Adhesive composition for the preparation of waterproof, breathable articles

Abstract

The present invention relates to an adhesive composition comprising at least one silyl polymer containing at least one hydrolysable alkoxysilane group; at least one polyvinyl ether compound; and at least one crosslinking catalyst, to the use of said composition as an adhesive, and to a self-adhesive article comprising at least one carrier layer and at least one layer of said composition.

Description

Invention Field

[0001] This invention relates to an adhesive composition and its use in the preparation of self-adhesive articles. Technical Background

[0002] Hot-Melt Pressure Sensitive Adhesives (HMPSA) are compositions that impart immediate adhesion (often referred to as "tack") to a carrier coated with them at room temperature. This tack advantageously allows the composition to adhere instantaneously to a substrate under gentle and brief pressure. HMPSA is widely used in the preparation of self-adhesive articles, such as self-adhesive labels attached to articles for displaying information (barcodes, names, prices, etc.) and / or for decorative purposes, whether this is during final or temporary adhesive bonding. HMPSA is also used in the preparation of self-adhesive tapes for various applications. Besides the widely used transparent tape in daily life, other applications include: forming and assembling cardboard packaging; protecting painted surfaces in construction; securing and supporting various components such as panels, bricks, and protrusions in the construction of buildings or towers; securing and supporting metal, plastic, or glass components that are flat or have a specific shape, such as cables, plastic films, window glass, metal plates, inscriptions, signs, seat components, dashboards, plastic or textile walls; pipes or conduits for fluid circulation, especially in the transportation industry; and bonding carpets with double-sided tape in the construction field.

[0003] Waterproof and breathable self-adhesive products can be used in medical applications such as bandages, dressings, electrodes, and plasters; in clothing applications such as breathable clothing for weather protection or breathable dry clothing for exposure to damp environments; and in building applications such as roofing or wall cladding, or in sealed window frame systems that still need to be breathable so that moisture is released into the environment.

[0004] In particular, adhesive materials used in the medical field, such as medical tapes, wound dressings, and consumer bandages, require high water vapor permeability (MVTR) to allow moisture generated by skin or wound exudate to escape. The high MVTR of adhesive products prevents moisture from remaining under the dressing, which would otherwise lead to skin maceration.

[0005] Therefore, breathable products must meet certain conditions, such as uniform appearance, wind resistance, high water vapor permeability, a certain degree of elasticity, and the ability to adhere to different substrates.

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

[0007] For example, document WO2013 / 136108A1 specifically relates to an adhesive composition comprising at least one silyl polymer, at least one tackifying resin and at least one catalyst, and its use in the preparation of waterproof and breathable articles.

[0008] WO2019 / 115952A1 specifically relates to a multi-component adhesive composition comprising composition A, said composition A comprising at least one silyl polymer having at least one hydrolyzable alkoxysilyl group, and at least one tackifying resin, and composition B comprising at least one catalyst, and at least one compound C. Compound C is selected from compound C1 having a number-average molecular weight of 300 g / mol to 500,000 g / mol and compound C2 having a vapor pressure greater than or equal to 0.08 kPa at 20°C.

[0009] WO2019 / 186014A1 specifically relates to adhesive compositions comprising at least one curable silyl polymer and catalytic compositions comprising tertiary amines and organometallic compounds.

[0010] WO03 / 087254A2 specifically relates to hydrophilic adhesive compositions, characterized in that they comprise a thermoplastic elastomer of the poly(styrene-olefin-styrene) block copolymer type, a tackifier, a liquid plasticizer, water, and an amphiphilic copolymer.

[0011] WO2020 / 016581A1 specifically relates to a composition comprising a polymer and a tackifying resin, the polymer comprising silyl groups functionalized with urea and amine groups, the composition being used as a hot melt pressure-sensitive adhesive.

[0012] These various waterproof and breathable self-adhesive products and the adhesive compositions comprising them exhibit satisfactory adhesive properties. However, these products and the compositions comprising them are not necessarily suitable for medical applications. In particular, these products and the compositions comprising them, such as medical tapes, bandages, and dressings, are not necessarily suitable for prolonged application to the skin or wounds. In fact, prolonged use of these items can lead to maceration of the skin or wound, which can cause discomfort to the patient and slow healing, among other things.

[0013] Therefore, there is indeed a need for an adhesive composition that allows for the preparation of self-adhesive articles suitable for medical use and having improved water vapor permeability without compromising good adhesive properties. There is also a need for an adhesive composition that allows for the preparation of self-adhesive articles suitable for extended application to skin or wounds—such as medical tapes, bandages, or dressings. There is also a need for an adhesive composition that allows for the preparation of self-adhesive articles—such as medical tapes, bandages, or dressings—to limit or even prevent maceration of the skin or the wound to which they are applied. There is also a need for an adhesive composition capable of preparing self-adhesive articles—such as medical tapes, bandages, or dressings—to promote wound healing. There is also a need for an adhesive composition that allows for the preparation of self-adhesive articles suitable for the construction market and having improved water vapor permeability without compromising good adhesive properties. Invention Summary

[0014] This invention first relates to an adhesive composition comprising:

[0015] At least one silyl polymer comprising at least one hydrolyzable alkoxysilyl group;

[0016] At least one polyvinyl ether compound; and

[0017] At least one crosslinking catalyst.

[0018] In some embodiments, the silyl polymer is selected from:

[0019] Silyl polymers having the general formula [Chemical Formula 2]

[0020] (R 5 O) 3-p (R 4 ) p Si-R 0 -OR 2 -OR 0 -Si(R 4 p(OR) 5 ) 3-p

[0021] Silyl polymers having the general formula [Chemical Formula 3]

[0022]

[0023] Silyl polymers having the general formula [Chemical Formula 4]

[0024]

[0025] Silyl polymers having the general formula [Chemical Formula 5]

[0026]

[0027] in:

[0028] X 1 and X 2 Each can independently represent an oxygen atom or an -NH- group;

[0029] R 1 It represents a divalent hydrocarbon group containing 5 to 15 carbon atoms, which can be aromatic or aliphatic, straight-chain, branched or cyclic;

[0030] R 0 This indicates a straight-chain or branched divalent alkylene group containing 3 to 6 carbon atoms;

[0031] R 3 R represents a straight-chain or branched divalent alkylene group containing 1 to 6 carbon atoms. 3 Preferably, it represents methylene or n-propylene;

[0032] R 2 Indicates polyether block-R pe -[OR pe ] n -, where R pe This indicates a straight-chain or branched divalent alkylene group containing 2 to 4 carbon atoms;

[0033] R 4 and R 5 They can be the same or different, each representing a straight-chain or branched alkyl group containing 1 to 4 carbon atoms;

[0034] R 6 It represents a hydrogen atom, a phenyl group, a straight-chain, branched, or cyclic alkyl group containing 1 to 6 carbon atoms, or a 2-succinate group having the general formula [Chemical Formula 6].

[0035]

[0036] Where R 7 It is a straight-chain or branched alkyl group containing 1 to 6 carbon atoms;

[0037] n is an integer such that the polyether block-[OR] in polymers having the general formulas [Formula 2], [Formula 3], and [Formula 4] is a polyether block-[OR] pe ] n - The number-average molecular weight ranges from 300 g / mol to 40000 g / mol;

[0038] m1 is zero or an integer;

[0039] m1 results in a polymer having a number-average molecular weight of 500 g / mol to 50000 g / mol, preferably 700 g / mol to 20000 g / mol;

[0040] m is a non-zero integer;

[0041] m such that the polymer having the general formula [Chemistry 4] has a number average molecular weight of 500 g / mol to 50000 g / mol, preferably 700 g / mol to 20000 g / mol;

[0042] p is an integer equal to 0, 1 or 2, preferably 0 or 1;

[0043] R al This indicates a divalent hydrocarbon group derived from a diol by substituting each of the two hydroxyl groups with a free valence, or indicates the group R. 2 ;

[0044] R ac This indicates a divalent hydrocarbon group generated from a dicarboxylic acid by replacing each of the two carboxyl groups (COOH) with a free valence.

[0045] [Y] q Represents repeating units with the general formula [Chemical Formula 28].

[0046]

[0047] t is a number that gives polyester diols with the general formula [Chemical Formula 7] a hydroxyl value of 4 to 60 mg KOH / g (IOH).

[0048]

[0049] q is a non-zero integer;

[0050] t and q result in polymers having the general formula [Chemical Formula 5] with a number-average molecular weight between 400 g / mol and 50000 g / mol.

[0051] In some embodiments, the crosslinking catalyst is selected from the group consisting of amines, organometallic compounds, acids and their derivatives, and mixtures thereof.

[0052] In some embodiments, the composition further comprises a tackifying resin; preferably a tackifying resin selected from terpene phenolic resins, hydrocarbon resins, rosin resins; acrylic resins and mixtures thereof.

[0053] In some embodiments, the polyvinyl ether compound comprises a unit 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 combinations thereof.

[0054] In some 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.

[0055] In some embodiments, the K value of the polyvinyl ether compound is 40 to 120, preferably 40 to 70.

[0056] In some embodiments, the glass transition temperature of the polyvinyl ether compound is -60 to 0°C, preferably -50 to -5°C.

[0057] In some embodiments, the content of the polyvinyl ether compound is from 1% to 60% by weight relative to the total weight of the composition, preferably from 5% to 40% by weight, and even more preferably from 5% to 25% by weight.

[0058] In some embodiments, the composition further comprises at least one sesquioxane.

[0059] In some embodiments, the composition is a one-component composition.

[0060] In some embodiments, the composition is a two-component composition comprising:

[0061] Part A comprising at least one silyl polymer; and

[0062] Part B includes at least one crosslinking catalyst;

[0063] The at least one polyvinyl ether compound is present in part A and / or part B of the composition.

[0064] The present invention also relates to the use of the above composition as an adhesive.

[0065] The present invention also relates to a self-adhesive article comprising at least one carrier layer and at least one layer of the above composition.

[0066] In some embodiments, the article is selected from dressings, bandages, and medical tapes.

[0067] The present invention can meet the above-mentioned needs. More specifically, it provides a composition for preparing articles with good and improved water vapor permeability without compromising good adhesive properties.

[0068] This is achieved through the composition according to the invention. More specifically, the inventors have surprisingly demonstrated that the adhesive compositions according to the invention—particularly compositions comprising at least one silyl polymer, at least one polyvinyl ether compound, and at least one crosslinking catalyst—make it possible to obtain adhesive articles with improved permeability without compromising good adhesion to substrates. In fact, the presence of the polyvinyl ether compound enables good compatibility with the other components of the composition, more specifically with the silyl polymer chains (which already possess good water vapor permeability), resulting in an adhesive composition with improved water vapor permeability. The term "good compatibility" herein refers to the storage stability and long-term stability of the composition.

[0069] Detailed description

[0070] The present invention will now be described in more detail in a non-limiting manner in the following description.

[0071] Adhesive composition

[0072] In a first aspect, the present invention relates to an adhesive composition comprising at least one silyl polymer containing at least one hydrolyzable alkoxysilyl group, at least one polyvinyl ether compound, and at least one crosslinking catalyst. Various additives may also be present in the adhesive composition.

