleic anhydride).

[0169] The filler can be an expanding agent (also called a blowing agent). The filler can be in the form of hollow beads, i.e., containing a gas, or of beads that can be expanded to form hollow beads, i.e., containing a vacuum or a gas.

[0170] Preferably, the filler is an inorganic filler.

[0171] According to one embodiment, the charge is chosen from sand, precipitated and / or pyrogenated silica, zeolites, glass beads, glass, quartz, barite, alumina, mica, talc, alkali or alkaline-earth metal carbonates (for example calcium carbonate).

[0172] The filler(s) preferably represent 0% to 15% by weight, preferably 0% to 10%, preferably 0% to 5% by weight, of the total weight of the adhesive composition.

[0173] According to one embodiment, the composition according to the invention does not include a filler. Plasticizing agent

[0174] The composition according to the invention may comprise at least one plasticizing agent. The total plasticizing agent content in the composition may range from 0% to 30% by weight, preferably from 1% to 30% by weight, or even, for example, from 1% to 15% by weight relative to the total weight of said composition.

[0175] As an example of a usable plasticizing agent, any plasticizing agent commonly used in the field of adhesives may be used, such as, for example, phthalates, benzoates, trimethylolpropane esters, trimethylolethane esters, trimethylolmethane esters, glycerol esters, pentaerythritol esters, naphthenic mineral oils, adipates, cyclohexyldicarboxylates, paraffinic oils, natural oils (possibly epoxidized), polypropylenes, polybutylenes, hydrogenated polyisoprenes, and mixtures thereof.

[0176] Examples of phthalates include diisononyl phthalate, di-isobutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate, diisododecyl phthalate, dibenzyl phthalate, and butylbenzyl phthalate.

[0177] Examples of benzoates include: neopentyl glycol dibenzoate (for example, available under the name UNIPLEX®< 512 from LANXESS), dipropylene glycol dibenzoate (for example, available under the name BENZOFLEX®< 9-88SG from EASTMAN), and a mixture of diethylene glycol dibenzoate and dipropylene glycol dibenzoate (for example, available under the name K-

[0178] FLEX ®< 850 S from KALAMA CHEMICAL), or a mixture of diethylene glycol dibenzoate, dipropylene glycol dibenzoate and triethylene glycol dibenzoate (for example available under the name BENZOFLEX ®< 2088 from EASTMAN).

[0179] Among the esters of pentaerythritol, one can cite for example pentaerythritol tetravalerate (for example available under the name PEVALEN ™ from the company PESTORP).

[0180] Among the cyclohexanedicarboxylates, we can cite for example diisononyl 1,2-cyclohexanedicarboxylate (for example available under the name HEXAMOLL DINCH ®< from BASF). Pigment

[0181] When a pigment is present in the composition according to the invention, its content is preferably less than or equal to 3% by weight, and even more preferably less than or equal to 2% by weight, relative to the total weight of the composition. When present, the pigment may, for example, represent from 0.1% to 3% by weight or from 0.4% to 2% by weight of the total weight of the composition according to the invention.

[0182] Pigments can be organic or inorganic.

[0183] For example, the pigment is TiO2, in particular KRONOS® <2059 marketed by the company KRONOS. Moisture absorber

[0184] The moisture absorber, if present, can be chosen, for example, from hydrolyzable, non-polymer alkoxysilane derivatives with a molecular weight of less than 500 g / mol, preferably from trimethoxysilane and triethoxysilane derivatives. Such an agent can typically extend the shelf life of the composition during storage and transport prior to use. Examples include gamma-metacryloxypropyltrimethoxysilane (e.g., available under the trade name SILQUEST®< A-174 from MOMENTIVE), methacryloxymethyltrimethoxysilane (e.g., available under the trade name GENIOSIL®< XL33 from WACKER), vinyltrimethoxysilane, isooctyltrimethoxysilane, or phenyltrimethoxysilane.

[0185] The moisture absorber content is preferably less than or equal to 3% by weight, and even more preferably less than or equal to 2% by weight, relative to the total weight of the composition according to the invention. When present, the moisture absorber may, for example, represent from 0.1% to 3% by weight or from 1% to 2% by weight relative to the total weight of the composition.

