Polyurethane-based moisture-curable windshield adhesive

Abstract

The present invention relates to a moisture-curable polyurethane composition, comprising: at least one isocyanate group-containing polyurethane polymer P1 having a content of at most 0.5% by weight of monomeric diisocyanates, said monomeric diisocyanates being at least one monomeric diisocyanate having an average molecular weight M of more than 2,500 g / mol, an NCO / OH ratio of at least 3 / 1, n and subsequently removing most of the monomeric diisocyanates using a suitable separation method, - more than 20% by weight, based on the total composition, of carbon black, - optionally up to 2% by weight, based on the total composition, of a polyurethane polymer P2 which is solid at room temperature and which is obtained by reacting at least one monomeric diisocyanate with at least one at least partially crystallized polyester or polycarbonate polyol having an NCO / OH ratio of at least 1.3 / 1, - optionally at least one monomeric diisocyanate with an average molecular weight M of up to 2,500 g / mol, with an NCO / OH ratio of at least 1.3 / 1, n and at most 5% by weight of a polyurethane polymer P3, based on the total composition, obtained by reacting at least one polyether diol having the formula:

Description

[Technical field]

[0001] The present invention relates to a moisture-curable polyurethane composition and its use as an elastic adhesive, particularly for vehicle glazing. [Background technology]

[0002] Curable compositions based on polyurethane are often used as adhesives for elastic bonding, for example in vehicle assembly. In particular, one-component moisture-curing systems are popular, especially due to their easy handling. They are used, for example, for direct glazing of vehicles. However, for this use, it is important that the adhesive has certain properties. In addition to good and lasting adhesion on substrates, such as vehicle paints, glass and / or screen-printed ceramics, they must also have good early strength and must not have any tendency to slip before curing. For these bonding applications, the premise is that the adhesive bond may be exposed to a certain level of mechanical stress immediately after application of the adhesive, for example because the components to be bonded should be moved or the fixing aid should be removed. To allow such early stress, the adhesive bond should in fact have what is called good early strength, i.e. if the adhesive is not yet chemically cured, it can be subjected to loads in a certain manner until the bond. This is important, for example, in the case of window bonding in car assembly, where the window to be inserted must not slip in the newly applied adhesive. However, despite this, the adhesive should have a sufficiently low viscosity to be easily transported and applied, for example, by pump.

[0003] One-component polyurethane compositions cure through reaction with moisture, typically air moisture, where the cure proceeds from the outside to the inside of the applied adhesive through the water diffusing therein. The cure speed decreases toward the inside, because the water required for cure must diffuse through an increasingly thick reactive crosslinked polymer layer ("skin"). Due to the relatively slow cure, it is often not possible to achieve good early strength with conventional one-component polyurethane adhesives. Despite this, one-component adhesives are popular among users because they do not require a mixing step as in the case of two- or multi-component compositions.

[0004] One way to improve the early strength of one-component compositions, especially regardless of curing, is the addition of relatively large amounts of reinforcing fillers, such as carbon black. Such fillers thicken the adhesive and allow good early strength even in the freshly applied state. However, the use of significant amounts of carbon black causes an excessive increase in the viscosity of the composition, and in the case of carbon black contents of more than 20% by weight, it is often no longer possible to pump the composition at all, since the viscosity is already too high, which interferes with the automatic conveying and application of the composition in industrial production. This has the additional effect that, for example, very high squeezing forces are required to apply the adhesive from a cartridge. For example, WO 2020 / 201419 A1, WO 2020 / 030608 A1 and WO 2020 / 201421 disclose one-component polyurethane adhesives with a carbon black content of less than 20% by weight.

[0005] Polyurethane adhesive compositions with good early strength are further obtained in the form of so-called warm melts, which have a pasty nature that makes their consistency substantially stable at room temperature, are heated for application to temperatures typically ranging from 40°C to 80°C, and are relatively liquid in the warmed state. The early strength of such adhesives is obtained not mainly through chemical reactions, but through a significant increase in viscosity in the course of cooling, which occurs as a result of physical solidification of the adhesive's constituents, called meltable components. Meltable components are substances that are solid at room temperature, melt and liquefy upon heating of the adhesive to the application temperature, and solidify again within a certain period of time if the adhesive is cooled again, for example via crystallization.