[0073] silyl polymer

[0074] The silyl polymer contains at least one hydrolyzable alkoxysilyl group, preferably an end group, and more preferably at least two hydrolyzable alkoxysilyl groups, preferably end groups.

[0075] The silyl polymer can be a polymer containing at least one group of the general formula [Chemical Formula 1], particularly a terminal group:

[0076] -Si(R 4 ) p (OR 5 ) 3-p

[0077] in:

[0078] R 4 and R 5 They are the same or different, each representing a straight-chain or branched alkyl group containing 1 to 4 carbon atoms; and

[0079] p is an integer equal to 0, 1, or 2.

[0080] When p = 2, group R 4 They can be the same or different.

[0081] When p = 1 or p = 0, group R 5 They can be the same or different.

[0082] The silyl polymer containing at least one, preferably at least two, hydrolyzable alkoxysilyl groups may have a backbone selected from the following: polyether, polyester, polyester-polyether-polyester, polyether-polyester-polyether, polyolefin, polycaprolactone, polyacrylate, polycarbonate, poly(ether-carbonate), poly(ester-carbonate), polyacetal, polyesteramide, polysulfide, polyurethane, polyester-polyurethane, polyether-polyurethane, polyether-polyester-polyurethane, polyolefin-polyurethane, polyether-polyolefin-polyurethane, polyurea, or poly(urethane-urea).

[0083] Preferably, the silyl polymer having at least one hydrolyzable alkoxysilyl group is selected from silyl polyether-polyurethane, silyl polyether, silyl polyester, silyl polyester-polyurethane, silyl polyether-polyester-polyurethane, silyl polyurea, silyl poly(urethane-urea) and mixtures thereof.

[0084] The silyl polymer may have a number average molecular weight (Mn) of 500 to 50,000 g / mol, preferably 700 to 30,000 g / mol, advantageously 1,000 to 25,000 g / mol, and particularly 1,000 to 21,000 g / mol.

[0085] The number-average molecular weight of silyl polymers can be measured by methods well known to those skilled in the art, such as size exclusion chromatography using polystyrene standards.

[0086] The silyl polymer containing at least one hydrolyzable alkoxysilyl group may be selected from polymers of general formula [Formula 2], [Formula 3], [Formula 4] or [Formula 5] as defined below and mixtures thereof:

[0087] [Chemical Formula 2]

[0088] (R 5 O) 3～ρ (R 4 ) ρ Si-R 0 -OR 2 -OR 0 -Si(R 4 )p(OR 5 ) 3-p

[0089] [Chemical Formula 3]

[0090]

[0091] [Chemical Formula 4]

[0092]

[0093] [Chemical Formula 5]

[0094]

[0095] in:

[0096] X 1 and X 2 Each can independently represent an oxygen atom or an -NH- group;

[0097] R 1 It represents a divalent hydrocarbon group containing 5 to 15 carbon atoms, which can be aromatic or aliphatic, straight-chain, branched or cyclic;

[0098] R 0 This indicates a straight-chain or branched divalent alkylene group containing 3 to 6 carbon atoms;

[0099] R 3 It represents a straight-chain or branched divalent alkylene group containing 1 to 6 carbon atoms, preferably R. 3 Indicates methylene or n-propylidene;

[0100] R 2 Indicates polyether block-R pe -[OR pe ] n -, where R pe This indicates a straight-chain or branched divalent alkylene group containing 2 to 4 carbon atoms;

[0101] n is an integer such that in polymers of general formulas [Formula 2], [Formula 3], and [Formula 4], the polyether block-[OR] pe ] n - The number-average molecular weight ranges from 300 g / mol to 40000 g / mol;

[0102] R 4 and R 5 As defined above;

[0103] R 6 It represents a hydrogen atom, a phenyl group, a straight-chain, branched, or cyclic alkyl group containing 1 to 6 carbon atoms, or a 2-succinate group having the general formula [Chemical Formula 6].

[0104]

[0105] Where R 7 It is a straight-chain or branched alkyl group containing 1 to 6 carbon atoms;

[0106] m1 is zero or an integer;

[0107] m1 results in a polymer having a number-average molecular weight of 500 g / mol to 50000 g / mol, preferably 700 g / mol to 20000 g / mol;

[0108] m is a non-zero integer;

[0109] m such that the polymer having the general formula [Chemical Formula 4] has a number average molecular weight of 500 g / mol to 50000 g / mol, preferably 700 g / mol to 20000 g / mol;

[0110] p is defined above, and p is preferably 0 or 1;

[0111] R al This indicates a divalent hydrocarbon group generated from a diol by substituting each of the two hydroxyl groups with a free valence, or indicates the group R. 2 ;

[0112] R ac This indicates a divalent hydrocarbon group generated from a dicarboxylic acid by replacing each of the two carboxyl groups (COOH) with a free valence.

[0113] [Y] q Represents repeating units with the general formula [Chemical Formula 28].

[0114]

[0115] t is a number that gives polyester diols with the general formula [Chemical Formula 7] a hydroxyl value I of 4-60 mg KOH / g. OH ;

[0116]

[0117] q is a non-zero integer; and

[0118] t and q result in polymers having the general formula [Chemical Formula 5] with a number-average molecular weight between 400 g / mol and 50000 g / mol.

[0119] According to some implementation plans, X 1 and X 2 All of them are oxygen atoms.

[0120] Or, X 1 and X 2 Both are -NH- groups.

[0121] Or perhaps, X 1 and X 2 One of them can be an oxygen atom and X1 and X2 Another one can be the -NH- group.

[0122] Preferably, the group R of general formulas [Chemical Formula 3], [Chemical Formula 4] and [Chemical Formula 5] 1 Selected from one of the following divalent groups, the following formula shows two free valences:

[0123] A divalent group derived from isophorone diisocyanate (IPDI) [Chemical Formula 8]

[0124]

[0125] Having a divalent group derived from 4,4′- and 2,4′-dicyclohexylmethane diisocyanate (HMDI) of formula [Chemical Formula 9] or [Chemical Formula 10]

[0126]

[0127] Having a group derived from 2,4- and 2,6-toluene diisocyanate (TDI) of formula [Chemical Formula 11] or formula [Chemical Formula 12]

[0128]

[0129] Having a group derived from 4,4′- and 2,4′-diphenylmethane diisocyanate (MDI) of formula [Chemical Formula 13] or formula [Chemical Formula 14]

[0130]

[0131] Groups derived from m-xylene diisocyanate (m-XDI) of formula

[15]

[0132]

[0133] The group of formula [Chemical Formula 16] derived from hexamethylene diisocyanate (HDI)

[0134] -(CH2)6-

[0135] Preferably, the group R of general formulas [Chemical Formula 3], [Chemical Formula 4] and [Chemical Formula 5] 1 It is a divalent group derived from isophorone diisocyanate or xylene diisocyanate.

[0136] Polymers of general formula [Chemical Formula 3] can be obtained, for example, by the methods described in EP2336208A1 and WO2009 / 106699A2.

[0137] In polymers corresponding to the general formula [Chemical Formula 3], for example, the following may be mentioned:

[0138] STP-E10 (available from Wacker): A polyether containing two dimethoxyl-type groups [Formula 1] (m1 equals 0, p equals 1 and R...) 4 and R 5 (representing methyl) has a number-average molecular weight of approximately 8889 g / mol, where R3 represents methylene;

[0139] STP-E30 (available from Wacker): A polyether containing two groups of the dimethoxy type of general formula [Chemical Formula 1] (m1 equals 0, p equals 1 and R...). 4 and R 5 (Indicating methyl) has a number-average molecular weight of approximately 14493 g / mol, where R 3 Represents methylene;

[0140] 1050MM (available from Momentive): Polyether-polyurethane containing two trimethoxy group of general formula [Formula 1] (m1 is not 0, p is equal to 0, R... 5 (representing methyl), has a number-average molecular weight of approximately 16393 g / mol, where R 3 Represents positive propylidene;

[0141] Y-19116 (purchased from Momentive): Polyether-polyurethane containing two trimethoxy group of general formula [Chemical Formula 1] (m1 is not 0, R 5 (representing methyl), having a number-average molecular weight of 15000 g / mol to 17000 g / mol, wherein R 3 Represents positive propylidene;

[0142] - S XP 2636 (available from Bayer): A polyether containing two trimethoxy groups of the general formula [Chemical Formula 1] (m1 = 0, p = 0, R5 represents methyl), having a number-average molecular weight of approximately 15038 g / mol, wherein R 3 It represents propylidene.

[0143] Polymers having the general formula [Chemical Formula 2] can be obtained by the hydrosilylation of polyether diallyl ether according to, for example, the method described in document EP1829928A1.

[0144] In polymers corresponding to the general formula [Chemical Formula 2], it can be mentioned that:

[0145] -MS Polymer TMS303H (available from Kaneka) corresponds to a group containing two dimethoxy groups of the general formula [Formula 1] (p equals 1 and R...). 4 The methyl group (indicating a number-average molecular weight of approximately 22,000 g / mol and a viscosity of 12.5 Pa·s at 23 °C) is described.

[0146] -MS Polymer TM S227 (available from Kaneka) corresponds to a group containing two dimethoxy groups of the general formula [Formula 1] (p = 1, R...). 5 and R 4 Each of the following is a polyether containing methyl groups, having a number-average molecular weight of about 27,000 g / mol and a viscosity of 34 Pa·s at 23 °C.

[0147] Polymers of general formula [Chemical Formula 4] can be obtained by the following methods (in the case that the polymer of general formula [Chemical Formula 4] is a silane polyurethane):

[0148] -To make a polyether polyol having the general formula [Chemical Formula 17] with a stoichiometric excess of the formula NCO-R 1 -NCO diisocyanate reaction

[0149] HO-R 2 -OH

[0150] To form a polyurethane-polyether block having at least two -NCO end groups, said block preferably containing 1.5 wt% to 1.9 wt% -NCO groups, then...

[0151] - React the block obtained in the previous step with a stoichiometric or slightly excess of an α-, β-, or γ-aminosilane having the general formula [Formula 18].

[0152] (R 5 O) 3-p (R 4 ) p Si-R 3 -NHR 6

[0153] Such a method is described, for example, in WO2013 / 136108A1.

[0154] In polymers corresponding to the general formula [Chemical Formula 4], for example, the following can be mentioned:

[0155] -Spur+1015LM (available from Momentive) corresponds to a [Formula 1] group containing two trimethoxy groups (p = 0, R...). 5The polyether-polyurethane (representing methyl) has a number-average molecular weight of about 25,000 g / mol and a viscosity of 50 Pa·s at 23 °C.

[0156] Polymers having the general formula [Chemical Formula 4] can be obtained by the following method (in the case that the polymer with the general formula [Chemical Formula 4] is a silyl polyurea):

[0157] - To react a stoichiometric excess of the general formula [chemical formula 19] diamine with NCO-R 1 -NCO diisocyanate reaction

[0158] H2N-R 2 -NH2

[0159] To form a polyurea-polyether block having at least two -NCO end groups, said block preferably containing 1.5% to 1.9% by weight of -NCO groups, then...

[0160] - React the block obtained in the previous step with a stoichiometric or slightly excess α-, β-, or γ-aminosilane having the general formula [Formula 18].