[0186] The composition according to the invention may comprise 0.1% to 3%, preferably 1% to 3% by weight, of at least one UV stabilizer or antioxidant. These compounds are typically introduced to protect the composition from degradation resulting from a reaction with oxygen that may be formed by the action of heat or light. These compounds may include primary antioxidants that scavenge free radicals. Primary antioxidants may be used alone or in combination with other secondary antioxidants or UV stabilizers. Examples include IRGANOX®< 1010, IRGANOX®< B561, IRGANOX®< 245, and IRGAFOS®< 168, marketed by BASF. Single-component or two-component composition

[0187] In some embodiments, the adhesive composition according to the invention is a single-component composition. In other words, a composition in which all the components are contained in a single compartment. In this case, the composition is preferably ready to use, meaning that the user (individual or professional) can apply the adhesive composition directly to the substrate to be covered and / or the flexible coating, without having to perform any prior mixing. In alternative embodiments, the adhesive composition according to the invention is a two-component composition. In other words, a composition in which the components are contained in two separate compartments.

[0188] In this case, the two-component composition may comprise a part A and a part B, the two parts being mixed before use and application of the adhesive composition to a substrate layer, for example. The components described above may be distributed in part A and / or in part B of the two-component composition.

[0189] In preferred embodiments, part A of the two-component composition may, for example, comprise the silylated polymer (as described above). Part B of the composition may then comprise the crosslinking catalyst (as described above). The polyvinyl ether compound and optional additives may be present in part A and / or part B of the composition. Additional components (other additives) may also be present in part A and / or part B of the two-component composition. Use of the composition

[0190] The composition according to the invention is used to manufacture self-adhesive articles. By "self-adhesive article" is meant any article that can be stuck to a surface only by the action of pressure with the hand or equipment, without the use of additional glues or adhesives.

[0191] Self-adhesive articles may include a support layer coated with a self-adhesive layer, said self-adhesive layer being the adhesive composition according to the invention in the crosslinked state.

[0192] Preferably, the self-adhesive item is a pressure-sensitive self-adhesive item.

[0193] These products are designed to be applied to a surface to be bonded in order to bring together, hold, fix, or simply immobilize and display shapes, logos, images, or information. They can be used in numerous fields, such as medicine, clothing, packaging, automotive (for example, for applying logos, lettering, interior soundproofing, interior trim, and interior decals), and construction (for example, for sound and thermal insulation and window assembly), particularly in the medical and construction sectors. They can be shaped according to their final application, for example, as tapes, such as industrial tapes, DIY tapes, or tapes for securing materials on construction sites, single or double-sided tapes, or as labels, bandages, dressings, patches, or graphic films.

[0194] According to one embodiment, the self-adhesive article is a self-adhesive multi-layer system, and in particular a self-adhesive label or tape, which may be single or double-sided.

[0195] The material that can be used for the backing layer can be any type of rigid or flexible substrate. Examples include foams, felts, non-woven fabrics, plastics, membranes, papers, or a single or multi-layered polymer film.

[0196] The support layer is made of a material, for example, 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 poly(vinyl 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 is based on acrylic polymers, polyethylene (PE), oriented, non-oriented or bi-oriented polypropylene (PP), polyimide, polyurethane, polyester such as polyethylene terephthalate (PET), or paper.

[0197] According to certain embodiments, the self-adhesive article obtained from the adhesive composition according to the invention comprises a permanent support layer coated with an adhesive layer. Preferably, the adhesive layer is further coated with a non-stick protective plastic or paper film, preferably silicone-coated.

[0198] As an alternative to the non-stick protective film, the back face of the permanent support layer, which is not coated with the adhesive layer, may have a non-stick surface, for example a silicone protective layer.

[0199] According to one embodiment, the permanent support layer 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.

[0200] Preferably, the support layer has a thickness ranging from 10 µm to 50 mm, preferably still ranging from 10 µm to 20 mm, preferably still ranging from 20 µm to 10 mm, preferably still ranging from 20 µm to 1 mm.

[0201] In certain specific cases, it is necessary to carry out surface treatment of the support layer to increase the adhesion of the adhesive layer during the coating stage.

