Thermally crosslinkable adhesive composition forming thermally stable adhesive seal

Abstract

To provide a thermally crosslinkable adhesive composition which gives a self-adhesive support that enables formation of an adhesive seal having improved cohesive power at high temperature.SOLUTION: A thermally crosslinkable adhesive composition contains: a polymer (A) containing at least one hydrolyzable alkoxysilane group; a silylated copolymer tackifier resin (B') containing a repeating unit (B'1) derived from a silylated olefin polymer, especially, a silylated (meth)acrylate monomer, and one or more repeating units (B'2) which is obtained by decomposing naphtha and is derived from an olefin or a diolefin monomer contained in a petroleum fraction selected from a C5 fraction, a C9 fraction and dicyclopentadiene; a non-silylated tackifier resin (C); and a crosslinking catalyst (D).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel thermally crosslinkable adhesive composition based on a polymer having at least one hydrolyzable alkoxysilane group. The present invention also relates to a self-adhesive article that, after assembly with a substrate, is capable of forming an adhesive seal whose cohesion is maintained at elevated temperatures. In particular, the present invention relates to a self-adhesive substrate having a substrate coated with a self-adhesive layer composed of the composition in a crosslinked state. Finally, the present invention relates to a method for producing the article. [Background technology]

[0002] Self-adhesive binders (also known as pressure-sensitive adhesives (PSA)) are substances that provide the substrate layer coated with them with instant tack at room temperature. This immediate tackiness, often referred to as "tack," allows these self-adhesive substrates to instantly adhere to any type of substrate under the influence of a short, light pressure. Their adhesive strength (usually assessed by a peel test) then allows them to be firmly attached to the substrate using an adhesive seal.

[0003] PSAs are widely used in the manufacture of self-adhesive articles, such as self-adhesive labels that are attached to articles during a permanent or temporary adhesive bonding operation for the purpose of presenting information (barcode, name, price, etc.) and / or for decorative purposes.

[0004] Another example of self-adhesive article is the self-adhesive tape for various uses.In addition to the transparent adhesive tape that is widely used in daily life, mention may be made of the following: forming and assembling cardboard packaging; protecting surfaces for painting work in construction; fixing and maintaining various elements such as panels, bricks, protrusions, etc. in the construction of buildings or structures; fixing and maintaining flat or contoured metal, plastic or glass parts, such as electric wires, plastic films, window glass, metal plates, inscriptions, logos, seat parts, instrument panels, plastic or fiber walls, tubes or pipes for fluid circulation, especially in the transportation industry; adhesive bonding of fitted carpets with double-sided adhesive tape in the construction field.

[0005] For the purpose of producing these self-adhesive articles, the self-adhesive adhesive is generally applied by a continuous coating process over the entire surface of a large-sized support layer (optionally a printable support) in a concentration, hereinafter indicated by the term "weight per unit area" (generally g / m 2 The amount of the self-adhesive composition is applied in an amount of 1000 ppm (represented by the formula (x, y, y)). The support layer is, for example, a paper or film made of a polymer material having one or more layers. The layer of the self-adhesive composition covering the support layer can itself be covered with a protective non-stick layer (often known as a release liner), made of, for example, a silicone film. The resulting multilayer system can generally be packaged, stored, and transported by being wound up in the form of a large reel having a width of up to 2 m and a diameter of up to 1 m.

[0006] These multilayer systems can then be converted into self-adhesive labels that can be applied by the end user through a conversion process that involves printing the desired informational and / or decorative elements onto the printable surface of the support layer, followed by cutting to the desired shape and size. The protective non-stick layer can be easily removed without altering the adhesive layer, which remains attached to the support layer. After peeling from the non-stick protective layer, the label can be applied to the article to be coated, either manually or using a labeling machine on an automated packaging line.

[0007] These multilayer systems can also be cut and packaged as rolls of a given width and length and converted into self-adhesive tapes by cutting or pre-cutting them into specific shapes that are useful for their end use, whether industrial or consumer, for example, the assembly of parts of various sizes and shapes in the electronics industry.

[0008] Thermally crosslinkable adhesive compositions comprising hydrolyzable alkoxysilane-terminated polyurethanes (or polyethers) are known, inter alia, from WO 09 / 106699 and EP 2 336 208 A1 to Bostik.

[0009] These adhesive compositions are coated on a support layer at a specific weight per unit area and heated, and after chemical crosslinking reaction in the presence of moisture, a self-adhesive support is produced that has the required adhesive strength (or peeling) and tackiness.This crosslinking reaction leads to the formation of an adhesive seal that has a three-dimensional polymer network structure containing siloxane bonds, which ensures the fixation of the self-adhesive support to the substrate.The above-mentioned self-adhesive support can thus be used to produce self-adhesive articles such as self-adhesive labels and / or tapes.

[0010] Therefore, the self-adhesive support included in the self-adhesive article can be firmly attached to a substrate by an adhesive seal to form an assembly, and the retention of cohesive strength of the adhesive seal over time ultimately determines the stability of the assembly formed by fixing the self-adhesive support to a substrate.

[0011] However, there are many applications for PSAs where the seal (and thus the assembly) must retain its cohesive strength when exposed to temperatures that may vary over a wide range, particularly elevated temperatures.

[0012] This need arises, for example, in the transportation industry, such as the aviation, aerospace, automotive, rail, and marine industries, where heat-resistant properties of assemblies, including adhesive seals, are required, along with associated flame-retardant properties, particularly for assemblies located near the engine. Examples of practical applications include labeling certain components located near the engine, or labeling items (e.g., tires) that are labeled while hot as they leave the production line. Other examples include the use of self-adhesive tapes, for example, in the interior trim of aircraft or other vehicles. Finally, battery component assemblies for electric or hybrid vehicles, where recharging batteries also involves elevated temperatures.

[0013] Such a need also arises in many industrial sectors (such as household appliances, electronic devices or solar panels) where adhesives are increasingly found as an alternative to durable assemblies obtained by rivets or spot welding. Another practical example is PSAs used to apply labels onto packaging designed to receive hot liquids inside the packaging.

[0014] The above-referenced WO 09 / 106699 meets the above-mentioned needs and describes a thermally crosslinkable adhesive composition comprising an alkoxysilane-terminated polyurethane, a compatible tackifying resin and a crosslinking catalyst. Summary of the Invention

[0015] One object of the present invention is to provide a thermally crosslinkable adhesive composition which, when coated onto a support layer, provides a self-adhesive support that, after crosslinking by heating, is capable of forming an adhesive seal with improved cohesive strength at high temperatures, which also leads to improved seal maintenance.

[0016] Another object of the present invention is to provide a thermally crosslinkable adhesive composition which can be coated onto a substrate at a high weight per unit area and which, after crosslinking, results in an adhesive seal with improved cohesive strength at elevated temperatures.

[0017] Another object of the present invention is to provide a thermally crosslinkable adhesive composition that, after coating on a substrate, crosslinks to provide a pressure sensitive adhesive with suitable release and tack properties.

[0018] It has been found that these objects can be achieved in whole or in part by the adhesive compositions and self-adhesive supports described below. [Brief explanation of the drawings]

[0019] [Figure 1] 1 is a schematic diagram of one embodiment of an installation suitable for carrying out a method for producing a self-adhesive article according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0020] The subject of the present invention therefore firstly comprises: a polymer (A) containing at least one hydrolyzable alkoxysilane group; a silylated tackifying resin (B) selected from the group consisting of silylated copolymer resins (B') and (B''), The resin (B') repeating units (B'1) derived from silylated olefin monomers, in particular from silylated (meth)acrylate monomers, and - containing one or more repeating units (B'2) derived from an olefin monomer or diolefin monomer contained in a petroleum fraction obtained by cracking naphtha and selected from a C5 fraction, a C9 fraction, dicyclopentadiene and mixtures thereof, the resin (B″) is obtained by hydrogenating the resin (B′); and a non-silylated tackifying resin (C) that is compatible with said polymer (A); a crosslinking catalyst (D); The thermally crosslinkable adhesive composition has the following structure.

[0021] Polymer (A): The thermally crosslinkable adhesive composition according to the present invention comprises one or more polymers (A) containing at least one hydrolyzable alkoxysilane group.

[0022] For the purposes of the present invention, the term "polymer (A) comprising at least one hydrolyzable alkoxysilane group" refers to a polymer having the formula (I): -Si(R 4 ) p (OR 5 ) 3-p (I) means a polymer containing at least one, preferably at least two hydrolyzable groups of the formula (In the formula, ·R 4 represents a linear or branched alkyl group containing 1 to 4 carbon atoms, and R 4 When more than one group is present, these groups may be the same or different; ·R 5 represents a linear or branched alkyl group containing 1 to 4 carbon atoms, and R 5 When multiple groups are present, these groups may be the same or different, and two OR 5 It is possible that groups may be attached to the same ring, and · p is an integer equal to 0, 1 or 2).

[0023] The hydrolyzable alkoxysilane groups are preferably at the terminal positions of the polymer, although positions at the center of the chain are not excluded.

[0024] The various groups, radicals and characters contained in the formulae described in this patent application retain the same definitions throughout the specification unless otherwise indicated.

[0025] Thus, polymer (A) is a silylated polymer that is generally in the form of a more or less viscous liquid. Preferably, polymer (A) has a viscosity in the range of 10 Pa·s to 200 Pa·s, preferably 20 Pa·s to 175 Pa·s, measured, for example, according to the Brookfield viscometer method at 23°C and 50% relative humidity (S28 needle). More generally, viscosities indicated herein are viscosities measured by the Brookfield viscometer method, unless otherwise indicated.

[0026] According to a preferred variant of the composition according to the invention, the hydrolyzable alkoxysilane group of formula (I) is such that p is equal to 1 or 2, more preferentially p is equal to 1.

[0027] The polymer (A) preferably contains two groups of formula (I), but may contain from three to six groups of formula (I).

[0028] Preferably, polymer (A) has a number average molar mass in the range from 500 to 60000 g / mol, for example in the range from 1000 to 30000 g / mol, more preferably in the range from 15000 to 50000 g / mol and more preferentially in the range from 15000 to 30000 g / mol.

[0029] Unless otherwise indicated, the number-average molar (or molecular) masses (Mn) and weight-average molar (or molecular) masses (Mw) given herein, particularly for polymer (A), silylated tackifying resin (B) and non-silylated tackifying resin (C), are measured by size exclusion chromatography, also known as gel permeation chromatography (GPC), using polystyrene standards.

[0030] According to one embodiment of the present invention, the polymer (A) is represented by formula (II), (III) or (IV): Corresponding to one of TIFF2023091776000001.tif73170 (In the formula, ·R 4 , R 5and p has the same meaning as in formula (I) above, P represents a saturated or unsaturated, linear or branched polymeric group, which may contain one or more heteroatoms, such as oxygen, nitrogen, sulfur or silicon, and which preferably has a number average molar mass ranging from 500 g / mol to 60 000 g / mol, for example from 1 000 g / mol to 30 000 g / mol, more particularly from 15 000 g / mol to 50 000 g / mol and more preferentially from 15 000 g / mol to 30 000 g / mol, ·R 1 represents a divalent hydrocarbon-based group containing 5 to 15 carbon atoms, which may be aromatic or aliphatic, linear, branched or cyclic, ·R 3 represents a linear or branched divalent alkylene group containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, X is -NH-, -NR 7 - or -S-, ·R 7 represents a linear or branched alkyl group containing 1 to 20 carbon atoms and optionally containing one or more heteroatoms; f is an integer ranging from 1 to 6, preferably ranging from 2 to 5, preferably ranging from 2 to 4, more preferably ranging from 2 to 3).

[0031] Preferably, in formulas (II), (III) and / or (IV) above, P represents a polymeric group selected from, but not limited to, polyether, polycarbonate, polyester, polyacrylate, polyurea, polyether polyurethane, polyester polyurethane, polyolefin polyurethane, polyacrylate polyurethane, polycarbonate polyurethane, and block polyether / polyester polyurethane.

[0032] For example, EP 2468783 describes silylated polymers of formula (II) where P represents a polymeric group containing polyurethane / polyester / polyether blocks.

[0033] According to one embodiment, the silylated polymer is selected from silylated polyurethanes, silylated polyethers, and mixtures thereof.

[0034] According to a particular embodiment, the silylated polymer (A) has the formula (II'), (III') or (IV'): Corresponding to one of TIFF2023091776000002.tif74170 (In the formula, ·R 1 , R 3 , R 4 , R 5 , X, R 7 and p has the same meaning as in formulas (II), (III) and (IV) above; ·R 2 represents a saturated or unsaturated, linear or branched, divalent hydrocarbon-based group, which may contain one or more heteroatoms such as oxygen, nitrogen, sulfur or silicon, and which preferably has a number average molar mass ranging from 500 g / mol to 60 000 g / mol, for example from 1 000 g / mol to 30 000 g / mol, more particularly from 15 000 g / mol to 50 000 g / mol and more preferentially from 15 000 g / mol to 30 000 g / mol, ·n is an integer greater than or equal to 0).

[0035] In the silylated polymers of formula (II'), (III') or (IV') defined above, R 2 If the group contains one or more heteroatoms, the heteroatoms are not at the ends of the chain. In other words, the divalent R bonded to the oxygen atom adjacent to the silylated polymer 2 Each free valence of the group comes from a carbon atom. 2 The main chain of the group is terminated at each of its two ends by a carbon atom, which consequently has a free valence.

