Isocyanate-functionalized organosilanes as adhesion promoters in sealant and primer compositions

Abstract

The present invention relates to a method for sealing a substrate, which comprises optionally a step (1) of applying a primer composition and necessarily a step (2) of applying a sealant composition, the sealant composition being obtainable by mixing together components (A) and (B) of a 2K sealing system, comprising in (A) a thiol group containing polymer component (a1) and in (B) a component (b) suitable for curing the sealant composition by at least partially inducing a chemical transformation of the thiol group of component (a1), comprising at least one hydrolyzable group X, at least one NCO group and at least one carboxyl group X, ... The present invention relates to a process in which a spacer unit comprising a moiety MS containing at least one sulfur atom and arranged between the X and NCO groups is at least present as component (a2) in the sealant composition applied in step (2) if no step is performed, or at least present as a component in the primer composition applied in step (1) if step (1) is performed, to sealed substrates obtainable by this process, to a process for the use of said organosilane component to improve adhesion, to sealant compositions used in step (2), to such 2K sealing systems, and to the organosilane component itself.

Description

[Technical Field]

[0001] The present invention relates to a method for sealing a substrate, which optionally includes the step (1) of applying a primer composition and necessarily includes the step (2) of applying a sealant composition, wherein the sealant composition obtained by mixing components (A) and (B) of a 2K sealing system comprises (A) containing thiol groups containing polymer components (a1), and (B) containing components (b) suitable for curing the sealant composition by at least partially inducing the chemical conversion of the thiol groups of component (a1), wherein the components include at least one hydrolyzable group X, at least one NCO group, and at least The present invention relates to a method by which a spacer unit comprising a partial MS containing at least one sulfur atom and positioned between X and NCO groups is present as a component (a2) in the sealant composition applied in step (2) when the step is not performed, or as a component in the primer composition applied in step (1) when step (1) is performed, a sealed substrate that can be obtained by this method, a method of using the organosilane component to improve adhesion, a sealant composition used in step (2), such a 2K sealing system, and the organosilane component itself. [Background technology]

[0002] Sealant has a wide range of applications. This is relevant, for example, in the aerospace sector, but it is also widely used in the automotive sector. Sealant is further used for sealing building elements, connecting metal plates to existing structures such as aircraft segments, and / or for corrosion protection where the corrosion protection layer of metal elements has been damaged or removed, for example, in the area of ​​a hole. It may also serve a temporary transport function, for example, during the transport of structures that are to be attached and which subsequently require permanent support connection elements.

[0003] Silanes, particularly organosilanes, are known to act as adhesion promoters for a variety of substrates, especially polar surfaces such as metals and glass, as well as ceramics and polymers. Because silanes are compatible with many chemical systems, they can be used in a wide variety of materials, including sealant materials. Compared to other chemically different adhesion promoters such as phenolic resins or polyolefins, silanes typically do not significantly affect the pH environment within the material in which they are used. This is particularly important in applications where ambient conditions, such as a constant pH environment, are crucial to the curing properties of the material, such as in the case of polysulfide and / or polythioether-based sealants. A further advantage of using silanes as adhesion promoters in such materials is that they can be used in conjunction with other adhesion promoters, such as organometallic compounds like polyolefins and / or titanates. Typically, silanes used for this purpose have aliphatic and / or aromatic spacers (linkers) bonded to functional groups such as amino, thiol, hydroxyl, or epoxide groups, depending on the system in which the silane is used.

[0004] EP3023429A1 discloses specific alicyclic OH-functionalized silanes for use as adhesion promoters and crosslinking agents. CN104937054A discloses adhesion improvers which are reaction products of isocyanate-functionalized silanes with further silanes having functional groups reactive to isocyanate groups. WO2006 / 050915A1 discloses a method for coating metal surfaces using an aqueous composition containing at least one Si-containing component such as an organosilane. US2019 / 0119539A1 discloses compositions including combinations of different silanes, such as aminohydrocarbylalkoxysilanes, alkenylalkoxysilanes, and mercaptohydrocarbylalkoxysilanes. These compositions are useful as water-based primers.

[0005] WO03 / 054049A1 relates to isocyanate-functional silanes prepared, for example, from the reaction of an amino-functional organosilane with a low-volatility polyisocyanate, for use as an adhesion promoter in polyurethane compositions. WO02 / 051954A2 relates to 2K coating compositions containing compounds containing an alkoxysilane group and a succinyl urea group.

[0006] However, sealant systems known in the prior art do not always provide sufficient adhesive properties, and silanes known in the prior art do not always provide sufficient adhesion-promoting properties, particularly in the field of sealants for the aerospace industry, and in sealant compositions containing polymers having thiol groups, such as polysulfide and / or polythioether-based sealant compositions, especially for a variety of different substrates. Furthermore, when silanes known from the prior art are incorporated into sealant compositions containing the aforementioned polymers having thiol groups, they often result in relatively poor processing properties, particularly with respect to undesirable viscosity changes, such as an undesirable decrease in viscosity over time. These unfavorable properties are often particularly observed when amino group-containing silanes, such as those disclosed in WO03 / 054049A1 and WO02 / 051954A2, are used either directly or derived from amino group-containing precursor silanes.

[0007] Functionalization of polymers with silanes is further known from, for example, US2016 / 0319068A1, EP3293217A1 and DE19821356A1, and US2018 / 112026A1. US2016 / 0319068A1 discloses polyester polyols containing esterification units, which are modified with amino-functionalized silanes. These polymers can be used as adhesion promoters for urethane systems. EP3293217A1 discloses silane-modified copolymers as adhesion improvers. US2018 / 112026A1 discloses modified polyisocyanates that can be obtained by reacting a 1,5-diisocyanatopentane-based polyisocyanate with an organosilane such as an amino-functionalized organosilane. DE19821356A1 discloses the preparation and use of silane-modified butyl rubber, for which mercapto-functionalized silanes are used. However, the use of such modified polymers disclosed in these documents inevitably requires a process of pre-modifying the polymer before use in materials such as sealants, which is undesirable, at least from an economic standpoint. Furthermore, pre-modifying the polymer limits the end user's flexibility in terms of the degree of freedom in formulating material compositions. As far as DE19821356A1 is concerned, the rubber / polymer disclosed herein exhibits poor resistance to non-polar solvents, at least to mineral oil-based fuels, and is therefore unsuitable for use as sealants, particularly aircraft sealants. This is especially unfavorable for sealants used for sealing the inside of aircraft fuel tanks.

[0008] Therefore, there is a need for sealing systems, sealing compositions, and sealing methods for substrates that do not exhibit the aforementioned drawbacks, especially when the substrate is a substrate used in the aerospace industry, such as fuel tanks. In particular, there is a demand for sealing systems and compositions containing thiol group-containing polymers that provide excellent adhesive properties to various different substrates and surfaces, and for widely available adhesion promoters that are suitable for such systems and compositions, are easy and economical to incorporate into these systems and compositions without imparting processing properties. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] EP3023429A1 [Patent Document 2] CN104937054A [Patent Document 3] WO2006 / 050915A1 [Patent Document 4] US2019 / 0119539A1 [Patent Document 5] WO03 / 054049A1 [Patent Document 6] WO02 / 051954A2 [Patent Document 7] US2016 / 0319068A1 [Patent Document 8] EP3293217A1 [Patent Document 9] DE19821356A1 [Patent Document 10] US2018 / 112026A1 [Overview of the project] [Problems that the invention aims to solve]

[0010] Therefore, the object underlying the present invention is to provide a sealing system and a sealing composition containing a thiol group-containing polymer, and a method for sealing a substrate using these systems and compositions, which, in particular, when the substrate is a substrate used in the aircraft industry such as a fuel tank, not only provides excellent adhesion properties to various different substrates and surfaces, but also enables the use of a widely available adhesion promoter suitable for such systems and compositions, the adhesion promoter being such that its incorporation into these systems and compositions is easy and economically advantageous and shows no drawbacks as regards the processability of these systems and compositions. At the same time, the sealed interior of the substrate, for example the sealed interior of a fuel tank, should exhibit excellent resistance to liquid media, particularly fuels.

Means for Solving the Problems

[0011] This object is solved by the subject matter of the claims of the present application and its preferred embodiments disclosed herein, i.e., by the subject matter described herein.