[0202] The self-adhesive article according to the invention can thus bond two substrates. The substrate onto which the self-adhesive article is intended to be applied (designated by " substrate to be gluedThe substrate can be flexible or rigid. In particular, it can have the same flexibility properties as the backing layer described above, so that it can be wound and packaged in the form of a reel. Alternatively, the substrate to be bonded can be rigid. In this case, the substrate cannot be wound and packaged in the form of a reel, for example, as described previously. The substrate to be bonded can, for example, be chosen from concrete, paper, polyolefin-type substrates, etc.

[0203] According to some embodiments, the self-adhesive article further comprises a protective non-stick layer (“ release liner » in English).

[0204] According to some embodiments, said non-stick layer is applied to the adhesive layer, after cross-linking of the adhesive composition.

[0205] The backing layer can be coated on one of its two sides—the uncoated side—with a non-stick protective layer, such as a silicone film. This allows the self-adhesive item to be rolled up and unrolled without any problems, as the adhesive layer will not stick to the silicone-coated side.

[0206] The self-adhesive article according to the invention can be obtained by the process comprising the following steps: the mixing of parts A and B of the adhesive composition according to the invention, in the case where it is a two-component composition; the heating of the adhesive composition to a temperature ranging from 40°C to 130°C; the coating of a carrier surface with the adhesive composition; the crosslinking of the coated adhesive composition, by heating to a temperature ranging from 50°C to 200°C, in particular in a gaseous environment where water molecules are present between 10 and 200 g per m³ of gas; the counter-bonding or transfer of the crosslinked adhesive layer onto a support layer or onto a non-stick protective film, said support layer or non-stick film being the reverse side of the carrier surface.

[0207] For the purposes of this invention, "carrying surface" means either a conveyor belt coated with a non-stick layer, a non-stick protective film (release liner), or a backing layer. Thus, the carrying surface becomes an integral part of the self-adhesive article, either as a non-stick protective film or as a backing layer.

[0208] In the case where the carrier surface is not a support layer, the last step of the above process involves transferring the crosslinked adhesive layer onto a support layer.

[0209] In the case where the carrier surface is a support layer, the last step of the above process involves counter-bonding the adhesive layer onto a non-stick protective film.

[0210] According to a preferred embodiment of the invention, the last step of the above process consists of transferring the crosslinked adhesive layer onto a flexible support layer (which may be a plastic film) after cooling the crosslinked adhesive layer to a temperature below the degradation or softening temperature of the material composing the support layer.

[0211] According to one embodiment, the self-adhesive article according to the invention can be obtained by the process as described above, without including a pretreatment step of the substrate layer surface. Such pretreatments aim to chemically and / or physically modify said surface to increase its surface energy and / or roughness, thereby improving the adhesion of the adhesive layer to said surface. Examples of known surface treatments include plasma treatment, corona treatment, abrasion, or the application of a chemical bonding agent (also called a primer) to said surface, capable of imparting a high surface energy to the substrate coated with said agent.

[0212] The manufacturing process for the self-adhesive article according to the invention may further include a step of coating a second layer of adhesive composition according to the invention onto the substrate layer, followed by a step of cross-linking the coated adhesive composition by heating at a temperature ranging from 20 to 200°C. According to this embodiment, a double-sided self-adhesive article is obtained.

[0213] The coating step(s) can be carried out using known coating devices, such as a lip or curtain nozzle, or a roller. These steps can utilize adhesive composition weights ranging from 3 to 5,000 g / m². The adhesive composition weight required for the manufacture of self-adhesive labels can range from 10 to 100 g / m², and preferably from 20 to 50 g / m². The weight required for the manufacture of self-adhesive tapes can vary over a much wider range, from 3 to 5,000 g / m², and preferably from 15 to 250 g / m² per side.

[0214] In some embodiments, the coated adhesive composition is further subjected, during the curing step, to treatment in a humid atmosphere characterized by its humidity level. Preferably, the humid atmosphere is one in which 2 to 100% of the molecules are water molecules, preferably 3 to 50%, and preferably 3 to 10% of the molecules are water molecules.

