Adhesive composition for producing waterproof, breathable articles

Abstract

The present invention relates to an adhesive composition comprising at least one silyl polymer containing at least one hydrolyzable alkoxysilane group, at least one polyvinyl ether compound, and at least one curing catalyst, as well as to the use of said composition as an adhesive, and also to a self-adhesive article comprising at least one support layer and at least one layer of said composition.

Description

[Technical Field]

[0001] The present invention relates to an adhesive composition and to the use of the adhesive composition for preparing a self-adhesive article. [Background technology]

[0002] Hot melt pressure-sensitive adhesives (HMPSA) are compositions that impart instantaneous adhesion (often referred to as "tack") to the substrate to which they are applied at room temperature. This tack advantageously allows the composition to instantly adhere to the substrate under the influence of gentle, brief pressure. HMPSA are widely used in the manufacture of self-adhesive articles, such as self-adhesive labels that are attached to articles for the purpose of presenting information (barcodes, names, prices, etc.) and / or for decorative purposes, whether during the operation of a final or temporary adhesive bond. HMPSA are also used in the manufacture of self-adhesive tapes for a variety of applications. Besides the transparent adhesive tapes that are widely used in everyday life, examples include the forming and assembly of cardboard packaging, the protection of surfaces for painting work in construction, the fastening and support of various elements such as panels, bricks, projections in the construction of buildings or edifices, the fastening and support of metal, plastic or glass parts that are flat or have a particular profile such as electric cables, plastic films, window panes, metal sheets, inscriptions, logos, parts of seats, dashboards, plastic or fabric walls, tubes or pipes for the circulation of fluids, especially in the transport industry, and the adhesive bonding of carpets attached with double-sided adhesive tapes in the construction sector.

[0003] The waterproof, breathable self-adhesive articles can be used in medical applications such as bandages, dressings, electrodes, adhesive plasters, clothing applications such as breathable garments to accommodate dry, breathable garments exposed to weather or moist environments, and architectural applications such as roofing or wall coverings or leak-proof window frame systems that still require breathability to ensure moisture is released into the environment.

[0004] In particular, adhesive materials used in the medical field, such as medical tapes, wound care dressings, and consumer bandages, require a high moisture vapor transmission rate (MVTR) to allow moisture generated by the skin or wound exudate to escape. A high MVTR in an adhesive product prevents moisture from being trapped under the dressing, which could otherwise cause skin maceration.

[0005] Breathable articles must therefore meet certain requirements such as a uniform appearance, wind resistance, high permeability to water vapor, a certain elasticity and the ability to adhere to different substrates.

[0006] Adhesive compositions suitable for preparing self-adhesive articles are already known.

[0007] For example, WO 2013 / 136108 A1 relates to an adhesive composition comprising, inter alia, at least one silyl polymer, at least one tackifying resin and at least one catalyst, and its use for producing waterproof and breathable articles.

[0008] WO 2019 / 115952 A1 relates in particular to a multi-component adhesive composition comprising a composition A containing at least one silyl polymer containing at least one hydrolyzable alkoxysilane group and at least one tackifying resin, and a composition B containing at least one catalyst and at least one compound C. Compound C is selected from compound C1 having a number average molecular weight in the range of 300 g / mol to 500,000 g / mol and compound C2 having a vapor pressure of 0.08 kPa or more at 20°C.

[0009] WO 2019 / 186014 A1 relates in particular to an adhesive composition comprising at least one curable silyl polymer and a catalyst composition comprising a tertiary amine and an organometallic compound.

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

[0011] WO 2020 / 016581 A1 relates in particular to compositions comprising a polymer containing silyl groups functionalized with urea groups and amine groups and a tackifying resin, which compositions are used as hot-melt pressure-sensitive adhesives.

[0012] These various waterproof, breathable self-adhesive articles and the adhesive compositions from which they are composed exhibit satisfactory adhesive properties. However, these articles and compositions containing them are not necessarily suitable for medical use. In particular, these articles and compositions containing them, such as medical tapes, bandages, and dressings, are not necessarily suitable for long-term application to skin or wounds. In fact, long-term application of these articles can lead to maceration of the skin or wound, causing discomfort to patients and delaying healing.

[0013] Therefore, there is a practical need to provide an adhesive composition that allows for the production of self-adhesive articles suitable for medical use and with improved water vapor transmission rates, without sacrificing good adhesive properties. There is also a practical need to provide an adhesive composition that allows for the production of self-adhesive articles, such as medical tapes, bandages, or dressings, that are suitable for long-term application to skin or wounds. There is also a practical need to provide an adhesive composition that allows for the production of self-adhesive articles, such as medical tapes, bandages, or dressings, that limit or prevent maceration of the skin or wound to which they are applied. There is also a practical need to provide an adhesive composition that allows for the production of self-adhesive articles, such as medical tapes, bandages, or dressings, that promote wound healing ..., without sacrificing good adhesive properties, that allow for the production of self-adhesive articles suitable for the construction market and with improved water vapor transmission rates. Summary of the Invention

[0014] The present invention first provides at least one silyl polymer containing at least one hydrolyzable alkoxysilane group; at least one polyvinyl ether compound; at least one curing catalyst; The present invention relates to an adhesive composition comprising:

[0015] In certain embodiments, the silyl polymer is General formula [Chemical formula 2] Silyl polymer in TIFF0007785060000001.tif11170 General formula [chemical formula 3] Silyl polymer in TIFF0007785060000002.tif26170 General formula [Chemical formula 4] Silyl polymer in TIFF0007785060000003.tif25170 General formula [Chemical formula 5] Silyl polymer in TIFF0007785060000004.tif18170 is selected from In the formula, X 1 and X 2 represent, independently of one another, an oxygen atom or an -NH- group, R 1 represents a divalent hydrocarbon radical containing 5 to 15 carbon atoms, which may be aromatic or aliphatic, linear, branched or cyclic; R 0 represents a linear or branched divalent alkylene radical containing 3 to 6 carbon atoms; R 3 represents a linear or branched divalent alkylene radical containing 1 to 6 carbon atoms, and R 3 preferably represents methylene or n-propylene, R 2 Polyether Block-R pe -[OR pe ] n - represents R pe represents a linear or branched divalent alkylene radical containing 2 to 4 carbon atoms, R 4 and R 5 may be the same or different and each represents a linear or branched alkyl radical containing 1 to 4 carbon atoms; R 6 is a hydrogen atom, a phenyl radical, a linear, branched or cyclic alkyl radical containing 1 to 6 carbon atoms, or a group of formula [Chemical formula 6] TIFF0007785060000005.tif17170 represents the 2-succinate radical, R 7 is a linear or branched alkyl radical containing 1 to 6 carbon atoms, n is a polyether block -[OR pe ] n - is an integer such that the number average molecular weight is in the range of 300 g / mol to 40,000 g / mol in the polymers of the general formulas [Chemical Formula 2], [Chemical Formula 3] and [Chemical Formula 4], m1 is zero or an integer, m1 is a polymer of the general formula [Chemical Formula 3] having a number average molecular weight in the range of 500 g / mol to 50,000 g / mol, preferably 700 g / mol to 20,000 g / mol; m is a non-zero integer, m is such that the number average molecular weight of the polymer of the general formula [Chemical Formula 4] is in the range of 500 g / mol to 50,000 g / mol, preferably 700 g / mol to 20,000 g / mol; p is an integer equal to 0, 1 or 2, p is preferably 0 or 1; R al denotes a divalent hydrocarbon-based radical derived from a diol by replacing each of the two hydroxyl groups with a free valence, or the radical R 2 represents R ac represents a divalent hydrocarbon radical derived from a dicarboxylic acid by replacing each of the two carboxyl groups COOH with a free valence, [Y] q is represented by the general formula [Chemical formula 28] TIFF0007785060000006.tif25170 represents the repeating unit, t is the general formula [Chemical formula 7] TIFF0007785060000007.tif21170 polyester diol has a hydroxyl number IOH between 4 mg KOH / g 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 [Chemical Formula 5] is between 400 g / mol and 50,000 g / mol.

[0016] In certain embodiments, the curing catalyst is selected from the group consisting of amines, organometallic compounds, acids and their derivatives, and mixtures thereof.

[0017] In certain embodiments, the composition also includes a tackifying resin, preferably selected from terpene phenolic resins, hydrocarbon resins, rosin resins, acrylic resins, and mixtures thereof.

[0018] In certain embodiments, the polyvinyl ether compound comprises units derived from monomers selected from methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, isopropyl vinyl ether, propyl vinyl ether, octyl vinyl ether, or combinations thereof.

[0019] In certain embodiments, the polyvinyl ether compound is selected 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), copolymers thereof, and mixtures thereof.

[0020] In certain embodiments, the polyvinyl ether compound has a K value of 40-120, preferably 40-70.

[0021] In a particular embodiment, the polyvinyl ether compound has a glass transition temperature of -60 to 0°C, preferably -50 to -5°C.

[0022] In a specific embodiment, the polyvinyl ether compound has a content of 1% to 60% by weight, preferably 5% to 40% by weight, preferably 5% to 25% by weight, relative to the total weight of the composition.

[0023] In certain embodiments, the composition also includes at least one silsesquioxane.

[0024] In certain embodiments, the composition is a one-component composition.

[0025] In certain embodiments, the composition comprises: an A part comprising at least one silyl polymer; Part B comprising at least one curing catalyst; A two-component composition comprising: At least one polyvinyl ether compound is present in Part A and / or Part B of the composition.

[0026] The present invention also relates to the use of the composition as an adhesive.

[0027] The present invention also relates to a self-adhesive article comprising at least one backing layer and at least one layer of the above composition.

[0028] In certain embodiments, the article is selected from a dressing, a bandage, and a medical tape.

[0029] The present invention makes it possible to meet the above-mentioned needs, more specifically to provide a composition that allows the manufacture of articles with good and improved water vapor transmission rates without compromising good adhesive properties.

[0030] This is achieved by the composition according to the present invention. More specifically, the inventors have surprisingly demonstrated that the adhesive composition according to the present invention, in particular a composition comprising at least one silyl polymer, at least one polyvinyl ether compound, and at least one curing catalyst, makes it possible to obtain self-adhesive articles with improved vapor permeability without impairing the good adhesive properties on the substrate. Indeed, the presence of the polyvinyl ether compound makes it possible to obtain good compatibility with the other components of the composition, more specifically the silyl polymer chains (which already have good water vapor permeability), resulting in an improvement in the water vapor permeability of the adhesive composition. The term "good compatibility" as used herein refers to the storage stability and long-term stability of the composition. DETAILED DESCRIPTION OF THE INVENTION

[0031] The invention will now be explained in more detail and in a non-limiting manner in the following description.