[0036] According to one embodiment, the silylated polymer (A) is obtained from a polyol selected from polyether polyols, polyester polyols, polycarbonate polyols, polyacrylate polyols, polysiloxane polyols and polyolefin polyols, and mixtures thereof, and more preferably from a diol selected from polyether diols, polyester diols, polycarbonate diols, polyacrylate diols, polysiloxane diols, polyolefin diols, and mixtures thereof. In the case of polymers of formula (II'), (III') or (IV') above, the aforementioned diol is a diol of formula HO-R 2 -OH, where R 2 has the same meaning as in formula (II'), (III') or (IV').

[0037] For example, R that may be present in formula (II'), (III') or (IV') 2 Among the radicals of this type, the following divalent radicals may be mentioned, of which the following formula: Derived from polypropylene glycol: TIFF2023091776000003.tif28170·Derived from polyester diol: TIFF2023091776000004.tif25170·Derived from polybutadiene diol: TIFF2023091776000005.tif29170·Derived from polyacrylate diol: TIFF2023091776000006.tif33170·Derived from polysiloxanediol: TIFF2023091776000007.tif29170 shows two free valences.

[0038] In the above formula, the groups and indices have the following meanings: q is R 2represents an integer such that the number average molecular weight of the group ranges from 500 g / mol to 60,000 g / mol, for example from 1,000 g / mol to 30,000 g / mol, preferably from 15,000 g / mol to 50,000 g / mol, more preferentially from 15,000 g / mol to 30,000 g / mol, r and s are R 2 represents a zero or non-zero integer such that the number average molecular weight of the group ranges from 500 g / mol to 60 000 g / mol, for example from 1 000 g / mol to 30 000 g / mol, preferably from 15 000 g / mol to 50 000 g / mol, more preferentially from 15 000 g / mol to 30 000 g / mol, and the sum r+s is understood to be non-zero, Q 1 represents a linear or branched, saturated or unsaturated, aromatic or aliphatic divalent alkylene group preferably containing 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms; Q 2 represents a linear or branched divalent alkylene group preferably containing 2 to 36 carbon atoms, more preferably 1 to 8 carbon atoms; Q 3 , Q 4 , Q 5 , Q 6 , Q 7 and Q 8 are each independently a hydrogen atom, or an alkyl, alkenyl or aromatic group preferably containing 1 to 12 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms.

[0039] According to one embodiment of the composition according to the invention, the silylated polymer (A) is selected from the group consisting of R appearing in formulae (II'), (III') and (IV'). 2 The group is such that it represents a polyether group, preferably a poly(oxyalkylene) group, even more preferably a group derived from polypropylene glycol corresponding to the above formula.

[0040] According to one embodiment, R 1 is selected from one of the following divalent groups, of which the following formula indicates two free valences: a) Divalent groups derived from isophorone diisocyanate (IPDI): TIFF2023091776000008.tif34170b) A divalent group derived from dicyclohexylmethane diisocyanate (H12MDI), TIFF2023091776000009.tif21170c) A divalent group derived from toluene diisocyanate (TDI), TIFF2023091776000010.tif38170d) Divalent groups derived from the 4,4' and 2,4' isomers of diphenylmethane diisocyanate (MDI), TIFF2023091776000011.tif27170e) A divalent group derived from hexamethylene diisocyanate (HDI)-(CH2)6-, f) A divalent group derived from m-xylylene diisocyanate (m-XDI). TIFF2023091776000012.tif34170

[0041] The polymers of formula (II) or (II') can be obtained according to the methods described in EP 2 336 208 and WO 2009 / 106699. Those skilled in the art know how to adapt the preparation methods described in the two documents to the use of different types of polyols. Among the polymers corresponding to formula (II), mention may be made of: GENIOSIL® STP-E10 (available from WACKER): 3 represents a methyl group, and is a dimethoxy type (n equals 0, p equals 1, R 4 and R 5 represents a methyl group); GENIOSIL® STP-E30 (available from WACKER): with a number-average molar mass of 24,000 g / mol, it is a polypropylene glycol with two end groups consisting of dimethoxy(methyl)silylmethylcarbamate, i.e. in formula (II′), n is equal to 0, p is equal to 1 and R 4 and R 5 indicates a methyl group, and R 3 indicates a methyl group; DESMOSEAL® S XP 2636 (available from BAYER): 3 represents an n-propylene group, and has a number average molar mass of 27900 g / mol. 5 represents a methyl group).

[0042] The polymers of formula (III) or (III') can be obtained, for example, by hydrosilylation of polyether diallyl ethers according to the method described in EP-A-1 829 928. Among the polymers corresponding to formula (III), mention may be made of: Polymer MSSAX510 (available from Kaneka Corporation): trimethoxy type (p equals 0, R 5 represents a methyl group), corresponding to a polyether containing two groups (I); Polymer MSS303H (available from Kaneka Corporation): dimethoxy type (p equals 1, R 4 represents a methyl group).

[0043] Polymers of formula (IV) or (IV') can be obtained, for example, by reacting a polyol with one or more diisocyanates, followed by reaction with aminosilanes or mercaptosilanes. A method for preparing polymers of formula (IV) or (IV') is described in EP-A-2 583 988. A person skilled in the art knows how to adapt the preparation methods described in the aforementioned document to the use of different types of polyols. Among the polymers corresponding to formula (IV), mention may be made of: SPUR+® 1050MM (available from MOMENTIVE): where R 3 represents an n-propyl group, and a trimethoxy type (where n is other than 0, p is equal to 0, and R 5 represents a methyl group); SPUR+® Y-19116 (available from MOMENTIVE): 3 represents an n-propyl group, and a trimethoxy type (where n is other than 0 and R 5 represents a methyl group).

[0044] According to a preferred embodiment of the present invention, the adhesive composition comprises at least one silylated polymer of formula (II) and / or (II') or at least one silylated polymer of formula (III) and / or (III').

[0045] According to a most particularly preferred embodiment of the present invention, the polymer (A) is a silylated polymer of formula (II′) where n is equal to 0 and R 2 is a divalent radical derived from a polyether, preferably from a poly(oxyalkylene)diol, and even more particularly from a polypropylene glycol).

[0046] Silylated copolymer resin (B): The thermally crosslinkable adhesive composition according to the present invention also comprises a silylated tackifying resin (B) selected from the group consisting of silylated copolymer resin (B') and silylated copolymer resin (B''): The resin (B') is repeating units (B'1) derived from silylated olefin monomers, in particular silylated (meth)acrylate monomers, and - containing one or more repeating units (B'2) derived from an olefin monomer or diolefin monomer contained in a petroleum fraction obtained by cracking naphtha and selected from a C5 fraction, a C9 fraction, dicyclopentadiene and mixtures thereof, The resin (B'') is obtained by hydrogenating the resin (B').

[0047] The term "silylated olefin" refers to a compound containing at least one carbon-carbon double bond, preferably of the vinyl type (CH=CH-), and at least one silicon atom directly bonded to at least one carbon atom. Preferably, the silylated olefin contains exactly one carbon-carbon double bond, preferably of the vinyl type, and exactly one silicon atom directly bonded to at least one carbon atom.

[0048] It is understood that mixtures of more than one of the silylated tackifying resins (B) as defined above may be used, in particular mixtures of resins (B') and (B'') as defined above.

[0049] According to a preferred variant, the silylated copolymer resin (B) is the resin (B') defined above.

[0050] The silylated olefin, particularly the silylated (meth)acrylate from which the repeating unit (B'1) is derived, preferably contains at least one alkoxysilyl group. The alkoxysilyl group may contain one or more heteroatoms other than oxygen directly bonded to the silicon atom, preferably oxygen. Preferably, the alkoxysilyl group does not contain any heteroatoms other than oxygen directly bonded to the silicon atom.

[0051] According to a preferred embodiment, the silylated olefin has the formula: CH2=CH(R 10 )-(C(O)O) a -(C m H 2m ) b -Si(R 11 )(R 12 )(R 13 ) Represented by (In the formula, ·R 10 represents a hydrogen atom or a methyl group, ·R 11 , R 12 and R 13 may be the same or different and each represents a hydrogen atom or an organic group selected from an alkyl group containing 1 to 20 carbon atoms, a cycloalkyl group containing 3 to 12 carbon atoms, an alkoxy group containing 1 to 12 carbon atoms, an acyloxy group containing 2 to 12 carbon atoms, an aryloxy group containing 6 to 30 carbon atoms, and an amino group containing 1 to 20 carbon atoms. Preferably, R 11 , R 12 and R 13 may be the same or different and each represents an alkyl group containing 1 to 6 carbon atoms or an alkoxy group containing 1 to 6 carbon atoms, a and b are integers, which may be identical or different, equal to 0 or 1; m is an integer between 1 and 12, preferably between 1 and 6, R 11 Group, R 12 Groups and R 13 At least one of the groups is understood to represent an alkoxy group containing 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms (especially 1 carbon atom).

[0052] Preferably, the silylated olefin has the formula: CH2=CH(R 10 )-(C(O)O) a -(C m H 2m ) b -Si(R11 )(R 12 )(R 13 ) Represented by (In the formula, ·R 10 represents a hydrogen atom or a methyl group, ·R 11 , R 12 and R 13 may be the same or different and each represents an alkyl group containing 1 to 6 carbon atoms or an alkoxy group containing 1 to 6 carbon atoms; a and b are integers, which may be identical or different, equal to 0 or 1; m is an integer from 1 to 6, R 11 Group, R 12 Groups and R 13 At least one of the groups is understood to represent an alkoxy group containing 1 to 6 carbon atoms, in particular containing 1 carbon atom).

[0053] The above-mentioned silylated olefins, in particular silylated (meth)acrylates, are preferably selected from vinyltrimethoxysilane, vinyltriethoxysilane, tris(2-methoxyethoxy)vinylsilane and 3-(trimethoxysilyl)propyl methacrylate, for example vinyltrimethoxysilane.

[0054] The silylated copolymer resin (B') preferably contains a plurality of repeating units (B'2) derived from cyclic or acyclic olefins contained in petroleum fractions obtained by cracking naphtha, the petroleum fractions being selected from the group consisting of C5 fractions, C9 fractions, dicyclopentadiene, and mixtures thereof.

[0055] The C5 fraction may contain olefins such as 1-pentene, 2-methyl-2-butene, n-pentane, propadiene, dicyclopentadiene, piperylene, isoprene, cyclopentene, and 1,3-pentadiene.

[0056] The C9 fraction may contain olefins such as styrene, vinyltoluene, indene, alpha-methylstyrene, benzene, toluene and xylene.

[0057] In addition to the above repeating units (B'1) and (B'2), the silylated copolymer resin (B') may also contain another repeating unit derived from a monomer selected from, for example, a cyclic anhydride, a C3 to C20 α-olefin, or a styrene derivative.

[0058] The silylated copolymer resin (B') can be prepared by copolymerization of monomers corresponding to the repeating units (B'1) and (B'2), in particular, the copolymerization corresponding to an addition reaction between the double bonds present in each monomer. Numerous polymerization methods can be used for this purpose, with thermal polymerization being particularly preferred. The copolymerization may be followed by a hydrogenation reaction, the product of which is the silylated copolymer resin (B'').

[0059] For more detailed information regarding silylated copolymer resin (B') and a description of its preparation, see EP-A-3176191, EP-A-3480225, EP-A-3521633 and EP-A-3647333.

[0060] According to a preferred variant, the silylated copolymer resin (B) has a number average molecular weight (Mn) between 100 and 5000 g / mol, preferably between 150 and 2000 g / mol and even more preferentially between 150 and 500 g / mol.

[0061] According to another preferred variant, the silylated tackifying resin (B) has a softening temperature between 70°C and 150°C.

[0062] The softening temperature is measured according to the standardized ASTM E28 test, which works as follows: A brass ring approximately 2 cm in diameter is filled with the resin to be tested in its molten state. After cooling to room temperature, the ring and solid resin are placed horizontally in a thermostatically controlled glycerol bath whose temperature can be changed by 5°C per minute. A steel ball approximately 9.5 mm in diameter is placed centrally on the solid resin disc. The softening temperature is determined by the temperature at which the resin disc yields to a height of 25.4 mm under the weight of the steel ball during the temperature increase phase of the bath at a rate of 5°C per minute.

[0063] Among the resins that can be used as silylated tackifying resin (B), mention may be made of Mkorez® HRR-100 resin, which has a number average molecular weight (Mn) of 334 g / mol and a softening temperature of 100° C., and is a (non-hydrogenated) resin (B′) available from Kolon Inc.

[0064] Non-silylated tackifying resin (C): The thermally crosslinkable adhesive composition according to the present invention also comprises one (or more) non-silylated tackifying resins (C) that are compatible with the polymer (A).

[0065] The aforementioned resin (C) may be any resin that is compatible with the polymer (A).

[0066] The term "compatible tackifying resin" refers to a tackifying resin that, when mixed 50% / 50% with polymer (A) of formula (I), provides a substantially homogeneous mixture.

[0067] The resin (C) is advantageously (i) Resins obtained by polymerization of terpene hydrocarbons and phenols in the presence of a Friedel-Crafts catalyst; (ii) resins obtained by a process involving the polymerization of α-methylstyrene, said process possibly including reaction with phenols; (iii) Rosin derived from natural sources (e.g., rosin extracted from pine rubber, wood rosin extracted from tree roots) and its derivatives, which are hydrogenated, dimerized, polymerized or esterified with monoalcohols or polyols (such as glycerol or pentaerythritol); (iv) Resins obtained by hydrogenation, polymerization or copolymerization (with aromatic hydrocarbons) of mixtures of unsaturated aliphatic hydrocarbons containing 5, 9 or 10 carbon atoms obtained from petroleum fractions; (v) terpene resins (generally resulting from the polymerization of terpene hydrocarbons, such as monoterpenes (or pinene), in the presence of Friedel-Crafts catalysts); (vi) copolymers based on natural terpenes (e.g., styrene / terpene, α-methylstyrene / terpene, and vinyltoluene / terpene), or (vii) an acrylic resin having a viscosity of less than 100 Pa·s at 100°C; and also from mixtures of these resins.