[0161] (R 5 O) 3-p (R 4 ) p Si-R 3 -NHR 6 .

[0162] For example, such a method is described in WO2020 / 016581A1.

[0163] The polymers of general formula [Chemical Formula 5] can be those described in patent application EP2865694A1. They can be prepared according to the methods described in that patent application.

[0164] Polymers of general formula [Chemical Formula 5] may be the first polymer of a specific general formula [Chemical Formula 5], wherein:

[0165] R al Represents a divalent hydrocarbon group, which is derived from a dimer fatty alcohol by substituting each of the two hydroxyl groups with a free valence, said alcohol having a hydroxyl value of 200-220 mg KOH / g. OH ;

[0166] R ac This indicates a divalent hydrocarbon group, which is derived from a dimer fatty acid by substituting each of the two carboxyl-COOH groups with a free valence, said acid having an acid value of 190 to 200 mg KOH / g. A ;

[0167] Preferably, the polyester diol having the general formula [Chemical Formula 7] has a hydroxyl value between 45-55 mg KOH / g. OH The number

[0168]

[0169] This first polymer having a specific general formula [Chemical Formula 5] can be obtained according to the method described in patent application EP2865728A1 (specifically pages 5 to 9).

[0170] Preferably, the first polymer having a specific general formula [Chemical Formula 5] has a number-average molecular weight in the range of 900 to 15000 g / mol.

[0171] Polymers of general formula [Chemical Formula 5] can be second polymers of a specific general formula [Chemical Formula 5], wherein:

[0172] R al This refers to a divalent hydrocarbon group derived from a saturated diol by substituting each of the two hydroxyl groups with a free valence, the diol having a hydroxyl value I greater than 220 mg KOH / g. OH ;

[0173] R ac This refers to a divalent hydrocarbon group derived from a saturated dicarboxylic acid by substituting each of the two carboxyl-COOH groups with a free valence, wherein the acid has an acid value I greater than 200 mg KOH / g. A ;

[0174] The preferred option is for the polyester diol having the general formula [Chemical Formula 7] to have a hydroxyl value of 4-24 mg KOH / g, particularly 9-24 mg KOH / g. OH The number

[0175]

[0176] The second polymer having a specific general formula [Chemical Formula 5] can be obtained by a method comprising multiple successive steps:

[0177] The first step of the method for obtaining a second polymer having a specific general formula [Chemical Formula 5] includes preparing a hydroxyl value I having a value of 4-24 mg KOH / g. OH Polyesters of the general formula [chemical formula 7]

[0178] Polyesters of general formula [Chemical Formula 7] can be prepared by polycondensation reaction between the following substances:

[0179] At least one acid value I with a value greater than 200 mg KOH / g A saturated dicarboxylic acids; and

[0180] At least one saturated diol having a hydroxyl value greater than 220 mg KOH / g.

[0181] In this article:

[0182] The acid value I of dicarboxylic acids A This is the number of carboxyl functional groups per gram of acid, expressed as milliequivalents of KOH required to neutralize the acidity of 1 gram of acid, determined by titration, and related to the number-average molecular weight M of the acid by the following relationship [Mathematical Formula 1]:

[0183] I A = (56, 1 × 2 × 1000) / M

[0184] Number of hydroxyl groups I of the diol OH This is the number of hydroxyl functional groups per gram of diol, expressed in milligram equivalents of KOH used in the determination of hydroxyl functional groups, determined by titration according to standard ISO 14900:2001, and related to the number-average molecular weight M′ of the diol by the following relationship [Mathematical Formula 2]:

[0185] l OH = (56, 1 × 2 × 1000) / M'

[0186] Preferably, the saturated dicarboxylic acid has an acid value I greater than or equal to 300 mg KOH / g, preferably greater than or equal to 400 mg KOH / g, more preferably greater than or equal to 500 mg KOH / g, particularly greater than or equal to 700 mg KOH / g, and advantageously greater than or equal to 800 mg KOH / g. A Preferably, the saturated dicarboxylic acid has an acid value IA equal to 555 mg KOH / g or 768 mg KOH / g.

[0187] Dicarboxylic acids can be linear or branched, preferably linear, aliphatic, or alicyclic.

[0188] The dicarboxylic acid according to the present invention may be selected from 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.

[0189] Preferably, the dicarboxylic acid is adipic acid or sebacic acid.

[0190] Preferably, the saturated diol has a hydroxyl value of 1 greater than or equal to 500 mg KOH / g, more preferably greater than or equal to 700 mg KOH / g, and even more preferably greater than or equal to 900 mg KOH / g. OH .

[0191] The diol used can be aromatic or aliphatic (preferably aliphatic), straight-chain or branched, preferably branched.

[0192] The diol according to the present invention may be selected from 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-3 ... 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 (neopentanediol-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: 1469) 0-00-7), 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: 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 Alkanediols (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.

[0193] Preferably, the diol is selected from 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 (neopentanediol-NPG, CAS: 126-30-7) and mixtures thereof.

[0194] Preferably, the polyester of general formula [Chemical Formula 7] is obtained by polycondensation reaction between the following substances: a mixture of adipic acid with neopentyl glycol, ethylene glycol and 1,6-hexanediol;

[0195] It can be obtained by the condensation reaction of the following substances: adipic acid and 3-methyl-1,5-pentanediol.

[0196] Preferably, the polyester diol of general formula [Chemical Formula 7] has a hydroxyl value of 4 to 24 mg KOH / g, preferably 7 to 24 mg KOH / g, more preferably 7 to 20 mg KOH / g, and especially 9 to 19 mg KOH / g. OH Preferably, the hydroxyl value is I. OH It is 9-24 mg KOH / g.

[0197] Polyester diols of general formula [Chemical Formula 7] may have a glass transition temperature of less than 0°C, preferably less than or equal to -20°C, preferably less than or equal to -40°C, preferably less than or equal to -50°C, particularly less than or equal to -60°C, for example less than or equal to -64°C.

[0198] Polyester diols of general formula [Chemical Formula 7] may have a number-average molecular weight of 5500 g / mol or greater, preferably 6000 g / mol or greater, particularly strictly greater than 6000 g / mol, preferably greater than 8000 g / mol or greater, particularly greater than 9000 g / mol or greater, for example greater than or equal to 10000 g / mol, advantageously greater than or equal to 12000 g / mol and particularly greater than or equal to 18000 g / mol.

[0199] The number-average molecular weight of polyester diols of general formula [Chemical Formula 7] can be determined by their I... OH Its functionality is determined.

[0200] Among amorphous polyester diols having the general formula [Chemical Formula 7], one can, for example, mention the one sold by Evonik. 7250 (polyester polyol, viscosity at 23℃ is 180 Pa·s, number-average molecular weight Mn is 5500 g / mol, and T...) g (Equal to -50℃), sold by Kuraray P-6010 (polyester polyol, viscosity at 23℃ is 68 Pa·s, number average molecular weight is 6000 g / mol, and T...) g (equal to -64℃), or sold by Kuraray P-10010 (a polyester polyol with a viscosity of 687 Pa·s at 23°C and a number-average molecular weight of 10,000 g / mol).

[0201] The second step of the method for obtaining a second polymer having a specific general formula [Chemical Formula 5] includes preparing a polymer having the general formula [Chemical Formula 5].

[0202] According to the first variant, the polyester of the above general formula [Chemical Formula 7] can be reacted with the isocyanate silane of the general formula [Chemical Formula 20] in an amount corresponding to a molar equivalent ratio of 0.90-1.05, preferably equal to about 1, of the number of NCO / OH functional groups.

[0203] NCO-R 3 -Si(R 4 ) p (OR 5 ) 3-p .

[0204] This step is specifically carried out under anhydrous conditions to avoid the hydrolysis of the alkoxysilane group. The typical temperature range for carrying out this reaction step is 30°C to 120°C, and more specifically 60°C to 105°C.

[0205] The isocyanate silanes of the above general formula [Chemical Formula 20] are widely available. Of particular note is the availability from Momentive. A-Link 35, namely (3-isocyanate propyl)trimethoxysilane, is available from Momentive. A-Link 25, namely (3-isocyanate propyl)triethoxysilane, is available from Gelest as well as (3-isocyanate propyl)methyldimethoxysilane, and from Wacker as well. XL42, namely (3-isocyanomethyl)methyldimethoxysilane, and available from Wacker XL 43, which stands for (3-isocyanomethyl)trimethoxysilane.

[0206] According to the second variant, silyl polymers can be obtained through the following two steps:

[0207] Polyester polyols of general formula [Chemical Formula 7] are reacted with NCO-R 1 -NCO diisocyanate is reacted in an amount corresponding to a molar equivalent ratio of 0.3-0.7 and preferably equal to about 0.5 NCO / OH functional groups to form a polyester-polyurethane block;

[0208] The block obtained in the preceding steps is reacted with the isocyanate silane of formula [Chemical Formula 20] in an amount corresponding to a molar equivalent ratio of 0.90-1.05, and preferably equal to about 1, of the number of NCO / OH functional groups.

[0209] Isocyanate silanes can be those mentioned above.

[0210] Preferably, the silyl polymer according to the present invention is a polymer having the general formula [Chemical Formula 3], wherein:

[0211] m1 is an integer equal to 0;

[0212] p = 1;

[0213] R 4 and R 5 Each represents a methyl group;

[0214] R 3 Indicates a divalent methylene group;

[0215] The number-average molar mass of the polymer is 5,000 to 30,000 g / mol, preferably 10,000 to 20,000 g / mol, and particularly 14,000 to 15,000 g / mol.

[0216] Preferably, the silyl polymer according to the present invention is a polymer having the general formula [Chemical Formula 3], wherein:

[0217] m1 is a non-zero integer;

[0218] p = 0;

[0219] R 3 Represents divalent propylidene;

[0220] R 5 Represents methyl;

[0221] The number-average molecular weight of the polymer is in the range of 5,000 to 30,000 g / mol, preferably 10,000 to 30,000 g / mol, and particularly 15,000 to 25,000 g / mol.

[0222] Preferably, the silyl polymer according to the present invention is a polymer having the general formula [Chemical Formula 5], wherein:

[0223] q is a non-zero integer;

[0224] p = 0;

[0225] R 3 Represents divalent propylidene;

[0226] R 5 Represents methyl;

[0227] The number-average molecular weight of the polymer is in the range of 5,000 to 30,000 g / mol, preferably 10,000 to 30,000 g / mol, and particularly 15,000 to 25,000 g / mol.

[0228] The adhesive composition may contain a single polymer as described above.

[0229] Alternatively, the adhesive composition may contain more than one silyl polymer, such as two, three, four, five, or more than five silyl polymers.

[0230] The adhesive composition according to the invention may contain 20% to 90%, preferably 30% to 70% by weight of a silyl polymer relative to the total weight of the adhesive composition.

[0231] Polyvinyl ether compounds

[0232] The polyvinyl ether compound according to the invention can be a homopolymer or a copolymer. In the context of this invention, the term "copolymer" refers to a polymer comprising at least two different monomers. Therefore, in the context of this invention, the term copolymer also includes terpolymers. Preferably, when the polyvinyl ether compound is a copolymer, it is a block copolymer. The term "block copolymer" refers to a copolymer comprising at least two homopolymer subunits covalently linked together.