[0032] adhesive composition In a first aspect, the present invention relates to an adhesive composition comprising at least one silyl polymer containing at least one hydrolyzable alkoxysilane group, at least one polyvinyl ether compound, and at least one curing catalyst. Various additives may also be present in the adhesive composition.

[0033] Silyl Polymer The silyl polymer preferably comprises, as an end group, at least one hydrolyzable alkoxysilane group, preferentially as an end group, preferably at least two hydrolyzable alkoxysilane groups.

[0034] Silyl polymers are particularly suitable for TIFF0007785060000008.tif11170, may be a polymer containing at least one group, preferably at least two groups, of the general formula [Chemical Formula 1]: During the ceremony, R 4 and R 5may be the same or different and each represents a linear or branched alkyl radical containing 1 to 4 carbon atoms; p is an integer equal to 0, 1, or 2.

[0035] When p=2, the group R 4 may be the same or different.

[0036] When p=1 or p=0, the group R 5 may be the same or different.

[0037] The silyl polymer comprising at least one, preferably at least two, hydrolyzable alkoxysilane groups may have a backbone selected from the following backbones: 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).

[0038] Preferably, the silyl polymer having at least one hydrolyzable alkoxysilane group is selected from silyl polyether-polyurethanes, silyl polyethers, silyl polyesters, silyl polyester-polyurethanes, silyl polyether-polyester-polyurethanes, silyl polyureas, silyl poly(urethane-ureas) and mixtures thereof.

[0039] The silyl polymer may have a number average molecular weight (Mn) in the range of 500 to 50 000 g / mol, preferably in the range of 700 to 30 000 g / mol, advantageously in the range of 1 000 to 25 000 g / mol, in particular in the range of 1 000 to 21 000 g / mol.

[0040] The number average molecular weight of the silyl polymer can be determined by methods well known to those skilled in the art, such as size exclusion chromatography using polystyrene standards.

[0041] The silyl polymer comprising at least one hydrolyzable alkoxysilane group may be selected from polymers of the general formula [Chemical Formula 2], [Chemical Formula 3], [Chemical Formula 4] or [Chemical Formula 5] as defined below, and mixtures thereof, [Case 2] TIFF0007785060000009.tif10170[3] TIFF0007785060000010.tif25170[C4] TIFF0007785060000011.tif25170[5] TIFF0007785060000012.tif20170 formula, X 1 and X 2 represent, independently of one another, an oxygen atom or an -NH- group, R 1 represents a divalent hydrocarbon radical containing 5 to 15 carbon atoms, which may be aromatic or aliphatic, linear, branched or cyclic; R 0 represents a linear or branched divalent alkylene radical containing 3 to 6 carbon atoms; R 3 represents a linear or branched divalent alkylene radical containing 1 to 6 carbon atoms, and R 3 preferably represents methylene or n-propylene, R 2 Polyether Block-R pe -[OR pe ] n - represents R pe represents a linear or branched divalent alkylene radical containing 2 to 4 carbon atoms, n is a polyether block -[OR pe ] n - is an integer such that the number average molecular weight is in the range of 300 g / mol to 40,000 g / mol in the polymers of the general formulas [Chemical Formula 2], [Chemical Formula 3] and [Chemical Formula 4], R 4 and R 5 is as defined above, R 6 is a hydrogen atom, a phenyl radical, a linear, branched or cyclic alkyl radical containing 1 to 6 carbon atoms, or a group of the general formula [Chemical Formula 6] TIFF0007785060000013.tif16170 represents the 2-succinate radical, R 7 is a linear or branched alkyl radical containing 1 to 6 carbon atoms, m1 is zero or an integer, m1 is a polymer of the general formula [Chemical Formula 3] having a number average molecular weight in the range of 500 g / mol to 50,000 g / mol, preferably 700 g / mol to 20,000 g / mol; m is a non-zero integer, m is such that the number average molecular weight of the polymer of the general formula [Chemical Formula 4] is in the range of 500 g / mol to 50,000 g / mol, preferably 700 g / mol to 20,000 g / mol; p is as defined above, p is preferably 0 or 1; R al denotes a divalent hydrocarbon-based radical derived from a diol by replacing each of the two hydroxyl groups with a free valence, or the radical R 2 represents R ac represents a divalent hydrocarbon radical derived from a dicarboxylic acid by replacing each of the two carboxyl groups COOH with a free valence, [Y] q is represented by the general formula [Chemical formula 28] TIFF0007785060000014.tif25170 represents the repeating unit, t is the general formula [Chemical formula 7] Polyesterdiols in TIFF0007785060000015.tif20170 have a hydroxyl value between 4 mg KOH / g and 60 mg KOH / g. OH is a number such that q is a non-zero integer, t and q are such that the number average molecular weight of the polymer of general formula [Chemical Formula 5] is between 400 g / mol and 50,000 g / mol.

[0042] According to a particular embodiment, X 1 and X 2 are both oxygen atoms.

[0043] Or X 1 and X 2 are both -NH- groups.

[0044] Or, alternatively, X 1 and X 2 One of the atoms is an oxygen atom, and X 1 and X 2 The other of these may be an -NH- group.

[0045] Preferably, the radical R of the general formulae [Chemical formula 3], [Chemical formula 4] and [Chemical formula 5] 1 is selected from one of the following divalent radicals, the following formula showing two free valencies: Isophorone diisocyanate (IPDI) [Chemical formula 8] Divalent radical derived from TIFF0007785060000016.tif35170 Formula [C9] TIFF0007785060000017.tif20170 or formula [Chemical formula 10] Divalent radicals derived from 4,4'- and 2,4'-dicyclohexylmethane diisocyanate (HMDI) in TIFF0007785060000018.tif23170 Formula [chemical formula 11] TIFF0007785060000019.tif37170 or formula [Chemical formula 12] Radicals derived from 2,4- and 2,6-toluene diisocyanate (TDI) in TIFF0007785060000020.tif29170 Formula [chemical formula 13] TIFF0007785060000021.tif20170 or formula [Chemical formula 14] Radicals derived from 4,4'- and 2,4'-diphenylmethane diisocyanate (MDI) in TIFF0007785060000022.tif25170 Formula [chemical formula 15] Radicals derived from m-xylylene diisocyanate (m-XDI) in TIFF0007785060000023.tif23170 Formula [chemical formula 16] Radicals derived from hexamethylene diisocyanate (HDI) in TIFF0007785060000024.tif11170

[0046] Preferably, the radical R of the general formulae [Chemical formula 3], [Chemical formula 4] and [Chemical formula 5] 1 is a divalent radical derived from isophorone diisocyanate or xylylene diisocyanate.

[0047] The polymer of general formula [Chemical Formula 3] can be obtained, for example, according to the methods described in EP 2336208 A1 and WO 2009 / 106699 A2.

[0048] Among the polymers corresponding to the general formula [Chemical Formula 3], for example, Geniosil® STP-E10 (available from Wacker): a polyether having a number average molecular weight of about 8889 g / mol and containing two groups of dimethoxy type [formula 1], where R3 represents a methylene group (m1 is equal to 0, p is equal to 1, R 4 and R 5 represents a methyl group), Geniosil® STP-E30 (available from Wacker): has a number average molecular weight of about 14493 g / mol, R 3 represents a methylene group, polyethers of the dimethoxy type containing two groups of the general formula [Chemical Formula 1] (where m1 is equal to 0, p is equal to 1, and R 4 and R 5 represents a methyl group), Spur+® 1050MM (available from Momentive): has a number average molecular weight of about 16393 g / mol, R 3 Polyether-polyurethanes containing two groups of the general formula [Chemical Formula 1] of trimethoxy type, where m1 is different from 0, p is equal to 0, and R 5 represents a methyl group), - Spur+® Y-19116 (available from Momentive): a number average molecular weight in the range of 15,000 to 17,000 g / mol; 3 represents an n-propylene group, and a trimethoxy-type polyether-polyurethane containing two groups of the general formula [Chemical Formula 1] (where m1 is other than 0 and R 5 represents a methyl group), Desmoseal® S XP 2636 (available from Bayer): has a number average molecular weight of about 15038 g / mol, R 3 Polyethers containing two groups of the general formula [Chemical Formula 1] of trimethoxy type, where m1 is equal to 0, p is equal to 0, and R5 is a methyl group, where m1 is equal to 0, p is equal to 0, and R5 is a methyl group. Examples include:

[0049] The polymer of general formula [2] can be obtained, for example, by hydrosilylation of polyether diallyl ethers according to the method described in EP 1829928 A1.

[0050] Among the polymers corresponding to the general formula [Chemical Formula 2], two groups of the general formula [1] (p equals 1 and R 4 represents a methyl group), and MS Polymer™ S303H (available from Kaneka), which corresponds to a polyether containing two groups of the general formula [1] (p equals 1 and R 5 and R 4MS Polymer™ S227 (available from Kaneka), which corresponds to a polyether containing Examples include:

[0051] The polymer of general formula [Chemical formula 4] can be obtained according to the following method (when the polymer of general formula [Chemical formula 4] is a silyl polyurethane): -General formula [Chemical formula 17] HO-R 2 -OH and a polyether polyol having the formula Stoichiometric excess of formula NCO-R 1 with an -NCO diisocyanate to form a polyurethane-polyether block having at least two -NCO end groups (the block preferably contains 1.5% to 1.9% by weight of -NCO groups), and then -The block obtained in the previous step and a stoichiometric amount or a slight excess of the general formula [Chemical formula 18] TIFF0007785060000025.tif11170 is reacted with α-, β-, or γ-aminosilane.

[0052] Such a method is described, for example, in WO 2013 / 136108 A1.

[0053] Among the polymers corresponding to the general formula [Chemical Formula 4], for example, two groups of formula [1] (p equals 0, R 5 Spur+1015 LM (available from Momentive), which corresponds to a polyether-polyurethane containing methyl groups. Examples include:

[0054] The polymer of general formula [Chemical formula 4] can be obtained according to the following method (when the polymer of general formula [Chemical formula 4] is a silylpolyurea): -General formula [Chemical formula 19] H2N-R 2-NH2 Diamine and Stoichiometric excess of formula NCO-R 1 with an -NCO diisocyanate to form a polyurea-polyether block having at least two -NCO end groups (the block preferably contains 1.5% to 1.9% by weight of -NCO groups), and then -The block obtained in the previous step and a stoichiometric or slightly substoichiometric amount of the general formula [Chemical formula 18] TIFF0007785060000026.tif11170 is reacted with α-, β-, or γ-aminosilane.

[0055] Such a method is described, for example, in WO 2020 / 016581 A1.

[0056] The polymers of general formula [Chemical Formula 5] may be those described in European Patent Application No. 2865694 A1. They can be prepared according to the method described in said patent application.