[0068] Such resins are commercially available and, among the resins of types (i), (ii), (iii) and (iv) defined above, the following products may be mentioned: Resins of type (i): Dertophene® 1510 (available from the company DRT and having a molar mass Mn of approximately 870 Da); Dertophene® H150 (available from the same company and having a molar mass Mn equal to approximately 630 Da); Dertophene® T105 (available from the same company and having a molar mass Mw of approximately 700 Da); Sylvarez® TP95 (available from Arizona Chemical and having a molar mass Mn of approximately 1200 Da); Resins of type (ii): Cleartack® W100 (available from Cray Valley, obtained by polymerization of α-methylstyrene without the addition of phenols, with a number-average molar mass of 900 Da); Sylvarez® 510 (available from Arizona Chemical, the preparation process of which also involves the addition of phenols, with a molar mass Mn of approximately 1740 Da); Resins of type (iii): Sylvalite® RE100 (ester of rosin and pentaerythritol available from Arizona Chemical Co., with a molar mass Mn of approximately 1700 Da); Resins of type (iv): Picco® AR100 (available from Eastman and having a molar mass Mn of approximately 550 g / mol).

[0069] According to a preferred variant, a resin chosen from resins of type (i) or (iv) is used as non-silylated tackifying resin (C).

[0070] Crosslinking catalyst (D): The thermally crosslinkable adhesive composition according to the present invention also comprises one (or more) crosslinking catalysts (D).

[0071] The catalyst can be any catalyst for the condensation of silanols known to those skilled in the art.

[0072] The crosslinking catalyst (D) is (D1) organometallic compound, (D2) amine, (D3) Acids and their derivatives, and mixtures thereof may be selected from the group consisting of:

[0073] The crosslinking catalyst (D) may also be a mixture of catalysts belonging to the same group (D1), (D2) or (D3) (e.g., a mixture of several amines), or a mixture of catalysts belonging to at least two different groups selected from groups (D1), (D2) and (D3) (e.g., a mixture of an amine and an organometallic compound).

[0074] In the context of the present invention, the term "organometallic compound" means a compound comprising an organic group and at least one metal. In the context of the present invention, the term "organic group" means a group comprising at least one carbon atom.

[0075] (D1) Organometallic compound: Organometallic compounds can include organometallic compounds (compounds containing at least one covalent metal-carbon bond), metal alkoxides, metal carboxylates, and metal coordination complexes with one or more organic ligands.

[0076] Examples of organic ligands include acetylacetonates and oximes.

[0077] The metal atom of the organometallic compound may be any metal atom known to those skilled in the art and may be selected from tin, aluminum, zinc, cobalt, iron, nickel, bismuth, titanium or zirconium, among others. The organometallic compound may also contain more than one type of metal atom.

[0078] Compounds containing at least one covalent metal-carbon bond: The compound containing at least one covalent metal-carbon bond (organometallic compound) may be a carboxylate of an organometallic compound selected from the group consisting of dibutyltin dilaurate (DBTL), dibutyltin diacetate, dibutyltin diethylhexanoate, dioctyltin dineodecanoate (e.g., available from TIB Chemicals under the name TIB KAT® 223), dibutyltin dioleate, dibutyltin benzyl maleate, diphenyltin diacetate, and mixtures thereof.

[0079] The metal alkoxide may be selected from the group consisting of titanium tetrabutoxide, titanium tetraisopropoxide, zirconium tetrabutoxide, zirconium tetraisopropoxide, and mixtures thereof.

[0080] The metal carboxylate may be selected from the group consisting of zinc 2-ethylcaproate, zinc diacetate, zinc dineodecanoate, zinc diundecenoate, zinc dimethacrylate, cobalt acetylacetonate, cobalt diacetate, iron acetylacetonate, iron diacetate, nickel acetylacetonate, nickel diacetate, bismuth acetate, bismuth trioctoate, bismuth dineodecanoate, bismuth zinc dineodecanoate, and mixtures thereof.

[0081] The metal coordination complex with one or more organic ligands can be selected from the group consisting of zinc acetylacetonate, titanium acetylacetonate (available, for example, from Dorf Ketal under the name Tyzor® AA75), titanium tetraacetylacetonate, aluminum trisacetylacetonate, aluminum chelates such as bis(ethylacetoacetate) monoacetylacetonate (available, for example, from King Industries under the name K-KAT® 5218), zirconium tetraacetylacetonate, diisopropoxybis(ethylacetonato)titanium, and mixtures thereof.

[0082] (D2) Amine: The amine can be a primary amine, a secondary amine, or a tertiary amine.

[0083] Preferably, the amine is selected from the group consisting of triethylamine, tributylamine, tetramethylguanidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene, N,N-bis(N,N-dimethyl-2-aminoethyl)methylamine, N,N-dimethylcyclohexylamine, N,N-dimethylphenylamine, N-ethylmorpholine, and mixtures thereof.

[0084] (D3) Acid catalysts and their derivatives: The acid catalyst may be selected from inorganic acid catalysts, organic acid catalysts, and mixtures thereof.

[0085] Among inorganic acid catalysts, mention may be made, for example, of phosphoric or orthophosphoric acid, phosphorous acid, hypophosphorous acid, sulfuric acid, and the like.

[0086] The organic acid catalyst may be selected from sulfonic acids, carboxylic acids, organic acid phosphates, organic acid phosphonates, phosphonic acids, and mixtures thereof.

[0087] Preferably, the organic and inorganic acid catalysts have a pKa of 6 or less, preferably 4 or less, advantageously 2 or less, advantageously 0 or less.

[0088] The sulfonic acids may be aliphatic or aromatic, may be substituted (e.g., with at least one substituent selected from halogen (such as fluorine), hydroxyl, alkyl, amine, and mixtures thereof), and may be mono- or disulfonic acids.

[0089] Sulfonic acids include N-alkylaminoalkylsulfonic acids and N,N-dialkylaminoalkylsulfonic acids (zwitterions), such as 2-(N-morpholino)ethanesulfonic acid, 3-(N-morpholino)propanesulfonic acid, 4-[N-morpholino]butanesulfonic acid, 1,4-piperazinediethanesulfonic acid, N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid, 2-(N-morpholino)ethanesulfonic acid, N-morpholinomethanesulfonic acid, N-(2-hydroxyethyl)piperazine-N'-methanesulfonic acid, The sulfonic acid may be selected from sulfonic 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, dodecylbenzenedisulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, trifluoromethylsulfonic acid, and mixtures thereof.

[0090] In particular, the sulfonic acid is selected from p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, dodecylbenzenesulfonic acid, dodecylbenzenedisulfonic acid, dinonylnaphthalenesulfonic acid, trifluoromethylsulfonic acid, and mixtures thereof.

[0091] Among the carboxylic acid catalysts, mention may be made, for example, of malonic acid, succinic acid, maleic acid, oxalic acid, acetic acid, lactic acid, benzoic acid, citric acid, glycolic acid, and mixtures thereof.

[0092] In the context of the present invention, unless otherwise specified, the term "organic acid phosphate" refers to a phosphoric acid ester containing at least one -OH group. For example, methyl phosphate is an organic acid phosphate containing two -OH groups and has the following structure: TIFF2023091776000013.tif36170

[0093] In particular, the organic acid phosphate has the formula: (RO) g -(P=O)-(OH) h have (In the formula, R is an organic radical, in particular a radical selected from linear or branched C1-C22 alkyl, cycloalkyl, aryl and mixtures thereof, the aforementioned alkyl, cycloalkyl and aryl radicals being optionally substituted, and ·g and h are integers, where g+h=3 and h=1 or 2).

[0094] The organic acid phosphate may be selected from the group consisting of, for example, C1 to C22 mono- or dialkyl acid 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.

[0095] In the context of the present invention, unless otherwise stated, the term "organic acid phosphonate" refers to a compound having the following general formula: R'-(P=O)-(OH)(OR'') wherein R' and R'' are preferably organic radicals selected independently from one another from linear or branched C1 to C22 alkyl, cycloalkyl, aryl groups, and mixtures thereof, wherein the aforementioned alkyl, cycloalkyl, and aryl groups may be substituted.

[0096] Among the organic acid phosphonates, for example, C1 to C22 monoalkyl acid phosphonates can be mentioned.

[0097] In the context of the present invention, unless otherwise stated, the term "phosphonic acid" refers to a compound of the following general formula: R'''-(P=O)-(OH)2 wherein R''' is an organic group, preferably selected from linear or branched C1 to C22 alkyl, cycloalkyl, aryl groups, and mixtures thereof, wherein the aforementioned alkyl, cycloalkyl, and aryl groups may be substituted.

[0098] Among the phosphonic acids, mention may be made, for example, of N-alkylaminoalkylphosphonic acids (zwitterions), N,N-dialkylaminoalkylphosphonic acids (zwitterions), C1-C20 alkylphosphonic acids, such as methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, t-butylphosphonic acid, isobutylphosphonic acid, hexylphosphonic acid, 2-ethylhexylphosphonic acid and the linear or branched higher homologues, benzylphosphonic acid, phenylphosphonic acid, tolylphosphonic acid or xylylphosphonic acid.

[0099] Examples of organic acid catalysts include Nacure® 155 (dinonylnaphthalenedisulfonic acid with 55% activator in isobutanol, sold by King Industries), Nacure® 1051 (dinonylnaphthalenesulfonic acid with 50% activator in 2-butoxyethanol, sold by King Industries), Nacure® 5076 (dodecylbenzenesulfonic acid with 70% activator in isopropanol, sold by King Industries), K-Cure® 1040 (p-toluenesulfonic acid with 40% activator in isopropanol, sold by King Industries), and Nacure® 4000 (a mixture of mono- and dialkyl acid phosphates, 100% activator, sold by King Industries).

[0100] The acid derivative according to the present invention may be an acid anhydride, an acid ester or an acid ammonium salt, the acid being as defined above.

[0101] The acid derivative is in particular a "masked" or "latent" acid, which can advantageously liberate the acid by thermal activation (e.g., at temperatures in the range of 70°C to 170°C, preferably 90°C to 120°C), or by hydrolysis, or by photoactivation, preferably by thermal activation. The masked acid advantageously liberates the acid, which is the catalytically active species. For example, the ammonium salt formed between aminomethylpropanol and p-toluenesulfonic acid is a masked acid (acid derivative), which liberates p-toluenesulfonic acid by thermal activation.

[0102] Acid derivatives can be prepared by any means known to those skilled in the art, starting from the corresponding acid, for example, by using typical acid / base reactions. For example, methods for producing esters typically involve condensation of an acid compound with a hydroxyl-containing compound (e.g., an alcohol) or with an oxirane-type compound. Ammonium salts may be prepared from any of the above acids using ammonia or primary, secondary, or tertiary amines. The amine may optionally contain at least one functional group, such as a hydroxyl group (alkanolamines) or a C1-C4 alkyl group. Ammonium salts (zwitterions) can also be prepared, for example, by altering the pH of a solution containing an N-alkylaminoalkylphosphonic acid, N,N-dialkylaminoalkylphosphonic acid, N-alkylaminoalkylsulfonic acid, or N,N-dialkylaminoalkylsulfonic acid.

[0103] Preferably, the catalyst is an ammonium salt of a sulfonic acid (wherein the sulfonic acid is as defined above), an ammonium salt of a phosphonic acid (wherein the phosphonic acid is as defined above), an ammonium salt of an organic acid phosphonate (wherein the organic acid phosphonate is as defined above), or an ammonium salt of an organic acid phosphate (wherein the organic acid phosphate is as defined above).

[0104] The amines for preparing the ammonium salts include, for example, 2-amino-2-methyl-1-propanol, triethylamine, aniline, pyridine, dimethylaminoethanol, alkylpyridines, diisopropanolamine, dimethylethanolamine, triethanolamine, oxazolidine, bicyclic oxazolidine, amidine, diazabicyclooctane, guanidine, N-alkylmorpholine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and mixtures thereof.Preferably, the amine is a tertiary amine.

[0105] Examples of acid derivatives are, for example, Nacure® 3327 or Nacure® 3525 (amine-masked dinonylnaphthalene disulfonic acid, containing 25% active agent in isopropanol and isobutanol, sold by King Industries), Nacure® 1557 or Nacure® 1953 (amine-masked dinonylnaphthalene sulfonic acid, containing 25% active agent in a mixture of butanol and 2-butoxyethanol, sold by King Industries), Nacure® 5225 or Nacure® 5528 or Nacure® 5925 (amine-masked dodecylbenzene sulfonic acid, containing 25% active agent in isopropanol, sold by King Industries), Examples of suitable amine-masked toluenesulfonic acid include Nacure® 2107 or Nacure® 2500 (amine-masked p-toluenesulfonic acid, 25% or 26% active in isopropanol, sold by King Industries), Nacure® 2501 or Nacure® 2530 (amine-masked p-toluenesulfonic acid, 25% active in a mixture of isopropanol and methanol, sold by King Industries), Nacure® 4167 (organic amine-masked dialkyl phosphate, 25% active in a mixture of isopropanol and isobutanol, sold by King Industries), and Nacure® 4575 (amine-blocked acid phosphate, 25% active in a mixture of methanol and butanol, sold by King Industries).

[0106] Preferably, the catalyst is selected from the group consisting of organometallic compounds (especially aluminum-based coordination complexes, more particularly aluminum chelates), orthophosphoric acid, organic acid phosphates (preferably C1-C22 mono- or dialkyl acid phosphates and mixtures thereof), ammonium salts (especially of sulfonic acids or organic acid phosphates), and mixtures thereof.