[0215] Humidity is expressed as a percentage of water per unit volume, which corresponds to the number of water molecules divided by the total number of molecules in a unit volume. Due to the linear nature of this scale, humidity is easily measured and controlled using, for example, PID (Proportional-Integral-Derivative) monitors. The weight percentage can be calculated by multiplying the percentage of water molecules relative to the total number of molecules by a factor of 0.622. General information on humidity in various environments is described by W. Wagner et al. in "International Steam Tables - Properties of Water and Steam based on the Industrial Formulation IAPWS-IF97".

[0216] The thermal crosslinking step results in the creation—between the hydrolyzable alkoxysilane-terminated polymer chains of the adhesive composition and under the influence of atmospheric humidity—of siloxane-type bonds that lead to the formation of a three-dimensional polymer network. The crosslinked adhesive composition is, in particular, a pressure-sensitive adhesive that imparts the desired adhesive strength and tack to the substrate layer it coats.

[0217] Preferably, the coating is applied uniformly to the backing layer or to the non-stick protective layer, but the coating can also be adapted to the desired shape of the final self-adhesive article.

[0218] In one embodiment, the adhesive composition is applied to at least part of both sides of the substrate layer. If both sides of the substrate 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.

[0219] According to certain embodiments of the invention, the self-adhesive article comprises an adhesive layer on at least part of one face or on at least part of both faces of the backing layer, said adhesive layer(s) optionally being coated with a protective non-stick layer. In one embodiment, the self-adhesive article comprises two protective non-stick layers on each of the two adhesive layers. In this case, the two protective layers may be made of the same or different materials and / or may have the same or different thicknesses.

[0220] The self-adhesive articles according to the present invention are waterproof and breathable articles. By " waterproof and breathable", We mean permeable to water vapor and impermeable to liquid water.

[0221] Preferably, the article obtained from the composition according to the invention has a moisture vapor transmission rate (MVTR) of at least 350 g / m² / 24 h at 37°C and 50% relative humidity, for a film thickness of 30 µm. More preferably, the MVTR of the film is at least 500 g / m² / 24 h, preferably at least 600 g / m² / 24 h, preferably at least 700 g / m² / 24 h, and even more preferably 800 g / m² / 24 h, at 37°C and 50% relative humidity, for a film thickness of 30 µm.In particular, the MVTR permeability of the membrane can be 350 to 400 g / m² / 24 h, or 400 to 500 g / m² / 24 h, or 500 to 600 g / m² / 24 h, or 600 to 700 g / m² / 24 h, or 700 to 800 g / m² / 24 h, or 800 to 900 g / m² / 24 h, or 900 to 1000 g / m² / 24 h, or 1000 to 1200 g / m² / 24 h, or 1200 to 1500 g / m² / 24 h, or 1500 to 2000 g / m² / 24 h, or 2000 to 2500 g / m² / 24 h, or 2500 to 3000 g / m² / 24 h, or 3000 to 3500 g / m² / 24 h, or 3500 to 4000 g / m² / 24 h, or 4000 to 4500 g / m² / 24 h, or 4500 to 5000 g / m² / 24 h, at 37°C, at a relative humidity of 50%, for a film thickness of 30 µm. The water vapor permeability (MVTR) of the film, at 37°C, for a relative humidity of 50%, for a film thickness of 30 µm, can be measured according to ASTM E96 B. The self-adhesive article according to the invention can be used in a bonding method comprising the following steps: remove the protective non-stick layer, where such a layer is present; apply the self-adhesive item to a surface of a product; and apply pressure to said item.

[0222] In the second step, the self-adhesive item is applied so that the self-adhesive part of the item (formed by the self-adhesive layer) is facing the surface of the product.

[0223] According to some embodiments in which the self-adhesive article is a double-sided article, the bonding method further comprises a step in which either a second surface of a product is applied to the article bonded to the first surface of a product, or the article bonded to the first surface of a product is applied to a second surface of a product. Examples

[0224] The following examples illustrate the invention without limiting it. Performance of "PSA" membership

[0225] The adhesive compositions were applied to a polyethylene terephthalate (PET) substrate layer to form a layer with a thickness of 50 µm.