[0057] The polymer of general formula [Chemical Formula 5] may be a first polymer of a specific general formula [Chemical Formula 5], wherein: R al represents a divalent hydrocarbon radical derived from a fatty alcohol dimerized by replacing each of the two hydroxyl groups with a free valence, the alcohol having a hydroxyl value I between 200 mg KOH / g and 220 mg KOH / g. OH and R ac represents a divalent hydrocarbon radical derived from a fatty acid dimerized by replacing each of the two carboxyl groups -COOH with a free valence, and the acid has an acid value I between 190 mg KOH / g and 200 mg KOH / g. A and t is preferably a group of the general formula [Chemical formula 7] TIFF0007785060000027.tif21170 polyester diol, Hydroxyl number between 45 mg KOH / g and 55 mg KOH / g IOH is a number that has

[0058] This particular first polymer of general formula [Chemical Formula 5] can be obtained according to the method described in European Patent Application No. 265728 A1 (in particular pages 5 to 9).

[0059] Preferably, the first polymer of this particular general formula [Chemical Formula 5] has a number average molecular weight in the range of 900 to 15,000 g / mol.

[0060] The polymer of formula [Chemical Formula 5] may be a second polymer of a specific formula [Chemical Formula 5], wherein: R al represents a divalent hydrocarbon-based radical derived from a saturated diol by replacing each of the two hydroxyl groups with a free valence, the diol having a hydroxyl number I of greater than 220 mg KOH / g OH and R ac represents a divalent hydrocarbon radical derived from a saturated dicarboxylic acid by replacing each of the two carboxyl groups -COOH with a free valence, and the acid has an acid number I of more than 200 mg KOH / g. A and t is preferably a group of the general formula [Chemical formula 7] TIFF0007785060000028.tif21170 polyester diol, Hydroxyl numbers I between 4 mg KOH / g and 24 mg KOH / g, especially between 9 mg KOH / g and 24 mg KOH / g OH It has.

[0061] The second polymer of the particular general formula [Chemical Formula 5] can be obtained by a process comprising several successive steps.

[0062] The first step of the process for obtaining the second polymer of the specific general formula [Chemical Formula 5] is to prepare a polymer having a hydroxyl number I between 4 mg KOH / g and 24 mg KOH / g. OH The method comprises preparing a polyester of the general formula [Chemical Formula 7]:

[0063] The polyester of the general formula [Chemical Formula 7] is Acid value I A at least one saturated dicarboxylic acid having a KOH / g or greater than 200 mg KOH / g; Hydroxyl Number I OH and at least one saturated diol having a KOH content greater than 220 mg KOH / g. It can be prepared by the polycondensation reaction of

[0064] In the text, Acid value of dicarboxylic acids I A is the number of carboxyl functional groups per gram of acid, expressed in the form of the equivalent amount in milligrams of KOH required to neutralize the acidity of 1 gram of acid, as determined by titration, and is determined by the following relationship: related to the number average molecular weight M of the acid by TIFF0007785060000029.tif11170, Hydroxyl number of diols I OH is the number of hydroxyl functional groups per gram of diol, expressed in the form of the equivalent amount in milligrams of KOH used in the assay of hydroxyl functional groups, determined by titration according to standard ISO 14900:2001, and which is determined by the relationship [Equation 2] The number average molecular weight M' of the diol is related by TIFF0007785060000030.tif11170.

[0065] Preferably, the saturated dicarboxylic acid has an acid number I of 300 mg KOH / g or more, preferably 400 mg KOH / g or more, preferentially 500 mg KOH / g or more, in particular 700 mg KOH / g or more, advantageously 800 mg KOH / g or more. A Preferably, the saturated dicarboxylic acid has an acid number I equal to 555 mg KOH / g or 768 mg KOH / g. A It has.

[0066] The dicarboxylic acids may be linear or branched, preferably linear, aliphatic or alicyclic.

[0067] The dicarboxylic acid according to the present invention may be selected from the group consisting of malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, 1,3- or 1,4-cyclohexanedicarboxylic 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.

[0068] Preferably, the dicarboxylic acid is adipic acid or sebacic acid.

[0069] Preferably, the saturated diol has a hydroxyl number I of 500 mg KOH / g or more, preferably 700 mg KOH / g or more, and even more preferentially 900 mg KOH / g or more. OH It has.

[0070] The diols used may be aromatic or aliphatic (preferably aliphatic), linear or branched, preferably branched.

[0071] Diols according to the present invention include 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-pentanediol, 2,3-diethyl-4-methyl-1,5-pentanediol, 3-ethyl-2,2,4-trimethyl-1,5-pentanediol, 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: 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), 2,2,6,6,10,10-hexamethyl-4,8-dioxa-1,11-undecanediol (CAS: 112548-49-9), 1-phenyl-1,11-undecanediol (CAS: 109217-58-5), 2-octyl -1,11-Undecanediol (CAS: 48074-21-1), 2,10-Diethyl-2,10-dimethyl-1,11-undecanediol (CAS: 85018-66-2), 2,2,10,10-Tetramethyl-1,11-undecanediol (CAS: 35449-37-7), 1-Phenyl-1,11-undecanediol (CAS: 109217-58-5), 1,2-Undecanediol (CAS: 13006-29-6), 1,2-Dodecanediol (CAS: 1119-87-5), 2,11-Dodecanediol (CAS S: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.

[0072] Preferably, the diol is selected 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.

[0073] Preferably, the polyester of general formula [7] is obtained by polycondensation reaction of adipic acid with a mixture of neopentyl glycol, ethylene glycol, and 1,6-hexanediol, or polycondensation reaction of adipic acid with 3-methyl-1,5-pentanediol.

[0074] Preferably, the polyester diol of general formula [Chemical Formula 7] has a hydroxyl number I between 4 mg KOH / g and 24 mg KOH / g, preferentially between 7 mg KOH / g and 24 mg KOH / g, preferably between 7 mg KOH / g and 20 mg KOH / g, in particular between 9 mg KOH / g and 19 mg KOH / g. OH Preferably, the hydroxyl number is I OH is between 9 mg KOH / g and 24 mg KOH / g.

[0075] The polyester diol of general formula [Chemical Formula 7] has a glass transition temperature T below 0°C, preferably below -20°C, preferably below -40°C, preferentially below -50°C, in particular below -60°C, for example below -64°C. g may have:

[0076] The polyester diol of general formula [Chemical Formula 7] may have a number average molecular weight of 5500 g / mol or more, preferably 6000 g / mol or more, particularly strictly more than 6000 g / mol, preferentially 8000 g / mol or more, in particular 9000 g / mol or more, for example 10000 g / mol or more, advantageously 12000 g / mol or more, in particular 18000 g / mol or more.

[0077] The number average molecular weight of the polyester diol of the general formula [Chemical Formula 7] isOH and its functionality.

[0078] Among the amorphous polyester diols of the general formula [Chemical Formula 7], for example, Dynacoll® 7250 (viscosity at 23°C of 180 Pa.s, number average molecular weight Mn equal to 5500 g / mol, T g Polyester polyol with viscosity equal to -50°C, Kuraray® P-6010 sold by Kuraray (viscosity at 23°C equal to 68 Pa.s, number average molecular weight equal to 6000 g / mol, T g or Kuraray® P-10010 sold by Kuraray (a polyester polyol having a viscosity of 687 Pa.s at 23°C and a number average molecular weight of 10,000 g / mol).

[0079] The second step of the method for obtaining the second polymer of the specific general formula [Formula 5] consists in preparing a polymer of the general formula [Formula 5].

[0080] According to a first variant, the polyester of general formula [7] above is mixed with a polyester of general formula

[20] in an amount corresponding to a molar equivalent ratio of NCO / OH functionalities between 0.90 and 1.05, preferably equal to about 1: It may also react with isocyanatosilane TIFF0007785060000031.tif11170.

[0081] This step is particularly carried out under anhydrous conditions to avoid hydrolysis of the alkoxysilane groups. Typical temperature ranges for carrying out this reaction step are 30°C to 120°C, more particularly 60°C to 105°C.

[0082] Isocyanatosilanes of the general formula [Chemical Formula 20] are widely available commercially, including, in particular, Silquest® A-Link 35, i.e., (3-isocyanatopropyl)trimethoxysilane available from Momentive, Silquest® A-Link 25, i.e., (3-isocyanatopropyl)triethoxysilane available from Momentive, (3-isocyanatopropyl)methyldimethoxysilane available from Gelest, Geniosil® XL 42, i.e., (3-isocyanatomethyl)methyldimethoxysilane available from Wacker, and Geniosil® XL 43, i.e., (3-isocyanatomethyl)trimethoxysilane available from Wacker.

[0083] According to a second variant, the silyl polymer is a polyester polyol of the general formula [Chemical Formula 7] and a polyol of the formula NCO-R in an amount corresponding to a molar equivalent ratio of NCO / OH functionalities between 0.3 and 0.7, preferably equal to about 0.5; 1 -NCO with diisocyanates to form polyester-polyurethane blocks, Reaction of the block obtained in the previous step with an isocyanatosilane of formula

[20] in an amount corresponding to a molar equivalent ratio of NCO / OH functionalities between 0.90 and 1.05, preferably equal to about 1. It can be obtained in two steps by

[0084] The isocyanatosilane may be as described above.

[0085] Preferably, the silyl polymer according to the present invention is a polymer of the general formula [Chemical Formula 3], wherein: m1 is an integer equal to 0, p=1, R 4 and R 5 represent a methyl radical, R 3 represents a divalent methylene radical, The number average molar mass of the polymer is in the range from 5000 to 30000 g / mol, preferentially from 10000 to 20000 g / mol, in particular from 14000 to 15000 g / mol.

[0086] Preferably, the silyl polymer according to the present invention is a polymer of the general formula [Chemical Formula 3], wherein: m1 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 weight of the polymer ranges from 5000 to 30000 g / mol, preferentially from 10000 to 30000 g / mol, in particular from 15000 to 25000 g / mol.

[0087] Preferably, the silyl polymer according to the present invention is a polymer of the general formula: q is a non-zero integer, p=0, R 3 represents a divalent propylene radical, R 5 represents a methyl radical, The number average molecular weight of the polymer ranges from 5000 to 30000 g / mol, preferentially from 10000 to 30000 g / mol, in particular from 15000 to 25000 g / mol.

[0088] The adhesive composition may include a single polymer as described above.

[0089] Alternatively, the adhesive composition may include two or more silyl polymers, for example, two, or three, or four, or five, or more than five silyl polymers.

[0090] The adhesive composition according to the present invention may contain 20% to 90% by weight, preferably 30% to 70% by weight of the silyl polymer, based on the total weight of the adhesive composition.

[0091] Polyvinyl ether compounds The polyvinyl ether compound according to the present invention may be a homopolymer or a copolymer. In the context of the present invention, the term "copolymer" refers to a polymer containing at least two different monomers. Therefore, in the context of the present invention, the term "copolymer" also includes terpolymers. When the polyvinyl ether compound is a copolymer, it is preferably a block copolymer. The term "block copolymer" refers to a copolymer containing at least two homopolymer subunits linked together via a covalent bond.