[0107] Even more preferably, the catalyst is selected from the group consisting of orthophosphoric acid, organic acid phosphates (preferably C1-C22 mono- or dialkyl acid phosphates and mixtures thereof), ammonium salts (especially of sulfonic acids or organic acid phosphates).

[0108] Other additives: The thermally crosslinkable adhesive composition according to the present invention may also comprise one or more additives selected from the group consisting of moisture absorbers, adhesion promoters, plasticizers, antioxidants, pigments, colorants, UV stabilizers, flame retardant additives, fillers (e.g. carbonate-based fillers of the calcium carbonate type, or silsesquioxane resins or polyvinyl ether compounds).

[0109] The moisture absorbent (or desiccant) can be selected from, for example, non-polymeric hydrolyzable alkoxysilane derivatives having a molecular mass of less than 500 g / mol, preferably from trimethoxysilane derivatives and triethoxysilane derivatives. Such agents can generally improve the storage stability of the composition during storage and transportation before use. Examples include γ-methacryloxypropyltrimethoxysilane (available, for example, from Momentive under the trade name Silquest® A-174), methacryloxymethyltrimethoxysilane (available, for example, from Wacker under the name Geniosil® XL33), vinyltrimethoxysilane, isooctyltrimethoxysilane, or phenyltrimethoxysilane.

[0110] The content of the moisture absorbent is preferably 3% by weight or less, more preferably 2% by weight or less, relative to the total weight of the composition of the present invention. If a moisture absorbent is present, it may represent, for example, 0.1% to 3% by weight or 1% to 2% by weight, relative to the total weight of the composition of the present invention.

[0111] Some of these hygroscopic compounds may also act as adhesion promoters, in particular trialkoxysilanes containing amino, mercapto or epoxy groups. N-(3-(trimethoxysilyl)propyl)ethylenediamine (sold under the name Geniosil® GF9 by Wacker), or 3-aminopropyltrimethoxysilane (sold by Momentive under the name Silquest A-1110) Examples include:

[0112] An amount of 0.5% to 2% by weight (based on the weight of said composition) will generally be suitable.

[0113] The composition according to the present invention may also comprise a plasticizer.

[0114] Examples of the plasticizer that can be used include any plasticizer commonly used in the field of adhesives, such as phthalate esters, benzoates, trimethylolpropane esters, trimethylolethane esters, trimethylolmethane esters, glycerol esters, pentaerythritol esters, naphthenic mineral oils, adipic acid esters, cyclohexyl dicarboxylate, liquid paraffin, natural oils (which may be epoxidized), polypropylene, polybutylene, hydrogenated polyisoprene, and mixtures thereof.

[0115] Among the phthalates, mention may be made, for example, of diisononyl phthalate, diisobutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate, diisododecyl phthalate, dibenzyl phthalate or butylbenzyl phthalate.

[0116] Among the benzoates, mention may be made, for example, of neopentyl glycol dibenzoate (available, for example, from Lanxess under the name Uniplex® 512), dipropylene glycol dibenzoate (available, for example, from Eastman under the name Benzoflex® 9-88SG), a mixture of diethylene glycol dibenzoate and dipropylene glycol dibenzoate (available, for example, from Kalama Chemical under the name K-Flex® 850 S), or a mixture of diethylene glycol dibenzoate, dipropylene glycol dibenzoate and triethylene glycol dibenzoate (available, for example, from Eastman under the name Benzoflex® 2088).

[0117] Among the pentaerythritol esters, mention may be made, for example, of pentaerythrityl tetravalerate (available, for example, under the trade name Pevalen™ from the company Perstorp).

[0118] Among cyclohexanedicarboxylates, mention may be made, for example, of diisononyl 1,2-cyclohexanedicarboxylate (available, for example, from BASF under the name Hexamoll Dinch®).

[0119] The total content of plasticizers in the composition according to the invention may range from 0% to 30% by weight, preferably from 1% to 30% by weight, or for example from 1% to 15% by weight, relative to the total weight of said composition.

[0120] The composition according to the invention may also comprise antioxidants (also referred to as UV stabilizers).

[0121] Antioxidants are compounds that can be incorporated to protect compositions from deterioration caused by reaction with oxygen, which may be formed by the action of heat or light.These compounds can include primary antioxidants that scavenge free radicals.The primary antioxidants can be used alone or in combination with other secondary antioxidants or UV stabilizers.

[0122] Mention may be made, for example, of Irganox® 1010, Irganox® B561, Irganox® 245, Irganox® 1076 and Irgafos® 168 sold by BASF.

[0123] The antioxidants are generally used in an amount ranging from 0.1% to 3% by weight, preferably from 1% to 3% by weight, based on the total weight of the composition according to the invention.

[0124] The composition according to the present invention may also contain a silsesquioxane resin, which advantageously allows the production of adhesive seals with improved mechanical properties, particularly with respect to elongation and breaking strength. Silsesquioxane resins are organosilicon compounds that can have a polyhedral or polymeric structure with Si-O-Si bonds. They have the following general formula: [RSiO 3 / 2 ]t where R, which may be the same or completely different, represents an organic group and t is an integer that may range from 6 to 12, with t being preferably equal to 6, 8, 10 or 12.

[0125] According to one embodiment, the silsesquioxane has a polyhedral structure (POSS: "Polyhedral Oligomeric Silsesquioxane").

[0126] Preferably, the silsesquioxane has the following general formula (V): Equivalent to TIFF2023091776000014.tif64170 (In the formula, R' 1 ~R' 8 Each of the groups independently represents a group selected from: hydrogen atoms, a group selected from the group consisting of a linear or branched C1-C4 alkoxy group, a linear or branched alkyl group containing 1 to 30 carbon atoms, an alkenyl group containing 2 to 30 carbon atoms, an aromatic group containing 6 to 30 carbon atoms, an aryl group containing 3 to 30 carbon atoms, a cycloaliphatic group containing 3 to 30 carbon atoms, and an acyl group containing 1 to 30 carbon atoms; -OSiR' 9 R' 10 group (in the formula, R' 9 and R' 10 are each independently a hydrogen atom or a group selected from the group consisting of a linear or branched C1 to C4 alkyl group, a linear or branched C1 to C4 alkoxy group, a C2 to C4 alkenyl group, a phenyl group, a C3 to C6 allyl group, a cyclic C3 to C8 aliphatic group, and a C1 to C4 acyl group, however: R' 1 ~R' 8 At least one of the groups is a C1-C4 alkoxy group, and R' 1 ~R' 8 At least one of the groups is a phenyl group.

[0127] Silsesquioxanes are known compounds, described in particular in WO 2008 / 107331. Some are also commercially available, such as Dow products sold under the names Dow Corning® 3074 and Dow Corning® 3037 (CAS number: 68957-04-0).

[0128] Silsesquioxane resins can be advantageously used in amounts up to 15% by weight, preferably in the range of 3% to 10% by weight, based on the total weight of the composition according to the invention.

[0129] The composition according to the invention may also finally comprise a polyvinyl ether compound, which then advantageously has improved water vapor permeability and is suitable for the manufacture of waterproof, breathable, self-adhesive articles suitable for medical, clothing or construction applications. Such polyvinyl ether compounds have the general formula: It may be a homopolymer or copolymer containing repeating units derived from the monomer of TIFF2023091776000015.tif15170 (In the formula, R represents a saturated or unsaturated, linear or branched group containing 1 to 24 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and ·R 8 and R 9 represent, independently of one another, a hydrogen atom or an alkyl group containing 1 to 10 carbon atoms).

[0130] Among the polyvinyl ether homopolymers, mention may be made in particular of 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).

[0131] Commercially available polyvinyl ether compounds include Lutonal® M 40, Lutonal® A 25, Lutonal® A 50, Lutonal® A 100, Lutonal® I 30, Lutonal® I 60, Lutonal® I 60 D, and Lutonal® I 65 D, available from BASF, and Gantrez® M, available from GAF.

[0132] Amounts of polyvinyl ether compounds ranging from 1% to 60% by weight, preferably from 5% to 40% by weight, based on the total weight of the composition according to the invention may be suitable for use.

[0133] The adhesive composition according to the present invention may be in the form of a one-component adhesive composition or a multi-component (preferably two-component) adhesive composition.

[0134] I. One-component adhesive composition: According to a first embodiment, the adhesive composition according to the invention is in the form of a one-component composition.

[0135] According to this embodiment, the one-part composition described above generally comprises: 10% to 90% by weight, preferably 15% to 80% by weight, and more preferentially 20% to 60% by weight, of a polymer (A) containing at least one hydrolyzable alkoxysilane group, 3% by weight to 50% by weight, preferably 6% by weight to 35% by weight, of a silylated tackifying resin (B); 15% to 80% by weight, preferably 20% to 70% by weight, and more preferentially 30% to 60% by weight of a non-silylated tackifying resin (C), 0.01% to 10% by weight, preferably 0.01% to 5% by weight, preferentially 0.05% to 4% by weight, advantageously 0.1% to 3% by weight and in particular 0.1% to 0.5% by weight of a crosslinking catalyst (D), Including, These weight percentages are given based on the total weight of the one-part composition.

[0136] The one-component composition is mixing, with the exclusion of air and preferably under an inert atmosphere, the polymer (A) with the silylated tackifying resin (B) and the non-silylated tackifying resin (C) (optionally, if present, a silsesquioxane resin) at a temperature between 50°C and 180°C, preferably between 100°C and 165°C, and then cooling the mixture to a temperature ranging from 50°C to 130°C, advantageously from 70°C to 100°C, and then incorporating a crosslinking catalyst (D) and, if necessary, other optional additives into the mixture; It can be prepared by a method comprising:

[0137] II. Multi-component adhesive compositions: According to a second embodiment, the adhesive composition according to the invention is in the form of a multi-component composition, The multi-component composition comprises A composition U (as a first component), a polymer (A) comprising at least one hydrolyzable alkoxysilane group as defined above, and silylated tackifying resin (B) as defined above, a non-silylated tackifying resin (C) as defined above a composition U comprising A composition V (as the second component), a crosslinking catalyst (D) as defined above, and, optionally, at least one compound (E) comprising: a compound (E1) having a number average molecular weight in the range of 300 g / mol to 100,000 g / mol, Compound (E2) having a vapor pressure of 0.08 kPa or more at 20°C, and A mixture of these At least one compound (E) selected from and a composition V comprising: It has.

[0138] The various components of the multi-component adhesive composition described above are intended to be mixed together in accordance with the method for producing the self-adhesive substrate described below when a crosslinking reaction is carried out.

[0139] The multi-component adhesive composition may contain one or more additional components in addition to Components U and V, and the aforementioned additional components may comprise any type of compound. For example, the multi-component adhesive composition may contain an additional component W, which comprises at least one silylated (B) and / or non-silylated (C) tackifying resin, for example, selected from those described above. The multi-component adhesive composition according to the present invention may also comprise a component W, which comprises water. The water may be in liquid or gas form, or may be encapsulated, absorbed, or included in the chemical structure of a component. The water may come from one or more components that can subsequently be liberated and made available.

[0140] The multi-component adhesive composition according to the invention advantageously increases the crosslinking speed of the method for producing a self-adhesive support described below. The improved reactivity advantageously makes it possible to avoid oven treatment or to reduce the residence time in the crosslinking oven during the preparation of the self-adhesive support, thus reducing the residence time in the oven to, for example, less than 5 minutes, preferably less than 1 minute, preferentially less than 30 seconds, and advantageously less than 10 seconds. Thus, the multi-component adhesive composition according to the invention advantageously increases the industrial production speed while simultaneously providing good self-adhesion after crosslinking.

[0141] The components U and V contained in the aforementioned adhesive composition (before mixing) are stable to temperature and / or moisture during storage. The greater stability over time advantageously allows for extended storage and handling with reduced risk of components U and V reacting, degrading, or crosslinking during manufacture and high temperature application.

[0142] The multi-component adhesive composition according to the invention advantageously allows for the formation of a uniform adhesive layer without any problems of uncontrolled and uneven formation of particles or gels and / or advantageously allows for uniform crosslinking throughout the substrate.

[0143] Multi-part adhesive compositions can advantageously contain high catalyst content without causing solids to set in the tubes through which the adhesive components circulate during the manufacture of self-adhesive articles.

[0144] According to an even more preferred embodiment, the multi-component adhesive composition according to the present invention is a two-component adhesive composition comprising compositions U and V described above.

[0145] II.1. Composition U: Composition U generally comprises: 10% to 90% by weight, preferably 15% to 80% by weight, and more preferentially 20% to 60% by weight, of a polymer (A) containing at least one hydrolyzable alkoxysilane group, 3% to 45% by weight, preferably 3% to 30% by weight, more preferentially 6% to 30% by weight, for example 6% to 20% by weight, of a silylated tackifying resin (B), 15% to 80% by weight, preferably 20% to 70% by weight, and more preferentially 30% to 60% by weight of a non-silylated tackifying resin (C), These weight percentages are based on the total weight of composition U.

[0146] Additionally, composition U may also include one or more additives as described above selected from the group consisting of moisture absorbers, plasticizers, antioxidants, pigments, colorants, adhesion promoters, UV stabilizers, fillers, silsesquioxane resins, and polyvinyl ether compounds, as described above.

[0147] According to one embodiment, composition U comprises: 10% to 90% by weight, preferably 15% to 80% by weight, and more preferentially 20% to 60% by weight, of a polymer (A) containing at least one hydrolyzable alkoxysilane group, 3% by weight to 30% by weight, preferably 6% by weight to 20% by weight, of a silylated tackifying resin (B); 15% to 80% by weight, preferably 20% to 70% by weight, and more preferentially 30% to 60% by weight of a non-silylated tackifying resin (C), These weight percentages are based on the total weight of composition U.