[0006] Such warm melt adhesives in the form of one-component polyurethane compositions are known, for example, from US Pat. No. 5,367,036. The compositions described therein contain, in addition to a polyurethane polymer having isocyanate groups, a meltable component in the form of a non-reactive polyurethane polymer, whose isocyanate groups have reacted with monoalcohols to give urethanes. The meltable component produces a temperature-dependent increase in viscosity and leads to good early strength. However, the use of a non-reactive polyurethane polymer as the meltable component has the drawback that it is not incorporated into the polyurethane matrix during the chemical curing of the composition by moisture. The meltable component can therefore migrate from the cured composition and thus cause undesirable effects on the surface of the bonded substrate or lead to lower chemical stability, lower mechanical strength and / or poorer bonding properties of the cured composition.

[0007] WO 95 / 00572 A1 describes a warm-applicable adhesive containing a liquid reactive prepolymer and a meltable component which is at least partially incompatible therewith, preferably a prepolymer with isocyanate end groups. US Patent Nos. 5,166,302 and 5,173,538 describe warm-applicable or hot-applicable adhesive compositions which contain, in addition to a liquid polyurethane polymer, a reactive meltable component in the form of a polyurethane polymer with isocyanate groups. The meltable components with isocyanate groups described in these patents are incorporated into the polyurethane matrix during the chemical curing of the adhesive by moisture, which clearly reduces undesirable effects such as occur in the case of non-reactive meltable components. However, they tend to solidify very quickly during cooling, thus resulting in short open times and / or causing stresses in the cured adhesive through reactive crosslinks in the polymer matrix, which may have a detrimental effect on the strength of the adhesive bond. A further disadvantage of the described reactive melting components is that they only have limited storage stability and can undergo premature crosslinking by reactive groups, which adversely affects their viscosity and solidification characteristics.In addition, they are prone to low ambient temperatures, for example when applied in factory halls in winter, because the warming composition in such cases cools too quickly and solidifies too quickly.

[0008] WO 2018 / 132242 A1 describes an advanced adhesive composition of this type, which comprises a polyester urethane polymer based on diphenylmethane 4,4'-diisocyanate (MDI) and a polyester polymer, can be applied at room temperature and nevertheless has a reduced tendency of slippage of the substrates bonded thereto as a result of the resulting improvement in early strength.

[0009] The aforementioned polyester urethane-based reactive melt components, due to their advantageous properties, are currently the most commonly used adhesives in such polyurethane adhesives for improved early strength, often in combination with carbon black.

[0010] However, all known polyurethane compositions containing such polyester urethane polymers as meltable components still have inherent drawbacks. In particular, the amount of this polyester urethane polymer required for sufficient initial strength and shear stability in the described adhesive application has a tendency to increase delamination, i.e. to cause loss of adhesion under stress on the bond. It is possible to minimize the amount of meltable components by additional use of reinforcing fillers, such as carbon black, which can solve this problem. However, this inevitably increases the viscosity and therefore the squeezing force required during application, which is undesirable. Moreover, it is necessary to compress the bond with high force to establish sufficient surface contact between the adhesive and the substrate.

[0011] It is still not sufficiently possible to provide one-component polyurethane compositions suitable as elastic structural adhesives in the manufacturing industry, which can be easily applied or pumped out with low squeezing forces and at the same time have very good early strength which prevents slippage of the newly bonded substrates and additionally allows for stable bonds which do not peel off under mechanical stress. Summary of the Invention [Problem to be solved by the invention]

[0012] The object of the present invention is to provide a one-component moisture-curing polyurethane composition with good early strength, which can be applied at room temperature or in heated form, and at the same time has a sufficiently low viscosity for problem-free application and transport by pumps, and whose bond does not lead to delamination under mechanical stress.In addition, the composition should have very good adhesion to substrates, such as automotive paints, glass and screen printing ceramics, should show robust mechanical properties even after heated storage, and should require low compression forces for the bond of the substrate. [Means for solving the problem]

[0013] This object is achieved by a moisture-curable composition according to claim 1. The composition comprises at least one monomeric diisocyanate with an average molecular weight M of more than 2500 g / mol and an NCO / OH ratio of at least 3 / 1. n and subsequent removal of most of the monomeric diisocyanates by a suitable separation method, and more than 20% by weight, based on the total composition, of carbon black. In addition, the composition contains a small amount of a polyurethane polymer P2 and / or a linear short-chain polyether urethane polymer P3, which is solid at room temperature.