[0092] The polyvinyl ether compound has the general formula [Chemical Formula 21] It may contain units derived from the monomer of TIFF0007785060000032.tif11170.

[0093] The group R represents a saturated or unsaturated, linear or branched group containing 1 to 24 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms.

[0094] The group R may be selected from the following groups: alkyl, cycloalkyl, aryl, arylalkyl, alkylaryl, and heterocyclic groups, including rings containing heteroatoms selected from oxygen, sulfur and nitrogen; preferably, the group R is an alkyl group.

[0095] Even more preferably, the group R is selected from the following groups: substituted or unsubstituted methyl, ethyl, butyl, isobutyl, propyl, isopropyl, octyl or allyl. Preferably, the group R is a methyl or ethyl group.

[0096] The group R may optionally be substituted with one or more atoms or groups that do not interfere with the polymerization. Examples of such groups may be halogens (fluorine, chlorine, bromine, iodine), cyano groups, alkoxy groups or acyloxy groups.

[0097] base R 8 and R9 are each independently a hydrogen atom or a group containing 1 to 10 carbon atoms.

[0098] base R 8 and R 9 may be selected independently from each other from the following groups: alkyl, cycloalkyl, aryl, arylalkyl, alkylaryl, and heterocyclic groups, including rings containing heteroatoms selected from oxygen, sulfur, and nitrogen. Alternatively, the groups R 8 and R 9 may represent a divalent group containing 3 to 10 carbon atoms. For example, the divalent group may include an aromatic ring containing 5 to 6 carbon atoms.

[0099] Preferably, R 8 and R 9 at least one of, preferably R 8 and R 9 are both hydrogen atoms.

[0100] As noted above, the polyvinyl ether compound may be a homopolymer selected 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).

[0101] Alternatively, the polyvinyl ether compound may be a copolymer containing at least two different monomers of the general formula [Chemical Formula 21]. In this case, the polyvinyl ether compound may be a copolymer containing two different monomers of the general formula [Chemical Formula 21] or three different monomers of the general formula [Chemical Formula 21]. At least one of these monomers is preferably selected from methyl vinyl ether or ethyl vinyl ether, and at least one of these monomers is preferably methyl vinyl ether.

[0102] The polyvinyl ether compounds according to the present invention may have a K value of 30 to 120, preferably 40 to 70. The term "K value" means a measure of the average degree of polymerization. The K value can be measured according to standard ISO 1628-1.

[0103] The polyvinyl ether compounds according to the present invention may also have a glass transition temperature of from -60 to 0°C, preferably from -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.

[0104] Commercially available polyvinyl ether compounds include Lutonal® M 40, Lutonal® A 25, Lutonal® A 50, Lutonal® A 100, Lutonal® I 30, Lutonal® I 60, Lutonal® I 60 D, and Lutonal® I 65 D, available from BASF, and Gantrez® M, available from GAF.

[0105] The adhesive composition according to the present invention may contain 1 to 60% by weight, preferably 5 to 40% by weight, more preferably 5 to 25% by weight of the polyvinyl ether compound relative to the total weight of the adhesive composition.

[0106] curing catalyst The catalyst of the adhesive composition can be selected 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 (e.g., a mixture of several amines) or a mixture of catalysts from different families (e.g., a mixture of amines and organometallic compounds).

[0107] In the context of the present invention, the term "organometallic compound" means a compound comprising an organic radical and at least one metal.

[0108] In the context of the present invention, the term "organic radical" means a radical containing at least one carbon atom.

[0109] Organometallic compounds can include organometallic compounds (compounds containing at least one covalent metal-carbon bond), metal alkoxides, metal carboxylates, and metal coordination complexes with one or more organic ligands.

[0110] Examples of organic ligands that may be mentioned include acetylacetonates and oximes.

[0111] The metal atom of the organometallic compound may be any metal atom known to those skilled in the art and may in particular be selected from tin, aluminum, zinc, cobalt, iron, nickel, bismuth, titanium or zirconium. The organometallic compound may further comprise several metal atoms.

[0112] The organometallic compound (a compound containing at least one covalent metal-carbon bond) may be a carboxylate of an organometallic compound.

[0113] The organometallic compound may be selected from the group consisting of dibutyltin dilaurate (DBTL), dibutyltin diacetate, dibutyltin diethylhexanoate, dioctyltin dineodecanoate (available, for example, from TIB Chemicals under the name TIB KAT® 223), dibutyltin dioleate, dibutyltin benzyl maleate, diphenyltin diacetate, and mixtures thereof.

[0114] The metal alkoxide may be selected from the group consisting of titanium tetrabutoxide, titanium tetraisopropoxide, zirconium tetrabutoxide, zirconium tetraisopropoxide, and mixtures thereof.

[0115] The metal carboxylate 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 trioctoate, bismuth dineodecanoate, zinc bismuth dineodecanoate, and mixtures thereof.

[0116] The metal coordination complex with one or more organic ligands can be selected from the group consisting of zinc acetylacetonate, titanium acetylacetonate (e.g., commercially available from Dorf Ketal under the designation Tyzor® AA75), titanium tetraacetylacetonate, aluminum trisacetylacetonate, aluminum chelates such as bis(ethylacetoacetate) monoacetylacetonate (e.g., commercially available from King Industries under the designation K-KAT® 5218), zirconium tetraacetylacetonate, diisopropoxybis(ethylacetonato)titanium, and mixtures thereof.

[0117] The amine can be a primary amine, a secondary amine, or a tertiary amine.

[0118] The amine can be an aminosilane, for example, aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, bis(gamma-trimethoxysilylpropyl)amine, N-ethyl-gamma-aminoisobutyltrimethoxysilane, or N-phenyl-gamma-aminopropyltrimethoxysilane.

[0119] Preferably, the catalyst is not an aminosilane.

[0120] Preferably, the amine is selected 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-dimethylcyclohexylamine, N,N-dimethylphenylamine, N-ethylmorpholine, and mixtures thereof.

[0121] The acid catalyst may be selected from organic acid catalysts, inorganic acid catalysts, and mixtures thereof.

[0122] Among inorganic acid catalysts, mention may be made, for example, of phosphoric or orthophosphoric acid, phosphorous acid, hypophosphorous acid, or sulfuric acid.

[0123] Preferably, the organic acid catalyst has a pKa of 6 or less, preferably 4 or less, advantageously 2 or less, advantageously 0 or less.

[0124] The organic acid catalyst may be selected from sulfonic acids, carboxylic acids, organophosphoric acids, organophosphonic acids, phosphonic acids, and mixtures thereof.

[0125] The sulfonic acids may be aliphatic or aromatic, may be substituted (e.g., substituted with at least one substituent selected from halogen (such as fluorine), hydroxyl, alkyl, amine, and mixtures thereof), and may be mono- or disulfones.

[0126] Sulfonic acids include N-alkylaminoalkylsulfonic acids and N,N-dialkylaminoalkylsulfonic acids (zwitterions), such as 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, The sulfonic acid may be selected from the group consisting of benzophenone, benzophenone-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, dodecylbenzenesulfonic acid, dodecylbenzenedisulfonic acid, dinonylnaphthalenesulfonic acid, trifluoromethylsulfonic acid, and mixtures thereof.

[0127] In particular, the sulfonic acid is selected from para-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, dodecylbenzenesulfonic acid, dodecylbenzenedisulfonic acid, dinonylnaphthalenesulfonic acid, trifluoromethylsulfonic acid, and mixtures thereof.

[0128] Among the carboxylic acid catalysts are, for example, malonic acid, succinic acid, maleic acid, oxalic acid, acetic acid, lactic acid, benzoic acid, citric acid, glycolic acid, and mixtures thereof.

[0129] In the context of the present invention, unless otherwise stated, the term "organophosphate" refers to a phosphate ester containing at least one -OH radical. For example, methyl phosphate contains two -OH radicals and has the general formula: It is an organic phosphate with TIFF0007785060000033.tif28170.

[0130] In particular, the organic phosphoric acid has the general formula [Chemical Formula 23] TIFF0007785060000034.tif11170, During the ceremony, R 10 is a radical selected from organic radicals, in particular linear or branched C1-C22 alkyl, cycloalkyl, aryl and mixtures thereof, in which the alkyl, cycloalkyl and aryl groups may be substituted, g and h are integers, and g+h=3 and h=1 or 2.

[0131] The organic phosphoric acid may, for example, be selected from the group consisting of C1 to C22 mono- or dialkyl phosphate acids and mixtures thereof, such as butyl phosphate, dibutyl phosphate, bis(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, alkylphenyl phosphates, and mixtures thereof.

[0132] In the context of the present invention, unless otherwise specified, the term "organophosphonic acid" refers to a compound of the general formula: TIFF0007785060000035.tif11170 means a phosphorus-based compound having In the formula, R 11 and R 12 are preferably, independently of one another, organic radicals selected from linear or branched C1-C22 alkyl, cycloalkyl, aryl, and mixtures thereof, in which the alkyl, cycloalkyl and aryl groups may be substituted.

[0133] Among organic phosphonic acids, for example, C1 to C22 monoalkyl phosphonic acids can be mentioned.

[0134] In the context of the present invention, unless otherwise specified, the term "phosphonic acid" refers to a compound of the general formula: TIFF0007785060000036.tif11170 means a phosphorus-based compound having In the formula, R 13 is an organic radical, preferably selected from linear or branched C1 to C22 alkyl, cycloalkyl, aryl, and mixtures thereof, wherein the alkyl, cycloalkyl, and aryl groups may be substituted.

[0135] Among the phosphonic acids, mention may be made, for example, of N-alkylaminoalkylphosphonic acids (zwitterions), N,N-dialkylaminoalkylphosphonic acids (zwitterions), C1-C20 alkylphosphonic acids, such as methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, t-butylphosphonic acid, isobutylphosphonic acid, hexylphosphonic acid, 2-ethylhexylphosphonic acid and the linear or branched higher homologues, benzylphosphonic acid, phenylphosphonic acid, tolylphosphonic acid or xylylphosphonic acid.

[0136] Examples of organic acid catalysts include Nacure® 155 (dinonylnaphthalenedisulfonic acid, 55% active material in isobutanol) sold by King Industries, Nacure® 1051 (dinonylnaphthalenesulfonic acid, 50% active material in 2-butoxyethanol) sold by King Industries, Nacure® 5076 (dodecylbenzenesulfonic acid, 70% active material in isopropanol) sold by King Industries, K-Cure® 1040 (para-toluenesulfonic acid, 40% active material in isopropanol) sold by King Industries, and Nacure® 4000 (mixture of mono- and dialkyl phosphates, 100% active material) sold by King Industries.