[0148] Composition U according to this embodiment may also include one or more additives, as described above for Composition U in general.

[0149] Composition U can be prepared by mixing all of the aforementioned components of Composition U, regardless of the order in which the various components are incorporated. Multiple components of Composition U may be combined and then mixed with other components of Composition U as described above.

[0150] The mixing can be carried out at a temperature ranging from 23°C to 200°C.

[0151] II.2. Composition V: Composition V is a crosslinking catalyst (D) as defined above, and optionally at least one compound (E), a compound (E1) having a number average molecular weight in the range of 300 g / mol to 500,000 g / mol, Compounds (E2) having a vapor pressure of 0.08 kPa or more at 20°C, and A mixture of (E1) and (E2) and at least one compound (E) selected from Includes.

[0152] According to one embodiment, composition V comprises: ·Compound (E1), various mixtures of compounds (E1), ·Compound (E2), various mixtures of compounds (E2), or A mixture of at least one compound (E1) and at least one compound (E2) Includes.

[0153] II.2.1. Compound (E): The presence of compound (E) makes it possible to dilute the crosslinking catalyst (D) in composition V and thus advantageously increase the flash point of said composition V. This has the effect of advantageously improving, in particular, the safety of the process for preparing the self-adhesive article.

[0154] Furthermore, the presence of compound (E), in particular in a content of 50% by weight or more of composition V, can advantageously reduce the risk of toxicity, for example during the use of organometallic catalysts.

[0155] Furthermore, the presence of compound (E) in composition V advantageously allows for better dispersion of catalyst (D) in the two-component adhesive composition (obtained after mixing compositions U and V). This better dispersion advantageously leads to coating with a uniform adhesive layer without any problems of particle and / or gel formation that would impair the optical quality of the final coating or prevent a defect-free application of the coating on the surfaces to be joined.

[0156] Furthermore, the presence of compound (E) in composition V advantageously allows the addition of very small amounts of catalyst (D).

[0157] Compound (E) is advantageously inert with respect to the crosslinking catalyst (D), ie compound (E) does not react with said catalyst.

[0158] II.2.1.1 Compound (E1): The compound (E1) preferably has a number average molecular weight in the range from 1000 g / mol to 50000 g / mol, preferably from 1000 g / mol to 20000 g / mol, in particular from 2000 g / mol to 20000 g / mol, preferentially from 3000 g / mol to 20000 g / mol, for example from 4000 g / mol to 18000 g / mol, advantageously from 5000 g / mol to 10000 g / mol, in particular from 7000 g / mol to 9000 g / mol.

[0159] The number average molecular weight of compound (E1) can be determined by methods well known to those skilled in the art, for example, by size exclusion chromatography using polystyrene standards.

[0160] Compound (E1) preferably has a viscosity at 23°C in the range from 10 mPa·s to 100 000 mPa·s, in particular from 500 to 50 000 mPa·s, preferably from 500 to 20 000 mPa·s, preferentially from 500 to 15 000 mPa·s, advantageously from 500 to 10 000 mPa·s, for example from 1 000 to 5 000 mPa·s, preferably from 1 000 to 3 000 mPa·s.

[0161] According to the invention, compound (E1) is (E1-1) polyol, (E1-2) organosilane, (E1-3) tackifying resin, (E1-4) polyol ester, (E1-5) monosilylated or disilylated polymers, (E1-6) polyetheramine, (E1-7) silsesquioxane resin, (E1-8) polyvinyl ether compounds, and mixtures thereof may be selected from the group consisting of:

[0162] According to the present invention, compound (E1) may be a reactive or non-reactive compound and may also be referred to as a reactive or non-reactive diluent. The term "reactive" means that it contains at least one functional group that can react with the alkoxysilane functional group of the silylated polymer of composition U during mixing of compositions U and V. For example, polyols, tackifying resins, and polyol esters are non-reactive compounds. For example, organosilanes and mono- or disilylated polymers are reactive compounds.

[0163] The use of reactive compound (E1) in composition V advantageously makes it possible to better control the performance of the adhesive composition obtained after mixing compositions U and V.

[0164] Polyol (E1-1): According to one embodiment, compound (E1) is a polyol selected from the group consisting of polyether polyols, polyester polyols, polytetrahydrofuran polyols, polyacrylate polyols, polycarbonate polyols, polyether carbonate polyols, polyester carbonate polyols, polyacetal polyols, poly(ester amide) polyols, polythioether polyols, polyolefin polyols, and mixtures thereof, and compound (E1) is preferably selected from polyether polyols, polyester polyols, and mixtures thereof.

[0165] In the context of the present invention, the term "polyol" refers to any linear or branched, cyclic or acyclic, saturated or unsaturated, aromatic or aliphatic hydrocarbon-based compound containing at least two hydroxyl (OH) functional groups. Polyols may be substituted with functional groups and / or contain one or more divalent groups selected from ether (-O-) and carboxyl (-C(=O)O- or -OC(=O)-) groups.

[0166] The polyol may be selected from diols, triols, and mixtures thereof.

[0167] According to one embodiment, compound (E1) has an I concentration ranging from 5 to 500 mg KOH / g, preferably from 5 to 250 mg KOH / g, preferentially from 6 to 50 mg KOH / g and in particular from 10 to 28 mg KOH / g. OH The polyol is selected from the group consisting of polyols having the formula:

[0168] Polyol Hydroxyl Number I OHrepresents the number of hydroxyl functional groups per gram of polyol, expressed in the form of the equivalent milligrams of potassium hydroxide (KOH) used in the determination of hydroxyl functional groups, and is determined experimentally by titration according to standard ISO 14900:2001. For polyol mixtures, I OH Also, the known I of each polyol OH It can also be calculated from the values ​​of the components and their respective weight contents in the aforementioned mixture.

[0169] Polyacetal polyols can be prepared, for example, by the reaction of a glycol (e.g., diethylene glycol) with formaldehyde. Polyacetals can also be prepared by the polymerization of cyclic acetals.

[0170] The polyolefin polyols may be butadiene homopolymers and copolymers having hydroxyl end groups.

[0171] The polycarbonate polyol may be obtained by reacting at least one diol containing 2 to 10 carbon atoms (e.g., 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, or tetraethylene glycol) with at least one diaryl carbonate containing 3 to 20 carbon atoms (e.g., diphenyl carbonate) or with phosgene.

[0172] The polyester polyol is - Polyester polyols derived from natural products such as castor oil, polyester diols derived from the polymerization of at least one diol with at least one lactone ring (preferably containing 3 to 7 carbon atoms) with ring opening, such as polycaprolactone polyols; Polyester polyols resulting from condensation, at least one dicarboxylic acid or its corresponding anhydride or diester, at least one diol, Polyester polyols resulting from the condensation between It can be either of the following.

[0173] The dicarboxylic acids that can be used to synthesize the polyester polyols preferably contain from 3 to 40 carbon atoms, preferentially from 6 to 10 carbon atoms.

[0174] Preferably, the dicarboxylic acids that can be used in the synthesis of the above-mentioned polyester polyols are selected from the group consisting of malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, 1,3- or 1,4-cyclohexanedicarboxylic acid, 3-methyl-1,5-pentanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, azelaic acid, sebacic acid, and mixtures thereof.

[0175] The diols that can be used in the synthesis of the polyester polyols may be selected from polyalkylenediols, polyoxyalkylenediols and mixtures thereof, the alkylene (saturated) moieties of these compounds being preferably linear or branched and containing preferably 2 to 40 carbon atoms, preferentially 2 to 8 carbon atoms.

[0176] Preferably, the diol that can be used in the synthesis of the polyester polyol is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, 1,6-hexanediol, butanediol, propylene glycol, dipropylene glycol, tetraethylene glycol, tripropylene glycol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, and mixtures thereof.

[0177] Among the polyester polyols, mention may be made, for example, of the following products with a hydroxyl functionality equal to 2: Tone® 0240 (available from Union Carbide): has a number average molecular weight of approximately 2000 Da and is OH caprolactone, which has a melting point of about 50°C and is equal to 56); Dynacoll® 7381 (available from Evonik): Number average molecular weight of approximately 3500 Da, OH is equal to 30 and has a melting point of approximately 65°C); Dynacoll® 7360 (available from Evonik): obtained from the condensation of adipic acid with hexanediol, with a number average molecular weight of approximately 3500 Da; OH is equal to 30 and has a melting point of approximately 55°C); Dynacoll® 7330 (available from Evonik): Number average molecular weight is approximately 3500 Da; OH is equal to 30 and has a melting point of approximately 85°C); Dynacoll® 7363 (available from Evonik): obtained from the condensation of adipic acid with hexanediol, with a number average molecular weight of approximately 5500 Da; OH is equal to 21 and has a melting point of approximately 57°C).

[0178] In the context of the present invention, the term "hydroxyl functionality of a polyester polyol" means the average number of hydroxyl functional groups per mole of polyester polyol.

[0179] The polyester polyol may be amorphous or crystalline, preferably amorphous.

[0180] Preferably, the polyester polyol is obtained by the condensation reaction between adipic acid and a mixture of neopentyl glycol, ethylene glycol and 1,6-hexanediol, or between adipic acid and 3-methyl-1,5-pentanediol.

[0181] The polyether polyols may be oxyalkyl derivatives of diols (e.g., ethylene glycol, propylene glycol, neopentyl glycol), triols (e.g., glycerol, trimethylolpropane, hexane-1,2,6 triol), or tetraols (e.g., pentaerythritol). Polyether polyols can be obtained by polymerization of the corresponding alkylene oxides in the presence of a catalyst.

[0182] Preferably, the polyether polyol is a polypropylene glycol (PPG), in particular having a hydroxyl functionality equal to 2 or 3 and preferably having a polydispersity index ranging from 1 to 1.6, preferably from 1 to 1.4.

[0183] In the context of the present invention, the term "polydispersity index" means the ratio of the weight average molecular weight to the number average molecular weight, determined in particular by GPC.

[0184] Among the polypropylene glycols with a hydroxyl functionality equal to 2, mention may be made of: Voranol® EP1900: Number average molecular weight of approximately 4008 g / mol, hydroxyl number I OH bifunctional PPG with a pH equal to 28 mg KOH / g; Acclaim® 8200: Number average molecular weight of 8016 g / mol, hydroxyl number I OH bifunctional PPG with a pH equal to 14 mg KOH / g; Acclaim® 12200: Number average molecular weight of 11,222 g / mol, hydroxyl number I OH bifunctional PPG with a pH equal to 10 mg KOH / g; Acclaim® 18200: Number average molecular weight of 17265 g / mol, hydroxyl number I OH Difunctional PPG with a pH equal to 6.5 mg KOH / g.

[0185] Among the polypropylene glycols with a hydroxyl functionality equal to 3, mention may be made of: Voranol® CP755: Number average molecular weight of approximately 710 g / mol, hydroxyl number I OH trifunctional PPG with a pH equal to 237 mg KOH / g; Voranol® CP3355: Number average molecular weight of approximately 3544 g / mol, hydroxyl number I OH trifunctional PPG with a pH equal to 47.5 mg KOH / g; Acclaim® 6300: Number average molecular weight of approximately 5948 g / mol, hydroxyl number I OH Trifunctional PPG with a pH equal to 28.3 mg KOH / g.

[0186] In the context of the present invention, the term "hydroxyl functionality of a polyether polyol" means the average number of hydroxyl functional groups per mole of polyether polyol.

[0187] According to a preferred embodiment, the polyether polyol has a functionality equal to 2 and a number average molecular weight preferably in the range from 3000 to 20000 g / mol, preferentially from 4000 to 19000 g / mol, in particular from 5000 to 15000 g / mol and advantageously from 7000 to 13000 g / mol.

[0188] According to a preferred embodiment, the polyether polyol has a functionality equal to 3 and a number average molecular weight preferably in the range from 500 to 20 000 g / mol, preferentially from 500 to 10 000 g / mol, in particular from 500 to 5 000 g / mol and advantageously from 500 to 4 000 g / mol.

[0189] Organosilanes (E1-2): According to one embodiment, compound (E1) is selected from organosilanes, in particular from the group consisting of aminosilanes, mercaptosilanes, glycidoxysilanes, vinylsilanes, epoxysilanes, (meth)acrylatesilanes, glycoxysilanes, anhydrosilanes, and mixtures thereof.

[0190] In the context of the present invention, the term "organosilane" means a compound containing an organic group attached to a Si atom by a Si-C bond.

[0191] Preferably, the organosilane contains at least one, preferably at least two, or alternatively three, alkoxy groups attached to the Si atom by Si—O bonds.

[0192] The organosilane can be monomeric or oligomeric.