[0014] The compositions of the present invention have very good application properties at room temperature with relatively low squeeze forces, very good early strength with low tendency to warp before curing, and very low tendency to delaminate the bond after curing of the composition as an adhesive.

[0015] It is particularly surprising that the composition of the present invention has unexpectedly good application properties even though it has a high carbon black content.

[0016] To improve early strength, sag resistance and stringiness, moisture-curing polyurethane adhesives, especially for automotive assembly, often additionally contain a meltable component, typically a small amount of a room-temperature solid polyurethane polymer based on a crystalline polyester polyol.However, the meltable component increases the squeeze force for the adhesive at room temperature and under cold conditions, and the sag resistance is highly shear-dependent, which can lead to problems in production and application.Surprisingly, the composition of the present invention is unexpectedly easy to squeeze, even when it additionally contains a small amount of room-temperature solid polyurethane polymer P2, and the rheological properties are significantly less shear-dependent.In particular, the composition of the present invention allows for adhesives in which such meltable components can be used in significantly less amounts than in the prior art, or can be completely omitted without compromising early strength.

[0017] The composition of the present invention in particular allows for application of moisture-curing elastic polyurethane adhesives at room temperature or in a heated state, which have improved application properties, in particular good squeezeability, but at the same time have very high early strength and, compared to the prior art, have unaltered good properties in terms of storage stability, cure speed, blister formation, strength, extensibility, elasticity and hazardous materials classification. The composition is therefore particularly suitable as an elastic adhesive in automobile assembly, in particular for the use of elastic bonded windscreens on automobiles in direct glazing applications.

[0018] Further aspects of the invention are the subject matter of further independent claims. Particularly preferred embodiments of the invention are the subject matter of the dependent claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] The present invention provides a moisture-curable polyurethane composition, - at least one monomeric diisocyanate with an average molecular weight M of more than 2500 g / mol, preferably from 2750 to 20 000 g / mol, more preferably from 3,000 to 15,000 g / mol, in particular from 4000 to 10 000 g / mol, in an NCO / OH ratio of at least 3 / 1; nand subsequent removal of most of the monomeric diisocyanates by suitable separation methods, and - more than 20% by weight of carbon black, preferably from 20.5% to 25% by weight of carbon black, in particular from 21% to 24% by weight of carbon black, based on the entire composition; - optionally up to 2% by weight, preferably between 0.5% and 1.5% by weight, based on the total composition, of a polyurethane polymer P2 solid at room temperature resulting from the reaction of at least one monomeric diisocyanate with at least one at least semicrystalline polyester polyol or polycarbonate polyol having an NCO / OH ratio of at least 1.3 / 1, - optionally at least one monomeric diisocyanate with an average molecular weight M of 2500 g / mol or less, with an NCO / OH ratio of at least 1.3 / 1 n and at most 5% by weight, preferably 0.5% to 2% by weight, based on the total composition, of a polyether urethane polymer P3 obtained from the reaction of at least one polyether diol having the formula with the proviso that at least one of polymers P2 and P3 is present in said composition.

[0020] "Monomeric diisocyanate" refers to an organic compound having two isocyanate groups separated from each other by a divalent hydrocarbyl radical having from 4 to 15 carbon atoms.

[0021] "Polyetherurethane polymer" refers to a polymer having ether groups as repeat units and additionally containing urethane groups.

[0022] "Polyester urethane polymer" refers to a polymer having ester groups as repeat units and additionally containing urethane groups.

[0023] "NCO content" refers to the weight percent of isocyanate groups relative to the total polymer.

[0024] "Molecular weight" refers to the molar mass (grams per mole) of a molecule or molecular residue. "Average molecular weight" refers to the number average molecular weight (M n ), which is determined by gel permeation chromatography (GPC) against polystyrene as the standard.

[0025] A substance or composition is said to be "storage-stable" or "storable" if it can be stored in a suitable container at room temperature for an extended period of time, typically at least 3 months and up to 6 months or more, without any change in its application or use characteristics to an extent appropriate for its use as a result of storage.

[0026] A composition referred to as a "one-component" composition is one in which all components of the composition are present in the same container and are shelf stable as is.