[0012] The first subject of the present invention is a method for sealing an optionally pre-coated substrate, comprising at least step (2) and optionally step (1), i.e., (1) a step of at least partially optionally applying a primer composition to the surface of an optionally pre-coated substrate to form at least a partial primer film on the surface, (2) a step of at least partially applying a sealant composition to the surface of an optionally pre-coated substrate if step (1) is not carried out, or on the primer film if step (1) is carried out, wherein the sealant composition is different from the primer composition optionally applied in step (1) and can be obtained by mixing the components of the sealing system with each other, and the sealing system is a two-component (2K) sealing system comprising two components (A) and (B) which are separate from each other. ​Component (A) of the sealing system comprises at least one polymer component (a1) containing two or more thiol groups selected from polyethers, polythioethers, polysulfides, polythioether-sulfide components and mixtures thereof, and Component (B) of the sealing system comprises at least one component (b) suitable for curing the sealant composition by at least partially inducing the chemical conversion of two or more thiol groups of component (a1), the following components, (i) at least one hydrolyzable group X, (ii) at least one isocyanate group, and (iii) a spacer unit disposed between at least one hydrolyzable group X and at least one isocyanate group, and containing at least one sulfur atom and at least one part( partial MS ) a spacer unit containing at least one organosilane component containing is at least present as component (a2) in component (A) of the sealing system used to prepare the sealant composition applied in step (2) when no optional step (1) is performed, or is at least present as a component in the primer composition applied in step (1) when step (1) is performed.

[0013] A further subject of the present invention is a sealed substrate obtainable by the method of the present invention.

[0014] A further subject of the present invention is a method of using the organosilane components as defined above and / or below, which, when incorporated into the primer composition as defined above and / or below, for example, the primer composition used in step (1) of the method of the present invention, or the sealant composition as defined above and / or below, for example, the sealant composition used in step (2) of the method of the present invention, in particular a component (A) of the sealing system used in the preparation of the sealant composition, is applied to at least a portion of the surface of a pre-coated substrate to improve the adhesion of the primer composition or sealant composition to the substrate.

[0015] Further subject matter of the present invention is a sealant composition as defined above and / or below, which can be obtained by mixing components (A) and (B) of the sealing system as defined above and / or below, wherein component (A) of the sealing system comprises at least one organosilane component as defined above and / or below.

[0016] A further subject of the present invention is a two-component (2K) sealing system comprising components (A) and (B) as defined above and / or below, wherein component (A) of the sealing system comprises at least one organosilane component as defined above and / or below.

[0017] A further subject of the present invention is the organosilane components defined above and / or below, which are optionally incorporated into the primer composition defined above and / or below. Thus, a further subject of the present invention is the primer composition defined above and / or below, which comprises at least the organosilane components defined above and / or below.

[0018] Particularly surprising, the aforementioned organosilane components were found to represent widely usable adhesion promoters when incorporated into sealant and / or primer compositions, especially when used in the method of the present invention. These adhesion promoters were found to be readily incorporated into various sealant compositions and also readily incorporated into suitable primer compositions applied before the actual sealant composition is applied to the substrate surface. Excellent adhesion to various substrates, including metal substrates and pre-coated substrates, such as metal substrates having at least one organic coating layer, was found to be achievable, and the adhesion promoters were found to be effectively chemically incorporated into the polymer matrix and network formed after application. Even more surprisingly, the organosilane components were found to function as linkers between the substrate surface and the applied primer / sealant.

[0019] Furthermore, and particularly surprisingly, it was found that one or more hydrolyzable groups X of the organosilane components, such as alkoxy / silyl ether groups, mediate the adhesion of the organosilane components to the surface to which they are applied, especially by reacting with OH groups in condensation reactions, and simultaneously, at least one NCO group of the organosilane components can react with a thiol group of component (a1) of the sealant composition. In particular, it was found that the remarkable improvement in adhesion in the sealant and / or primer materials used is a result of at least one partial MS present in the spacer unit of the organosilane components. The presence of at least one partial MS is assumed to have an additional adhesion-promoting effect based on the formation of hydrogen bonds. It has been found that the use of conventional organosilanes, such as (3-glycidyloxypropyl)trimethoxysilane and (3-mercaptopropyl)-trimethoxysilane, and organosilanes without a partial MS containing at least one sulfur atom, such as organosilanes prepared from diisocyanates, and amino-functional silane precursors, such as bis[3-(trimethoxysilyl)propyl]amine, does not produce the desired effect of significantly improving adhesion.

[0020] Furthermore, surprisingly, it was found that the aforementioned organosilane components provide high flexibility and freedom in the formulation of sealant and primer compositions.

[0021] In particular, a pre-modification step that modifies any polymer component of the sealant composition is unnecessary to improve adhesion; instead, the aforementioned organosilane components can be simply incorporated into the various sealant compositions themselves.

[0022] Furthermore, surprisingly, sealant and primer compositions containing the aforementioned organosilane components are applicable particularly in the aircraft and aerospace fields, for example, as aircraft sealants, especially for sealing the inside of aircraft fuel tanks, and it has been found that the sealed corresponding substrates exhibit excellent resistance to liquid media, such as organic solvents and fuels, particularly non-polar solvents such as mineral oil-based fuels.

[0023] Furthermore, surprisingly, it was found that sealant and primer compositions containing the aforementioned organosilane components can provide sealed substrates exhibiting excellent physical and mechanical properties, such as tensile strength.

[0024] Finally, and surprisingly, the sealant and primer compositions containing the aforementioned organosilane components exhibited excellent processing properties, and in particular, they were found to have excellent viscosity properties, as no undesirable viscosity changes, such as an undesirable decrease in viscosity, were observed during storage. [Modes for carrying out the invention]

[0025] In the meaning of the present invention, the term "comprising" preferably means "consisting of," for example, in relation to a sealant composition. For example, with respect to a sealant composition, in addition to all essential components present therein, one or more of the further optional components specified below may also be included. In each case, any component may be present in their preferred embodiments as specified below.

[0026] In each case, the wt% (mass%) proportion and amount of any of the following components present in each component of the sealing system shall be added to the total mass of each component up to 100% by mass. Similarly, in each case, the wt% (mass%) proportion and amount of any of the following components present in the sealant or primer composition shall be added to the total mass of each composition up to 100% by mass.

[0027] A method for sealing an arbitrarily pre-coated substrate. The first subject of the present invention is a method for encapsulating an optionally pre-coated substrate, comprising at least step (2) and optionally step (1).

[0028] At least one organosilane component is present as component (a2) in component (A) of the sealing system used to prepare the sealant composition applied in step (2) if step (1) is not performed, or as component (a2) in the primer composition applied in step (1) if step (1) is performed.

[0029] Preferably, the organosilane component is present in component (A) used to prepare the sealant composition applied in step (2), and not in the primer composition optionally applied in step (1). Alternatively, however also preferably, the organosilane component is not present in component (A) used to prepare the sealant composition applied in step (2), but is present in the primer composition applied in step (1). In this case, step (1) is necessarily performed. Further alternatively, however also preferably, the organosilane component is present in component (A) used to prepare the sealant composition applied in step (2), and is also present in the primer composition optionally applied in step (1).

[0030] Preferably, the organosilane component is present in at least component (A) used to prepare the sealant composition applied in step (2). In particular, the organosilane component is present in component (A) used to prepare the sealant composition applied in step (2) and is not present in the primer composition optionally applied in step (1).

[0031] Any step (1) and primer composition According to optional step (1), the primer composition is applied at least partially to the surface of an optionally pre-coated substrate to form at least partially a primer film on the surface. Any type of contact may be used to carry out step (1), such as dipping, brushing, and / or spraying.

[0032] Any step (1) is preferably performed using a 1K-compressed air support cartridge device equipped with a 1K-low pressure or 1K-high pressure supply system. Alternatively, it may be performed manually.

[0033] Step (1) is preferably carried out at a temperature in the range of 0 to 60°C, more preferably 5 to 45°C. In particular, no heating is performed.

[0034] Base material A suitable substrate is a metal substrate, but plastic substrates, such as polymer substrates and / or fiber-based composites, can also be used. A preferred substrate is one usable in the aerospace industry, for example, in fuel tanks. Preferably, the sealed surface in this case is the inner surface of the fuel tank.

[0035] Suitable metal substrates for use in the present invention are any conventionally used substrates known to those skilled in the art. Preferably, the substrates used in the present invention are metal substrates including steel substrates. However, aluminum and / or aluminum alloy substrates are most preferred.