[0233] Polyvinyl ether compounds may contain units derived from monomers of general formula [Chemical Formula 21].

[0234] ROC(R 8 )=CH(R 9 )

[0235] Group R represents a saturated or unsaturated straight-chain or branched group containing 1 to 24 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms.

[0236] The group R may be selected from the following groups: alkyl, cycloalkyl, aryl, arylalkyl, alkylaryl, and heterocyclic groups containing a ring, wherein the ring contains a heteroatom selected from oxygen, sulfur, and nitrogen; preferably, the group R is an alkyl group.

[0237] Even more preferably, the group R is selected from the following groups: methyl, ethyl, butyl, isobutyl, propyl, isopropyl, octyl, or allyl, which may be substituted or unsubstituted. Preferably, the group R is methyl or ethyl.

[0238] The group R may optionally be substituted by 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 acyl groups.

[0239] Group R 8 and R 9 Each can be a hydrogen atom or a group containing 1 to 10 carbon atoms, representing them independently.

[0240] Group R 8 and R 9 It can be independently selected from the following groups: alkyl, cycloalkyl, aryl, arylalkyl, alkylaryl, and heterocyclic groups containing a ring containing a heteroatom selected from oxygen, sulfur, and nitrogen. Alternatively, group R 8 and R 9 It can represent a divalent group containing 3 to 10 carbon atoms. For example, a divalent group can contain an aromatic ring containing 5 or 6 carbon atoms.

[0241] Preferably R 8 and R 9 At least one of them, and preferably R 8 and R 9 Both are hydrogen atoms.

[0242] As described above, the polyvinyl ether compound can be a homopolymer. This homopolymer can be 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), and poly(octyl vinyl ether).

[0243] Alternatively, the polyvinyl ether compound may be a copolymer comprising at least two different monomers having the general formula [Chemical Formula 21]. In this case, the polyvinyl ether compound may be a copolymer comprising two different monomers having the general formula [Chemical Formula 21] or three different monomers having the general formula [Chemical Formula 21]. Preferably, at least one of these monomers is selected from methyl vinyl ether or ethyl vinyl ether, and more preferably, at least one of these monomers is methyl vinyl ether.

[0244] The polyvinyl ether compounds according to the invention may have a K value of 30 to 120, preferably 40 to 70. The term "K value" refers to a measure of the average degree of polymerization. The K value can be measured according to standard ISO 1628-1.

[0245] The polyvinyl ether compounds according to the invention may also have a glass transition temperature of -60 to 0°C, preferably -50 to -5°C. The glass transition temperature has been measured by differential scanning calorimetry (DSC). The glass transition temperature can be measured according to standard NF EN ISO 11357-2.

[0246] Commercial polyvinyl ether compounds may include those available from BASF. M40 A 25、 A 50、 A 100、 I 30、 I 60、 I 60D and I 65D, and available from GAF. M.

[0247] The adhesive composition according to the invention may contain 1% to 60%, preferably 5% to 40%, and more preferably 5% to 25% by weight of a polyvinyl ether compound relative to the total weight of the adhesive composition.

[0248] Crosslinking catalyst

[0249] The catalyst for the binder composition may be selected from amines, organometallic compounds, acids and their derivatives, as well as mixtures thereof. It may be a mixture of catalysts from the same family (e.g., a mixture of multiple amines) or a mixture of catalysts from different families (e.g., a mixture of amines and organometallic compounds).

[0250] In the context of this invention, the term "organometallic compound" refers to a compound comprising an organic group and at least one metal.

[0251] In the context of this invention, the term "organic group" refers to a group containing at least one carbon atom.

[0252] Organometallic compounds may include organometallic compounds (compounds containing at least one metal-carbon covalent bond), metal alkoxides, metal carboxylates, and metal coordination complexes having one or more organic ligands.

[0253] Examples of organic ligands include acetylacetone and oxime.

[0254] The metal atoms in organometallic compounds can be any metal atoms known to those skilled in the art, and can be particularly selected from tin, aluminum, zinc, cobalt, iron, nickel, bismuth, titanium, or zirconium. Furthermore, organometallic compounds may also contain several metal atoms.

[0255] Organometallic compounds (compounds containing at least one metal-carbon covalent bond) can be carboxylates of organometallic compounds.

[0256] Organometallic compounds may be selected from dibutyltin dilaurate (DBTL), dibutyltin diacetate, di(ethylhexanoate)dibutyltin, dioctyltin dineodecanate (e.g., under the name TIB). 223 (obtained from TIB Chemicals), dibutyltin dioleate, dibutyltin benzyl maleate, diphenyltin diacetate, and mixtures thereof.

[0257] The metal alkoxide can be selected from tetrabutoxytitanium, tetraisopropoxytitanium, tetrabutoxyzirconium, tetraisopropoxyzirconium and mixtures thereof.

[0258] The metal carboxylates may be selected from zinc 2-ethylhexanoate, zinc diacetate, zinc dinedecanoate, zinc di(undecenoate), zinc di(methacrylate), cobalt acetylacetonate, cobalt diacetate, iron acetylacetonate, iron diacetate, nickel acetylacetonate, nickel diacetate, bismuth acetate, bismuth trioctanoate, bismuth dinedecanoate, zinc bismuth dinedecanoate, and mixtures thereof.

[0259] Metal coordination complexes having one or more organic ligands may be selected from zinc acetylacetone, titanium acetylacetone (e.g., by name...). AA75 was purchased from Dorf Ketal, tetraacetylacetone titanium, triacetylacetone aluminum, aluminum chelates, such as bis(ethyl acetoacetone) monoacetylacetone salts (e.g., by name). 5218 (purchased from King Industries), tetraacetylacetone zirconium, diisopropoxybis(ethyl acetone) titanium and mixtures thereof.

[0260] Amines can be primary, secondary, or tertiary amines.

[0261] The amine can be an aminosilane, such as aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, bis(γ-trimethoxysilylpropyl)amine, N-ethyl-γ-aminoisobutyltrimethoxysilane, or N-phenyl-γ-aminopropyltrimethoxysilane.

[0262] Preferably, the catalyst is not an aminosilane.

[0263] Preferably, the amine is selected from 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-dimethylaniline, N-ethylmorpholine, and mixtures thereof.

[0264] The acid catalyst can be selected from organic acid catalysts, inorganic acid catalysts, and mixtures thereof.

[0265] Among inorganic acid catalysts, phosphoric acid or orthophosphoric acid, phosphorous acid, hypophosphoric acid, or sulfuric acid may be mentioned, for example.

[0266] Preferably, the organic acid catalyst has a pKa of less than or equal to 6, preferably less than or equal to 4, advantageously less than or equal to 2, or advantageously less than or equal to 0.

[0267] The organic acid catalyst can be selected from sulfonic acids, carboxylic acids, organophosphate acids, organophosphonic acids, phosphonic acids, and mixtures thereof.

[0268] Sulfonic acids can be aliphatic or aromatic, optionally substituted (e.g., substituted by at least one substituent selected from halogens (e.g., fluorine), hydroxyl, alkyl, amines and mixtures thereof), and can be monosulfonic or disulfonic.

[0269] Sulfonic acids can be selected from N-alkylaminoalkylsulfonic acids and N,N-dialkylaminoalkylsulfonic acids (zwitterionic), such as 2-(N-morpholino)ethanesulfonic acid, 3-(N-morpholino)propanesulfonic acid, 4-[N-morpholino]butanesulfonic acid, 1,4-piperazine diethanesulfonic acid, N-2-hydroxyethylpiperazine-N′-2-ethanesulfonic acid, 2-(N-morpholino)ethanesulfonic acid, N-morpholinomethanesulfonic acid, N-(2-hydroxyethyl)piperazine-N′-methanesulfonic acid, piperazine-N,N′-bis(methanesulfonic acid), cyclohexylaminomethanesulfonic acid, N-[tris(hydroxymethyl)methyl]aminomethanesulfonic acid, N,N-bis(2-hydroxyethyl)aminomethanesulfonic acid; p-toluenesulfonic acid; benzenesulfonic acid; methanesulfonic acid; dodecylbenzenesulfonic acid; dodecylbenzene disulfonic acid; dinonylnaphthalene disulfonic acid; dinonylnaphthalenesulfonic acid; trifluoromethanesulfonic acid; and mixtures thereof.

[0270] Specifically, the sulfonic acid is selected from p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, dodecylbenzenesulfonic acid, dodecylbenzene disulfonic acid, dinonylnaphthalene disulfonic acid, dinonylnaphthalene sulfonic acid, trifluoromethylsulfonic acid, and mixtures thereof.

[0271] Among carboxylic acid catalysts, examples include malonic acid, succinic acid, maleic acid, oxalic acid, acetic acid, lactic acid, benzoic acid, citric acid, glycolic acid, and mixtures thereof.

[0272] In the context of this invention, unless otherwise stated, the term "organophosphate" refers to a phosphate ester containing at least one -OH group. For example, methyl phosphate is an organophosphate containing two -OH groups and having the general formula [Chemical Formula 22].

[0273]

[0274] In particular, organophosphates have the general formula [Chemical Formula 23].

[0275] (R 10 O) g -(P=O)-(OH) h

[0276] in:

[0277] R 10 It is an organic group, particularly selected from straight-chain or branched C1-C22 alkyl, cycloalkyl, aryl, and mixtures thereof (the alkyl, cycloalkyl, and aryl groups may optionally be substituted); and

[0278] g and h are integers, where g + h = 3 and h = 1 or 2.

[0279] Organophosphate acids may be selected, for example, from C1-C22 monoalkyl or dialkyl phosphates 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.

[0280] In the context of this invention, unless otherwise stated, the term "organophosphonic acid" refers to a phosphorus-containing compound having the general formula [Chemical Formula 24].

[0281] R 11 -(P=O)-(OH)(OR 12 )

[0282] Where R 11 and R 12It is an organic group, preferably selected independently from straight-chain or branched C1-C22 alkyl, cycloalkyl, aryl and mixtures thereof (the alkyl, cycloalkyl and aryl groups may optionally be substituted).

[0283] Among organophosphonates, C1-C22 monoalkylphosphonates may be mentioned, for example.

[0284] In the context of this invention, unless otherwise stated, the term "phosphonic acid" refers to a phosphorus-containing compound having the general formula [Chemical Formula 25].

[0285] R 13 -(P=O)-(OH)2

[0286] Where R 13 It is an organic group, preferably selected from straight-chain or branched C1-C22 alkyl, cycloalkyl, aryl and mixtures thereof (the alkyl, cycloalkyl and aryl groups may optionally be substituted).

[0287] Among phosphonic acids, for example, N-alkylaminoalkylphosphonic acids (zwitterions), N,N-dialkylaminoalkylphosphonic acids (zwitterions), C1-C20 alkylphosphonic acids, such as methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, tert-butylphosphonic acid, isobutylphosphonic acid, hexylphosphonic acid, 2-ethylhexylphosphonic acid and its straight-chain or branched higher homologues, benzylphosphonic acid, phenylphosphonic acid, tolylphosphonic acid or xylylphosphonic acid may be mentioned.