[0193] Among organosilanes, for example, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane (available, for example, from Momentive under the name Silquest® A1110), 3-glycidoxypropyltrimethoxysilane (available, for example, from Momentive under the name Silquest® A-187), 3-mercaptopropyltrimethoxysilane (available, for example, from Momentive under the name Silquest® A-189), mercaptopropyltriethoxysilane, mercaptopropylmethyldimethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxy ... Examples of suitable silanes include hydroxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane (available, for example, from Momentive under the name Silquest® A-174NT), tris(3-trimethoxysilylpropyl)isocyanurate (available, for example, from Momentive under the name Silquest® Y-11597), bis(3-triethoxysilylpropyl)polysulfide (available, for example, from Momentive under the name Silquest® A-1289), bis(3-triethoxysilyl)disulfide (available, for example, from Momentive under the name Silquest® A-1589), β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (available, for example, from Momentive under the name Silquest® A-186), bis(triethoxysilyl)ethane (available, for example, from Momentive under the name Silquest® Y-9805), gamma-isocyanatopropyltrimethoxysilane (available, for example, from Momentive under the name Silquest® A-Link35), (methacryloxymethyl)tri(m)ethoxysilane (available, for example, from Wacker under the name Geniosil® XL33 or Geniosil® XL36), (methacryloxymethyl)(m)ethyldimethoxysilane (available, for example, from Wacker under the name Geniosil® XL32 or Geniosil® XL34), (isocyanatomethyl)methyldimethoxysilane (available, for example, from Wacker under the name Geniosil® XL35 or Geniosil® XL36), Examples of suitable silanes include those available from Wacker under the name Geniosil® XL42 (available from Wacker under the name Geniosil® XL43), (isocyanatomethyl)trimethoxysilane (available from Wacker under the name Geniosil® XL43), (methacryloxymethyl)methyldiethoxysilane, 2-acryloxyethylmethyldimethoxysilane, 2-methacryloxyethyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 2-acryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltripropoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriacetoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and glycosylated silanes derived from the reaction of 2-methyl-1,3-propanediol with vinyltrimethoxysilane, and mixtures thereof.

[0194] Tackifying resin (E1-3): According to one embodiment, compound (E1) is chosen in particular from tackifying resins having a number average molecular weight ranging from 100 g / mol to 6000 g / mol, preferably from 300 g / mol to 4000 g / mol.

[0195] The tackifying resin may be, for example, any silylated (B) or non-silylated (C) tackifying resin as defined above.

[0196] Polyol ester (E1-4): According to one embodiment, compound (E1) is chosen from polyol esters, which can be prepared, for example, by esterification of a polyol, for example of a tetraol, for example of pentaerythritol.

[0197] An example of a polyol ester is pentaerythritol tetravalerate.

[0198] Monosilylated or disilylated polymers (E1-5): According to one embodiment, compound (E1) is chosen from monosilylated polymers, disilylated polymers and mixtures thereof.

[0199] The disilylated polymer may be any of those previously described in the definition of silylated polymer (A), in particular of the polymers of formula (II'), (III') or (IV') above.

[0200] Preferably, the monosilylated polymer comprises a group of formula (I) above.

[0201] Polyetheramine (E1-6): In the context of the present invention, unless otherwise stated, the term "polyetheramine" refers to a compound comprising a polyether backbone and at least one amine functional group (alternatively at least two amine functional groups).

[0202] According to one embodiment, compound (E1) is chosen from polyetheramines.

[0203] Among the polyetheramines, mention may be made in particular of the Jeffamine products sold by Huntsman, such as the polyetherdiamine of formula HN-CH-CH-O-CH-CH-O-CH-CH-NH (available, for example, under the trade name Jeffamine® ED148 from Huntsman) with a primary alkalinity of 13.49 meq / g.

[0204] Silsesquioxane resin (E1-7): According to one embodiment, compound (E1) is chosen from the silsesquioxane resins mentioned above.

[0205] Polyvinyl ether compounds (E1-8): According to yet another embodiment, compound (E1) is chosen from the polyvinyl ether resins mentioned above.

[0206] II.2.1.2 Compound (E2): The compound (E) contained in composition V may also be a compound (E2) (denoted by the term "non-reactive diluent") having a vapor pressure of 0.08 kPa or more at 20°C.

[0207] Compound (E2) preferably has a vapor pressure at 20° C. of between 0.08 kPa and 13 kPa, preferentially between 0.08 kPa and 8 kPa, and even more preferentially between 0.1 kPa and 5 kPa.

[0208] Compound (E2) is chosen from alcohols such as isopropanol, isobutanol, butanol, methanol, 2-butoxyethanol and mixtures thereof.

[0209] Advantageously, compound (E2) evaporates during application of the adhesive composition to the support layer.

[0210] According to a preferred embodiment, when the crosslinking catalyst contained in composition V is the above-mentioned acid derivative, compound (E) is compound (E1).

[0211] According to a preferred embodiment, when the crosslinking catalyst is not an acid derivative as described above, compound (E) is compound (E1) or (E2).

[0212] Preferably, when the catalyst is an inorganic acid, such as orthophosphoric acid, compound (E) is not selected from polyols.

[0213] II.2.2. Content by weight of the components of composition V: Composition V generally comprises: 0.01% to 100% by weight, preferably 1% to 90% by weight, preferentially 5% to 90%, more preferentially 10% to 80%, even more preferentially 10% to 70%, advantageously 20% to 60%, in particular 20% to 50% of a crosslinking catalyst (D), and 0% to 99.99% by weight, preferably 10% to 99%, for example 10% to 95%, preferentially 20% to 90%, even more preferentially 30% to 80%, advantageously 40% to 70% of compound (E), These weight percentages are based on the total weight of Composition V.

[0214] In the context of the present invention, unless otherwise stated, the mass content of the catalyst is the content of solids (called activator).

[0215] II.2.3. Optional additives contained in composition V: Composition V may comprise water. The water may come from the compounds of Composition V and / or may be added to Composition V.

[0216] The water content in composition V may range from 0.05% to 50% by weight, preferably from 0.1% to 30% by weight, preferentially from 0.5% to 15% by weight, advantageously from 0.5% to 10% by weight and in particular from 0.5% to 5% by weight, relative to the total weight of composition V.

[0217] According to one embodiment, composition V comprises water, in particular when compound (E) comprises at least one compound (E1) which is neither an organosilane nor a monosilylated or disilylated polymer.

[0218] According to one embodiment, composition V comprises water, especially when compound (E) is compound (E2).

[0219] According to one embodiment, composition V is water-free. The term "water-free" means that the water content is 200 ppm or less, preferably 100 ppm or less, for example 50 ppm or less, or even 20 ppm or less. Preferably, composition V is water-free when compound (E) comprises at least one compound (E1) selected from organosilanes, monosilylated or disilylated polymers, and mixtures thereof.

[0220] The water content can be measured, for example, by the Karl Fischer method according to standard ISO760.

[0221] The water contained in Composition V may be in liquid or gaseous form, or may be encapsulated, absorbed, or included in the chemical structure of components that can subsequently make the water liberated and available.

[0222] The water may come from one or more components of Composition V above.

[0223] Composition V may contain at least one additive selected from the aforementioned group and the group consisting of moisture absorbers, plasticizers, antioxidants, pigments, colorants, adhesion promoters, UV stabilizers and fillers.

[0224] Composition V may contain a compound selected from NHF, BuNF, HF, BF, EtNSF, HSOF, polymers of the type polyether polyol PPG containing at least one fluoro group, compounds having at least one Si-F bond, and mixtures thereof.

[0225] Composition V can be prepared by mixing all of the components of the aforementioned compositions, regardless of the order in which the various components are incorporated. Multiple components of Composition V may be combined and then mixed with other components of Composition V described above.

[0226] The mixing can be carried out at a temperature ranging from 23°C to 200°C.

[0227] II.2.4. Characteristics of composition V: According to one embodiment, composition V has a viscosity at 23°C in the range from 3 mPa·s to 50000 mPa·s, preferably from 600 mPa·s to 25000 mPa·s, preferentially from 800 mPa·s to 16000 mPa·s, advantageously from 1000 mPa·s to 5000 mPa·s, for example from 1100 mPa·s to 2000 mPa·s, in particular from 1200 mPa·s to 1500 mPa·s.

[0228] According to one embodiment, composition V has a viscosity in the range of 50 mPa·s to 500000 mPa·s, preferably 600 mPa·s to 100000 mPa·s, preferentially 1200 mPa·s to 50000 mPa·s, advantageously 1200 mPa·s to 10000 mPa·s, for example 1200 mPa·s to 5000 mPa·s, at a temperature in the range of 40°C to 160°C, preferably 60°C to 100°C.

[0229] The components of composition V are preferably selected so that composition V is advantageously stable over time. (V final -V initial ) / V initial is not more than 30%, preferably not more than 20%, preferentially not more than 10%: ·V final is the viscosity of composition V measured at 23°C after heating at 40°C for 28 days, ·V initial is the viscosity of the composition V measured at 23°C before heating.

[0230] The crosslinking catalyst (D) is advantageously selected to be soluble in the above compound (E) (and, where appropriate, the silsesquioxane resin) and to form a homogeneous composition V, in particular on storage at 23° C. or after heating at 40° C. for 28 days. The term “homogeneous” means that there is no phase separation (flocculation or sedimentation) between the catalyst and compound C in composition V.

[0231] II.3. Other characteristics of the multi-component adhesive composition: According to a preferred variant of said multi-component adhesive composition, the weight of composition V divided by the total weight of said multi-component (preferably two-component) adhesive composition is in the range of 0.02% to 40%, preferably 0.05% to 40%, preferentially 0.05% to 20%, more preferentially 0.05% to 15%.

[0232] The catalyst contained in the multi-component adhesive composition is the crosslinking catalyst (D) contained in composition V.

[0233] The total content of the crosslinking catalyst (D) in the multi-component (preferably two-component) adhesive composition according to the present invention may be in the range of 0.01% to 10% by weight, preferably 0.01% to 5% by weight, preferentially 0.05% to 4% by weight, advantageously 0.1% to 3% by weight, and in particular 0.5% to 2% by weight, based on the total weight of the two-component adhesive composition.

[0234] According to one embodiment, when the crosslinking catalyst (D) is selected from acids and their derivatives, the total content of crosslinking catalyst (D) in the multi-component (preferably two-component) adhesive composition is less than or equal to 1%, preferably less than or equal to 0.5%, advantageously less than or equal to 0.2%, preferentially less than or equal to 0.1%, or even less than or equal to 0.05%, relative to the total weight of said composition.

[0235] Preferably, the adhesive composition according to the invention is packaged in a kit comprising at least two separate compartments, a first compartment for composition U and a second compartment for composition V, and optionally other compartments for further compositions.

[0236] kit: The present invention also relates to a kit comprising at least the above-described composition U and composition V in two separate compartments. The compartments may be, for example, drums, cartridges, or bags. If the multi-component adhesive composition comprises other components, the other components are contained in other compartments of the kit.

[0237] Self-adhesive articles: A subject of the present invention is also a self-adhesive article comprising a substrate coated with a self-adhesive layer, characterized in that said self-adhesive layer is composed of an adhesive composition according to the invention, in crosslinked form.

[0238] For purposes of the present invention, the term "self-adhesive article" includes any article that can be adhesively bonded to a surface solely by the action of pressure, either manually or by a device, without the use of additional glue or adhesive.

[0239] The self-adhesive article is a pressure-sensitive self-adhesive article.

[0240] A support layer coated with a self-adhesive layer is also referred to by the term "self-adhesive support".

[0241] These articles are specifically intended to be applied to a surface to bond, hold, adhere, or simply fix and present shapes, logos, images, or information. They can be used in many fields, such as the medical field, clothing, packaging, motor vehicles (e.g., logo application, lettering, interior soundproofing, interior trim, interior bonding), or construction (e.g., for sound and heat insulation, window assembly). Depending on the end use, these articles can be fashioned, for example, in the form of tapes (industrial tapes, tapes for DIY or job site fastening, single-sided or double-sided tapes, etc.), or in the form of labels, bandages, wound dressings, patches, or graphic films.

[0242] According to one embodiment, the self-adhesive article is a self-adhesive multi-layer system, in particular a self-adhesive label or tape, which may be single-sided or double-sided.

[0243] The support layer may be made of any type of rigid or flexible support, such as foam, felt, nonwoven fabric, plastic, membrane, paper, or a film of one or more layers of polymeric material, particularly a non-stick protective paper or plastic film.

[0244] The support layer is made of a material selected from, for example, polyolefins (polyethylenes such as high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and linear very low-density polyethylene, polypropylene, and polybutylene), polystyrene, natural or synthetic rubber, vinyl copolymers (such as polyvinyl chloride, which may be plasticized or unplasticized, and poly(vinyl acetate)), olefin-based 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. The support layer is preferably based on acrylic polymers, polyethylene (PE), polypropylene (PP), which may be oriented, unoriented, or oriented by biaxial stretching, polyimide, polyurethane, polyester (such as polyethylene terephthalate (PET)), or paper.

[0245] According to one embodiment, the self-adhesive article obtained from the adhesive composition according to the invention comprises a permanent backing layer coated with an adhesive layer, which is preferably also coated with a non-stick protective paper or plastic film, preferably siliconized.

[0246] According to another embodiment, the self-adhesive article obtained from the adhesive composition according to the invention comprises a non-permanent support layer, preferably composed of a first, silicone-treated, non-stick protective paper or plastic film, which is coated with an adhesive layer and may itself be coated with a second, non-stick protective paper or plastic film. This embodiment is particularly suitable for adhesively assembling windows, more particularly for assembling rigid panels composed of double- or triple-paned windows with a window frame. According to this embodiment, the non-permanent support layer is intended to be removed by the user when applying the self-adhesive article for the purpose of assembling the window.

[0247] As an alternative to a non-stick protective film, the back side of the permanent backing layer that is not coated with an adhesive layer may be provided with a non-stick surface, for example a silicone treated protective layer.

[0248] According to another embodiment, both sides of the permanent support layer are coated with adhesive compositions, which may be the same or different, at least one of the two adhesive compositions being the adhesive composition according to the invention, advantageously leading to the production of a "double-sided" tape.

[0249] Preferably, the support layer has a thickness in the range of 10 microns to 50 mm, more preferably in the range of 10 microns to 20 mm, preferably in the range of 20 microns to 10 mm, more preferably in the range of 20 microns to 1 mm.