[0036] Preferably, when the substrate is a plastic substrate, a thermoplastic polymer is used. Suitable polymers include polyesters, polyamides, polyolefins, such as polyethylene, polypropylene, polystyrene, polymethyl (meth)acrylate, polyethylene terephthalate, polybutylene terephthalate, polyvinylidene fluoride, polyvinyl chloride, polycarbonate, and polyvinyl acetate, as well as polybutadiene, polyacrylonitrile, polyacetal, polyacrylonitrile-ethylene-propylene-diene-styrene copolymer (A-EPDM), ASA (acrylonitrile-styrene-acrylic acid ester copolymer) and ABS (acrylonitrile-butadiene-styrene copolymer), polyetherimide, phenolic resin, urea resin, melamine resin, alkyd resin, epoxy resin, polyurethane including TPU, polyether ketone, polyphenylene sulfide, polyether, polyvinyl alcohol, and mixtures thereof. Polycarbonate and poly(meth)acrylate are particularly preferred.

[0037] However, fiber-based composites, such as carbon fiber composites, may also be used as substrates.

[0038] The substrate used may be subjected to pretreatment leading to pre-coating. For example, steps (1) and (2) may be performed after applying an epoxy-based coating. Preferably, the substrate used has at least one preferably cured coating layer, such as an epoxy-based coating layer, before any steps (1) and (2) are performed.

[0039] Primer composition If step (1) is performed, at least one organosilane component is present as a component in the primer composition applied in step (1).

[0040] The organosilane component comprises (i) at least one hydrolyzable group X, (ii) at least one isocyanate group, and (iii) a spacer unit disposed between at least one hydrolyzable group X and at least one isocyanate group, wherein the spacer unit comprises the aforementioned at least one partial MS.

[0041] The organosilane components that may be present in the primer composition applied in step (1) are described in more detail below in relation to their optional presence as component (a2) in the sealant composition applied in step (2). This related disclosure regarding component (a2) also applies if the organosilane components are present in the primer composition.

[0042] Preferably, if the organosilane component is present as a component in the primer composition applied in step (1), it is present in an amount ranging from 0.10 to 15.0% by mass, preferably 0.20 to 12.5% ​​by mass, more preferably 0.30 to 10.0% by mass, even more preferably 0.40 to 7.5% by mass, and still more preferably 0.50 to 6.0% by mass, in each case relative to the total mass of the primer composition.

[0043] The primer composition is different from the sealant composition applied in step (2). The primer composition may preferably contain each of the components (a3) ​​to (a6) specified and discussed below in relation to the sealant composition. Preferably, the primer composition does not contain any component (a1), i.e., it does not contain any polymer components containing two or more thiol groups selected from polyethers, polythioethers, polysulfides, polythioether-sulfide components and mixtures thereof. Preferably, the primer composition does not contain any component (b), and in particular does not contain any components (b1) to (b4).

[0044] Preferably, the primer composition is an organic solvent (solubilistic, non-aqueous) based composition. The terms “solubilistic” or “non-aqueous” are understood, preferably in this respect for the purposes of the present invention, to mean that the organic solvent (or more) is present as a solvent (or more) and / or diluent (or more) as the main component of any solvent and / or diluent present in the primer composition. Preferably, the organic solvent (or more) is present in an amount of at least 35% by mass relative to the total mass of the primer composition. Solubilistic primer compositions preferably contain at least 40 or 45% by mass, more preferably at least 50 or 55% by mass, and very preferably at least 60 or 65% by mass of the organic solvent (or more), in each case relative to the total mass of the composition. Any conventional organic solvent known to those skilled in the art may be used as the organic solvent. The term “organic solvent” is known to those skilled in the art, in particular from Council Directive 1999 / 13 / EC of March 11, 1999. Examples of such organic solvents include heterocyclic, aliphatic, or aromatic hydrocarbons, monohydric or polyhydric alcohols, particularly ethanol and / or propanol, ethers, esters, ketones, xylene, butanol, ethyl glycol and butyl glycol, and their acetates, butyl diglycol, diethylene glycol dimethyl ether, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, acetone, isophorone, or mixtures thereof. The solvent composition is preferably water-free or essentially water-free. In this context, the term "essentially" preferably means that water is not intentionally added when preparing the composition.

[0045] Preferably, the primer composition contains at least 40 or 45% by mass, more preferably at least 50 or 55% by mass, and very preferably at least 60% by mass, of a non-alcoholic organic solvent fraction, in each case relative to the total mass of the composition. Most preferably, aromatic hydrocarbons such as xylene and / or aliphatic hydrocarbons such as gasoline ethers.

[0046] Preferably, the primer composition contains 0 to 30% by mass, more preferably 0 to 25% by mass, and very preferably 0 to 20% by mass, of an alcohol organic solvent fraction, in each case relative to the total mass of the composition. Most preferred are isopropyl alcohol, butanol, and / or methoxypropanol.

[0047] In addition to at least one organosilane component, the primer composition may contain, preferably, at least one further adhesion promoter, such as at least one additional organosilane different from the aforementioned organosilane components. Examples include, for example, (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)triethoxysilane, (3-glycidyloxypropyl)trimethoxysilane and / or (3-glycidyloxypropyl)triethoxysilane, vinyltrimethoxysilane. Additionally or alternatively, other adhesion promoters may be used, such as titanates, such as titanium acetylacetonate (TAA) and / or Ti-n-butanolate (TnBt) and / or isopropyl titanate, and, for example, zirconate. If present, additional adhesion promoters are preferably present in the primer composition in an amount of 0 to 7.5% by mass, more preferably 0 to 6.5% by mass, and particularly 0 to 5.0% by mass, relative to the total mass of the composition. Most preferably, at least one additional titanate and / or zirconate is present in one of the aforementioned amounts.

[0048] Step (2), sealant composition and sealing system According to step (2), if step (1) is not performed, the sealant composition is applied at least partially to the surface of the optionally pre-coated substrate, or if step (1) is performed, to the primer film.

[0049] To carry out step (2), any type of contact may be used, such as extrusion brush coating and / or spraying. Step (2) is preferably carried out at a temperature in the range of 0 to 60°C, more preferably 5 to 45°C. In particular, no heating is performed.

[0050] Preferably, step (2) is carried out using a 2K-compressed air support cartridge device equipped with a 2K-low pressure or 2K-high pressure supply system. Alternatively, it may be carried out manually.

[0051] Sealant composition and sealing system Unlike the primer composition optionally applied in step (1), the sealant composition can be obtained by mixing components of a sealing system with each other, wherein the sealing system is a two-component (2K) sealing system comprising, preferably comprising, two distinct components (A) and (B). For example, components (A) and (B) of the sealing system can be stored separately until they are mixed with each other to prepare the sealant composition.

[0052] Each of the two components (A) and (B) of the sealing system may contain water and / or at least one organic solvent. However, it is possible, and even preferable, that the organic solvent and / or water are not present in them.

[0053] The amount of water present in component (A) is preferably less than 3.0% by mass, more preferably less than 2.0% by mass, even more preferably less than 1.0% by mass, and still more preferably less than 0.5% by mass, and these amounts are relative to the total mass of component (A) in each case.

[0054] If at least one component (b1) and / or at least one component (b3) and / or at least one component (b4) are present in each case as component (b) in (B), the amount of water present in component (B) is preferably less than 3.0% by mass, more preferably less than 2.0% by mass, even more preferably less than 1.0% by mass, and still more preferably less than 0.5% by mass, and these are relative to the total mass of component (B) in each case. Components (b1), (b3) and (b4) are defined below.

[0055] If at least one component (b2), such as manganese dioxide, is present as component (b) in component (B), the amount of water present in component (B) is preferably less than 8.5% by mass, more preferably less than 7.5% by mass, even more preferably less than 7.0% by mass, and still more preferably less than 6.0% by mass, and these are relative to the total mass of component (B) in each case. Component (b2) is defined below.

[0056] If at least one organic solvent is present, and especially if the sealant composition is a sprayable composition, the organic solvent(s) are preferably present in an amount of up to 70% by mass or up to 65% by mass of the total mass of the sealant composition. In this case, the sealant composition preferably contains an organic solvent(s) fraction of up to 60% by mass of the total mass of the composition in each case. Alternatively, if at least one organic solvent is present, and especially if the sealant composition is not a sprayable composition, the organic solvent(s) are preferably present in an amount of up to 10% by mass of the total mass of the sealant composition. In this case, the sealant composition preferably contains an organic solvent(s) fraction of up to 7.5% by mass, more preferably up to 5% by mass, these amounts in each case relative to the total mass of the composition. Any conventional organic solvent known to those skilled in the art can be used as the organic solvent. The term “organic solvent” is known to those skilled in the art, in particular from Council Directive 1999 / 13 / EC of March 11, 1999. Examples of such organic solvents include heterocyclic, aliphatic, or aromatic hydrocarbons, monohydric or polyhydric alcohols, particularly ethanol and / or propanol, ethers, esters, ketones, xylene, butanol, ethyl glycol and butyl glycol, and their acetates, butyl diglycol, diethylene glycol dimethyl ether, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, acetone, isophorone, or mixtures thereof. The solvents present may be identical or different from each other.