[0226] The substrate layers coated with the adhesive compositions were stored for 7 days at 70°C to ensure complete crosslinking of the composition.

[0227] The adhesion performance of the compositions was measured by a 180° peel test according to the Finat 1 standard. According to this standard, two-thirds of an adhesive specimen (15 cm x 2.5 cm) is placed on a test plate (sanded stainless steel, HDPE, etc.). A 2 kg roller is passed twice over the specimen to promote wettability. A waiting period of 10 minutes is observed before the pull test. The specimen is positioned parallel to the pull test and folded back on itself at a 180° angle. The portion of the specimen not bonded to the test plate provides a grip for the jaw, allowing the pull test to be performed at a standardized speed of 300 mm / min. The apparatus measures the force required to detach the specimen under the conditions described above.

[0228] The principle of this test consists in determining the force required to separate (or peel) the adhesive composition layer from the substrate layer.

[0229] The tack of the adhesive compositions was measured according to the Finat 9 standard. According to this standard, a 15 cm x 2.5 cm adhesive sample is folded into a loop, with the adhesive on the outer surface of the loop. At a speed of 300 mm / min, the loop is brought together and then gently placed on a glass plate. Once a 1 inch square is placed on the plate, the loop is removed from the plate and the force required to remove the adhesive is measured. Water vapor permeability (MVTR)

[0230] This test allows us to measure the water vapor that can pass through the layer of adhesive composition.

[0231] This test was carried out by applying the NF EN 13726-2 standard at 37°C

[0232] The adhesive compositions were applied to a non-woven (NW) substrate layer with an MVTR of 5,861 g / m² / 24h or to a polyurethane (PU) substrate layer with an MVTR of 7,826 g / m² / 24h, so as to form a layer with a thickness of 0.03 mm without the backing (support to reinforce the PU film during lamination, thickness of 0.104 mm with backing).

[0233] The substrate layers coated with the adhesive compositions were stored for 7 days at 70°C to ensure complete crosslinking of the composition. Example 1:

[0234] The following components were used to prepare composition A (according to the invention) and composition B (reference): - CLEARTACK®< W100, available from CRAY VALLEY, is a tackifying resin obtained by polymerization of alpha-methyl styrene without the action of phenols, having a number-average molecular weight of 900 Da; - SYLVALITE®< RE 100, available from ARIZONA CHEMICAL, is a rosin-type resin, having a number-average molecular weight of approximately 1700 Da; - Lutonal®< M40, available from BASF, is a polyvinyl ether; - IRGANOX®< 1010, available from BASF, is a hindered phenol-type antioxidant; - SPUR Y-19204, available from MOMENTIVE, is a silylated polypropylene glycol polyurethane prepolymer with trimethoxysilane terminations and an average molecular weight Mn of 24,000 g / mol;- K-KAT ®< 5218, available from KING INDUSTRIES, is an aluminum chelate type catalyst. ; [Table 1] Composition (%) A (inv) Brief) CLEARTACK ®< W100 18,48 23,43 SYLVALITE ®< RE 100 18,48 23,43 Lutonal ®< M40 9,90 - IRGANOX ®< 1010 0,50 0,50 SPUR Y-19204 51,64 51,64 K-KAT ®< 5218 1,00 1,00

[0235] Composition B is free of polyvinyl ether compound.

[0236] Adhesion performance and vapor permeability were measured as detailed above. The results are illustrated in the table below: [Table 2] Performance at 50 gsm Compositions A (inv) Brief) 180° SS (N / inch) / PET fur 15.2 + / - 0.51 AF 17.2 + / - 0.13 AF 180° peel HDPE (N / inch) / PET 10.3 + / - 0.74 AF 15.4 + / - 0.35 AF Tack power (N / inch) / PET 19.2 + / -1.4 AF 18.5 + / - 2.4 AF MVTR (g / m² / 24h) / NW 1107 + / - 51 865 + / - 60 Legend :

[0237] SS = sanded stainless steel; AF = "Adhesive Failure" (no residue remains, the loss of adhesion explains the test result, the product has good cohesion); HDPE = "High-density polyethylene"

[0238] It is observed that composition A according to the invention makes it possible to obtain articles with improved vapor permeability, without compromising good adhesion properties. Example 2