[0288] As an example of an organic acid catalyst, one could mention the one sold by King Industries. 155 (dinonylnaphthalene disulfonic acid, containing 55% active ingredient in isobutanol), sold by King Industries. 1051 (dinonylnaphthalenesulfonic acid, containing 50% active ingredient in 2-butoxyethanol), sold by King Industries. 5076 (dodecylbenzenesulfonic acid, containing 70% active ingredient in isopropanol), sold by King Industries. 1040 (p-toluenesulfonic acid, containing 40% active ingredient in isopropanol), sold by King Industries. 4000 (mixture of monoalkyl phosphate and dialkyl phosphate, 100% active material).

[0289] The acid derivatives according to the present invention can be acid anhydrides, acid esters, or acidic ammonium salts, wherein the acid is as described above.

[0290] The acid derivatives are particularly “masked” or “latent” acids, which advantageously allow the acid to be released by thermal activation (e.g., at a temperature of 70°C to 170°C, preferably at a temperature of 90°C to 120°C) or by hydrolysis, or by photoactivation, preferably by thermal activation.

[0291] Masking acids advantageously allow the release of acids that are catalytically active substances. For example, the ammonium salt formed between aminomethylpropanol and p-toluenesulfonic acid is a masking acid (acid derivative) that releases p-toluenesulfonic acid upon thermal activation.

[0292] Acid derivatives can be prepared from the corresponding acid in any manner known to those skilled in the art, for example by using typical acid / base reactions. For example, methods for preparing esters typically involve the condensation of an acid compound with a compound containing a hydroxyl group, such as an alcohol, or with a compound of the ethylene oxide type. Ammonium salts can be prepared from any of the above-mentioned acids with ammonia or with a primary, secondary, or tertiary amine. Amines may optionally contain at least one functional group, such as a hydroxyl group (alkanolamine) or a C1-C4 alkyl group. Ammonium salts (zwitterions) can also be prepared by changing the pH of a solution containing, for example, N-alkylaminoalkylphosphonic acid, N,N-dialkylaminoalkylphosphonic acid, N-alkylaminoalkylsulfonic acid, or N,N-dialkylaminoalkylsulfonic acid.

[0293] Preferably, the catalyst is an ammonium sulfonate (the sulfonic acid is as described above), an ammonium phosphonate (the phosphonic acid is as described above), an ammonium organophosphonate (the organophosphonic acid is as described above), or an ammonium organophosphate (organophosphoric acid is as described above).

[0294] Examples of amines used for preparing ammonium salts include, for example, 2-amino-2-methyl-1-propanol, triethylamine, aniline, pyridine, dimethylaminoethanol, alkylpyridine, diisopropanolamine, dimethylethanolamine, triethanolamine, oxazolidine, bicyclooxazolidine, 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.

[0295] An example of an acid derivative may be mentioned: sold by King Industries. 3327 or 3525 (amine-masked dinonylnaphthalene disulfonic acid containing 25% active ingredient in isopropanol and isobutanol), sold by King Industries. 1557 or 1953 (amine-masked dinonylnaphthalenesulfonic acid, containing 25% active ingredient in a mixture of butanol and 2-butoxyethanol), sold by King Industries. 5225 or 5528 or 5925 (Amine-masked dodecylbenzenesulfonic acid containing 25% active ingredient in isopropanol), sold by King Industries. 2107 or 2500 (amine-masked p-toluenesulfonic acid containing 25% or 26% active ingredient in isopropanol), sold by King Industries. 2501 or 2530 (p-toluenesulfonic acid masked with amine, containing 25% active ingredient in a mixture of isopropanol and methanol), sold by King Industries. 4167 (a dialkyl phosphate masked with an organic amine, containing 25% active ingredient in a mixture of isopropanol and isobutanol), sold by King Industries. 4575 (Amine-masked phosphoric acid containing 25% active material in a mixture of methanol and butanol).

[0296] Preferably, the catalyst is selected from organometallic compounds (particularly aluminum-based coordination complexes), orthophosphoric acid, organophosphoric acid (preferably C1-C22 mono- or dialkyl phosphates and mixtures thereof), ammonium salts (particularly sulfonic acids or organophosphoric acid esters), and mixtures thereof. Even more preferably, the catalyst is selected from orthophosphoric acid, organophosphoric acid esters (preferably C1-C22 mono- or dialkyl phosphates and mixtures thereof), and ammonium salts (particularly sulfonic acids or organophosphoric acid esters).

[0297] The adhesive composition according to the invention may contain 0.1% to 4%, preferably 0.2% to 2%, and more preferably 0.3% to 2% by weight of a crosslinking catalyst relative to the total weight of the adhesive composition.

[0298] In the case that the composition according to the invention is a single-component composition, it is preferable to use one of the catalysts listed above, excluding inorganic acids and their salts, and excluding carboxylic acids.

[0299] In the case that the composition according to the invention is a two-component composition (described in detail below), the crosslinking catalyst can be mixed in 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. Therefore, the term "reactive diluent" refers to a diluent that reacts in the presence of the catalyst. The diluent may be selected from low-reactivity silanes (Geniosil XM25, MS RD359), water scavengers (XL33), and silsesquioxane resins.

[0300] Non-reactive: polyols, tackifying resins, rheology modifiers (mentioned in other additives), etc.

[0301] The diluent may have a number average molecular weight (Mn) of 300 to 50,000 g / mol, preferably 1,000 to 20,000 g / mol. This allows the diluent to be prevented from migrating into the crosslinked adhesive.

[0302] The diluent may also have a viscosity of 10-100000 mPa·s at 23°C, and even more preferably a viscosity of 500-15000 mPa·s at 23°C.

[0303] The viscosity was measured using a Brookfield viscometer (cone-plate type, CAP2000+).

[0304] Other additives

[0305] The compositions according to the invention may contain at least one other additive, such as those selected from tackifying resins, silsesquioxanes, plasticizers, solvents, pigments, dyes, adhesion promoters, hygroscopic agents, UV stabilizers, antioxidants, glitter flakes, fluorescent materials, rheology modifiers, fillers, flame retardants, waxes, and mixtures thereof.

[0306] Tackifying resin

[0307] The adhesive composition according to the invention may further contain at least one tackifying resin.

[0308] The resin used within the scope of this invention may be any resin compatible with silyl polymers.

[0309] The term "compatible tackifying resin" refers to a tackifying resin that, when mixed with a silyl polymer in a 50 / 50 weight ratio, yields a substantially homogeneous mixture (without visible phase separation). Within the scope of this invention, tackifying resins differ from polyvinyl ether compounds.

[0310] The tackifying resin is advantageously selected from:

[0311] - Terpene phenolic resin;

[0312] - Hydrocarbon resin;

[0313] - Rosin resin; and

[0314] - Acrylic resin.

[0315] Terpene-phenolic resins have softening points ranging from 85 to 150°C. Hydrocarbon resins have softening points ranging from 15 to 140°C. Rosin resins have softening points ranging from 15 to 115°C. Softening points can be measured according to standard ASTM E28.

[0316] Terpene-phenolic resins can be obtained by polymerization of terpenes and phenols in the presence of Friedel-Crafts catalysts.

[0317] Hydrocarbon resins may be selected from: resins obtained by means of polymerization including α-methylstyrene and optionally in the presence of phenol; resins obtained by hydrogenation, preferably partial hydrogenation, polymerization or copolymerization (with aromatics) of a mixture of unsaturated aliphatic hydrocarbons containing about 5, 9 or 10 carbon atoms from petroleum fractions, optionally grafted with maleic anhydride; terpene resins; generally produced by polymerization of terpenes, such as monoterpenes (or pinenes), in the presence of a Friedel-Crafts catalyst; copolymers based on natural terpenes, such as styrene / terpene, α-methylstyrene / terpene and vinyltoluene / terpene; and mixtures thereof.

[0318] Rosin resins can be selected from rosin or modified rosin of natural origin (e.g., rosin extracted from pine resin, wood rosin extracted from tree roots) and their derivatives hydrogenated, dimerized, polymerized or esterified with monohydric or polyhydric alcohols (e.g., glycerol or pentaerythritol).

[0319] Acrylic resins are defined as polymers or oligomers consisting of a large amount of (meth)acrylic acid and / or (meth)acrylate monomers (preferably at least 5% by weight (w / w), more preferably at least 10% w / w, even more preferably at least 20% w / w, even more preferably at least 30% w / w) in the polymer chain.

[0320] (Meth)acrylic acid monomers can be selected from: acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-heptyl acrylate, n-heptyl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl methacrylate, alkyl crotonate, vinyl acetate, di-n-butyl maleate, dioctyl maleate, acetylacetoxyethyl methacrylate, acetylacetoxyethyl methyl methacrylate, acetylacetoxypropyl methacrylate, acetylacetoxypropyl methacrylate, diacetone acrylamide, acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxyethyl methacrylate. Allyl methacrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, cyclohexyl acrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, isodecyl methacrylate, isodecyl acrylate, 2-methoxyacrylate, 2-methoxymethacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, caprolactone, caprolactone methacrylate, polypropylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol acrylate (400), polypropylene glycol methacrylate (400), benzyl acrylate, benzyl methacrylate, N-vinylpyrrolidone or N-vinyl lactam.

[0321] Preferably, the (meth)acrylic acid monomer contains up to 20 carbon atoms; more preferably, the (meth)acrylic acid monomer is selected from acrylic acid, methacrylic acid, butyl acrylate, 2-ethylhexyl acrylate and hydroxyethyl acrylate.

[0322] Acrylic resins may be selected from polymers containing at least one (meth)acrylic acid functional group or chain portion and at least one hydrocarbon-based chain portion, said polymers may be in the form of grafted or reactive or block copolymers.

[0323] The acrylic resin preferably has a viscosity of less than 100 Pa·s at 100°C and less than or equal to 100 Pa·s at 150°C.

[0324] Acrylic resins may contain repeating units of at least one hydrocarbon-based monomer and at least one acrylate monomer.

[0325] Hydrocarbon-based monomers are selected from styrene, α-methylstyrene, vinyltoluene, indene, methylindene, divinylbenzene, dicyclopentadiene, and methyldicyclopentadiene, as well as polymerizable monomers contained in C5-isoprene and C5-isoprene and C9-aromatic streams in the petrochemical industry. These hydrocarbon-based monomers are typically polymerized together in various proportions using cationic polymerization with Lewis acid catalysts.

[0326] The acrylate monomers are selected from methyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, n-heptyl acrylate, heptyl methacrylate, 2-methylheptyl acrylate, octyl acrylate, octyl methacrylate, isooctyl acrylate, n-nonyl acrylate, isononyl acrylate, decyl acrylate, isodecyl acrylate, isodecyl acrylate, dodecyl acrylate, isobornyl acrylate, lauryl acrylate, lauryl methacrylate, tridecyl acrylate, tridecyl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl methacrylate, alkyl crotonate, vinyl acetate, di-n-butyl maleate, dioctyl maleate, acetylacetoxyethyl methacrylate, acetylacetoxyethyl acrylate. Acetoacetoxypropyl methacrylate, acetoacetoxypropyl acrylate, diacetone acrylamide, acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, allyl methacrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, cyclohexyl acrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, isodecyl methacrylate, isodecyl acrylate, 2-methoxyacrylate, 2-methoxy 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.