[0137] The acid derivative according to the present invention may be an acid anhydride, an acid ester or an acid ammonium salt, the acid being as defined above.

[0138] Acid derivatives are in particular "masked" or "latent" acids which allow the acid to be advantageously released by thermal activation (for example at temperatures in the range of 70°C to 170°C, preferably in the range of 90°C to 120°C), or by hydrolysis, or by photoactivation, preferably by thermal activation.

[0139] The masked acid advantageously allows for the release of the acid, which is the catalytically active species. For example, the ammonium salt formed between aminomethylpropanol and para-toluenesulfonic acid is a masked acid (acid derivative) that releases para-toluenesulfonic acid upon thermal activation.

[0140] Acid derivatives can be prepared by any means known to those skilled in the art, starting from the corresponding acid, for example, by using typical acid / base reactions. For example, methods for producing esters typically involve condensation of the acid compound with a compound containing a hydroxyl group, such as an alcohol or an oxirane-type compound. Ammonium salts may be prepared from any of the above acids using ammonia or a primary, secondary, or tertiary amine. The amine may optionally contain at least one functional group, such as a hydroxyl group (alkanolamine), a C1-C4 alkyl group, or the like. Ammonium salts (zwitterions) can also be prepared, for example, by altering the pH of a solution containing an N-alkylaminoalkylphosphonic acid, an N,N-dialkylaminoalkylphosphonic acid, an N-alkylaminoalkylsulfonic acid, or an N,N-dialkylaminoalkylsulfonic acid.

[0141] Preferably, the catalyst is an ammonium salt of a sulfonic acid (wherein sulfonic acid is as defined above), an ammonium salt of a phosphonic acid (wherein phosphonic acid is as defined above), an ammonium salt of an organic phosphonic acid (wherein organic phosphonic acid is as defined above), or an ammonium salt of an organic phosphoric acid (wherein organic phosphoric acid is as defined above).

[0142] The amine for preparing ammonium salt includes, for example, 2-amino-2-methyl-1-propanol, triethylamine, aniline, pyridine, dimethylaminoethanol, alkylpyridine, diisopropanolamine, dimethylethanolamine, triethanolamine, oxazolidine, bicyclic oxazolidine, amidine, diazabicyclooctane, guanidine, N-alkylmorpholine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine and mixtures thereof.Preferably, the amine is a tertiary amine.

[0143] Examples of acid derivatives include Nacure® 3327 or Nacure® 3525 sold by King Industries (amine-masked dinonylnaphthalene disulfonic acid, containing 25% active material in isopropanol and isobutanol), Nacure® 1557 or Nacure® 1953 sold by King Industries (amine-masked dinonylnaphthalene sulfonic acid, containing 25% active material in a mixture of butanol and 2-butoxyethanol), Nacure® 5225 or Nacure® 5528 or Nacure® 5925 sold by King Industries (amine-masked dodecylbenzene sulfonic acid, containing 25% active material in isopropanol), King Industries Examples of such active materials include Nacure® 2107 or Nacure® 2500 sold by King Industries (amine-masked para-toluenesulfonic acid, 25% or 26% active material in isopropanol), Nacure® 2501 or Nacure® 2530 sold by King Industries (amine-masked para-toluenesulfonic acid, 25% active material in a mixture of isopropanol and methanol), Nacure® 4167 sold by King Industries (organic amine-masked dialkyl phosphate, 25% active material in a mixture of isopropanol and isobutanol), and Nacure® 4575 sold by King Industries (amine-blocked phosphoric acid, 25% active material in a mixture of methanol and ethanol).

[0144] Preferably, the catalyst is selected from the group consisting of organometallic compounds (especially aluminum-based coordination complexes), orthophosphoric acid, organophosphoric acid (preferably C1-C22 mono- or dialkylphosphoric acid and mixtures thereof), ammonium salts (especially of sulfonic acid or organophosphoric acid), and mixtures thereof. Even more preferably, the catalyst is selected from the group consisting of orthophosphoric acid, organophosphoric acid (preferably C1-C22 mono- or dialkylphosphoric acid and mixtures thereof), ammonium salts (especially of sulfonic acid or organophosphoric acid).

[0145] The adhesive composition according to the present invention may contain 0.1 to 4% by weight, preferably 0.2 to 2% by weight, more preferably 0.3 to 2% by weight of the curing catalyst, based on the total weight of the adhesive composition.

[0146] When the composition according to the invention is a one-component composition, it is preferred to use one of the above catalysts other than inorganic acids and their salts and other than carboxylic acids.

[0147] When the composition according to the present invention is a two-component composition (described in detail below), the curing catalyst may be mixed with a reactive or non-reactive diluent. The term "non-reactive diluent" refers to a diluent that does not react in the presence of the catalyst. Accordingly, the term "reactive diluent" refers to a diluent that reacts in the presence of the catalyst. The diluent may be selected from a poorly reactive monosilane (Geniosil XM25, MS RD359), a water scavenger (XL33), and a silsesquioxane resin. Non-reactive: Polyols, tackifying resins, rheology modifiers (mentioned under other additives), etc.

[0148] The diluent may have a number average molecular weight (Mn) in the range of 300 to 50,000 g / mol, preferably 1,000 to 20,000 g / mol, which prevents migration of the diluent into the cured adhesive.

[0149] This diluent may also have a viscosity ranging from 10 to 100,000 mPa.s at 23°C, and even more preferentially from 500 to 15,000 mPa.s at 23°C.

[0150] The viscosity is measured with a Brookfield viscometer (cone and plate, CAP2000+).

[0151] Other additives The composition according to the present invention may comprise at least one other additive selected from the group consisting of, for example, tackifying resins, silsesquioxanes, plasticizers, solvents, pigments, dyes, adhesion promoters, moisture absorbers, UV stabilizers, antioxidants, glitter flakes, fluorescent materials, rheological additives, fillers, flame retardants, waxes, and mixtures thereof.

[0152] tackifying resin The adhesive composition according to the present invention may also include at least one tackifying resin.

[0153] The resin used in the context of the present invention may be any resin that is compatible with the silyl polymer.

[0154] The term "compatible tackifying resin" means a tackifying resin that, when mixed with a silyl polymer in a 50 / 50 weight ratio, provides a substantially homogeneous mixture (no visually observable phase separation). In the context of this invention, a tackifying resin is different from a polyvinyl ether compound.

[0155] The tackifying resin is advantageously -terpene-phenolic resins, hydrocarbon resins, rosin resin, and -acrylic resin is selected from.

[0156] The terpene-phenol resins may have a softening point of 85 to 150° C. The hydrocarbon resins may have a softening point of 15 to 140° C. The rosin resins may have a softening point of 15 to 115° C. The softening point can be measured according to standard ASTM E28.

[0157] Terpene-phenol resins can be obtained by polymerizing terpene hydrocarbons and phenols in the presence of a Friedel-Crafts catalyst.

[0158] The hydrocarbon resins may be chosen from resins obtained by a process comprising the polymerization of α-methylstyrene, optionally in the presence of phenols; resins obtained by hydrogenation, preferably partial hydrogenation, polymerization or copolymerization (with aromatic hydrocarbons) of a mixture of unsaturated aliphatic hydrocarbons containing about 5, 9 or 10 carbon atoms derived from petroleum fractions, optionally grafted with maleic anhydride; terpene resins, generally copolymers based on natural terpenes, such as styrene / terpene, α-methylstyrene / terpene and vinyltoluene / terpene, resulting from the polymerization of terpene hydrocarbons, such as monoterpenes (or pinene), in the presence of(one or more) Friedel-Crafts catalysts, and mixtures thereof.

[0159] The rosin resin may be selected from naturally occurring rosins or modified rosins (e.g., rosin extracted from pine resin, wood rosin extracted from tree roots) and derivatives thereof that have been hydrogenated, dimerized, polymerized or esterified with monoalcohols or polyols (e.g., glycerol or pentaerythritol).

[0160] Acrylic resins are defined as polymers or oligomers composed of a significant amount of (meth)acrylic and / or (meth)acrylate monomers in the polymer chain, preferably at least 5% by weight / weight (w / w), more preferably at least 10% (w / w), even more preferably at least 20% (w / w), and even more preferably at least 30% (w / w).

[0161] (Meth)acrylic monomers include 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 crotonate, vinyl acetate, di-n-butyl maleate, dioctyl maleate, acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, acetoacetoxypropyl methacrylate, acetoacetoxypropyl acrylate, diacetone acrylamide, acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, allyl methacrylate, tetramethyl ... The acrylate may be selected from tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 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)ethyl acrylate, 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-vinylpyrrolidone, or N-vinyl lactam.

[0162] Preferably, the (meth)acrylic monomer contains not more than 20 carbon atoms and more preferentially the (meth)acrylic monomer is chosen from acrylic acid, methacrylic acid, butyl acrylate, 2-ethylhexyl acrylate and hydroxyethyl acrylate.

[0163] The acrylic resin may be selected from polymers containing at least one (meth)acrylic functional group or chain moiety and at least one hydrocarbon-based chain moiety, and the polymer may be in the form of a copolymer, graft copolymer, or reaction copolymer or block copolymer.

[0164] The acrylic resin preferably has a viscosity of less than 100 Pa·s at 100°C and a viscosity of 100 Pa·s or less at 150°C.

[0165] The acrylic resin may include repeating units of at least one hydrocarbon-based monomer and at least one acrylate monomer.

[0166] The hydrocarbon monomers are selected from the group consisting of styrene, α-methylstyrene, vinyltoluene, indene, methylindene, divinylbenzene, dicyclopentadiene and methyldicyclopentadiene, as well as polymerizable monomers contained in the C5-piperylene and C5-isoprene and C9-aromatic streams of the petrochemical industry. These hydrocarbon monomers are typically polymerized together in various ratios by cationic polymerization using Lewis acid catalysts.

[0167] Acrylate monomers include 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 acrylate, ethylhexyl methacrylate, n-heptyl acrylate, heptyl methacrylate, 2-methylheptyl (meth)acrylate, octyl acrylate, octyl methacrylate, and isooctyl (meth)acrylate. acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, isobornyl (meth)acrylate, lauryl acrylate, lauryl (meth)acrylate, tridecyl acrylate, tridecyl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl methacrylate, alkyl crotonate, vinyl acetate, di-n-butyl maleate, dioctyl maleate, acetoacetate Diethyl 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, 2-methoxyacrylate, 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 (400) acrylate,Polypropylene glycol (400) methacrylate, benzyl acrylate, benzyl methacrylate, sodium 1-allyloxy-2-hydroxypropyl sulfonate, acrylonitrile, and mixtures thereof.

[0168] Preferably, the hydrocarbon-based monomer is selected from the group of aromatic monomers or polymerizable monomers from C9 aromatic streams from petrochemical sources, dicyclopentadiene or polymerizable monomers from C5-piperylene or C5-isoprene streams from petrochemical sources.