[0057] Ingredient (A) Constituent component (a1) The sealing component (A) comprises at least one polymer component (a1) containing two or more thiol groups (mercapto groups), which is selected from polyethers, polythioethers, polysulfides, polythioether-sulfide components and mixtures thereof, preferably selected from polythioethers, polysulfides, polythioether-sulfide components and mixtures thereof, more preferably selected from polythioethers, polysulfide components and mixtures thereof, and particularly selected from polysulfide components.

[0058] The terms "polymer" and "polymer" are known to those skilled in the art, and for the purposes of this invention, they encompass polyadditives, polymers, and polycondensates. The term "polymer" includes both homopolymers and copolymers.

[0059] Due to the presence of the thiol group, (a1) is necessarily a sulfur atom-containing component. The thiol group of (a1) can react chemically with component (b) or a part thereof, for example, with its preferred functional group. For example, if component (b1) exists as component (b), its epoxide group can react to form at least one of a hydroxythioether, a hydroxythioether sulfide, and / or a hydroxysulfide moiety. For example, if component (b2) exists as component (b), for example, manganese oxide, an SS bond is formed.

[0060] Preferably, polymer component (a1) contains terminal thiol groups. Component (a1) may be branched or linear. Preferably, polymer component (a1) is liquid under ambient conditions (18-23°C, 50% relative humidity).

[0061] Suitable polymer components for use as (a1) are disclosed, for example, in US2004 / 097643A1, WO2016 / 128548A1, and WO2015 / 014876A2.

[0062] At least one polythioether, when used as (a1), is preferably a liquid (under ambient conditions) polythioether. The polythioether may contain up to about 50 mol% disulfide groups in its molecule. Each polymer may then be named polythioether sulfide. Preferred compounds of this type are described in WO2015 / 014876A2.

[0063] Preferably, polymer component (a1) has a number-average molecular weight in the range of 500 to 10000 g / mol, more preferably 900 to 5000 g / mol. Most preferably, in particular when (a1) is at least one polysulfide, the number-average molecular weight is in the range of 2500 to 6000 g / mol, more preferably 3300 to 5000 g / mol. Examples of such polymers include polysulfides commercially available as Thioplast® G131, Thioplast® G10, Thioplast® G12, Thiokol® LP32 and / or Thiokol® LP12. Polymer component (a1) having a number-average molecular weight in the range of 500 to 2500 g / mol, more preferably 700 to 2000 g / mol or 800 to 1200 g / mol is also preferred. In this case, examples of such polymers include polysulfides that are commercially available as Thiokol® LP3, Thioplast® G4, or Thioplast® G44.

[0064] Optionally, if at least two components (a1) having different number-average molecular weights are present in component (A): particularly long-chain polymers having number-average molecular weights in the range of 2500 to 6000 g / mol, particularly preferably 3300 to 5000 g / mol, may be present in addition to short-chain polymers having number-average molecular weights in the range of 500 to 2500 g / mol, particularly preferably 800 to 1500 g / mol. Optionally, at least one of the aforementioned short-chain polymers used in combination with at least one of the aforementioned long-chain polymers may be replaced by at least one polymer, oligomer, or monomer mercaptan, which is preferably solid or liquid, has three thiol groups, and has a number-average molecular weight in the range of 160 to 1200 g / mol. Alternatively, the mercaptan may be further added to the combination of at least one short-chain polymer and at least one long-chain polymer. Examples of such suitable mercaptans are thiocyanuric acid (1,3,5-triazine-2,4,6-trithiol) and benzene-1,3,5-trithiol (1,3,5-trimercaptobenzene). If the mercaptan used is nonpolymeric, it formally represents component (a6) of component (A). Preferably, if present, the at least one mercaptan is present in an amount ranging from 0.05 to 3.0% by mass relative to the total mass of component (A).

[0065] The sulfur-containing polymer component (a1) preferably has a mercaptan content referring to reactive SH- groups in the range of 0.5 to 10.0% by mass, more preferably 0.8 to 8.0% by mass, and particularly 1.2 to 7.0% by mass, based on the total mass of (a1). The mercaptan content can be determined by directly titrating the SH-terminated polymer with an iodine solution. The polymer is dissolved in a solvent mixture consisting of 40% by volume pyridine and 60% by volume benzene, and titrated with benzene-iodine solution while stirring until a faint yellow color remains.

[0066] Preferably, component (a1) has a total sulfur content in the range of 1 to 50% by mass, more preferably 5 to 45% by mass, and particularly 12 to 36% by mass.

[0067] Preferably, component (a1) has an average functional value in the range of 1.5 to 2.5 or 1.9 to 2.2 as the reactive terminal group of the mercapto group per molecule. The functional value represents the average number of mercapto groups per molecule. This is calculated as the ratio of molecular weight to equivalent weight and determined by NMR.

[0068] Preferably, component (a1) has an average glass transition temperature T in the range of -80 to -30°C or -60 to -40°C, measured in accordance with the AITM1-0003 Airbus Industrie test method of June 1995. g It holds.

[0069] Preferably, component (A) and the sealant composition itself do not contain any components containing (meth)acrylate groups (methacrylate groups and / or acrylate groups).

[0070] Preferably, component (a1) is present in the sealant composition obtained after mixing components (A) and (B) of the sealing system in an amount ranging from 50 to 95% by mass relative to the total mass of the sealant composition.

[0071] Component (a2) If step (1) is not performed, at least one organosilane component is present as component (a2) in component (A) of the sealing system used to prepare the sealant composition applied in step (2).

[0072] Preferably, the organosilane component is present in component (A) used to prepare the sealant composition applied in step (2) as component (a2) in an amount ranging from 0.05 to 10.0% by mass, more preferably 0.10 to 7.5% by mass, even more preferably 0.15 to 7.5% by mass, even more preferably 0.20 to 5.0% by mass, and even more preferably 0.25 to 4.5% by mass, in each case being relative to the total mass of component (A).

[0073] Preferably, the organosilane component is present in component (A) used to prepare the sealant composition applied in step (2) as component (a2) in an amount ranging from 0.02 to 7.5% by mass, preferably 0.10 to 7.0% by mass, more preferably 0.20 to 6.5% by mass, even more preferably 0.40 to 6.0% by mass, and still more preferably 0.50 to 5.5% by mass, in each case relating to the total mass of the sealant composition that can be obtained by mixing at least components (A) and (B) of the sealant system with each other.

[0074] The organosilane components include (i) at least one hydrolyzable group X, (ii) at least one isocyanate group, and (iii) a spacer unit positioned between at least one hydrolyzable group X and at least one isocyanate group, wherein the spacer unit includes at least one partial MS, and at least one partial MS includes at least one sulfur atom, and is preferably selected from the group consisting of thiocarbamate, thiourea, thioester, thioketo, thiourethane, and thioamide moieties. Each of the partial MS is preferably a divalent moiety present within the spacer unit. The term thiocarbamate preferably includes O-thiocarbamate (-OC(=S)-N-) and S-thiocarbamate (-S-(C=O)-N-). Preferably, the thiocarbamate moiety is an S-thiocarbamate moiety. Therefore, preferably, the partial MS contains at least one divalent -C(=X)- group, where X is a chalcogen atom selected from oxygen and sulfur. Preferably, the organosilane component contains exactly one partial MS.

[0075] Preferably, the organosilane components include at least two, preferably at least three, hydrolyzable groups X, where X is preferably an alkoxy group. The hydrolyzable groups X may be identical, or at least two of these groups may be different from each other. Preferably, the hydrolyzable groups X are alkoxy groups, particularly C1-C4 alkoxy groups. Particularly preferred are methoxy groups, ethoxy groups, n-propoxy groups, iso-propoxy groups, n-butoxy groups, sec-butoxy groups, and tert-butoxy groups. Most preferred are ethoxy groups and methoxy groups.

[0076] The organosilane components can be monomers, oligomers, or polymers. Preferably, they are nonpolymers, and more preferably monomers.

[0077] Preferably, at least one organosilane component has a number-average molecular weight in the range of 200 to 2000 g / mol, more preferably 250 to 1800 g / mol, even more preferably 300 to 1500 g / mol, and still more preferably 350 to 650 g / mol.