[0327] Preferably, the hydrocarbon-based monomer is selected from aromatic monomers or polymerizable monomers from C9 aromatic streams derived from petrochemical sources; or from C5-isoprene or C5-isoprene streams derived from petrochemical sources, or from dicyclopentadiene or polymerizable monomers.

[0328] Preferably, the acrylate monomer is selected from acrylic acid, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methacrylic acid, and butyl acrylate.

[0329] The softening point of these acrylic resins is preferably from room temperature to a maximum of 180°C, more preferably below or equal to 150°C, more preferably below or equal to 120°C, and even more preferably 70-120°C. The softening point can be measured according to standard ASTM E28.

[0330] These resins are commercially available, and products such as the following may be mentioned:

[0331] For resins obtained by polymerization of terpenes and phenols in the presence of Friedel-Crafts catalysts:

[0332] Available from DRT 1510, which has a number-average molecular weight M of approximately 870 Da. n ;

[0333] Available from DRT H150 has a number-average molecular weight Mn of approximately 630 Da;

[0334] Available from DRT T, which has a number-average molecular weight of approximately 500 Da. n ;

[0335] Available from Arizona Chemical TP 95 has a number-average molecular weight of approximately 1200 Da.

[0336] For resins optionally obtained in the presence of phenol via a method including the polymerization of α-methylstyrene:

[0337] Available from Cray Valley W100, obtained by polymerization of α-methylstyrene without the presence of phenol, has a number-average molecular weight of 900 Da;

[0338] Available from Arizona Chemical 510, which has a number-average molecular weight of approximately 1740 Da, is produced by adding phenol.

[0339] For natural rosin or modified rosin: RE100, an ester of rosin and pentaerythritol, is available from Arizona Chemical and has a number-average molecular weight of approximately 1700 Da.

[0340] According to a preferred embodiment, the tackifying resin is selected from resins obtained by polymerization of terpenes and phenols in the presence of a Friedel-Crafts catalyst.

[0341] The tackifying resin preferably has a number average molecular weight of 100 to 6000 g / mol, more preferably 300 to 4000 g / mol, and more preferably 500 to 2000 g / mol.

[0342] The number-average molecular weight of tackifying resins can be measured using methods well known to those skilled in the art, such as size exclusion chromatography using polystyrene-type standards.

[0343] The tackifying resin may have a hydroxyl value of 10 to 300 mg KOH / g, preferably 100 to 200 mg KOH / g, and more preferably 140 to 160 mg KOH / g. OH In particular, the tackifying resin has a hydroxyl value of 145 mg KOH / g.

[0344] The hydroxyl value of a tackifying resin indicates the number of hydroxyl functional groups per gram of tackifying resin, and is expressed as the milliequivalents of potassium hydroxide per gram of tackifying resin (mg KOH / g) used to quantify the hydroxyl functional groups.

[0345] The acid value of rosin ester-type tackifying resins can be from 0 to 10 mg KOH / g, and preferably from 0 to 5 mg KOH / g. The acid value of the tackifying resin indicates the number of acid functional groups per gram of tackifying resin, and is expressed in the form of milliequivalents of potassium hydroxide per gram of tackifying resin (mg KOH / g) used to quantify the acid functional groups.

[0346] The adhesive composition according to the invention may contain 0.1% to 80%, preferably 20% to 70%, and more preferably 30% to 60% by weight of tackifying resin relative to the total weight of the adhesive composition.

[0347] When the composition according to the invention contains at least one tackifying resin, the mass ratio of the polyvinyl ether compound to the tackifying resin may be from 3% to 100%.

[0348] According to some embodiments, the adhesive composition comprises a single tackifying resin.

[0349] According to alternative embodiments, the adhesive composition comprises different tackifying resins, such as two, three, four, or five different tackifying resins.

[0350] Silsesquioxane

[0351] Silsesquioxanes are typical organosilicon compounds that can take on polyhedral or polymeric structures and possess Si-O-Si bonds. They typically have the general formula [Chemical Formula 26].

[0352] [R′SiO 3 / 2 ] t

[0353] Where R′ has the same or different properties, represents an organic group, and t can be an integer from 6 to 12, preferably equal to 6, 8, 10 or 12.

[0354] According to one embodiment, the silsesquioxane has a polyhedral structure (or POSS, "polyhedral oligomeric silsesquioxane").

[0355] Preferably, the silsesquioxane corresponds to the general formula [Chemical Formula 27].

[0356]

[0357] Where R′ 1 To R′ 8 Each of the groups in the group represents a group selected from the following:

[0358] hydrogen atom;

[0359] The group is selected from the following: straight-chain or branched C1-C4 alkoxy groups, straight-chain or branched alkyl groups containing 1 to 30 carbon atoms, alkenyl groups containing 2 to 30 carbon atoms, aromatic groups containing 6 to 30 carbon atoms, allyl groups containing 3 to 30 carbon atoms, cycloaliphatic groups containing 3 to 30 carbon atoms, and acyl groups containing 1 to 30 carbon atoms; and

[0360] -OSiR′ 9 R′ 10 Group, wherein R′ 9 and R′ 10 Each of the groups represents a hydrogen atom or a group independently, the group being selected from straight-chain or branched C1-C4 alkyl, straight-chain or branched C1-C4 alkoxy, C2-C4 alkenyl, phenyl, C3-C6 allyl, cyclic C3-C8 aliphatic and C1-C4 acyl groups;

[0361] The conditions are:

[0362] R′ 1 To R′ 8 At least one group in it is a C1-C4 alkoxy group; and

[0363] R′ 1 To R′ 8 At least one group in it is phenyl.

[0364] Silsesquioxanes are known compounds, particularly described in patent application WO2008 / 107331A1. Some are also commercially available under the name Dow. 3074 and Dow Products from Dow sold by 3037 (CAS No. = 68957-04-0).

[0365] The adhesive composition according to the invention may contain 0 to 40% by weight, preferably 0 to 20% by weight and more preferably 0 to 10% by weight of silsesquioxane relative to the total weight of the adhesive composition.

[0366] filler

[0367] The packing material can be selected from organic packing materials, inorganic packing materials, and mixtures thereof.

[0368] As an organic filler, any organic filler can be used, particularly polymer fillers commonly used in the adhesives field. Examples include, for instance, polyvinyl chloride (PVC), polyolefins, rubber, ethylene vinyl acetate (EVA), and aromatic polyamide fibers. Expandable or non-expandable thermoplastic polymer hollow microspheres (e.g., hollow microspheres made of vinylidene chloride / acrylonitrile) are selected from thermoplastic polymers used to prepare HMPSA, such as ethylene vinyl acetate (EVA), or styrene block copolymers (e.g., SIS, SBS, SIBS, SEBS, SEPS and their grafted derivatives, e.g., derivatives grafted with maleic anhydride).

[0369] The filler can be an expanding agent (also known as a swelling agent).

[0370] The filler can be in the form of hollow beads, i.e. beads containing gas, or beads that can expand and form hollow beads, i.e. beads containing voids or gas.

[0371] Preferably, the packing material is an inorganic packing material.

[0372] According to one embodiment, the filler is selected from sand, precipitated and / or pyrolytic silica, zeolite, glass beads, glass, quartz, barite, alumina, mica, talc, alkali metal or alkaline earth metal carbonates (e.g., calcium carbonate).

[0373] The filler preferably accounts for 0% to 15% of the total weight of the adhesive composition, more preferably 0% to 10% by weight, and even more preferably 0% to 5% by weight.

[0374] According to one embodiment, the composition according to the invention does not contain any fillers.

[0375] plasticizer

[0376] The compositions according to the invention may contain at least one plasticizer. The total content of the plasticizer in the composition relative to the total weight of the composition may be from 0% to 30% by weight, preferably from 1% to 30% by weight, or even, for example, from 1% to 15% by weight.

[0377] As examples of plasticizers that can be used, any plasticizer commonly used in the field of adhesives may be used, such as phthalates, benzoates, trimethylolpropane, trimethylolethane, trimethylolmethane, glycerides, pentaerythritol esters, cycloalkane mineral oils, adipates, cyclohexyldicarboxylate, liquid paraffin, natural oils (optionally epoxidized), polypropylene, polybutene, hydrogenated polyisoprene, and mixtures thereof.

[0378] Phthalate esters may include, for example, diisononyl phthalate, diisobutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate, diisododecyl phthalate, dibenzyl phthalate or butyl benzyl phthalate.

[0379] In benzoate esters, for example, neopentyl glycol dibenzoate (e.g., by name) may be mentioned. 512 obtained from Lanxess), dipropylene glycol dibenzoate (e.g., by name) 9-88SG (obtained from Eastman), a mixture of diethylene glycol dibenzoate and dipropylene glycol dibenzoate (e.g., available from Kalama Chemical under the name...). 850S (obtained), or a mixture of diethylene glycol dibenzoate, dipropylene glycol dibenzoate, and triethylene glycol dibenzoate (e.g., available from Eastman under the name...). (Obtained in 2088).

[0380] Among pentaerythritol esters, pentaerythritol tetravalerate may be mentioned, for example (e.g., available from Perstorp under the name Pevalen). TM get).

[0381] Among cyclohexane dicarboxylic esters, diisononyl 1,2-cyclohexanedicarboxylate may be mentioned, for example (e.g., available from BASF under the name Hexamoll). get).

[0382] pigment

[0383] When the pigment is present in the composition according to the invention, its content relative to the total weight of the composition is preferably less than or equal to 3% by weight, more preferably less than or equal to 2% by weight. When it is present, the pigment may, for example, account for 0.1% to 3% or 0.4% to 2% by weight relative to the total weight of the composition according to the invention.

[0384] Pigments can be organic or inorganic.

[0385] For example, the pigment is TiO2, specifically sold by Kronos. 2059.

[0386] desiccant

[0387] If present, the hygroscopic agent may be selected, for example, from non-polymerizable, hydrolyzable alkoxysilane derivatives with a molecular weight less than 500 g / mol, preferably from derivatives of trimethoxysilane and triethoxysilane. Such an agent typically extends the shelf life of the composition during storage and transportation before use. For example, γ-methacryloyloxypropyltrimethoxysilane (e.g., under the trade name...) may be mentioned. A-174 is available from Momentive, and methacryloyloxymethyltrimethoxysilane (e.g., under trade name) XL33 is available from Wacker, and can be vinyltrimethoxysilane, isooctyltrimethoxysilane, or phenyltrimethoxysilane.

[0388] The content of the desiccant relative to the total weight of the composition according to the invention is preferably less than or equal to 3% by weight, more preferably less than or equal to 2% by weight. When the desiccant is present, it may, for example, account for 0.1% to 3% or 1% to 2% by weight relative to the total weight of the composition.

[0389] The compositions according to the invention may contain at least one UV stabilizer or antioxidant in an amount of 0.1% to 3%, preferably 1% to 3%, by weight. These compounds are typically introduced to protect the composition from degradation by reaction with oxygen, which is readily formed by the action of heat or light. These compounds may include primary antioxidants that scavenge free radicals. The primary antioxidant may be used alone or in combination with other auxiliary antioxidants or UV stabilizers.