[0169] Preferably, the acrylate monomer is selected from acrylic acid, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methacrylic acid, butyl acrylate.

[0170] The softening point of these acrylic resins is preferably from room temperature to 180° C., preferably not more than 150° C., more preferably not more than 120° C., and even more preferably from 70 to 120° C. The softening point can be measured according to standard ASTM E28.

[0171] Such resins are commercially available, for example, as follows:

[0172] Resins obtained by polymerization of terpene hydrocarbons and phenols in the presence of a Friedel-Crafts catalyst. Available from DRT. Number average molecular weight M n Dertophene® 1510, available from DRT, has a number average molecular weight M of about 870 Da. n Dertophene® H150, available from DRT, has a number average molecular weight M of about 630 Da. n Dertophene® T, available from Arizona Chemical Company, having a number average molecular weight of about 500 Da; Sylvarez® TP 95, available from Arizona Chemical Company, having a number average molecular weight of about 1200 Da.

[0173] Resins obtained by a process including the polymerization of α-methylstyrene optionally in the presence of phenols: Cleartack® W100, available from Cray Valley, is obtained by the polymerization of α-methylstyrene without the addition of phenols and has a number average molecular weight of 900 Da; and Sylvarez® 510, available from Arizona Chemical Co., has a number average molecular weight of approximately 1740 Da and is produced by a process including the addition of phenols.

[0174] For naturally occurring or modified rosin: Sylvalite® RE 100, an ester of rosin and pentaerythritol, having a number average molecular weight of about 1700 Da, available from Arizona Chemical.

[0175] According to a preferred embodiment, the tackifying resin is chosen from resins obtained by polymerization of terpene hydrocarbons and phenolics in the presence of a Friedel-Crafts catalyst.

[0176] The tackifying resin preferably has a number average molecular weight in the range of 100 to 6000 g / mol, preferably 300 to 4000 g / mol, preferentially 500 to 2000 g / mol.

[0177] The number average molecular weight of a tackifying resin can be determined by methods well known to those skilled in the art, such as size exclusion chromatography using polystyrene-type standards.

[0178] The tackifying resin has a hydroxyl number I in the range of 10 to 300 mg KOH / g, preferably 100 to 200 mg KOH / g, preferentially 140 to 160 mg KOH / g. OH In particular, the tackifying resin may have a hydroxyl number of 145 mg KOH / g.

[0179] The hydroxyl number of a tackifying resin represents the number of hydroxyl functional groups per gram of tackifying resin and is expressed in the form of milligrams of potassium hydroxide equivalent per gram of tackifying resin (mg KOH / g) for the assay of hydroxyl functionality.

[0180] The acid number of the rosin ester tackifying resin may range from 0 to 10 mg KOH / g, preferentially from 0 to 5 mg KOH / g. The acid number of the tackifying resin represents the number of acid functional groups per gram of tackifying resin and is expressed in the form of milligrams of potassium hydroxide equivalent per gram of tackifying resin (mg KOH / g) for the assay of acid functionality.

[0181] The adhesive composition according to the present invention may contain 0.1 to 80% by weight, preferably 20 to 70% by weight, more preferably 30 to 60% by weight of a tackifying resin, based on the total weight of the adhesive composition.

[0182] When the composition according to the invention comprises at least one tackifying resin, the weight ratio of polyvinyl ether compound to tackifying resin may be from 3% to 100%.

[0183] According to certain embodiments, the adhesive composition comprises a single tackifying resin.

[0184] According to an alternative embodiment, the adhesive composition comprises different tackifying resins, for example, two or three or four or five different tackifying resins.

[0185] Silsesquioxane Silsesquioxanes are organosilicon compounds that can have polyhedral or polymeric structures with Si-O-Si bonds. They typically have the general formula: [R'SiO 3 / 2 ] t and wherein R', which may be essentially the same or different, represents an organic radical, and t is an integer which may range from 6 to 12, with t being preferably equal to 6, 8, 10 or 12.

[0186] According to one embodiment, the silsesquioxane has a polyhedral structure (or POSS for "polyhedral oligomeric silsesquioxane").

[0187] Preferably, the silsesquioxane has the general formula: Corresponding to TIFF0007785060000037.tif45170, In the formula, R' 1 ~R' 8 Each of the Radical R' 1 ~R' 8 at least one radical is a C1-C4 alkoxy radical; and Radical R' 1 ~R' 8 At least one radical of the formula (I) is a phenyl radical. Under the condition that, Independently of each other, hydrogen atoms, a radical selected from the group consisting of a linear or branched C1-C4 alkoxy radical, a linear or branched alkyl radical containing 1 to 30 carbon atoms, an alkenyl radical containing 2 to 30 carbon atoms, an aromatic radical containing 6 to 30 carbon atoms, an aryl radical containing 3 to 30 carbon atoms, a cycloaliphatic radical containing 3 to 30 carbon atoms and an acyl radical containing 1 to 30 carbon atoms, and Group-OSiR' 9 R' 10 (In the formula, R' 9 and R' 10 each independently represent a hydrogen atom or a radical selected from the group consisting of linear or branched C1-C4 alkyl, linear or branched C1-C4 alkoxy, C2-C4 alkenyl, phenyl, C3-C6 aryl radicals, cyclic C3-C8 aliphatic radicals and C1-C4 acyl radicals represents a group selected from:

[0188] Silsesquioxanes are known compounds, described in particular in patent application WO2008 / 107331 A1. Several products are also commercially available, such as those from Dow sold under the names Dow Corning® 3074 and Dow Corning® 3037 (CAS number = 68957-04-0).

[0189] The adhesive composition according to the present invention may contain 0 to 40% by weight, preferably 0 to 20% by weight, and more preferably 0 to 10% by weight of silsesquioxane, based on the total weight of the adhesive composition.

[0190] Filler The filler may be selected from organic fillers, inorganic fillers and mixtures thereof.

[0191] As the organic filler, any organic filler, particularly a polymer filler typically used in the field of adhesives, can be used, such as polyvinyl chloride (PVC), polyolefin, rubber, ethylene vinyl acetate (EVA), aramid fibers such as Kevlar®, expandable or non-expandable thermoplastic polymer hollow microspheres (e.g. hollow microspheres made of vinylidene chloride / acrylonitrile), thermoplastic polymers selected from those used to prepare HMPSA, such as ethylene vinyl acetate (EVA), or styrene block copolymers (e.g. SIS, SBS, SIBS, SEBS, SEPS, and their derivatives grafted with maleic anhydride).

[0192] The filler may be a bulking agent (also known as a swelling agent).

[0193] The filler may be in the form of hollow beads, i.e., beads containing gas, or beads that can be expanded to form hollow beads, i.e., beads containing voids or gas.

[0194] Preferably, the filler is an inorganic filler.

[0195] According to one embodiment, the filler is selected from sand, precipitated and / or fumed silica, zeolite, glass beads, glass, quartz, barite, alumina, mica, talc, alkali metal or alkaline earth metal carbonates (e.g., calcium carbonate).

[0196] The filler preferably represents 0% to 15% by weight, preferably 0% to 10% by weight, and preferentially 0% to 5% by weight, relative to the total weight of the adhesive composition.

[0197] According to one embodiment, the composition according to the invention does not comprise any fillers.

[0198] plasticizer The composition according to the invention may comprise at least one plasticizer. The total content of plasticizers in the composition may range from 0% to 30% by weight, preferably from 1% to 30% by weight, or further for example from 1% to 15% by weight, relative to the total weight of the composition.

[0199] Examples of plasticizers that can be used include any plasticizers commonly used in the field of adhesives, such as phthalates, benzoates, trimethylolpropane esters, trimethylolethane esters, trimethylolmethane esters, glycerol esters, pentaerythritol esters, naphthenic mineral oils, adipates, cyclohexyl dicarboxylates, liquid paraffins, natural oils (which may be epoxidized), polypropylenes, polybutylenes, hydrogenated polyisoprenes, and mixtures thereof.

[0200] Among the phthalates, mention may be made, for example, of diisononyl phthalate, diisobutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate, diisododecyl phthalate, dibenzyl phthalate or butylbenzyl phthalate.

[0201] Among the benzoates, mention may be made, for example, of neopentyl glycol dibenzoate (available, for example, from Lanxess under the name Uniplex® 512), dipropylene glycol dibenzoate (available, for example, from Eastman under the name Benzoflex® 9-88SG), a mixture of diethylene glycol dibenzoate and dipropylene glycol dibenzoate (available, for example, from Kalama Chemical under the name K-Flex® 850 S), or a mixture of diethylene glycol dibenzoate, dipropylene glycol dibenzoate and triethylene glycol dibenzoate (available, for example, from Eastman under the name Benzoflex® 2088).

[0202] Among the pentaerythritol esters, mention may be made, for example, of pentaerythrityl tetravalerate (available, for example, under the name Pevalen™ from Perstorp).

[0203] Among the cyclohexanedicarboxylates, mention may be made, for example, of diisononyl 1,2-cyclohexanedicarboxylate (available, for example, under the name Hexamoll Dinch® from BASF).

[0204] pigment If pigments are present in the composition according to the invention, their content is preferably not more than 3% by weight, more preferably not more than 2% by weight, relative to the total weight of the composition. If present, the pigments may represent, for example, from 0.1% to 3% by weight or from 0.4% to 2% by weight, relative to the total weight of the composition according to the invention.

[0205] The pigment may be an organic pigment or an inorganic pigment.

[0206] For example, the pigment is TiO2, in particular Kronos® 2059 sold by the company Kronos.

[0207] moisture absorbent When a moisture absorbent is present, it may be selected from, for example, non-polymeric hydrolyzable alkoxysilane derivatives having a molecular weight of less than 500 g / mol, preferably from trimethoxysilane and triethoxysilane derivatives. Such agents can typically extend the shelf life of the composition during storage and transportation before use. For example, γ-methacryloxypropyltrimethoxysilane (e.g., available from Momentive under the trade name Silquest® A-174), methacryloxymethyltrimethoxysilane (e.g., available from Wacker under the name Geniosil® XL33), vinyltrimethoxysilane, isooctyltrimethoxysilane, or phenyltrimethoxysilane.

[0208] The content of the moisture absorbent is preferably not more than 3% by weight, more preferably not more than 2% by weight, relative to the total weight of the composition of the invention. If present, the moisture absorbent may represent, for example, from 0.1% to 3% by weight, or from 1% to 2% by weight, relative to the total weight of the composition.

[0209] The compositions according to the present invention may contain at least one UV stabilizer or antioxidant in an amount of 0.1% to 3% by weight, preferably 1% to 3% by weight. These compounds are typically incorporated to protect the composition from degradation due to reaction with oxygen, which is likely to be formed by the action of heat or light. These compounds may include primary antioxidants, which scavenge free radicals. Primary antioxidants may be used alone or in combination with other secondary antioxidants or UV stabilizers.