[0239] The following components were used to prepare a composition C (according to the invention) and a composition D (reference): - PICCO ®< AR100, available from EASTMAN, is a hydrocarbon resin; - Lutonal ®< M40, available from BASF, is a polyvinyl ether; - GENIOSIL ®< STPE-30, available from WACKER, is a polyether having dimethoxy(methyl)silylmethylcarbamate terminations and having an average molecular weight of 24,000 g / mol; - K-KAT ®< 5218, available from KING INDUSTRIES, is an aluminum chelate type catalyst. [Table 3] Composition (%) C (inv) D (ref) PICCO ®< AR100 44,14 53,36 Lutonal ®< M40 10,22 - GENIOSIL ®< STPE-30 44,64 44,64 K-KAT ®< 5218 1,00 1,00

[0240] Composition D is free of polyvinyl ether compound.

[0241] Adhesion performance and vapor permeability were measured as detailed above. The results are illustrated in Table 4 below: [Table 4] Compositions Performance at 50 gsm C (inv) D (ref) 180° SS (N / inch) / PET fur 32.5 + / - 0.85 AF 34.2 + / - 2.5 AF 180° peel HDPE high density polyethylene, (N / inch) / PET 22.2 + / - 0.70 AF 24.7 + / - 0.34 AF Tack power (N / inch) / PET 39.7 + / -2.9 AF 48.4 + / - 1.0 AF MVTR (g / m² / 24h) / NW 772 + / - 32 488 + / -118

[0242] It is observed that composition C according to the invention makes it possible to obtain articles with improved vapor permeability, without compromising good adhesion properties. Example 3:

[0243] The following components were used to prepare composition E (according to the invention) and composition F (comparative): CLEARTACK®< W100, available from CRAY VALLEY, is a tackifying resin obtained by polymerization of alpha-methyl styrene without the action of phenols, having a number-average molecular weight of 900 Da; SYLVALITE®< RE 100, available from ARIZONA CHEMICAL, is a rosin-type resin, having a number-average molecular weight of approximately 1,700 Da; Lutonal®< M40, available from BASF, is a polyvinyl ether; IRGANOX®< 1010, available from BASF, is a hindered phenol-type antioxidant; SPUR Y-19204, available from MOMENTIVE, is a silylated polypropylene glycol polyurethane prepolymer with trimethoxysilane terminations and an average molecular weight Mn of 24,000g / mol. TnBT is a titanium tetrabutanolate type catalyst. [Table 5] Composition (%) E (inv) F (comp) CLEARTACK ®< W100 13,5 23,4 SYLVALITE ®< RE 100 13,5 23,4 Lutonal ®< M40 19,8 - IRGANOX ®< 1010 0,5 0,5 SPUR Y-19204 51,6 51,6 TnBT 1 1

[0244] Composition F is free of polyvinyl ether compound.

[0245] Adhesion performance and vapor permeability were measured as detailed above. The results are illustrated in the table below: [Table 6] Composition 150 gsm E (inv) F (comp) 180° SS (N / inch) / PET fur 16.9 + / - 0.1 AF 18.1 + / - 0.4 AF MVTR (g / m² / 24h) / PU 395,6 + / - 6,04 215,6 + / - 2,77

[0246] It is observed that composition E according to the invention makes it possible to obtain articles with improved vapor permeability, without compromising good adhesion properties.

Claims

1. Adhesive composition comprising: at least one silyl polymer comprising at least one hydrolyzable alkoxysilane group; at least one polyvinyl ether compound; and at least one curing catalyst, in which the polyvinyl ether compound is a homopolymer chosen from poly(methyl vinyl ether), poly(ethyl vinyl ether), poly(butyl vinyl ether), poly(isobutyl vinyl ether), poly(isopropyl vinyl ether), poly(propyl vinyl ether), poly(octyl vinyl ether), and mixtures thereof.