[0390] For example, one could mention that it was sold by BASF. 1010 B561 245 and 168.

[0391] One-component or two-component compositions

[0392] 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 compounds are packaged in the same compartment. In this case, the composition is preferably ready for immediate use, i.e., the user (individual or professional) can apply the adhesive composition directly to the substrate and / or flexible coating to be covered without any premixing.

[0393] According to an alternative embodiment, the adhesive composition according to the invention is a two-component composition. In other words, it is a composition in which the components are packaged in two separate compartments.

[0394] In this case, the two-component composition may comprise portion A and portion B, for example, by mixing the two portions before use and application of the adhesive composition to the substrate layer. The aforementioned components may be distributed in portion A and / or portion B of the two-component composition.

[0395] According to a preferred embodiment, portion A of the two-component composition may, for example, comprise a silyl polymer (as described above). In this case, portion B of the composition may comprise a crosslinking catalyst (as described above). Polyvinyl ether compounds and optional additives may be present in portions A and / or B of the composition. Additional components (other additives) may be present in portions A and / or B of the two-component composition.

[0396] Use of the composition

[0397] The compositions according to the invention are used to prepare self-adhesive articles. The term "self-adhesive article" refers to any article that can be bonded to a surface by pressure applied by hand or equipment alone, without the use of additional glue or adhesive.

[0398] Self-adhesive articles may include a carrier layer coated with a self-adhesive layer, said self-adhesive layer being a cross-linked adhesive composition according to the invention.

[0399] Preferably, the self-adhesive product is a pressure-sensitive self-adhesive product.

[0400] These articles are intended, in particular, for use on surfaces to be bonded, in order to re-bond, maintain, secure, or simply fix or display said shapes, signs, images, or information. These articles can be used in many fields, such as the medical field, clothing, packaging, motor vehicles (e.g., for mounting signs, lettering, interior soundproofing, interior trim, bonding in passenger compartments), or construction (e.g., for sound and heat insulation, window assembly); especially in the medical and construction sectors. They can be processed according to their end application, for example, in the form of tapes, such as industrial tapes, tapes for temporary repairs or on-site fixing, single-sided or double-sided tapes, or in the form of labels, bandages, dressings, patches, or graphic films.

[0401] According to one implementation, self-adhesive products are self-adhesive multilayer systems, particularly self-adhesive labels or tapes, which can be single-sided or double-sided.

[0402] The materials that can be used for the carrier layer can be, for example, any type of rigid or flexible carrier. Examples include foam, felt, nonwoven carriers, plastics, films, paper, or thin film-type carriers of polymer materials having one or more layers.

[0403] The carrier layer is made of materials selected from, for example, polyolefins, such as polyethylene, including high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and linear ultra-low-density polyethylene; polypropylene and polybutene; polystyrene; natural or synthetic rubber; vinyl copolymers, such as plasticized or unplasticized polyvinyl chloride, and poly(vinyl acetate); olefin copolymers, such as ethylene / methacrylate copolymers, ethylene / vinyl acetate copolymers, acrylonitrile / butadiene / styrene copolymers, and ethylene / propylene copolymers; acrylic polymers and copolymers; polyurethanes; polyethers; polyesters; and mixtures thereof. Preferably, the carrier layer is based on acrylic polymers, polyethylene (PE), polypropylene (PP), which may be oriented, non-oriented, or bioriented, polyimide, polyurethane, polyester such as polyethylene terephthalate (PET), or paper.

[0404] According to some embodiments, self-adhesive articles obtained from the adhesive compositions according to the invention comprise a permanent carrier layer coated with an adhesive layer. Preferably, the adhesive layer is also covered with a non-adhesive protective paper or plastic film, which is preferably treated with silicone.

[0405] As an alternative to non-stick protective films, the back of a permanent carrier layer that is not coated with an adhesive layer can have a non-stick surface, such as a silicone-treated protective layer.

[0406] According to one embodiment, a permanent carrier layer is coated with an adhesive composition on both sides, the adhesive composition being the same or different, at least one of the two adhesive compositions being according to the invention.

[0407] Preferably, the carrier layer has a thickness of 10 μm to 50 mm, more preferably 10 μm to 20 mm, more preferably 20 μm to 10 mm, and even more preferably 20 μm to 1 mm.

[0408] In certain specific cases, surface treatment of the carrier layer is required to increase the adhesion of the adhesive layer (during the coating step).

[0409] Therefore, the self-adhesive article according to the invention can bond two substrates. The substrate on which the self-adhesive article is intended to be applied (referred to as the "substrate to be bonded") can be flexible or rigid. In particular, it can have the same flexible properties as the carrier layer described above, so as to be rolled up and packaged in a roll. Alternatively, the substrate to be bonded can be rigid. In this case, the substrate cannot be rolled up and packaged in a roll, for example as described above. The substrate to be bonded can be selected, for example, from concrete, paper, polyolefin substrates, etc.

[0410] According to some implementation schemes, self-adhesive products also include a protective non-stick layer (relevant lining).

[0411] According to some embodiments, the non-adhesive layer is applied to the adhesive layer after the adhesive composition has been crosslinked.

[0412] The carrier layer can be covered with a protective non-stick layer, such as a silicone-treated film, on one of its two sides, the back side without the adhesive layer. In this way, since the adhesive layer does not adhere to the silicone-treated surface, the self-adhesive article can roll up and unroll itself without any problems.

[0413] The self-adhesive article according to the present invention can be obtained by a method comprising the following steps:

[0414] - Mixing portions A and B of the adhesive composition according to the invention, in the case that it is a two-component composition;

[0415] - Heat the adhesive composition to a temperature of 40°C to 130°C;

[0416] - Coat the support surface with an adhesive composition;

[0417] - The coated adhesive composition is crosslinked by heating to a temperature of 50°C to 200°C, particularly in which water molecules are present at a concentration of 10 to 200 g / m³. 3 In a gaseous environment where the gas exists;

[0418] - The cross-linked adhesive layer is bonded or transferred in reverse to a carrier layer or a non-stick protective film, which may be the reverse side of the supporting surface.

[0419] In the context of this invention, the term "support surface" should be understood to mean a conveyor belt coated with a non-stick layer or non-stick protective film (in English, "release liner") or carrier layer. Thus, the support surface becomes an integral part of the self-adhesive article, serving as a non-stick protective film or as a carrier layer.

[0420] If the support surface is not the carrier layer, the final step of the above method involves transferring the cross-linked adhesive layer onto the carrier layer.

[0421] When the supporting surface is a carrier layer, the final step of the above method includes reversibly bonding the adhesive layer to the non-stick protective film.

[0422] According to a preferred variant of the invention, the final step of the above method includes transferring the crosslinked adhesive layer onto a flexible carrier layer (which may be a plastic film) after cooling the crosslinked adhesive layer to a temperature below the degradation temperature or softening point of the material constituting the carrier layer.

[0423] According to one embodiment, the self-adhesive article according to the invention can be obtained by a method as described above that does not include the step of pretreating the surface of the carrier layer. These pretreatments aim to chemically and / or physically modify the surface to increase its surface energy and / or roughness, thereby improving the adhesion of the adhesive layer to the surface. Examples of known surface treatments include plasma treatment, corona treatment, polishing, or the application of a chemical adhesive (also known as a primer) to the surface, which imparts high surface energy to the substrate coated with the agent.

[0424] The method for preparing the self-adhesive article according to the invention may further include the step of coating a second adhesive composition layer according to the invention onto a carrier layer, followed by crosslinking the coated adhesive composition by heating to a temperature of 20-200°C. According to this embodiment, a double-sided self-adhesive article is obtained.

[0425] The coating step can be performed using known coating devices, such as lip nozzles or curtain nozzles, or using rollers. These steps can use coating strengths ranging from 3 to 5000 g / m². 2 The adhesive composition per unit area weight. The adhesive composition required for preparing self-adhesive labels can have a unit area weight of 10 to 100 g / m². 2 And preferably 20 to 50 g / m 2 The required unit area weight for preparing self-adhesive tape can range from 3 to 5000 g / m² per side. 2 Preferably, each surface has a content of 15 to 250 g / m². 2 Variations within a wider range.

[0426] According to some embodiments, the coated adhesive composition is further subjected to treatment in a humid atmosphere characterized by its humidity level during the crosslinking step. Preferably, the humid atmosphere is one in which 2% to 100% of the molecules are water molecules, more preferably 3% to 50%, and more preferably 3% to 10% of the molecules are water molecules.

[0427] Moisture content is expressed as a percentage of water per unit volume, corresponding to the number of water molecules divided by the total number of molecules per unit volume. Due to the linear nature of this ratio, moisture content is easily measured and monitored using monitors of the PID (Proportional-Integral-Derivative) type, for example. The weight percentage can be calculated by multiplying the percentage of water molecules relative to the total number of molecules by a factor of 0.622. W. Wagner et al. described general information about moisture content in various environments in "International Steam Tables - Properties of Water and Steam based on the Industrial Formulation IAPWS-IF97".

[0428] The thermal crosslinking step is particularly effective—creating siloxane-type bonds between polymer chains with hydrolyzable alkoxysilane end groups in the adhesive composition, and in the presence of atmospheric moisture—leading to the formation of a three-dimensional polymer network. Such crosslinked adhesive compositions are particularly pressure-sensitive adhesives, imparting the desired adhesion and tack to the carrier layer coated with them.

[0429] Preferably, the coating is applied uniformly to a carrier layer or a non-stick protective layer, but the coating can also be adapted to the desired shape of the final self-adhesive article.

[0430] According to one embodiment, the adhesive composition is applied to at least a portion of both sides of a carrier layer. If both sides of the carrier layer are coated, the adhesive compositions on the two sides may be the same or different, and the unit area weight may be the same or different on the two sides.

[0431] According to some embodiments of the invention, the self-adhesive article comprises an adhesive layer on at least a portion of one side or at least a portion of both sides of a carrier layer, said adhesive layer 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 two adhesive layers. In this case, the two protective layers may be made of the same or different materials and / or they may have the same or different thicknesses.

[0432] The self-adhesive articles according to the present invention are waterproof and breathable articles. The term "waterproof and breathable" means that water vapor can pass through but liquid water cannot.

[0433] Preferably, the article obtained from the composition according to the invention has a film thickness of 30 μm and a yield of at least 350 g / m² per 24 hours at 37°C and 50% relative humidity. 2The water vapor permeability (MVTR, used for "moisture permeation rate"). More preferably, for a membrane thickness of 30 μm, at 37°C and 50% relative humidity, the membrane's water vapor permeability (MVTR) is at least 500 g / m. 2 / 24h, preferably at least 600g / m 2 / 24h, preferably at least 700g / m 2 / 24h, and more preferably 800g / m 2 / 24h. Specifically, at 37°C and 50% relative humidity, the MVTR membrane permeability can reach 350 to 400 g / m² for a film thickness of 30 μm. 2 / 24h, or 400 to 500g / m 2 / 24h, or 500 to 600g / m 2 / 24h, or 600 to 700g / m 2 / 24h, or 700 to 800g / m 2 / 24h, or 800 to 900g / m 2 / 24h, or 900 to 1000 g / m 2 / 24h, or 1000 to 1200 g / m 2 / 24h, or 1200 to 1500 g / m 2 / 24h, or 1500 to 2000 g / m 2 / 24h, or 2000 to 2500 g / m 2 / 24h, or 2500 to 3000 g / m 2 / 24h, or 3000 to 3500 g / m 2 / 24h, or 3500 to 4000 g / m 2 / 24h, or 4000 to 4500 g / m 2 / 24 hours, or from 4500 to 5000 g / m 2 / 24 hours. At 37°C, 50% relative humidity, and a film thickness of 30 μm, the water vapor permeability (MVTR) of the film can be measured according to standard ASTM E96 B. The self-adhesive article according to the invention can be used in an adhesive method comprising the following steps:

[0434] - Remove the non-stick protective layer when it is present;

[0435] - Apply self-adhesive materials to one surface of the product; and

[0436] - Apply pressure to the item.