[0210] Examples include Irganox® 1010, Irganox® B561, Irganox® 245 and Irganox® 168 sold by BASF.

[0211] One- or two-component compositions According to one embodiment, the adhesive composition according to the invention is a one-component composition. In other words, it is a composition in which all components are packaged in the same compartment. In this case, the composition is preferably ready to use, i.e. the user (individual or professional) can apply the adhesive composition directly to the substrate and / or flexible coating to be coated without the need for prior mixing.

[0212] According to another embodiment, the adhesive composition according to the invention is a two-component composition, in other words a composition in which the components are packaged in two separate compartments.

[0213] In this case, the two-component composition may comprise part A and part B, and the two parts are mixed, for example, before use of the adhesive composition and application to a substrate layer. The above components may be distributed in part A and / or part B of the two-component composition.

[0214] According to a preferred embodiment, part A of the two-component composition may, for example, comprise a silyl polymer (as described above). Part B of the composition may then comprise a curing catalyst (as described above). The polyvinyl ether compound and any optional additives may also be present in part A and / or part B of the composition. Additional components (other additives) may be present in part A and / or part B of the two-component composition.

[0215] Use of the composition The compositions according to the invention are used to manufacture self-adhesive articles. The term "self-adhesive article" means any article that can be adhesively bonded to a surface solely by the action of pressure by hand or an item of equipment, without the use of additional glue or adhesive.

[0216] The self-adhesive article can include a backing layer coated with a self-adhesive layer, the self-adhesive layer being an adhesive composition according to the present invention in cured form.

[0217] Preferably, the self-adhesive article is a pressure-sensitive self-adhesive article.

[0218] These articles are intended, in particular, to be applied to surfaces to be joined to hold together, maintain, fix, or simply fix and expose features, logos, images, or information. These articles can be used in many fields, particularly in the medical and construction fields, such as in the medical field, clothing, packaging, automotive (e.g., logos, lettering, interior soundproofing, interior trim, interior adhesion), or construction (e.g., for sound and heat insulation, window assembly). They can be formed as a function of the end use, for example, in the form of tapes, such as industrial tapes, tapes for DIY work or for fixing at work sites, single-sided or double-sided tapes, or in the form of labels, bandages, dressings, patches, or graphic films.

[0219] According to one embodiment, the self-adhesive article is a self-adhesive multi-layer system, in particular a self-adhesive label or tape, which may be single-sided or double-sided.

[0220] The material that can be used for the support layer can be, for example, any type of rigid or flexible support, such as foam, felt, nonwoven support, plastic, membrane, paper, or film of polymeric material having one or more layers.

[0221] The support layer is made of a material selected from polyolefins, such as polyethylenes including high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and linear very low-density polyethylene, polypropylene and polybutylene, polystyrene, natural or synthetic rubber, vinyl copolymers such as polyvinyl chloride, which may be plasticized or unplasticized, and olefin-based copolymers such as poly(vinyl acetate), 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), polypropylene (PP), which may be oriented, unoriented, or biaxially oriented, polyimides, polyurethanes, polyesters such as polyethylene terephthalate (PET), or paper.

[0222] According to a particular embodiment, the self-adhesive article obtained from the adhesive composition according to the invention comprises a permanent backing layer coated with an adhesive layer, which is preferably also coated with a non-stick protective paper or plastic film, preferably siliconized.

[0223] As an alternative to a non-stick protective film, the rear surface of the permanent support layer that is not coated with the adhesive layer may have a non-stick surface, for example a siliconized protective layer.

[0224] According to one embodiment, the permanent support layer is coated on both sides with adhesive compositions which may be the same or different, at least one of the two adhesive compositions being according to the invention.

[0225] Preferably, the support layer has a thickness in the range of 10 μm to 50 mm, more preferably in the range of 10 μm to 20 mm, preferably in the range of 20 μm to 10 mm, more preferably in the range of 20 μm to 1 mm.

[0226] In certain cases, it may be necessary to provide a surface treatment on the support layer to increase adhesion of the adhesive layer during the coating process thereon.

[0227] Thus, the self-adhesive article according to the present invention can bond two substrates. The substrate to which the self-adhesive article is intended to be applied (referred to as the "bonded substrate") can be flexible or rigid. In particular, it can have the same flexibility as the support layer described above so that it can be wound up and packaged in the form of a reel. Alternatively, the bonded substrate can be rigid. In this case, the substrate cannot be wound up and packaged in the form of a reel as described above. The bonded substrate can be selected from, for example, concrete, paper, polyolefin-type substrates, etc.

[0228] According to certain embodiments, the self-adhesive article also includes a protective non-stick layer ("release liner").

[0229] According to certain embodiments, the non-stick layer is applied to the adhesive layer after the adhesive composition has been cured.

[0230] The support layer may be covered on one of its two sides, the rear side not coated with the adhesive layer, with a protective non-stick layer, such as a silicone film, so that the self-adhesive article can be rolled up on itself and then unrolled without any problems, since there is no adhesion of the adhesive layer to the silicone-treated side.

[0231] The self-adhesive article according to the invention can be obtained by a method comprising the following steps: - mixing part A and part B of the adhesive composition according to the invention, if it is a two-component composition, - heating the adhesive composition to a temperature in the range of 40°C to 130°C; - coating the bearing surface with an adhesive composition; -In particular, water molecules are gaseous 1m 3curing the coated adhesive composition by heating to a temperature in the range of 50°C to 200°C in a gaseous environment presenting between 10g and 200g per 100g of adhesive; Counter-bonding or transferring the cured adhesive layer onto a support layer or onto a non-stick protective film, which is optionally the backside of the bearing surface.

[0232] For the purposes of the present invention, the term "bearing surface" should be understood to mean a belt conveyor coated with a non-stick layer, or a non-stick protective film ("release liner"), or a support layer. The support surface is thus intended to be an integral part of the self-adhesive article, either as a non-stick protective film or as a support layer.

[0233] If the bearing surface is not the support layer, the final step of the method involves transferring the cured adhesive layer onto the support layer.

[0234] If the bearing surface is a support layer, the final step of the method involves counter-bonding an adhesive layer onto a non-stick protective film.

[0235] According to a preferred variant of the invention, the final step of the method consists in transferring the cured adhesive layer onto a flexible support layer, which may be a plastic film, after cooling the cured adhesive layer to a temperature below the degradation temperature or softening point of the material that constitutes the support layer.

[0236] According to one embodiment, the self-adhesive article according to the invention can be obtained by the aforementioned method without a step of pre-treatment of the surface of the support layer. These pre-treatments aim to chemically and / or physically modify the surface in order to increase the surface energy and / or roughness of the surface and thus improve the adhesion of the adhesive layer to the surface. Examples of known surface treatments include plasma, corona treatment, abrasion, or application of chemical adhesives (also known as primers) to the surface, which can impart a high surface energy to substrates coated with chemicals.

[0237] The method for producing a self-adhesive article according to the present invention may also comprise the step of coating a second layer of the adhesive composition according to the present invention onto a support layer, followed by curing the coated adhesive composition by heating to a temperature in the range of 20 to 200° C. According to this embodiment, a double-sided self-adhesive article is obtained.

[0238] The coating process may be carried out by known coating equipment, such as lip or curtain type nozzles, or by rollers. 2 The weight per unit area of ​​the adhesive composition required for the production of self-adhesive labels is in the range of 10 to 100 g / m. 2 , preferably 20 to 50 g / m 2 The weight per unit area required for the production of self-adhesive tapes can range from 3 to 5000 g / m². 2 , preferably 15 to 250 g / m 2 The temperature can vary within a much wider range.

[0239] According to certain embodiments, the coated adhesive composition is also subjected to treatment during the curing step in a humid atmosphere characterized by its humidity level, preferably an atmosphere in which 2% to 100% of the molecules are water molecules, preferably 3% to 50%, more preferably 3% to 10% of the molecules are water molecules.

[0240] Water content is expressed as the percentage of water per unit volume and corresponds to the number of water molecules divided by the total number of molecules in the unit volume. Due to the linearity of this scale, water content is easily measured and monitored, for example, by using a PID (proportional-integral-derivative) monitor. The weight percent 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 water content in various environments can be found in W. Wagner et al.'s International Steam Tables - Properties of Water and Steam based on the Industrial Formulations IAPWS-IF97.

[0241] The thermal curing step has the effect of generating siloxane-type bonds between the polymer chains of the adhesive composition that have hydrolyzable alkoxysilane end groups, and which, under the action of atmospheric moisture, result in the formation of a three-dimensional polymer network. The adhesive composition thus cured is a pressure-sensitive adhesive that imparts desirable adhesion and tack to the substrate coated therewith.

[0242] Preferably, the coating is applied uniformly onto the support layer or onto the non-stick protective layer, but the coating may also be conformed to the desired shape of the final self-adhesive article.

[0243] According to one embodiment, the adhesive composition is coated over at least a portion of both sides of the support layer. When coating the two sides of the support layer, the adhesive composition may be the same or different on the two sides, and the weight per unit area may be the same or different on the two sides.

[0244] According to certain embodiments of the present invention, the self-adhesive article comprises an adhesive layer on at least a portion of one side or on at least a portion of both sides of a support layer, the adhesive layer being optionally coated with a non-stick protective layer. According to one embodiment, the self-adhesive article comprises two non-stick protective layers on each of the two adhesive layers. In this case, the two protective layers can be made of the same or different materials and / or have the same or different thicknesses.

[0245] The self-adhesive article according to the present invention is a waterproof, breathable article. The term "waterproof, breathable" means permeable to water vapor and impermeable to liquid water.

[0246] Preferably, the articles obtained from the compositions according to the invention have a coating density of at least 350 g / m² per 24 hours at 37°C, 50% relative humidity and a film thickness of 30 μm. 2 More preferably, the film has a water vapor transmission rate (MVTR) of at least 500 g / m at 37° C., 50% relative humidity, and a film thickness of 30 μm. 2 / 24h, preferably at least 600g / m 2 / 24h, more preferably at least 700g / m 2 / 24h, preferably 800g / m 2 In particular, the MVTR membrane permeability is 350-400 g / m at 37°C, relative humidity 50%, and a film thickness of 30 μm. 2 / 24h, or 400-500g / m 2 / 24h, or 500-600g / m 2 / 24h, or 600-700g / m 2 / 24h, or 700-800g / m 2 / 24h, or 800-900g / m 2 / 24h, or 900-1000g / m 2 / 24h, or 1000-1200g / m 2 / 24h, or 1200-1500g / m 2 / 24h, or 1500-2000g / m 2 / 24h, or 2000-2500g / m2 / 24h, or 2500-3000g / m 2 / 24h, or 3000-3500g / m 2 / 24h, or 3500-4000g / m 2 / 24h, or 4000-4500g / m 2 / 24h, or 4500-5000g / m 2 / 24h. The moisture vapor transmission rate (MVTR) of the film can be measured according to standard ASTM E96 B at 37°C, 50% relative humidity and a film thickness of 30 μm. The self-adhesive article according to the present invention can be used in an adhesion method comprising the following steps: - removing the non-stick protective layer, if present; - applying a self-adhesive article to one surface of the product; -The process of applying pressure to an item.