[0078] Preferably, the spacer unit, located between at least one hydrolyzable group X and at least one isocyanate group and containing at least one partial MS, is a trivalent or divalent, more preferably divalent, non-hydrolyzable organic residue, preferably an aliphatic including an alicyclic, a heteroaliphatic including a heteroalicyclic and / or aromatic including a heteroaromatic. The residues are preferably C1-C 20 Aliphatic group, C1~C 20 Heteroaliphatic group, C3~C 20 Alicyclic group, 3-20 membered heteroalicyclic group, 5-20 membered aryl or heteroaryl group, C 1~10 C3-C linked via aliphatic groups 20 Alicyclic group, C 1~10 A 3-20 member heteroalicyclic group linked via an aliphatic group, C 1~10The group is selected from those comprising 5-20 membered aryl or heteroaryl groups linked via aliphatic groups. Partial MSs are further positioned within each of these residues. Preferably, the spacer unit has a chain length that separates at least one hydrolyzable group X from at least six carbon and / or heteroatom at least one isocyanate group, and preferably contains at least one atom of partial MS in the chain.

[0079] Preferably, at least one portion MS of the spacer unit of the organosilane component represents a thiocarbamate and / or thiourea portion. Preferably, the thiocarbamate portion is an S-thiocarbamate portion.

[0080] Preferably, at least one organosilane component contains exactly one isocyanate group.

[0081] Preferably, at least one organosilane component can be preferably obtained from the reaction of at least one diisocyanate and / or polyisocyanate with at least one organosilane precursor containing at least one functional group reactive to an isocyanate group, wherein the at least one functional group reactive to an isocyanate group is preferably a thiol group. Diisocyanates have exactly two NCO- groups, while polyisocyanates have more than two NCO- groups. Suitable polyisocyanates are, for example, isocyanurates, such as isophorone diisocyanate (IPDI) and HMDI (hexamethylene diisocyanate) trimers. Suitable diisocyanates include aliphatic and alicyclic diisocyanates, such as isophorone diisocyanate (IPDI) and HMDI (hexamethylene diisocyanate), HMDI and / or IPDI urezion and / or allophanate, and hydrogenated MDI (methylenediphenyl isocyanate). Aromatic diisocyanates such as TDI and XDI are also suitable. However, the use of aliphatic and alicyclic diisocyanates is preferred.

[0082] Preferably, at least one organosilane constituent can preferably be obtained from the reaction of at least one diisocyanate with at least one organosilane precursor containing at least one functional group reactive with an isocyanate group, and the at least one functional group reactive with an isocyanate group is preferably a thiol group, especially when at least one diisocyanate and at least one organosilane precursor are each used in approximately equimolar amounts. Suitable diisocyanates are aliphatic and cycloaliphatic diisocyanates such as isophorone diisocyanate (IPDI) and HMDI (hexamethylene diisocyanate). Aromatic diisocyanates such as TDI and XDI are also suitable. However, the use of aliphatic and cycloaliphatic diisocyanates is preferred.

[0083] Preferably, at least one organosilane constituent can be obtained from the reaction of at least one preferably aliphatic and / or cycloaliphatic diisocyanate with at least one organosilane precursor containing at least one thiol group as a functional group reactive with an isocyanate group.

[0084] At least one organosilane precursor is preferably a monosilane, preferably having at least two, particularly preferably three hydrolyzable groups X, and / or at least one bis(silane), preferably having at least four, particularly preferably six hydrolyzable groups X.

[0085] Preferably, at least one organosilane precursor represented by general formula (I) and / or (II) is used in the reaction with at least one diisocyanate. Si(X) 4-y (R) y , (I), Si(X) 3-z (T) z -(RA)-Si(X) 3-z (T) z (II), In the case of general formula (I), in the formula, Each of X is independently a hydrolyzable group, preferably each independently of OC. 1~4 Selected from alkyl groups, The parameter y is an integer in the range of 1 to 3, but is at least 1, preferably exactly 1, and R is a non-hydrolyzable organic group, and at least one of the groups R comprises at least one functional group that is reactive to an isocyanate group, in particular at least one thiol group. And in the case of general formula (II), in the formula, X independently represents a hydrolyzable group in each case, preferably OC independently in each case. 1~4 - Selected from alkyl groups, RA represents a divalent, non-hydrolyzable organic group containing at least one functional group reactive to an isocyanate group, particularly at least one thiol group. The parameter z is an integer in the range of 0 to 3 in each case, preferably 0 in each case, and T is a non-hydrolyzable organic group distinct from group (RA), and preferably does not have a functional group that is reactive with isocyanate groups.

[0086] Any constituent components (a3) ​​and (a4) Component (A) may additionally contain at least one filler (a3) ​​and / or at least one pigment (a4).

[0087] The term “filler” is known to those skilled in the art, for example, from DIN 55943 (dated: October 2001). For the purposes of the present invention, the “filler” is preferably a substantially, preferably completely insoluble component in the surrounding medium, e.g., each of components (A) and (B) and the sealant composition, and is used in particular to adjust the viscosity and thixotropy of the components and the sealant composition, to adjust the specific density of the cured sealant, and / or to increase the mechanical properties of the cured sealant. In the sense of the present invention, the “filler” differs from the “pigment” in refractive index, with the refractive index of the filler being less than 1.7, while the refractive index of the pigment is 1.7 or greater. Preferably, the “filler” for the purposes of the present invention is an inorganic and / or organic filler. Examples of inorganic fillers are chalk and talcum. Examples of organic fillers are powders prepared from heat-resistant polymers such as polyamides, polysulfones, polyphenylene sulfides, polyether ketones, and polymer hollow spheres.

[0088] Preferably, the amount of filler present in component (A) of the sealing system is in the range of 0 to 55.0 mass%, more preferably in the range of 0 to 50.0 mass%, even more preferably in the range of 0 to 45.0 mass%, even more preferably in the range of 0 to 40.0 mass%, and more preferably in the range of 0 to 35.0 mass% or 0 to 30.0 mass%, particularly in the range of 0 to 25.0 mass%, and in each case these are relative to the total mass of component (A).

[0089] Preferably, the amount of any pigment present in component (A) of the sealing system is in the range of 0 to 35.0% by mass, more preferably 0 to 30.0% by mass, even more preferably 0 to 25.0% by mass, even more preferably 0 to 20.0% by mass, and even more preferably 0 to 15.0% by mass, and in each case these are relative to the total mass of component (A).

[0090] The term "pigment" is known to those skilled in the art, for example, from DIN 55943 (dated October 2001). In the sense of the present invention, "pigment" refers, preferably, to a component in the form of a powder or flake that is substantially, preferably completely insoluble in the surrounding medium, e.g., each of components (A) and (B) and the sealant composition, and which can be used as a colorant and / or pigment due to its magnetic, electrical and / or electromagnetic properties. Preferably, the "pigment" for the purposes of the present invention is an inorganic and / or organic pigment. An example of an inorganic pigment is titanium dioxide.

[0091] Any component (a5) Component (A) may, and preferably contains, at least one curing catalyst (a5) if component (B) of the sealing system contains at least one component (b1) as component (b) which contains two or more epoxide groups. Preferred curing catalysts are amines, particularly tertiary amines, amidines and / or guanidines. Examples include 1,4-diazabicyclo(2.2.2)octane, 1,5-diazabicyclo(4.3.0)non-5-ene (DBN), and 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU).

[0092] Further optional components (a6) The sealing component (A) may contain one or more arbitrary constituent components (a6).

[0093] Component (a6) may be a phosphorus-containing flame retardant, particularly a flame retardant such as at least one phosphate ester. When used, the flame retardant is preferably in liquid form (at 1 bar and 23°C). When the flame retardant is present in component (A), it is preferably present in (A) in an amount of 0.1 to 30.0% by mass, more preferably 1.0 to 25.0% by mass, and particularly 5.0 to 20.0% by mass, relative to the total mass of component (A).

[0094] Component (a6) may be a light stabilizer, particularly a UV stabilizer. Examples include sterically hindered amines (HALS: hindered amine light stabilizers). In principle, any light stabilizer commercially available from the Tinuvin® series or other manufacturers can be used. Liquid light stabilizers are preferred. If the light stabilizer is present in component (A), it is preferably present in (A) in an amount of 0.05 to 5.0% by mass, more preferably 0.1 to 3.5% by mass, and particularly 0.1 to 2.0% by mass, relative to the total mass of component (A).

[0095] Component (a6) may be an additional adhesion promoter other than the organosilane component described above. In particular, an organosilane different from component (a2) can be used. Examples include (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)triethoxysilane, (3-glycidyloxypropyl)trimethoxysilane and / or (3-glycidyloxypropyl)triethoxysilane, vinyltrimethoxysilane. Additionally or alternatively, other adhesion promoters, such as titanates and / or zirconates, such as titanium acetylacetonate (TAA) and / or Ti-n-butanolate (TnBt) and / or isopropyl titanate, may be used. If additional adhesion promoters are present in component (A), they are preferably present in component (A) in an amount of 0.05 to 5.0% by mass, more preferably 0.1 to 3.5% by mass, and particularly 0.1 to 2.0% by mass, relative to the total mass of component (A).