[0027] "Room temperature" refers to a temperature of 23°C.

[0028] All industry standards and standards cited herein relate to the version in effect at the date of first filing.

[0029] A percentage by weight (wt %) refers to the ratio by mass of a component of a composition or molecule to the entire composition or molecule, unless otherwise specified. The terms "mass" and "weight" are used interchangeably herein.

[0030] The moisture-curable composition comprises at least one monomeric diisocyanate having an average molecular weight M of more than 2500 g / mol and an NCO / OH ratio of at least 3 / 1. nand subsequent removal of most of the monomeric diisocyanates by suitable separation methods.

[0031] This is preferably at least one polyetherurethane polymer P1 having a content of 1,2-propyleneoxy units in the polyether segments of at least 80% by weight.

[0032] The polyether urethane polymer P1 preferably contains 80% to 100% by weight of 1,2-propyleneoxy units and 0% to 20% by weight of 1,2-ethyleneoxy units in the polyether segments.

[0033] The polyetherurethane polymer P1 preferably has an average NCO functionality ranging from 1.5 to 3.5, preferably from 1.8 to 3.2.

[0034] The polyetherurethane polymer P1 preferably has an NCO content in the range from 1% to 5% by weight, in particular from 1% to 3% by weight.

[0035] The polyether urethane polymer P1 preferably has an average molecular weight M in the range of 3000 to 20000 g / mol, preferably 4500 to 15000 g / mol. n has.

[0036] The polyether urethane polymer P1 preferably has a viscosity at 20° C. in the range of 5 to 300 Pa·s, more preferably 5 to 200 Pa·s, in particular 5 to 100 Pa·s. The viscosity is measured here as a viscosity of 50 s in a cone-plate viscometer having a cone diameter of 25 mm, a cone angle of 1°, and a cone tip-plate distance of 0.5 mm. -1 is determined at a shear rate of

[0037] The preferred polyether urethane polymer P1 allows for efficiently processable moisture-curable compositions with high elasticity and extensibility combined with high strength.

[0038] The polyether urethane polymer P1 is composed of at least one monomeric diisocyanate and an average molecular weight M of more than 2500 g / mol. n and at least one suitable polyether polyol having the formula: Preferred forms of the preferred polyether polyols are described further below.

[0039] The reaction is preferably carried out at a temperature in the range of 20 to 160° C., in particular 40 to 140° C., with the exclusion of moisture, optionally in the presence of a suitable catalyst.

[0040] The NCO / OH ratio is at least 3 / 1, preferably in the range from 3 / 1 to 10 / 1. The monomeric diisocyanates remaining in the reaction mixture after reaction of the OH groups are removed, in particular by distillation.

[0041] The NCO / OH ratio in the reaction is preferably in the range of from 3 / 1 to 10 / 1, in particular from 4 / 1 to 7 / 1, and the resulting polyetherurethane polymer containing isocyanate groups after distillation contains not more than 0.5% by weight, preferably not more than 0.3% by weight, more preferably not more than 0.2% by weight of monomeric diisocyanates, based on the distillation residue containing the polyetherurethane polymer.

[0042] Polyether urethane polymers that are not prepared by the above process and have a lower NCO / OH ratio, for example 2 / 1, are not suitable as polymer P1, because, surprisingly, they cannot produce the inventive properties of the composition.In this regard, it should be noted that the NCO / OH ratio in the preparation of polyurethane polymer has a large effect on the chain length and polydispersity of the polyurethane polymer obtained.

[0043] Suitable monomeric diisocyanates for the preparation of the polyether urethane polymers P1 are commercially available aromatic, aliphatic or cycloaliphatic diisocyanates, in particular diphenylmethane 4,4'-diisocyanate (MDI), optionally with small amounts of diphenylmethane 2,4'- and / or 2,2'-diisocyanate, tolylene 2,4-diisocyanate or mixtures thereof with tolylene 2,6-diisocyanate (TDI), phenylene 1,4-diisocyanate (PDI), naphthalene 1,5-diisocyanate (NDI), hexane 1,6-diisocyanate (HDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane (IPDI), 2,2(4),4-trimethylhexamethylene 1,6-diisocyanate (TMDI), cyclohexane 1,3- or 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI), perhydro(diphenylmethane 2,4'- or 4,4'-diisocyanate) (HMDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, m- or p-xylylene diisocyanate (XDI), or mixtures thereof.