[0437] In the second step, apply the self-adhesive product so that the self-adhesive portion of the product (formed by the self-adhesive layer) faces the product surface.

[0438] According to some embodiments in which the self-adhesive article is a double-sided article, the bonding method further includes the step of applying a second surface of the product to an article that is bonded to a first surface of the product, or applying an article that is bonded to a first surface of the product to a second surface of the product. Example

[0439] The following examples illustrate the present invention but do not limit it.

[0440] "PSA" adhesive properties

[0441] An adhesive composition is applied to a polyethylene terephthalate (PET) substrate layer to form a 50 μm thick layer.

[0442] The substrate layer coated with the adhesive composition was stored at 70°C for 7 days to ensure complete cross-linking of the composition.

[0443] The adhesive properties of the composition were measured according to standard Finat 1 by a 180° peel test. Therefore, according to this standard, two-thirds of the adhesive sample (15cm × 2.5cm) was placed on a test plate (sandblasted stainless steel, HDPE, etc.). A 2kg roller was passed over the sample twice to improve wettability. A 10-minute waiting period was allowed before traction. The sample was placed parallel to the traction and folded back at a 180° angle. The portion of the sample not bonded to the test plate provided clamping for the fixture, thus allowing traction at a standard speed of 300 mm / min. The apparatus measured the force required to debond the sample under the conditions described above.

[0444] The principle behind this test is to determine the force required to separate (or peel) the adhesive composition layer from the substrate layer.

[0445] The adhesiveness (tack) of the composition was measured according to standard Finat 9. Therefore, according to this standard, a 15cm × 2.5cm adhesive sample was folded into a ring with the adhesive on the outer surface of the ring. The ring was then placed together at a speed of 300 mm / min and gently placed on a flat plate (glass). Once a 1 square inch square was placed on the plate, the ring was removed from the plate, and the force required to remove the adhesive was measured.

[0446] Water vapor permeability (MVTR)

[0447] This test allows for the measurement of the amount of water vapor that can pass through the adhesive composition layer.

[0448] The test was conducted at 37°C using the standard NF EN 13726-2.

[0449] The adhesive composition was applied to a surface with an MVTR of 5861 g / m³.2 The MVTR of the nonwoven (NW) material substrate layer is 7826 g / m² for 24 hours. 2 On a polyurethane (PU) substrate layer with a thickness of 0.03 mm, a layer without backing (a layer with backing, used to reinforce the PU film during lamination, and with a thickness of 0.104 mm) is formed with a backing on the substrate layer for 24 hours.

[0450] The substrate layer coated with the adhesive composition was stored at 70°C for 7 days to ensure complete cross-linking of the composition.

[0451] Example 1:

[0452] The following components are used to prepare composition A (according to the present invention) and composition B (reference):

[0453] 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.

[0454] RE100, available from Arizona Chemical, is a rosin-type resin with a number-average molecular weight of approximately 1700 Da.

[0455] - M40, available from BASF, is a polyvinyl ether.

[0456] - 1010, available from BASF, is a hindered phenolic antioxidant;

[0457] -SPUR Y-19204, available from Momentive, is a silyl polypropylene glycol polyurethane prepolymer with trimethoxysilane end groups and an average molecular weight Mn of 24,000 g / mol.

[0458] - 5218, available from King Industries, is an aluminum chelate catalyst.

[0459] [Table 1]

[0460]

[0461] Composition B does not contain polyvinyl ether compounds.

[0462] The adhesive properties and vapor permeability were measured as detailed above. The results are shown in the table below:

[0463] [Table 2]

[0464]

[0465] Description:

[0466] -SS = Polished Stainless Steel

[0467] -AF = Adhesion failure (no residue, adhesive loss explains the test result; the product has good cohesion).

[0468] HDPE = High-density polyethylene

[0469] It can be seen that composition A according to the present invention allows for the obtaining of articles with improved vapor permeability without compromising good adhesion properties.

[0470] Example 2

[0471] The following components were used to prepare composition C (according to the present invention) and composition D (reference):

[0472] - AR100, available from Eastman, is a hydrocarbon-based resin.

[0473] - M40, available from BASF, is a polyvinyl ether.

[0474] - STPE-30, available from Wacker, is a dimethoxy(methyl)silyl methyl carbamate-terminated polyether with an average molecular weight of 24,000 g / mol.

[0475] - 5218, available from King Industries, is an aluminum chelate catalyst.

[0476] [Table 3]

[0477]

[0478] Composition D does not contain polyvinyl ether compounds.

[0479] The adhesive properties and vapor permeability were measured as described above. The results are shown in the table below [Table 4]:

[0480] [Table 4]

[0481]

[0482] It has been observed that composition C according to the invention allows for articles with improved vapor permeability without compromising good adhesive properties.

[0483] Example 3:

[0484] The following compositions are used to prepare composition E (according to the present invention) and composition F (comparative):

[0485] - 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.

[0486] - RE 100, available from Arizona Chemical, is a rosin-type resin with a number-average molecular weight of approximately 1700 Da.

[0487] - M40, available from BASF, is a polyvinyl ether.

[0488] - 1010, available from BASF, is a hindered phenolic antioxidant;

[0489] -Spur Y-19204, available from Momentive, is a silyl polypropylene glycol polyurethane prepolymer with trimethoxysilane end groups and an average molecular weight Mn of 24000 g / mol.

[0490] -TnBT is a titanium tetrabutoxide type catalyst.

[0491] [Table 5]

[0492]

[0493] Composition F does not contain polyvinyl ether compounds.

[0494] Adhesion properties and vapor permeability were measured as described above. The results are shown in the table below:

[0495] [Table 6]

[0496]

[0497] It has been observed that composition E according to the invention allows for articles with improved vapor permeability without compromising good adhesive properties.

Claims

1. An adhesive composition comprising: From 30% to 70% by weight, at least one silyl polymer comprising at least one hydrolyzable alkoxysilyl group, said silyl polymer having a main chain selected from the following: polyether, polyester, polyester-polyether-polyester, polyether-polyester-polyether, polyolefin, polyacrylate, polycarbonate, poly(ether-carbonate), poly(ester-carbonate), polyacetal, polyesteramide, polysulfide, polyurethane, polyester-polyurethane, polyether-polyurethane, polyether-polyester-polyurethane, polyolefin-polyurethane, polyether-polyolefin-polyurethane, polyurea, or poly(urethane-urea); From 5% to 25% by weight of at least one polyvinyl ether compound, 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), and mixtures thereof; 20% to 60% by weight of tackifying resin; and At least one crosslinking catalyst, in, The total amount of all components is 100 by weight.

2. The composition according to claim 1, wherein the silyl polymer is selected from: Silyl polymers having the general formula [Chemical Formula 2] Silyl polymers having the general formula [Chemical Formula 3] Silyl polymers having the general formula [Chemical Formula 4] Silyl polymers having the general formula [Chemical Formula 5] in: X 1 and X 2 Each can independently represent an oxygen atom or an -NH- group; R 1 It indicates a divalent hydrocarbon group containing 5 to 15 carbon atoms, which is aromatic or aliphatic; R 0 This indicates a straight-chain or branched divalent alkylene group containing 3 to 6 carbon atoms; R 3 This indicates a straight-chain or branched divalent alkylene group containing 1 to 6 carbon atoms; R 2 Indicates polyether block-R pe -[OR pe ] n -, where R pe This indicates a straight-chain or branched divalent alkylene group containing 2 to 4 carbon atoms; R 4 and R 5 They are the same or different, each representing a straight-chain or branched alkyl group containing 1 to 4 carbon atoms; R 6 It represents a hydrogen atom, a phenyl group, a straight-chain, branched, or cyclic alkyl group containing 1 to 6 carbon atoms, or a 2-succinate group having the general formula [Chemical Formula 6]. Where R 7 It is a straight-chain or branched alkyl group containing 1 to 6 carbon atoms; n is an integer such that in polymers having the general formulas [Formula 2], [Formula 3], and [Formula 4], the polyether block-[OR] pe ] n - The number-average molecular weight ranges from 300 g / mol to 40000 g / mol; m1 is an integer; m1 results in polymers having the general formula [Chemical Formula 3] with a number-average molecular weight of 500 g / mol to 50000 g / mol; m is a non-zero integer; m makes the number-average molecular weight of polymers having the general formula [Chemical Formula 4] range from 500 g / mol to 50000 g / mol; p is an integer equal to 0, 1, or 2; R al This indicates a divalent hydrocarbon group generated from a diol by substituting each of the two hydroxyl groups with a free valence, or indicates the group R. 2 ; R ac This indicates a divalent hydrocarbon group generated from a dicarboxylic acid by replacing each of the two carboxyl groups (COOH) with a free valence. [Y] q Represents repeating units with the general formula [Chemical Formula 28]. t is a number that gives polyester diols with the general formula [Chemical Formula 7] a hydroxyl value I of 4-60 mg KOH / g. OH ; q is a non-zero integer; and t and q result in polymers having the general formula [Chemical Formula 5] having a number-average molecular weight of 400 g / mol to 50000 g / mol.

3. The composition according to any one of claims 1-2, wherein the crosslinking catalyst is selected from amines, organometallic compounds, acids and their derivatives, and mixtures thereof.

4. The composition according to any one of claims 1-2, wherein the polyvinyl ether compound has a K value of 40 to 120.

5. The composition according to any one of claims 1-2, wherein the polyvinyl ether compound has a glass transition temperature of -60 to 0°C.

6. The composition according to any one of claims 1-2 further comprises at least one sesquioxane.

7. The composition according to any one of claims 1-2, wherein the composition is a single-component composition.

8. The composition according to any one of claims 1 to 2, wherein the composition is a two-component composition comprising: Part A, comprising at least one of the silyl polymers; and Part B, which comprises at least one of the crosslinking catalysts; The at least one polyvinyl ether compound is present in part A and / or part B of the composition.

9. The composition according to claim 1, wherein the silyl polymer has a main chain selected from polycaprolactone.

10. The composition according to claim 2, wherein m1 is zero.

11. Use of the composition according to any one of claims 1 to 10 as an adhesive.

12. A self-adhesive article comprising at least one carrier layer and at least one layer of the composition according to any one of claims 1 to 10.

13. The self-adhesive article of claim 12, wherein the article is selected from dressings, bandages and medical tapes.

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