[0096] Component (a6) may be an additive selected from the group consisting of defoamers, rheological additives, plasticizers such as phthalates, and viscosity reducers, particularly non-reactive viscosity reducers, such as hydrocarbon mixtures based on naphthalene derivatives and / or indene-coumarone resin, tall oil and rapeseed methyl ester (biodiesel), diluents based on rapeseed oil and / or other esters, and mixtures of such additives. At least one additive is present in component (A), preferably in an amount of 0.05 to 40.0% by mass, more preferably 0.1 to 30.0% by mass, and particularly 0.1 to 20.0% by mass, relative to the total mass of component (A). Specifically, if at least one defoamer is present, its amount is preferably in the range of 0.1 to 2.5% by mass relative to the total mass of component (A). Specifically, if at least one reactive diluent is present, its amount is preferably in the range of 0.1 to 20.0% by mass, relative to the total mass of component (A). Specifically, if at least one rheological additive is present, its amount is preferably in the range of 0.1 to 5.0% by mass relative to the total mass of component (A). Specifically, if at least one plasticizer is present, its amount is preferably in the range of 0.1 to 2.5% by mass relative to the total mass of component (A). Specifically, if at least one viscosity reducing agent is present, its amount is preferably in the range of 0.1 to 20.0% by mass relative to the total mass of component (A).

[0097] As outlined above in relation to component (a1), component (a6) may further consist of three thiol groups and at least one nonpolymer mercaptan having a number-average molecular weight in the range of 160 to 800 g / mol. Preferably, if present, the at least one nonpolymer mercaptan is present as component (a6) in an amount in the range of 0.05 to 3.0% by mass, more preferably 0.05 to 1.5% by mass, in each case relative to the total mass of component (A).

[0098] Component (B) and constituent component (b) Component (B) of the sealing system comprises at least one component (b), which is suitable for curing the sealant composition by at least partially inducing a chemical transformation of two or more thiol groups of component (a1). In other words, component (b) or a part thereof can be chemically reacted with the thiol groups of component (a1). Thus, component (b) represents a curing agent. The resulting chemical transformation may be applied to any thiol groups of component (a1), or to only some of the thiol groups of component (a1). However, preferably, the chemical transformation is induced not only partially but substantially on all thiol groups of component (a1).

[0099] Preferably, at least one component (b) is selected from the group consisting of a component containing two or more epoxide groups (component (b1)), a component that is a metal oxide and / or metal peroxide, particularly manganese dioxide (component (b2)), a component that is an organic peroxide (component (b3)), a component containing two or more vinyl groups (component (b4)), and mixtures thereof. More preferably, it is selected from the group consisting of a component containing two or more epoxide groups (component (b1)), a component that is a metal oxide and / or metal peroxide, particularly manganese dioxide (component (b2)), and mixtures thereof, in particular, that component (b1) represents at least one component containing two or more epoxide groups, or that component (b2) represents at least one metal oxide and / or metal peroxide, particularly manganese dioxide.

[0100] Preferably, component (b) is present in component (B) of the sealing system used to prepare the sealant composition applied in step (2) in an amount ranging from 30 to 100% by mass relative to the total mass of component (B).

[0101] Constituent component (b1) Component (b1) comprises two or more epoxide groups. Preferably, the epoxide groups are present in (b1) as terminal groups. Component (b1) can be a monomer, oligomer, or polymer. Preferably, component (b1) is aliphatic and / or aromatic.

[0102] Preferably, component (b1) is present in component (B) of the sealing system used to prepare the sealant composition applied in step (2) in an amount ranging from 50 to 100% by mass relative to the total mass of component (B).

[0103] Preferably, (b1) has an epoxide functional value of 2.0 to 5.0, more preferably 2.0 to 3.0, and particularly 2.2 to 2.8.

[0104] Component (b1) is particularly selected from diglycidyl ethers of bisphenol A, diglycidyl ethers of bisphenol F, and aliphatic polyglycols and / or hydantoin epoxy derivatives. Epoxy-terminated polythioethers or polythioether sulfides and / or epoxidized polysulfides may also be used. Particularly preferred are at least one epoxy novolac resin (epoxidized phenol formaldehyde resin), preferably a crosslinked epoxy novolac resin. It is also possible to use more than component (b1), for example, bisphenol A / F epoxy resins or bisphenol F novolac resins, based on some of the above classes. Component (B) may additionally contain diluents, for example, to adjust viscosity and flexibility. Examples of diluents include 1,4-butanediol diglycidyl ether, 2-ethylhexyl-glycidyl ether, and 1,6-hexanediol diglycidyl ether.

[0105] Preferably, (b1) is an epoxide-terminated polysulfide polymer and / or polythioether polymer and / or polythioether sulfide polymer that does not have terminal mercapto groups, and functions as a curing agent by its two terminal epoxide groups. This polymer preferably exists as a liquid or high-viscosity polymer having an epoxy equivalent in the range of 200 to 800 g / eq.

[0106] Preferably, the epoxy (epoxide) equivalent of (b1) is in the range of 120 to 800 g / eq, particularly preferably in the range of 140 to 700 g / eq, and most preferably in the range of 170 to 400 g / eq.

[0107] Most particularly preferred are components (b1) based on a bisphenol A epoxy resin having an epoxy equivalent in the range of 170-200 g / eq, a bisphenol F resin having an epoxy equivalent in the range of 150-180 g / eq, and an epoxy novolac resin having an epoxy equivalent in the range of 160-220 g / eq.

[0108] Examples of suitable commercially available products include, for example, bisphenol F epoxy resins, e.g., DEN354 (Olin Epoxy); bisphenol A resins, e.g., DER336, DER331 (Olin Epoxy); bisphenol A / F epoxy resins, e.g., DER351, DER324, DER335 (Olin Epoxy); epoxy novolac resins, e.g., DEN431, DEN438, DEN439 (Olin Epoxy); epoxy-terminated prepolymers based on polysulfide and / or polythioethers, e.g., Thioplast EPS25 (Akzo Nobel); and epoxy-terminated reactive diluents based on alcohol / glycols, e.g., 1,4-butanediol diglycidyl ether (DER731; Olin Epoxy) and 1,6-hexanediol diglycidyl ether (DER734; Olin Epoxy).

[0109] Preferably, the molar ratio of each component (b1) to each component (a1) is in the range of 0.90:1 to 2:1.

[0110] Constituent (b2) The component (b2) is at least one metal oxide and / or metal peroxide, in particular manganese dioxide. Manganese dioxide means manganese(IV) oxide. Another preferred component (b2) is calcium peroxide.

[0111] Preferably, component (b2) is present in component (B) of the sealing system used to prepare the sealant composition applied in step (2) in an amount ranging from 30 to 90% by mass relative to the total mass of component (B).

[0112] Constituent component (b3) Component (b3) is at least one organic peroxide. Examples of suitable organic peroxides include organic hydroperoxides, such as coumenyl hydroperoxide.

[0113] Preferably, component (b3) is present in component (B) of the sealing system used to prepare the sealant composition applied in step (2) in an amount ranging from 30% to 100% by mass relative to the total mass of component (B).

[0114] Constituent (b4) Component (b4) comprises two or more vinyl groups. Preferably, the vinyl groups are present in (b4) as terminal groups. Component (b4) can be a monomer, oligomer, or polymer, and is preferably a monomer. Preferably, (b4) is aliphatic and / or aromatic. Examples of component (b4) are divinyl ethers, such as diethylene glycol divinyl ether, triethylene glycol divinyl ether, and butanediol divinyl ether.

[0115] Preferably, component (b4) is present in component (B) of the sealing system used to prepare the sealant composition applied in step (2) in an amount ranging from 30 to 100% by mass relative to the total mass of component (B).

[0116] When component (b4) is used as component (b) of component (B), it is preferably present in combination with at least one radical generator. Examples of suitable radical generators are 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one.

[0117] Any component (b5) The sealing system component (B) may contain one or more arbitrary components (b5). Component (b5) may be an additive selected from the group consisting of reactive diluents, such as bis-oxazolidine and / or aldimines, and plasticizers such as phthalates. In particular, at least one plasticizer component (b5) is present in component (B) if the sealing system component (B) contains at least one component (b2), in particular manganese dioxide.