[0044] Of these, MDI, TDI, HDI or IPDI is preferred, and IPDI or MDI is particularly preferred.

[0045] Most preferred is MDI, especially diphenylmethane 4,4'-diisocyanate (4,4'-MDI), especially qualities that contain only traces of diphenylmethane 2,4'- and / or 2,2'-diisocyanate and that are solid at room temperature.

[0046] The isocyanate groups of the polyetherurethane polymer P1 are therefore preferably derived from diphenylmethane 4,4'-diisocyanate. Such polymers cure particularly quickly and allow particularly high strengths.

[0047] Suitable polyether polyols for the preparation of the polyether urethane polymers P1 are in particular polyether polyols having at least 80% by weight of 1,2-propyleneoxy units in the polyether segments, in particular polyoxypropylene diols or triols or so-called ethylene oxide-terminated (EO-capped or EO-terminated) polyoxypropylene diols or triols, the latter being polyoxyethylene / polyoxypropylene copolyols, which are in particular obtained by further alkoxylation of polyoxypropylene diols or triols with ethylene oxide upon completion of the propoxylation reaction, so that they bear primary hydroxyl groups.

[0048] Preferred are polyether polyols having an OH number in the range of 6 to 280 mg KOH / g, in particular 7.5 to 112 mg KOH / g.

[0049] Preferred are those with average molecular weights M in the range of 2750 to 20000 g / mol, preferably 3000 to 15000 g / mol, in particular 4000 to 10000 g / mol. n It is a polyether polyol having the formula:

[0050] Preferred are polyether polyols having an average OH functionality in the range of 1.6-3.

[0051] In the preparation of the polyetherurethane polymers P1 containing isocyanate groups, it is also possible to include a proportion of di- or polyfunctional alcohols.

[0052] More preferably, the polyetherurethane polymer P1 is obtained from the reaction of at least one monomeric diisocyanate with at least one optionally ethylene oxide-terminated polyoxypropylene diol or triol having an OH number in the range from 7.5 to 112 mg KOH / g, in particular from 11 to 58 mg KOH / g.

[0053] A preferred separation method for removing the monomeric diisocyanates is a distillation method, in particular thin film distillation or short path distillation, preferably applying reduced pressure.

[0054] Particularly preferred is a multi-stage process in which the monomeric diisocyanates are removed in a short-path still with a jacket temperature in the range of 120° C. to 200° C. and a pressure of 0.001 to 0.5 mbar.

[0055] In the case of 4,4'-MDI, which is preferred as monomeric diisocyanate, the distillative removal is particularly demanding. For example, it must be ensured that the condensate does not solidify and block the system. Preference is given to operating at 0.001 to 0.5 mbar with a jacket temperature in the range of 160°C to 200°C and condensing the monomer to be removed at a temperature in the range of 40°C to 60°C.

[0056] Preference is given to reacting the monomeric diisocyanates with the polyether polyols followed by removal of most of the monomeric diisocyanates remaining in the reaction mixture without the use of a solvent or entrainer.

[0057] The monomeric diisocyanates removed after the reaction are preferably subsequently reused, i.e. used again in the preparation of polymers containing isocyanate groups.

[0058] The polymer P1 preferably comprises at least one polymer P1a obtained from a polyether diol and at least one polymer P1b obtained from a polyether triol. Such a polymer P1a is linear and allows good extensibility. In combination with such a polymer P1b, particularly good strength is additionally obtained.

[0059] More preferably, the polyetherurethane polymer P1 contains a polymer P1a having an NCO content in the range of 1% to 2.5% by weight, in particular 1.3% to 2.1% by weight, and a monomeric diisocyanate content of 0.3% by weight or less, obtained from the reaction of at least one monomeric diisocyanate with a polyetherdiol having an OH number in the range of 13 to 38 mg KOH / g, in particular 22 to 32 mg KOH / g, with an NCO / OH ratio of at least 3 / 1, and subsequent removal of the majority of the monomeric diisocyanates by suitable separation methods. Preferred monomeric diisocyanates are IPDI or 4,4'-MDI, in particular 4,4'-MDI.