[0250] In certain cases, it may be necessary to provide a surface treatment on the support layer to improve adhesion of the adhesive layer during the coating process on the support layer.

[0251] Therefore, the self-adhesive article according to the present invention can bond two substrates. The substrate to which the self-adhesive article is intended to be applied (called the "substrate to be adhered") can be flexible or rigid. In particular, the substrate to be adhered can have the same flexibility as the support layer described above, for example, so that it can be wound and packaged in the form of a reel as described above.

[0252] Alternatively, the substrate may be rigid, i.e., the substrate cannot be wound and packaged, for example, in the form of a reel, as described above. The substrate may be selected, for example, from concrete, paper, polyolefin-type substrates, glass, ceramics and metals (especially aluminum).

[0253] In the self-adhesive article according to the invention, the self-adhesive layer which is made of the adhesive composition according to the invention in a crosslinked state and which covers the support layer can have a thickness which ranges widely, preferably from 10 μm to 5000 μm.

[0254] For self-adhesive labels, thicknesses in the range of 10 μm to 100 μm, preferably 20 μm to 50 μm, are more particularly preferred, while for self-adhesive tapes, a wider range of thicknesses from 3 μm to 5000 μm is often found.

[0255] According to one embodiment, the self-adhesive article also comprises a protective non-stick layer (release liner).

[0256] According to one embodiment, the aforementioned non-stick layer is applied to the adhesive layer after crosslinking of the adhesive composition.

[0257] The support layer may be coated on one of its two sides (the back side not coated with the adhesive layer) with a protective non-stick layer, such as a silicone film, so that after the self-adhesive article has been rolled up onto itself, it can be unrolled without any problems, since the adhesive layer will not adhere to the silicone-treated surface.

[0258] Method for producing a self-adhesive article: The subject of the present invention is also a method for producing a self-adhesive article as defined above, said method comprising the steps of: (a) preheating the thermally crosslinkable adhesive composition defined above to a temperature of 40°C to 130°C; (b) applying the composition onto a support surface by coating; (c) crosslinking the composition by heating to a temperature in the range of 50°C to 200°C; and then (d) laminating or transferring a layer of the crosslinked adhesive composition onto a support layer or onto a non-stick protective film; The present invention is characterized by comprising:

[0259] When the thermally crosslinkable adhesive composition is a one-component composition as in the first embodiment described in subsection I, said one-component composition is preheated as in step (a), then applied to a support surface as in step (b), and finally crosslinked as in step (c).

[0260] When the thermally crosslinkable adhesive composition is a multi-component composition, preferably a two-component composition, as per the second embodiment described in subdivision II, the preheating as per step (a) relates to each component of the composition as described above.

[0261] Preferably, the preheating concerns each of the two components U and V of the two-part composition.

[0262] The preheating step (a) is then followed by a step (a') of mixing compositions U and V at a temperature ranging from 40°C to 130°C, and the composition obtained from the mixture formed is then applied to a support surface as per step (b) and then crosslinked as per step (c).

[0263] For the purposes of the present invention, the term "bearing surface" is understood to mean a belt conveyor coated with a non-stick layer, or a non-stick protective film ("release liner"), or a support layer.

[0264] When the carrier surface is a non-stick protective film, the method for producing a self-adhesive article according to the present invention may include a step (d) of transferring the crosslinked adhesive layer onto a support layer.

[0265] When the bearing surface is a support layer or a non-stick protective film, the method for producing a self-adhesive article according to the present invention may also include step (d) of laminating an adhesive layer onto the non-stick protective film.

[0266] According to a preferred variant of the invention, step (d) of the above-described method consists in transferring the crosslinked adhesive layer onto a flexible support layer (which may be a plastic film) after cooling the crosslinked adhesive layer to a temperature below the degradation temperature or softening point of the material constituting the support layer.

[0267] According to one embodiment, the method for producing a self-adhesive article according to the invention also comprises step (e) of coating a second layer of the adhesive composition according to the invention onto a support layer, followed by step (f) of crosslinking the adhesive composition coated in step (e) by heating to a temperature in the range of 20° C. to 200° C. According to this embodiment, a double-sided self-adhesive article is obtained.

[0268] The coating step (b) may be carried out by known coating equipment, such as a lip nozzle or a curtain nozzle, or by a roller. In the coating step (b), the weight per unit area is 10 g / m 2 ~5000g / m 2 Adhesive compositions in the range of

[0269] The weight per unit area of ​​the adhesive composition required for the production of self-adhesive labels is 10 to 100 g / m 2 , preferably 20 to 50 g / m 2 The weight per unit area required for the production of self-adhesive tapes can range from 3 to 5000 g / m 2 , preferably 15 to 250 g / m 2The temperature may vary within a wider range.

[0270] According to one embodiment, the coated adhesive composition is also subjected during step (c) to a humid atmosphere characterized by a moisture level, and in particular a temperature at which water molecules are in the gaseous state. 3 It is processed in a gaseous environment where there is between 10 and 200 g per unit area.

[0271] Preferably, the humid atmosphere is an atmosphere in which 2% to 100% of the molecules are water molecules, preferably 3% to 50%, and more preferably 3% to 10% of the molecules are water molecules.

[0272] Moisture content is expressed as the percentage of water per unit volume and corresponds to the number of water molecules divided by the total number of molecules in a unit volume. Due to the linearity of this scale, moisture content is easily measured and monitored, for example, using a PID (proportional-integral-derivative) control monitor. The weight percentage can be calculated by multiplying the percentage of water molecules relative to the total number of molecules by the coefficient 0.622. General information on moisture content in various environments can be found in International Steam Tables - Properties of Water and Steam based on the Industrial Formulation IAPWS-IF97 by W. Wagner et al.

[0273] The thermal crosslinking step has the effect of generating, under the action of atmospheric moisture, siloxane-type bonds between the polymer chains of the adhesive composition that have hydrolyzable alkoxysilane end groups, which lead to the formation of a three-dimensional polymer network. The adhesive composition crosslinked in this way is a pressure-sensitive adhesive that imparts, in particular, the desired adhesion and tack to the substrate on which it is coated.

[0274] Preferably, the coating is applied uniformly onto the support layer or onto the non-stick protective layer, but the coating may also be conformed to the desired shape of the final self-adhesive article.

[0275] According to one embodiment, the adhesive composition is coated on at least a portion of both sides of the support layer, and when both sides of the support layer are coated, the adhesive composition may be the same or different on both sides, and the weight per unit area may be the same or different on both sides.

[0276] According to one embodiment of the present invention, the self-adhesive article comprises an adhesive layer provided on at least a portion of one side or at least a portion of both sides of a support layer, and the adhesive layer may be coated with a non-stick protective layer. According to one embodiment, the self-adhesive article comprises two non-stick protective layers provided on the two adhesive layers, respectively. In this case, the two protective layers may be made of the same or different materials and / or may have the same or different thicknesses.

[0277] According to a preferred variant of the method for producing a self-adhesive article according to the invention, step (b) of applying by coating onto a bearing surface, for example onto a support layer (96), using a multi-component adhesive composition as defined above, is carried out by means of an installation (20) for the hot application of the adhesive composition as described above, which comprises: a nozzle (50) for applying the multi-component adhesive composition; a line (88a) for supplying a composition U contained in a multi-component adhesive composition to be applied in fluid form; a line (66a) for supplying a composition V contained in a multi-component adhesive composition to be applied in fluid form; a line (88) for supplying the nozzle (50) with a multi-component adhesive composition to be applied in fluid form, and a mixer (30) for mixing at least components U and V of the multi-component adhesive composition; Equipped with The aforementioned step (b) supplying at least a composition U to the supply line (88a); supplying at least composition V to the supply line (66a); Mixing at least the components U and V of the multi-component composition using a mixer (30); Hot-applying the mixed multi-component adhesive composition (80) to a support layer or a bearing surface using an application nozzle (50); Includes.

[0278] The mixer may be a static mixer or a dynamic mixer.

[0279] Preferably, the static or dynamic mixer should be temperature controllable. Preferably, the mixer (30) is advantageously a dynamic mixer, which allows for high shear mixing and better homogeneity of the adhesive composition resulting from mixing at least components U and V of the multi-part composition.

[0280] The mixer (30) can be disposed between the supply line (88) and at least the line (88a) for supplying composition U and the line (66a) for supplying composition V, and can enable uniform mixing of the components constituting the multi-component (particularly two-component) adhesive composition.

[0281] The method according to the present invention includes mixing at least components U and V of the multi-part composition using a mixer 30. The mixing step may involve mixing components U and V, optionally with one or more additional components of the multi-part composition.

[0282] The installation may comprise heating means (44) suitable for placement in a reservoir (82) containing composition U or composition V or another additional component of the multi-component composition, in order to heat said compositions to a pumping temperature, preferably at least composition U, to a pumping temperature of between 50°C and 140°C, preferably between 80°C and 120°C, more preferentially between 90°C and 110°C.

[0283] Preferably, the multi-component adhesive composition is applied (after mixing at least compositions U and V) at a temperature of 50°C to 140°C, preferably 50°C to 120°C, more preferentially 60°C to 90°C.

[0284] FIG. 1 shows a schematic diagram of one embodiment of an installation 20 suitable for carrying out the method for producing self-adhesive articles according to the present invention.

[0285] According to one embodiment, composition V (66) is separated from composition U (68) as a result of at least two-way feeding to a mixer (30) located between the lines feeding at least compositions U (88a) and V (66a) on the one hand, and the line feeding the multi-component adhesive composition to be applied on the other hand (88). In other words, the mixer (30) is of the in-line type, allowing for a homogeneous mixing process of the separately fed compositions (66) and (68). The injection of composition V (66) into composition U (68) is carried out in the mixer (30), as shown in FIG. 1, for example, allowing for immediate mixing of these compositions.

[0286] The various components that make up the multi-component adhesive composition according to the present invention may be completely separated, i.e., each component is fed separately to the hot coating equipment (20). In particular, the injection of components U (68), V (66) and optional additional components of the multi-component adhesive composition takes place in the mixer (30).

[0287] In the installation according to the invention, composition U (68) can be heated in storage tank (82) by heating means (44) without causing crosslinking of composition U (68), since composition U (68) is separated from composition V (66) containing at least a crosslinking catalyst. Heating in storage tank (82) in the form of a drum makes it possible, in particular, to reduce the viscosity of composition U (68), facilitating pumping within installation (20) using pump (46) or the like, before contacting composition U (68) with the separated composition V (66).

[0288] The heating means (44), preferably a hot plate, contributes in particular to bringing composition U (68) to an application temperature, which corresponds in particular to a temperature at which the adhesive composition to be applied has a sufficiently low viscosity to allow application, or in other words coating, of the mixed multi-component adhesive composition (80) onto surface (96).

[0289] Specifically, after mixing components V (66) and U (68), a multi-component adhesive composition (80) is formed, which can be hot-applied to a substrate (96) using an application nozzle (50). Accordingly, the temperature for applying the multi-component adhesive composition (80) can correspond to a temperature at which the viscosity of the multi-component adhesive composition is 50 Pa·s or less, preferably 10 Pa·s or less. By way of example, the multi-component adhesive composition (80) can have a viscosity of 5±1 Pa·s at an application temperature ranging from 60°C to 120°C. After applying the multi-component adhesive composition (80) to a surface (96), the coated substrate (98) can be subjected to a controlled temperature and, optionally, a controlled moisture level to allow crosslinking of the multi-component adhesive composition.

[0290] The controlled temperature can be achieved using an oven or a chamber. The controlled temperature corresponds to the crosslinking temperature of the multi-component adhesive composition (80), and is, for example, 50°C to 200°C, preferably 80°C to 160°C, and particularly 100°C to 150°C.

[0291] Similarly, composition V (66) itself can be heated before mixing with composition U (68) without risking crosslinking before mixing, as can any of the components of the multi-part composition of the present invention.

[0292] The separate compositions V (66) and U (68) are all heated before being mixed together, which allows these components to be brought to application temperature without the risk of crosslinking prior to being mixed together in the mixer (30).

[0293] The self-adhesive article according to the invention is a bonding method which is also the subject of the present invention, comprising the following steps: a) removing a non-stick protective layer, if present; b) applying a self-adhesive article to one surface of the product; c) applying pressure to said article; The method can be finally used in a method comprising the steps of:

[0294] In step b), the self-adhesive article is applied so that the self-adhesive part of the article (formed by the self-adhesive layer) faces the surface of the product.

[0295] According to embodiments in which the self-adhesive article is a double-sided article, the bonding method also includes a step in which the second surface of the product is applied to the article bonded to the first surface of the product, or the article bonded to the first surface of the product is applied to the second surface of the product.

[0296] The following examples are given purely as illustrations of the present invention and should not be construed as limiting its scope. [Example]

[0297] The following examples are given purely as illustrations of the present invention and should not be construed as limiting its scope.

[0298] Example A (reference): Thermally crosslinkable adhesive composition based on Geniosil® STP-E30 without silylated tackifying resin A1. Preparation of the composition: The composition shown in Table 1 is prepared by first introducing the non-silylated tackifying resin Dertophene® T105 into a glass reactor under vacuum and heating to about 160° C. Then, once the resin is completely melted, Geniosil® STP-E30 is added.

[0299] The mixture is stirred under vacuum for 15 minutes and then cooled to 90° C. The catalyst (K-KAT® 5218) is then introduced with vigorous stirring. The mixture is kept under vacuum with stirring for an additional 10 minutes.

[0300] A2.60g / m 2 Preparation of a PET support layer coated with a crosslinking composition at a weight per unit area equal to: A rectangular sheet of polyethylene terephthalate (PET) with a thickness of 50 μm and dimensions of 20 cm x 40 cm is used as the support layer.