[0118] Specifically, if at least one reactive diluent is present, its amount is preferably in the range of 0.1 to 20.0% by mass relative to the total mass of component (B). Specifically, if at least one plasticizer is present, its amount is preferably in the range of 10.0 to 70.0% by mass relative to the total mass of component (B).

[0119] Any component (b6) Component (B) may additionally contain at least one curing catalyst (b6), and preferably contains one.

[0120] As outlined above, if component (B) of the sealing system includes, as component (b), at least one component (b1) containing two or more epoxide groups, then at least one curing catalyst, if present, is preferably present in component (A) as component (a5) and not present in component (B). Suitable curing catalysts in this case are amines, particularly tertiary amines, amidines and / or guanidines. Examples include 1,4-diazabicyclo(2.2.2)octane, 1,5-diazabicyclo(4.3.0)non-5-ene (DBN), and 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU).

[0121] If the sealing component (B) contains at least one component (b2) as component (b), then preferably at least one curing catalyst (b6) is present in component (B). Suitable curing catalysts in this case include, for example, tetrabenzyl thiuram disulfide, diphenylguanidine, and / or zinc bis(diethyldithiocarbamate).

[0122] If the sealing system component (B) contains at least one component (b3) as component (b), then preferably at least one curing catalyst (b6) is present in component (B). A suitable curing catalyst in this case is, for example, zinc diethylcarbamate.

[0123] If the sealing system component (B) contains at least one component (b4) as component (b), then preferably at least one curing catalyst (b6) is present in component (B). In this case, suitable curing catalysts are particularly suitable photoinitiators, such as acetophenone, benzoin ether and / or benzoyl oxime. Curing is preferably carried out via UV light.

[0124] Any component (b7) Component (B) may additionally contain at least one flame retardant (b7). Component (b7) may be a phosphorus-containing flame retardant, particularly at least one phosphate ester. When used, the flame retardant is preferably in liquid form (at 1 bar and 23°C). When the flame retardant is present in component (A), it is preferably present in component (A) in an amount of 5.0 to 65.0% by mass, more preferably 25.0 to 65.0% by mass, particularly 40.0 to 65.0% by mass, in each case relative to the total mass of component (B).

[0125] Optional step (3) Preferably, the method of the present invention includes a curing step (3), i.e. (3) A step of curing at least the sealant composition applied in step (2) at ambient temperature (18-23°C) or a high temperature such as 80°C for 0.5 hours to 14 days. It also includes.

[0126] Preferably, curing in step (3) means chemical curing, such as chemical crosslinking, at ambient temperature or high temperature. If at least one component (b1) or (b4) is used as component (b), curing may be additionally or alternatively induced via UV light.

[0127] Preferably, the sealant composition is applied with a dry layer thickness in the range of 15 μm to 20 mm, more preferably 50 μm to 15 mm, and particularly 0.5 to 10 mm.

[0128] Encapsulated substrate A further subject of the present invention is a sealed substrate that can be obtained by the method of the present invention.

[0129] In relation to the method and preferred embodiments thereof of the present invention, all preferred embodiments described herein are also preferred embodiments of the sealed substrate of the present invention.

[0130] Use of organosilane components to improve adhesion A further subject of the present invention is a method of using the organosilane components defined above, which, when incorporated into the primer composition defined above, for example the primer composition used in step (1) of the method of the present invention, or the sealant composition defined above, for example the sealant composition used in step (2) of the method of the present invention, in particular, when applied to at least a portion of the surface of a pre-coated substrate, improves the adhesion of the primer composition or sealant composition to the substrate.

[0131] In relation to the methods of the present invention and the sealed substrates and their preferred embodiments, all preferred embodiments described herein are also preferred embodiments of the methods of use of the present invention.

[0132] Sealant composition and sealing system A further subject of the present invention is the sealant composition as defined above, which can be obtained by mixing the sealing system components (A) and (B) as defined above, wherein the sealing system component (A) comprises at least one organosilane component as defined above.

[0133] The resulting sealing composition may be sprayable, but it is not required to be sprayable.

[0134] Preferably, the sealing composition can be obtained by mixing components (A) and (B) in a mass ratio (component (A) / component (B)) in the range of 100:1 to 1:1. More preferably, the mixing is carried out in a mass ratio in the range of 100:1 to 1.1:1, even more preferably in the range of 100:1 to 2:1, particularly in the range of 100:1 to 3:1, and most preferably in the range of 20:1 to 4:1.

[0135] A further subject of the present invention is a two-component (2K) sealing system comprising components (A) and (B) defined above, which are distinct from each other, wherein component (A) of the sealing system comprises at least one organosilane component defined above.

[0136] In relation to the methods of the present invention, the sealed substrates of the present invention, the methods of use of the present invention, and preferred embodiments thereof, all preferred embodiments described herein are also preferred embodiments of the sealant compositions and sealing systems of the present invention.

[0137] Preferably, the sealing system consists of components (A) and (B).

[0138] Organosilane components A further subject of the present invention is the organosilane components defined above, which can be optionally incorporated into the primer composition defined above.

[0139] In relation to the methods of the present invention, the sealed substrates of the present invention, the methods of use of the present invention, the sealant compositions of the present invention, and the sealing systems of the present invention, and any preferred embodiments thereof described herein are also preferred embodiments of the organosilane components of the present invention.

[0140] Primer composition A further subject of the present invention is the primer composition defined above, comprising at least one of the organosilane components defined above.

[0141] In relation to the methods of the present invention, the sealed substrates of the present invention, the methods of use of the present invention, the sealant compositions of the present invention and the sealing systems of the present invention, and the organosilane components of the present invention, and any preferred embodiments thereof described herein are also preferred embodiments of the primer compositions of the present invention.

[0142] method 1. Peel test The peel test was conducted in accordance with AMS-C-27725.

[0143] 2. Immersion Test The immersion test was conducted in accordance with AMS2629 (Type 1, 7 days).

[0144] 3. Number average molecular weight The number-average molecular weights of components (a1) and (b1) were measured by GPC (gel permeation chromatography) against a polystyrene standard. THF (tetrahydrofuran) was used as the mobile phase. The number-average molecular weight of organosilane component (a2) was measured by NMR spectroscopy for monomer and oligomer components, and by GPC for polymer components. [Examples]

[0145] The following embodiments further illustrate the present invention, but are not intended to limit its scope. "pbw" means parts by mass. Unless otherwise defined, "parts" means "parts by mass".

[0146] 1. Synthesis of NCO-functionalized organosilanes OS1-OS4 1.1 Synthesis of OS1 containing urea (comparative example) OS1 was prepared by slowly adding IPDI (isophorone diisocyanate) dropwise to bis[3-(trimethoxysilyl)propyl]amine with stirring. IPDI and bis[3-(trimethoxysilyl)propyl]amine were used in equimolar amounts. The resulting product was used as OS1 without purification.

[0147] 1.2 Synthesis of OS2 containing the S-thiocarbamate moiety (Example of invention) OS2 was prepared by heating an equimolar mixture of IPDI and (3-mercaptopropyl)methyldimethoxysilane, which additionally contained 0.0005 moles of 1,4-dimethylpiperazine, at 75°C for 4 hours under an inert gas atmosphere with stirring. The resulting product was used as OS2 without purification. The NCO content of OS2 was 10.2% by mass.

[0148] 1.3 Synthesis of OS3 containing the S-thiocarbamate moiety (Example of invention) OS3 was prepared by heating an equimolar mixture of HMDI (hexamethylene diisocyanate) and (3-mercaptopropyl)trimethoxysilane, which additionally contained 0.0005 moles of 1,4-dimethylpiperazine, at 75°C for 4 hours under an inert gas atmosphere with stirring. The resulting product was used as OS3 without purification. The NCO content of OS3 was 11.6% by mass.

[0149] 1.4 Synthesis of OS4 containing the S-thiocarbamate moiety (Example of invention) OS4 was prepared by heating an equimolar mixture of IPDI and (3-mercaptopropyl)trimethoxysilane, which additionally contained 0.0005 moles of 1,4-dimethylpiperazine, at 75°C for 4 hours under an inert gas atmosphere with stirring. The resulting product was used as OS4 without purification. The NCO content of OS4 was 9.9% by mass.

[0150] 2. Preparation of sealant composition and sealed substrate 2.1 Numerous exemplary sealant compositions were prepared. Each sealant composition was prepared by mixing two components (A) and (B) of a two-component sealing system. The composition of component (A) of each sealing system is shown in Table 1. Component (A) was prepared by mixing the constituent components shown in Table 1 in the order shown in Table 1.