[0060] In addition, the polyetherurethane polymer P1 more preferably comprises a polymer P1b having an NCO content in the range of 1% to 2.5% by weight, in particular 1.3% to 2.1% by weight, and a monomeric diisocyanate content of 0.3% by weight or less, obtained from the reaction of at least one monomeric diisocyanate with a polyether triol having an average OH functionality in the range of 2.2 to 3 and an OH number in the range of 20 to 42 mg KOH / g, with an NCO / OH ratio of at least 3 / 1, and subsequent removal of the majority of the monomeric diisocyanates by suitable separation methods. Preferred monomeric diisocyanates are IPDI or 4,4'-MDI, in particular 4,4'-MDI.

[0061] In addition, a more preferred polyetherurethane polymer P1 is a mixture of these two particularly preferred polyetherurethane polymers P1a and P1b mentioned above.

[0062] The moisture-curable composition preferably contains 20% to 60% by weight, in particular 25% to 50% by weight, of the polyether urethane polymer P1.

[0063] In the case of a mixture of polymers P1a and P1b in the polyetherurethane polymer P1, there is preferably a weight ratio P1a:P1b of from 5:1 to 1:5, preferably from 4:1 to 1:2, more preferably from 4:1 to 1:1.

[0064] The moisture-curable composition additionally optionally contains up to 2% by weight, based on the total composition, of a room-temperature solid polyurethane polymer P2 obtained from the reaction of at least one monomeric diisocyanate with at least one at least semi-crystalline polyester polyol or polycarbonate polyol having an NCO / OH ratio of at least 1.3 / 1.

[0065] Such polymers P2 are primarily suitable for adhesives that are applied in a heated state, for example at a temperature of about 60° C., and that have a high initial strength very quickly after application, so that the bonded parts are self-supporting and do not need fixing. The polymer P2 here is in molten form in the heated adhesive when applied, and crystallizes as the applied adhesive cools. In addition, such polymers P2 are suitable for adhesives that are applied at ambient temperature, in which case the meltable component is in a crystallized form, resulting in an increase in sag resistance. However, this meltable component in the form of the present polymer P2 is difficult to handle, and the sag resistance achieved thereby is highly shear-dependent, which can lead to problems in production and application. Furthermore, a relatively large amount of polymer P2 makes it difficult to squeeze the adhesive at room temperature and at low ambient or adhesive temperatures.

[0066] In addition, a maximum of 2% by weight of polymer P2 should be used in the composition. A polymer P2 content of more than 2% by weight based on the entire composition firstly leads to an increased risk of delamination of the bonded substrate under stress, i.e. loss of adhesion. Furthermore, this leads to an undesirable increase in the compression force required during bonding when the material cools. Furthermore, this leads to a significant reduction in the open time during cooling.

[0067] The present invention, in particular the use of polymer P3, which is further described below, makes it possible to provide adhesives that can be formulated with up to 2% by weight of polymer P2 or other meltable components and thus have excellent slippage tendencies and maximum early strength, without their drawbacks.

[0068] A preferred embodiment of the composition of the invention contains 0.5% to 1.5% by weight of polymer P2, based on the total composition, which makes it possible to take advantage of the advantageous properties of such room temperature solid polymers without the above-mentioned disadvantages occurring to any significant extent.

[0069] A preferred embodiment of the composition of the present invention does not contain polymer P2, but only polymer P3.Such a composition has good suitability especially for low ambient temperatures during application, and yet shows a particularly low tendency to peel off of the bond.Nevertheless, it has a sufficiently high initial strength and a sufficiently low tendency to slip during application.

[0070] The at least one polyurethane polymer P2 is obtained from the reaction, by known methods, of at least one at least partially crystalline polyester polyol or polycarbonate polyol having an NCO / OH ratio of at least 1.3 / 1 with at least one monomeric diisocyanate.

[0071] The monomeric diisocyanates used in the reaction are preferably diphenylmethane 4,4'-diisocyanate (4,4'-MDI), diphenylmethane 2,4'-diisocyanate (2,4'-MDI), tolylene 2,4-diisocyanate or its mixture with tolylene 2,6-diisocyanate (TDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI) or hexane 1,6-diisocyanate (HDI). These diisocyanates are easily obtained, inexpensive and allow good mechanical strength. It is also possible to use a combination of two or more of these monomeric diisocyanates.