[0301] The composition obtained in accordance with item A1 is preheated to a temperature close to 100° C. and introduced into a cartridge from which drops are extruded, the drops falling close to the edge parallel to the width of the sheet.

[0302] The composition contained in this drop is then spread over the entire surface of the sheet, so as to obtain a uniform layer of substantially constant thickness. This is done using a film spreader (also known as a film applicator), moving from one edge of the sheet to the opposite edge. In this way, a coating of 60 g / m2 per unit area is obtained. 2 A layer of the composition equivalent to a weight of about 60 μm is deposited, which means a thickness of about 60 μm.

[0303] The PET sheet thus coated is then placed in an oven at 140°C and in a humid atmosphere (relative humidity 2.4%) for 5 minutes to crosslink the composition, before being laminated onto a protective non-stick layer consisting of a rectangular silicone-treated film sheet of the same dimensions.

[0304] The resulting triple layer is subjected to the following tests.

[0305] A3. 180° peel test on stainless steel plate: Adhesion is assessed by a 180° peel test against a stainless steel plate, as described in FINAT Method No. 1 in the FINAT Technical Handbook, 6th edition, 2001. FINAT stands for International Federation of Self-Adhesive Label Manufacturers and Converters. The principle of this test is as follows:

[0306] Test pieces in the form of rectangular strips (25 mm x 150 mm) are cut out from the triple layer previously obtained.

[0307] After preparation, the specimens are stored for 7 days in an atmosphere at 23°C and 50% relative humidity. Then, more than two-thirds of the specimen's length (after removing the corresponding portion of the protective non-stick layer) is attached to a substrate consisting of a stainless steel plate. The resulting assembly is left at room temperature for 20 minutes. The stack is then placed in a tensile testing device. This device allows the strip to be peeled or pulled apart at an angle of 180°, starting from the end of the rectangular strip that remains free, at a separation speed of 300 mm per minute. The testing device measures the force required to peel the strip under these conditions.

[0308] The corresponding results, expressed in N / 25mm, are shown in Table 1.

[0309] A4. 180° peel test against ABS (acrylonitrile butadiene styrene polymer) plate: The stainless steel plate is replaced by an ABS plate, and the evaluation of adhesion strength by the above test is repeated.

[0310] The corresponding results, also expressed in N / 25mm, are shown in Table 1.

[0311] A5.Shear strength time at 125℃: This test is carried out to evaluate the retention of cohesion of the adhesive seal formed by the self-adhesive PET support layer obtained in A2 when attached to a substrate at elevated temperatures. The test determines the static shear strength time of the aforementioned adhesive seals at 125°C in accordance with FINAT method No. 8. The principle is as follows:

[0312] Test specimens in the form of rectangular strips (25 mm x 75 mm) are cut out from the triple layer obtained in A2 and stored at room temperature (23°C, humidity 50%) for 7 days.

[0313] After removing all protective non-stick layers, a square section with a side length of 25 mm located at the end of the adhesive strip is attached to a polished stainless steel plate.

[0314] The test plate thus obtained is placed in a substantially vertical position in an oven at 125°C using suitable supports, so that the 50 mm long part of the strip that is not bonded by adhesive is located below the test plate. After thermal equilibration, the part of the strip that remains free is connected to a 1 kg weight and the entire apparatus is kept in the aforementioned oven at 125°C for the duration of the test.

[0315] Under the influence of the weight, the adhesive seal attaching the strip to the test plate is subjected to shear stresses, and in order to control these stresses more effectively, the test plate is actually mounted at an angle of 2° to the vertical.

[0316] The time taken for the strip to fall off the test plate after failure of the adhesive seal under the influence of this stress is recorded.

[0317] The results are expressed in hours and are shown in Table 1.

[0318] A6. Static shear failure temperature (SAFT): This test is carried out to further evaluate the retention of cohesion of the adhesive seal formed by the self-adhesive PET support layer obtained in A2 at elevated temperatures when attached to a substrate.

[0319] This test determines the temperature at which an adhesive seal fails under static shear and is also known as the Shear Adhesion Failure Temperature (SAFT) test.

[0320] The procedure described in test A5 above is repeated, except that an oven with an initial temperature of 30°C is used both for the initial thermal equilibration of the test plate and for placing the entire apparatus, with a mass of 1 kg, in the oven. The oven is programmed to increase the temperature at a rate of 0.5°C per minute (Finat 8 standard).

[0321] The temperature at which the strip falls off the test plate as a result of failure of the adhesive seal is recorded.

[0322] The temperatures are expressed in °C and are shown in Table 1.

[0323] Examples 1 and 2 (according to the invention): Thermally crosslinkable adhesive compositions based on Geniosil® STP-E30 containing silylated tackifying resins Example A is repeated using the compositions shown in Table 1.

[0324] These compositions are prepared as per protocol A1, except that the silylated tackifying resin Mkorez® HRR-100 is incorporated simultaneously with the non-silylated tackifying resin.

[0325] The results of the peel test, 125°C shear strength test and SAFT test are also shown in Table 1. TIFF2023091776000016.tif74170

[0326] The results of the 180° peel test are very similar to those of Example A (both steel and ABS plates), but the self-adhesive PET substrates made with the compositions of Examples 1 and 2 show a significant increase in SAFT temperature (by at least 25°C) and a more than four-fold increase in shear strength time at 125°C.

[0327] Thus, these results demonstrate that the compositions of Examples 1 and 2 advantageously allow for the formation of adhesive seals with significantly improved cohesive strength at elevated temperatures while retaining adhesive strength.

Claims

1. a polymer (A) containing at least one hydrolyzable alkoxysilane group, a silylated tackifying resin (B) selected from the group consisting of silylated copolymer resins (B') and (B"), The resin (B') repeating units (B'1) derived from silylated olefin monomers, in particular silylated (meth)acrylate monomers; and - Contains one or more repeating units (B'2) derived from an olefin monomer or diolefin monomer obtained by cracking naphtha and contained in a petroleum fraction selected from a C5 fraction, a C9 fraction, dicyclopentadiene, and mixtures thereof; the silylated tackifying resin (B), wherein the resin (B″) is obtained by hydrogenating the resin (B′); a non-silylated tackifying resin (C) that is compatible with the polymer (A); a crosslinking catalyst (D), A thermally crosslinkable adhesive composition comprising:

2. The polymer (A) has the formula (I): -Si(R ４ ) ｐ (OR ５ ) ３－ｐ (I) (In the formula, ・R ４ represents a linear or branched alkyl group containing 1 to 4 carbon atoms, R ４ When more than one group is present, these groups may be the same or different; ・R ５ represents a linear or branched alkyl group containing 1 to 4 carbon atoms, R ５ When multiple groups are present, these groups may be the same or different, and two OR ５ groups may be attached to the same ring, p is an integer equal to 0, 1 or 2), 2. The adhesive composition according to claim 1, characterized in that it contains at least one, preferably at least two hydrolyzable groups of the formula:

3. 3. Adhesive composition according to claim 2, characterized in that in the hydrolyzable alkoxysilane group of formula (I), p is equal to 1 or 2, more preferentially p is equal to 1.

4. The polymer (A) is represented by formula (II), (III) or (IV): (In the formula, P represents a saturated or unsaturated, linear or branched polymeric group, which may contain one or more heteroatoms such as oxygen, nitrogen, sulfur or silicon, and which preferably has a number average molar mass ranging from 500 g / mol to 60 000 g / mol, for example from 1 000 g / mol to 30 000 g / mol, more particularly from 15 000 g / mol to 50 000 g / mol and more preferentially from 15 000 g / mol to 30 000 g / mol, the number average molar mass being determined by size exclusion chromatography using polystyrene standards, ・R １ represents a divalent hydrocarbon-based group containing 5 to 15 carbon atoms, which may be aromatic or aliphatic, linear, branched or cyclic; ・R ３ represents a linear or branched divalent alkylene group containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, X is -NH-, -NR ７ - or -S-, ・R ７ represents a straight or branched chain alkyl group containing 1 to 20 carbon atoms and optionally containing one or more heteroatoms; f is an integer in the range of 1 to 6, preferably in the range of 2 to 5, preferably in the range of 2 to 4, more preferably in the range of 2 to 3); 3. The adhesive composition according to claim 2, wherein the adhesive composition corresponds to any one of the following:

5. The polymer (A) has the formula (II′), (III′) or (IV′): (In the formula, ・R ２ represents a saturated or unsaturated, linear or branched, divalent hydrocarbon-based group, which may contain one or more heteroatoms, such as oxygen, nitrogen, sulfur or silicon, and which preferably has a number average molar mass ranging from 500 g / mol to 60 000 g / mol, for example from 1 000 g / mol to 30 000 g / mol, more particularly from 15 000 g / mol to 50 000 g / mol and more preferentially from 15 000 g / mol to 30 000 g / mol, the number average molar mass being determined by size exclusion chromatography using polystyrene standards, n is an integer equal to or greater than 0), 5. The adhesive composition according to claim 4, characterized in that it corresponds to any one of the following:

6. The polymer (A) has the formula (II′) where n is equal to 0 and R ２ 6. The adhesive composition according to claim 5, wherein the silylated polymer is a divalent group derived from a polyether.

7. 2. The adhesive composition according to claim 1, wherein the silylated tackifying resin (B) is a silylated copolymer resin (B').

8. 2. The adhesive composition of claim 1, wherein the silylated olefin from which the repeating unit (B'1) is derived contains at least one alkoxysilyl group.

9. The adhesive composition according to claim 1, wherein the silylated copolymer resin (B') contains, in addition to the repeating units (B'1) and (B'2), a repeating unit derived from a monomer selected from a cyclic anhydride, a C3 to C20 α-olefin, or a styrene derivative.

10. 2. The adhesive composition of claim 1, wherein the silylated copolymer resin (B) has a number average molecular weight (Mn) of between 100 and 5000 g / mol, the number average molecular weight being measured by size exclusion chromatography using a polystyrene standard.

11. The non-silylated tackifying resin (C) is (i) Resins obtained by polymerization of terpene hydrocarbons and phenols in the presence of a Friedel-Crafts catalyst; (ii) resins obtained by a process comprising the polymerization of α-methylstyrene, said process optionally comprising reaction with phenols; (iii) naturally occurring rosins and their derivatives, which are hydrogenated, dimerized, polymerized, or esterified with monoalcohols or polyols; (iv) Resins obtained by hydrogenation, polymerization or copolymerization (with aromatic hydrocarbons) of mixtures of unsaturated aliphatic hydrocarbons containing 5, 9 or 10 carbon atoms obtained from petroleum fractions; (v) terpene resins, (vi) copolymers based on natural terpenes, or (vii) an acrylic resin having a viscosity at 100°C measured by a Brookfield viscometer method of less than 100 Pa s; The adhesive composition according to claim 1, characterized in that it is selected from the group consisting of:

12. The weight percentages are based on the total weight of the one-component composition. 10% to 90% by weight of a polymer (A) containing at least one hydrolyzable alkoxysilane group; 3% to 50% by weight of a silylated tackifying resin (B); 15% to 80% by weight of a non-silylated tackifying resin (C); 0.01% to 10% by weight of a crosslinking catalyst (D); 2. The adhesive composition according to claim 1, which is in the form of a one-component composition comprising:

13. 2. The adhesive composition of claim 1, Composition U, polymer (A), and silylated tackifying resin (B), non-silylated tackifying resin (C), A composition U comprising: Composition V, a crosslinking catalyst (D), and optionally at least one compound (E), a compound (E1) having a number average molecular weight of 300 g / mol to 100,000 g / mol, as measured by size exclusion chromatography using polystyrene standards, and at least one compound (E) selected from compounds (E2) having a vapor pressure at 20°C of 0.08 kPa or more; and a composition V comprising: An adhesive composition, characterized in that it is in the form of a multi-component composition comprising:

14. A self-adhesive article comprising a support layer coated with a self-adhesive layer, characterized in that the self-adhesive layer is made of an adhesive composition according to any one of claims 1 to 13 in a crosslinked state.

15. 15. A method for making the self-adhesive article of claim 14, comprising: (a) preheating the thermally crosslinkable adhesive composition according to any one of claims 1 to 12 to a temperature between 40°C and 130°C; (b) applying the composition onto a support surface by coating; (c) crosslinking the composition by heating to a temperature in the range of 50°C to 200°C; and then (d) laminating or transferring a layer of the crosslinked adhesive composition onto a support layer or onto a non-stick protective film; A method comprising:

16. 16. The method of claim 15, 14. A method for applying a multi-component adhesive composition according to claim 13, characterized in that step (b) of applying the adhesive composition by coating onto a support surface is carried out using equipment (20) for the hot application of the adhesive composition, the equipment comprising: a nozzle (50) for applying the multi-component adhesive composition; a line (88a) for supplying a composition U contained in a multi-component adhesive composition to be applied in fluid form; a line (66a) for supplying composition V contained in a multi-component adhesive composition to be applied in fluid form; a line (88) for supplying the nozzle (50) with a multi-component adhesive composition to be applied in fluid form; and a mixer (30) for mixing at least components U and V of the multi-component adhesive composition; Equipped with The step (b) - supplying at least composition U to the supply line (88a); - feeding at least composition V into the feed line (66a); Mixing at least composition U and composition V of the multi-component composition using a mixer (30); and - hot application of the mixed multi-component adhesive composition (80) to a support layer or bearing surface using an application nozzle (50); A method comprising:

17. a) removing the non-stick protective layer, if present; b) applying a self-adhesive article to one surface of the product; c) applying pressure to the article; 15. A method of bonding using the self-adhesive article of claim 14, comprising:

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