[0151] [Table 1]

[0152] Thioplast® LP12 and Thioplast® LP33 are commercially available SH group-containing polysulfides. Filler 1 and Filler 2 are commercially available fillers. Pigment 1 is a commercially available pigment. Rheology additive 1 is a commercially available hydrophobic fumed silica. OS is one of NCO-functionalized organosilanes OS1 to OS4, or one of the commercially available organosilanes (3-glycidyloxypropyl)trimethoxysilane (COS1) and (3-mercaptopropyl)trimethoxysilane (COS2).

[0153] Depending on which of the organosilanes OS1 to OS4, COS1, and COS2 was used, different sealing system components "A" were obtained in this manner, namely SC-A-OS1, SC-A-OS2, SC-A-OS3, SC-A-OS4, SC-A-COS1, and SC-A-COS2.

[0154] 2.2 100 parts by mass of each of component "A" SC-A-OS1, SC-A-OS2, SC-A-OS3, SC-A-OS4, SC-A-COS1, and SC-A-COS2 were mixed with 10 parts by mass of curing agent component "B". Component "B" contains manganese dioxide curing agent. In each case, a commercially available product was used as component (B) (Naftoseal® MC780B-2 curing agent from Chemetall GmbH).

[0155] 2.3 Each of component "A", namely SC-A-OS1, SC-A-OS2, SC-A-OS3, SC-A-OS4, SC-A-COS1, and SC-A-COS2, was mixed with component "B". The resulting sealant compositions, namely SC-OS1, SC-OS2, SC-OS3, SC-OS4, SC-COS1, and SC-COS2, were then applied to the substrate in each case by applying air pressure to the cartridge. The following substrates S1 to S3 were used:

[0156] Substrate S1: Aluminum substrate (AL2024), Substrate S2: Aluminum substrate (AL2024) coated with a commercially available base coat (Mankiewicz Seevenax 313-81), Substrate S3: Aluminum substrate (AL2024) coated with a commercially available integrated fuel tank coating (DeSoto823-707).

[0157] After application to one of the substrates, the applied sealant composition was cured for 14 days at room temperature (23°C) and 50% relative humidity. The sealed substrates were then subjected to numerous tests, as outlined below.

[0158] 3. Investigation of the properties of the sealed substrate 3.1 Sealant applied to the surface of substrate S1 Several properties of the sealed and cured substrate were investigated. Measurements were performed by the methods disclosed in the "Methods" section. The results are shown in Table 3.1.

[0159] [Table 2]

[0160] 3.2 Sealant applied to the surface of substrate S2 Several properties of the sealed and cured substrate were investigated. Measurements were performed according to the methods disclosed in the "Methods" section. The results are shown in Table 3.2.

[0161] [Table 3]

[0162] 3.3 Sealant applied to the surface of substrate S3 Several properties of the sealed and cured substrate were investigated. Measurements were performed by the methods disclosed in the "Methods" section. The results are shown in Table 3.3.

[0163] [Table 4]

Claims

1. At least step (2), i.e. (2) A step of applying a sealant composition at least partially to the surface of a substrate that has been optionally pre-coated. A method for sealing an optionally pre-coated substrate, including, The sealant composition can be obtained by mixing components of a sealing system with each other, and the sealing system is a two-component (2K) sealing system comprising two components (A) and (B) which are distinct from each other. The sealing system component (A) comprises at least one polymer component (a1) containing two or more thiol groups selected from polyethers, polythioethers, polysulfides, polythioether-sulfide components and mixtures thereof, and The sealing system component (B) comprises at least one component (b) suitable for curing the sealant composition by at least partially inducing the chemical transformation of two or more thiol groups of component (a1), The following ingredients, (i) at least one hydrolyzable group X, (ii) at least one isocyanate group, and (iii) A spacer unit disposed between at least one hydrolyzable group X and at least one isocyanate group, the spacer unit comprising at least one portion containing at least one sulfur atom. A method characterized in that at least one organosilane component containing is present as component (a2) in component (A) of the sealing system used to prepare the sealant composition applied in step (2).

2. The method according to claim 1, characterized in that at least one organosilane component is present in component (A) used to prepare the sealant composition applied in step (2).

3. The method according to claim 1, characterized in that the at least one organosilane component is present in (A) in an amount ranging from 0.05 to 10.0% by mass, preferably 0.10 to 7.5% by mass, more preferably 0.15 to 7.5% by mass, even more preferably 0.20 to 5.0% by mass, and still more preferably 0.25 to 4.5% by mass, and in each case these amounts are relative to the total mass of the sealing system component (A).

4. The method according to claim 1, characterized in that the at least one portion of the spacer unit of the organosilane component, which contains at least one sulfur atom, is selected from the group consisting of thiocarbamate, thiourea, thioester, thioketo, thiourethane, and thioamide portions, preferably representing a thiocarbamate, thiourethane, and / or thiourea portion.

5. The method according to claim 1, characterized in that the at least one organosilane component comprises exactly one isocyanate group.

6. The method according to claim 1, characterized in that the at least one organosilane component can be obtained by the reaction of at least one preferably aliphatic and / or alicyclic diisocyanate with at least one organosilane precursor containing at least one thiol group as a functional group reactive with the isocyanate group, particularly when at least one diisocyanate and at least one organosilane precursor are used in approximately equimolar amounts.

7. The method according to claim 1, wherein the at least one organosilane component is a monomer, preferably the spacer unit has a chain length that separates the at least one hydrolyzable group X from the at least one isocyanate group of at least six carbon and / or heteroatoms, and preferably the chain contains at least one part of an atom.

8. The method according to claim 1, characterized in that the organosilane component comprises at least two, preferably at least three, hydrolyzable groups X, wherein X is preferably an alkoxy group having 1 to 4 carbon atoms.

9. The at least one organosilane component comprises at least one preferably aliphatic and / or alicyclic diisocyanate and a component of general formula (I) and / or (II), i.e. Si(X) ４－ｙ (R) ｙ , (I) Si(X) ３－ｚ (T) ｚ -(1A)-Si(X) ３－ｚ (T) ｚ (II) (In the case of general formula (I), in the formula, Each of X is independently a hydrolyzable group, preferably independently O-C １～４ Selected from alkyl groups, The parameter y is an integer in the range of 1 to 3, but is at least 1, preferably exactly 1, and R is a non-hydrolyzable organic group, and at least one of the groups R contains at least one thiol group that is reactive to an isocyanate group. And in the case of general formula (II), in the formula, X independently represents a hydrolyzable group in each case, preferably O-C independently in each case. １～４ - Selected from alkyl groups, RA represents a divalent, non-hydrolyzable organic group containing at least one thiol group that is reactive to an isocyanate group. The parameter z is an integer in the range of 0 to 3 in each case, preferably 0 in each case, and T is a non-hydrolyzable organic group different from group (RA), and preferably does not have a functional group that is reactive with the isocyanate group. The method according to claim 1, characterized in that it is obtained by reaction with at least one organosilane precursor represented by .

10. The method according to claim 1, wherein the at least one component (b) present in component (B) and suitable for curing the sealant composition is selected from the group consisting of a component comprising two or more epoxide groups (component (b1)), a component being a metal oxide and / or metal peroxide, particularly manganese dioxide (component (b2)), a component being an organic peroxide (component (b3)), a component comprising two or more vinyl groups (component (b4)), and mixtures thereof, and preferably selected from the group consisting of a component comprising two or more epoxide groups (component (b1)), a component being a metal oxide and / or metal peroxide, particularly manganese dioxide (component (b2)), and mixtures thereof, and in particular, component (b1) represents at least one component comprising two or more epoxide groups, or component (b2) represents at least one metal oxide and / or metal peroxide, particularly manganese dioxide.

11. A sealed substrate that can be obtained by the method described in any one of claims 1 to 10.

12. A method for using an organosilane component as defined in any one of claims 1 to 10, wherein the organosilane component is incorporated into a primer composition as defined in any one of claims 1 to 10, or a sealant composition as defined in any one of claims 1 to 10, and is applied to at least a portion of the surface of an optionally pre-coated substrate to improve the adhesion of the primer composition or the sealant composition to the substrate.

13. A two-component (2K) sealing system comprising components (A) and (B) defined in any one of claims 1 to 10, wherein component (A) of the sealing system comprises at least one organosilane component defined in any one of claims 1 to 10.

14. A sealant composition as defined in any one of Claims 1 to 10, which can be obtained by mixing together sealing system components (A) and (B) as defined in any one of Claims 1 to 10 or as defined in Claim 13, wherein the sealing system component (A) comprises at least one organosilane component as defined in any one of Claims 1 to 10.

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