[0072] A particularly preferred monomeric diisocyanate is IPDI.Such polymers P2 are particularly suitable for moisture-curable compositions having a particularly high light stability.

[0073] The most preferred monomeric diisocyanate is 4,4'-MDI, in particular those qualities which contain only small amounts of diphenylmethane 2,4'- and / or 2,2'-diisocyanate and are solid at room temperature. Such polymers P2 allow particularly rapid curing and high strength.

[0074] The reaction of at least one monomeric diisocyanate with at least one semicrystalline polyester polyol or polycarbonate polyol for the preparation of the polymer P2 is preferably carried out with the exclusion of moisture at temperatures in the range from 20 to 160° C., in particular from 40 to 140° C., optionally in the presence of a suitable catalyst.

[0075] The NCO / OH ratio is preferably in the range from 1.3 / 1 to 10 / 1. The monomeric diisocyanates remaining in the reaction mixture after reaction of the OH groups can be removed in particular by distillation.

[0076] If excess monomeric diisocyanates are removed by distillation, the NCO / OH ratio in the reaction is preferably in the range of from 3 / 1 to 10 / 1, in particular from 4 / 1 to 7 / 1, and the resulting polymer containing isocyanate groups after distillation preferably contains not more than 0.5% by weight, more preferably not more than 0.3% by weight, of monomeric diisocyanates.

[0077] If excess monomeric diisocyanates are not removed from the polymer, the NCO / OH ratio in the reaction is preferably in the range from 1.3 / 1 to 2.5 / 1. Such polymers in particular contain not more than 3% by weight, preferably not more than 2% by weight, of monomeric diisocyanates.

[0078] Polyols particularly suitable for the preparation of the polyurethane polymers P2 are, first of all, polyester polyols, also called oligoesterols, which are prepared, for example, from di- to trihydric alcohols, such as ethane-1,2-diol, diethylene glycol, propane-1,2-diol, dipropylene glycol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, neopentyl glycol, glycerol, 1,1,1-trimethylolpropane or mixtures of the said alcohols, with organic dicarboxylic acids or their anhydrides or esters, such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid and hexahydrophthalic acid or mixtures of the said acids, and also polyester polyols formed from lactones, such as ε-caprolactone.

[0079] Preference is given to amorphous, semi-crystalline and crystalline polyester di- and triols, especially polyester diols, which are liquid at room temperature. Suitable polyester diols which are liquid at room temperature are solid at temperatures not significantly below room temperature, for example at temperatures between 0° C. and 25° C., and like the amorphous polyester polyols, are always used in combination with at least one semi-crystalline or crystalline polyester polyol.

[0080] Particularly preferred polyester diols are adipic acid / hexanediol polyesters, azelaic acid / hexanediol polyesters and dodecanedicarboxylic acid / hexanediol polyesters having melting points in the range of 40°C to 80°C, particularly 50°C to 70°C.

[0081] Particularly suitable polyols for preparing the polyurethane polymer P2 are polycarbonate polyols obtained by reacting the alcohols mentioned above, for example those used to form the polyester polyols, with dialkyl carboxylates, for example dimethyl carbonate, diaryl carbonates, for example diphenyl carbonate or phosgene. Particularly suitable are amorphous, semi-crystalline or crystalline polycarbonate diols that are liquid at room temperature. Suitable polycarbonate diols that are liquid at room temperature are solid at temperatures slightly below room temperature, for example between 0°C and 25°C, and are always used in combination with at least one semi-crystalline or crystalline polycarbonate polyol, just like the amorphous polycarbonate polyols.

[0082] Preferred are polyester diols and polycarbonate diols.

[0083] Suitable polyesterdiols are especially the OH-functional polyesters of adipic acid or sebacic acid or dodecanedicarboxylic acid with butane-1,4-diol or hexane-1,6-diol.

[0084] Suitable polycarbonate diols are especially the OH-functional polycarbonates of hexane-1,6-diol.

[0085] Such polymers P2 are typically solid at room temperature and have at least partially crystalline character.

[0086] The polyurethane polymer P2 is solid at room temperature and preferably has a melting point in the range from 40°C to 80°C, in particular in the range from 50°C to 70°C.