2. Composition according to Claim 1, in which the silyl polymer is chosen from: a silyl polymer of general formula [Chem 2]         (R5O)3-p(R4)pSi-R0-O-R2-O-R0-Si(R4)p(OR5)3-p a silyl polymer of general formula [Chem 3] a silyl polymer of general formula [Chem 4] a silyl polymer of general formula [Chem 5] in which: X1 and X2 represent, independently of each other, an oxygen atom or an -NH- group; R1 represents a divalent hydrocarbon-based radical comprising from 5 to 15 carbon atoms, which may be aromatic or aliphatic, linear, branched or cyclic; R0 represents a linear or branched divalent alkylene radical comprising from 3 to 6 carbon atoms; R3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, R3 preferably representing methylene or n-propylene; R2 represents a polyether block -Rpe-[ORpe]n- in which Rpe represents a linear or branched divalent alkylene radical comprising from 2 to 4 carbon atoms; R4 and R5, which may be identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms; R6 represents a hydrogen atom, a phenyl radical, a linear, branched or cyclic alkyl radical comprising from 1 to 6 carbon atoms, or a 2-succinate radical of formula [Chem 6] in which R7 is a linear or branched alkyl radical comprising from 1 to 6 carbon atoms; n is an integer such that the number-average molecular mass of the polyether block -[ORpe]n- ranges from 300 g / mol to 40 000 g / mol in the polymers of general formulae [Chem 2], [Chem 3] and [Chem 4]; m1 is zero or an integer; m1 is such that the number-average molecular mass of the polymer of general formula [Chem 3] ranges from 500 g / mol to 50 000 g / mol, preferably from 700 g / mol to 20 000 g / mol; m is an integer other than zero; m is such that the number-average molecular mass of the polymer of general formula [Chem 4] ranges from 500 g / mol to 50 000 g / mol, preferably from 700 g / mol to 20 000 g / mol; p is an integer equal to 0, 1 or 2, p preferably being 0 or 1; Ral represents a divalent hydrocarbon-based radical derived from a diol by replacement of each of the two hydroxyl groups with a free valency or represents the radical R2; Rac represents a divalent hydrocarbon-based radical derived from a dicarboxylic acid by replacement of each of the two carboxyl groups COOH with a free valency; [Y]q represents a repeating unit of general formula [Chem 28] t is a number such that the polyester diol of general formula [Chem 7] has a hydroxyl number IOH of between 4 and 60 mg KOH / g; q is an integer other than zero; t and q are such that the number-average molecular mass of the polymer of general formula [Chem 5] is between 400 g / mol and 50 000 g / mol, said hydroxyl number IOH and said average molecular mass being determined according to the standard ISO 14900:2001.

3. Composition according to either of the preceding claims, in which the curing catalyst is chosen from the group consisting of amines, organometallic compounds, acids and derivatives thereof, and mixtures thereof.

4. Composition according to one of the preceding claims, also comprising a tackifying resin; preferably a tackifying resin chosen from terpene phenolic resins, hydrocarbon resins, rosin resins; acrylic resins and mixtures thereof.

5. Composition according to one of the preceding claims, in which the polyvinyl ether compound has a K value of from 40 to 120, and preferably from 40 to 70, said K value being measured according to the standard ISO 1628-1.

6. Composition according to any one of the preceding claims, in which the polyvinyl ether compound has a glass transition temperature of from -60 to 0°C, and preferably from -50 to -5°C, said glass transition temperature being measured according to the standard NF EN ISO 11357-2.

7. Composition according to one of the preceding claims, in which the polyvinyl ether compound has a content of from 1% to 60% by weight, preferably from 5% to 40% by weight, and preferably from 5% to 25% by weight relative to the total weight of the composition.

8. Composition according to one of the preceding claims, also comprising at least one silsesquioxane.

9. Composition according to one of the preceding claims, said composition being a one-component composition.

10. Composition according to any one of Claims 1 to 9, said composition being a two-component composition comprising: a part A comprising said at least one silyl polymer; and a part B comprising said at least one curing catalyst; said at least one polyvinyl ether compound being present in part A and / or in part B of the composition.

11. Use of the composition according to one of the preceding claims as an adhesive.

12. Self-adhesive article comprising at least one support layer and at least one layer of the composition according to one of the preceding claims.

13. Self-adhesive article according to Claim 12, said article being chosen from dressings, bandages and medical tapes.