[0247] In a second step, the self-adhesive article is applied so that the self-adhesive portion of the article (formed by the self-adhesive layer) faces the surface of the product.

[0248] According to certain embodiments in which the self-adhesive article is a double-sided article, the bonding method also includes a step in which the second surface of the product is applied to the article bonded to the first surface of the product, or the article bonded to the first surface of the product is applied to the second surface of the product. [Example]

[0249] The following examples illustrate the invention without limiting it.

[0250] "PSA" adhesive performance The adhesive composition was applied to a polyethylene terephthalate (PET) substrate layer to form a layer with a thickness of 50 μm.

[0251] The substrate layer coated with the adhesive composition was stored at 70° C. for 7 days to ensure complete curing of the composition.

[0252] The adhesive performance of the composition was measured by a 180° peel test according to standard Finat 1. According to this standard, 2 / 3 of the adhesive specimen (15 cm x 2.5 cm) is placed on a test plate (polished stainless steel, HDPE, etc.). To promote wetting, a 2 kg roller is passed over the specimen twice. A waiting period of 10 minutes is observed before towing. The specimen is positioned parallel to the tow and bent back at an angle of 180°. The part of the specimen not bonded to the test plate provides grip for the jaws, thus allowing towing at a standard speed of 300 mm / min. The device measures the force required to peel the specimen under the aforementioned conditions.

[0253] The principle of this test is to determine the force required to separate (or peel) an adhesive composition layer from a substrate layer.

[0254] The tack of the composition was measured according to the Finat 9 standard. According to this standard, a 15 cm x 2.5 cm adhesive test piece was folded into a loop with the adhesive on the outer surface of the loop. The loop was folded at a speed of 300 mm / min and then gently placed on a plate (glass). 2 Once the square is placed on the plate, the loop is removed from the plate and the force required to remove the adhesive is measured.

[0255] Water Vapor Transmission Rate (MVTR) This test measures the amount of water vapor that can pass through a layer of adhesive composition.

[0256] The test was carried out by applying the standard NF EN 13726-2 at 37°C.

[0257] The adhesive composition was applied at 5861 g / m 2 / 24h MVTR to a substrate layer of nonwoven (NW) material, or 7826 g / m 2 / 24h MVTR to form a layer with a thickness of 0.03 mm without backing (support for reinforcing the PU film during lamination, thickness 0.104 mm, with backing).

[0258] The substrate layer coated with the adhesive composition was stored at 70° C. for 7 days to ensure complete curing of the composition.

[0259] Example 1: Composition A (according to the invention) and composition B (reference) were prepared using the following ingredients: Cleartack® W100, available from Cray Valley, is a tackifying resin obtained by polymerizing α-methylstyrene without the action of phenols and has a number average molecular weight of 900 Da; Sylvalite® RE 100, a rosin-type resin with a number average molecular weight of about 1700 Da, available from Arizona Chemical Company; Lutonal® M40, available from BASF, which is a polyvinyl ether; Irganox® 1010, a hindered phenolic antioxidant available from BASF; SPUR Y-19204, available from Momentive, which is a silyl polypropylene glycol polyurethane prepolymer with trimethoxysilane end groups and has an average molecular weight Mn of 24,000 g / mol; - K-KAT® 5218, available from King Industries, which is an aluminum chelate type catalyst. [Table 1] TIFF0007785060000038.tif36170

[0260] Composition B does not contain a polyvinyl ether compound.

[0261] Adhesion performance and vapor permeability were measured as described above and the results are shown in the table below. [Table 2] TIFF0007785060000039.tif28170

[0262] Legend: -SS = Polished Stainless Steel -AF = adhesive failure (no residue left, loss of adhesion explains the test result, product has good cohesion) -HDPE = High Density Polyethylene

[0263] It can be seen that composition A according to the invention makes it possible to obtain articles with improved vapor permeability, without compromising the good adhesive properties.

[0264] Example 2 Composition C (according to the invention) and composition D (reference) were prepared using the following ingredients: Picco® AR100, available from Eastman, is a hydrocarbon-based resin; Lutonal® M40, available from BASF, which is a polyvinyl ether; Geniosil® STPE-30, a dimethoxy(methyl)silylmethylcarbamate-terminated polyether with an average molecular weight of 24000 g / mol, available from Wacker; - K-KAT® 5218, available from King Industries, which is an aluminum chelate type catalyst. [Table 3] TIFF0007785060000040.tif26170

[0265] Composition D does not contain a polyvinyl ether compound.

[0266] The adhesive performance and vapor permeability were measured as described above, and the results are shown in the following table [Table 4]: [Table 4] TIFF0007785060000041.tif32170

[0267] It can be seen that composition C according to the invention makes it possible to obtain articles with improved vapor permeability, without compromising the good adhesive properties.

[0268] Example 3: Composition E (in accordance with the invention) and composition F (comparative example) were prepared using the following ingredients: Cleartack® W100, available from Cray Valley, is a tackifying resin obtained by polymerizing α-methylstyrene without the action of phenols and has a number average molecular weight of 900 Da; Sylvalite® RE 100, a rosin-type resin with a number average molecular weight of about 1700 Da, available from Arizona Chemical Company; Lutonal® M40, available from BASF, which is a polyvinyl ether; Irganox® 1010, a hindered phenolic antioxidant available from BASF; Spur Y-19204, available from Momentive, which is a silyl polypropylene glycol polyurethane prepolymer with trimethoxysilane end groups and has an average molecular weight Mn of 24000 g / mol; -TnBT, a titanium tetrabutoxide catalyst. [Table 5] TIFF0007785060000042.tif35170

[0269] Composition F does not contain a polyvinyl ether compound.

[0270] Adhesion performance and vapor permeability were measured as described above and the results are shown in the table below. [Table 6] TIFF0007785060000043.tif21170

[0271] It can be seen that composition E according to the invention makes it possible to obtain articles with improved vapor permeability, without compromising the good adhesive properties.

Claims

1. at least one silyl polymer containing at least one hydrolyzable alkoxysilane group; at least one polyvinyl ether compound; at least one curing catalyst; 1. An adhesive composition comprising:

2. The silyl polymer is General formula [Chemical formula 2] Silyl polymer of General formula [Chemical formula 3] Silyl polymer of General formula [Chemical formula 4] Silyl polymer of General formula [Chemical formula 5] Silyl polymer of (In the formula, X １ and X ２ represent, independently of one another, an oxygen atom or an —NH— group, R １ represents a divalent hydrocarbon-based radical containing 5 to 15 carbon atoms, which may be aromatic or aliphatic, linear, branched or cyclic; R ０ represents a linear or branched divalent alkylene radical containing 3 to 6 carbon atoms; R ３ represents a linear or branched divalent alkylene radical containing 1 to 6 carbon atoms; R ２ is a polyether block -R ｐｅ - [OR ｐｅ ] ｎ represents -, and R ｐｅ represents a linear or branched divalent alkylene radical containing 2 to 4 carbon atoms, R ４ and R ５ may be the same or different and each represents a linear or branched alkyl radical containing 1 to 4 carbon atoms; R ６ is a hydrogen atom, a phenyl radical, a linear, branched or cyclic alkyl radical containing 1 to 6 carbon atoms, or a group of formula [Chemical formula 6] represents a 2-succinate radical of the formula R ７ is a linear or branched alkyl radical containing 1 to 6 carbon atoms, n is a polyether block -[OR ｐｅ ] ｎ - is an integer such that the number average molecular weight is in the range of 300 g / mol to 40,000 g / mol in the polymers of the general formulas [Chemical Formula 2], [Chemical Formula 3] and [Chemical Formula 4], m １ is zero or an integer, m １ is such that the number average molecular weight of the polymer of general formula [Chemical Formula 3] is in the range of 500 g / mol to 50,000 g / mol, m is a non-zero integer, m is such that the number average molecular weight of the polymer of general formula [Chemical Formula 4] is in the range of 500 g / mol to 50,000 g / mol; p is an integer equal to 0, 1 or 2; R ａｌ represents a divalent hydrocarbon-based radical derived from a diol by replacing each of the two hydroxyl groups with a free valence, or the radical R ２ represents R ａｃ represents a divalent hydrocarbon-based radical derived from a dicarboxylic acid by replacing each of the two carboxyl groups COOH with a free valence, [Y] ｑ is represented by the general formula [Chemical Formula 28] represents a repeating unit of t is the general formula [Chemical formula 7] is a number such that the polyester diol has a hydroxyl number IOH between 4 mg KOH / g 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 [Chemical Formula 5] is between 400 g / mol and 50,000 g / mol. The composition of claim 1 selected from:

3. 3. The composition of claim 1 or 2, wherein the curing catalyst is selected from the group consisting of amines, organometallic compounds, acids and their derivatives, and mixtures thereof.

4. The composition of any one of claims 1 to 3, also comprising a tackifying resin.

5. 5. The composition of any one of claims 1 to 4, wherein the polyvinyl ether compound comprises units derived from a monomer selected from methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, isopropyl vinyl ether, propyl vinyl ether, octyl vinyl ether, or a combination thereof.

6. 6. The composition of any one of claims 1 to 5, wherein the polyvinyl ether compound is selected 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), copolymers thereof, and mixtures thereof.

7. 7. The composition of claim 1, wherein the polyvinyl ether compound has a K value of 40 to 120.

8. The composition according to any one of claims 1 to 7, wherein the polyvinyl ether compound has a glass transition temperature of from -60 to 0°C.

9. The composition according to any one of claims 1 to 8, wherein the polyvinyl ether compound has a content of 1% by weight to 60% by weight relative to the total weight of the composition.

10. 10. The composition of claim 1, also comprising at least one silsesquioxane.

11. 11. The composition of claim 1, which is a one-component composition.

12. The composition comprises: a part A comprising said at least one silyl polymer; Part B comprising said at least one curing catalyst; A two-component composition comprising:

11. The composition of claim 1, wherein the at least one polyvinyl ether compound is present in part A and / or part B of the composition.

13. 13. Use of a composition according to any one of claims 1 to 12 as an adhesive.

14. A self-adhesive article comprising at least one support layer and at least one layer of the composition of any one of claims 1 to 13.

15. 15. The self-adhesive article of claim 14, selected from a dressing, a bandage, and a medical tape.

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