[0087] The polyurethane polymer P2 preferably has an average molecular weight M of 500 g / mol or more. n In particular, the polyurethane polymer P2 has an average molecular weight M in the range from 1000 to 30 000 g / mol, preferably from 2000 to 10 000 g / mol. n In addition, the polyurethane polymer P2 preferably has an average functionality in the range from 1.8 to 2.2.

[0088] The moisture-curable composition optionally comprises at least one monomeric diisocyanate having an average molecular weight M of 2500 g / mol or less and an NCO / OH ratio of at least 1.3 / 1. n The composition also contains up to 5% by weight of a polyether urethane polymer P3, based on the total composition, obtained from the reaction of at least one polyether diol having the formula:

[0089] The use of polymer P3 is optional but preferred because it provides improved properties of the present invention, such as significantly lower slippage tendency and significantly higher early strength. In particular, polymer P3 may provide the advantages of polymer P2 without its disadvantages. The combination of polymer P3 and a small amount of polymer P2 may provide particularly good properties in terms of slippage characteristics and early strength.

[0090] The composition preferably contains 0.5% to 2% by weight of polymer P3, based on the total composition. More than 2% by weight of polymer P3 has no direct detrimental effect, but does not bring about any further significant improvement of the properties.

[0091] The polymer P3 has an average molecular weight M of less than or equal to 2500 g / mol with an NCO / OH ratio of at least 1.3 / 1. n The polymer is prepared from at least one polyether diol having the formula:

[0092] Any polyether diol having these characteristics is suitable.

[0093] Preferred is a polyoxypropylene diol having an OH number of 50 to 300 mg KOH / g.

[0094] A suitable example is a hydroxyl group having an OH number of 54 to 58 mg KOH / g and an average molecular weight M of about 2000 g / mol. n The Acclaim® 2200N (Covestro) has the following characteristics:

[0095] Also suitable and preferred is a hydroxyl group having an OH number of 260 mg KOH / g and an average molecular weight M of about 431 g / mol. n The diol-based polymer P3 makes it possible to achieve particularly low slippage characteristics and particularly low compression forces when the composition is used as an adhesive.

[0096] The most preferred polyether diol for polymer P3 is poly(oxy-1,4-butylene) diol.

[0097] Poly(oxy-1,4-butylene)diol is a polyether diol with 1,4-butyleneoxy units. Such diols are also called polytetramethylene ether glycols (PTMEG or PTMG). The polymer P3 based on this diol makes it possible to achieve particularly low squeeze forces and therefore particularly good pumpability and applicability when the composition is used as an adhesive.

[0098] The at least one polyol is more preferably poly(oxy-1,4-butylene) diol or a mixture of poly(oxy-1,4-butylene) diols.

[0099] More preferably, the isocyanate-functional polymer is obtained by reaction of isophorone diisocyanate, optionally in combination with at least one chain extender, with a poly(oxy-1,4-butylene)diol or a mixture of poly(oxy-1,4-butylene)diols.

[0100] The poly(oxy-1,4-butylene)diol or mixture of poly(oxy-1,4-butylene)diols preferably has an average total OH number in the range of 80 to 200 mg KOH / g, preferably 100 to 180 mg KOH / g.

[0101] When a mixture of two or more poly(oxy-1,4-butylene) diols is used, the total average OH number is the average of the OH numbers of the diols in the mixture.

[0102] The poly(oxy-1,4-butylene)diol is preferably - OH number in the range of 170-180 mg KOH / g and average molecular weight M of about 650 g / mol n Poly(oxy-1,4-butylene)diol having the formula - OH number in the range of 108-118 mg KOH / g and average molecular weight M of about 1000 g / mol n Poly(oxy-1,4-butylene)diol having the formula - OH number in the range of 75-85 mg KOH / g and average molecular weight M of about 1400 g / mol n Poly(oxy-1,4-butylene)diol having the formula - OH number in the range of 60-65 mg KOH / g and average molecular weight M of about 1800 g / mol n Poly(oxy-1,4-butylene)diol having the formula - OH number in the range of 50-60 mg KOH / g and average molecular weight M of about 2000 g / mol n Poly(oxy-1,4-butylene)diol having the formula and mixtures thereof is selected from the group consisting of:

[0103] Such diols are commercially available, for example, in the form of Terathane® 650, Terathane® 1000, Terathane® 1400, Terathane® 1800 or Terathane® 2000 (all from Invista) or PolyTHF 650, PolyTHF 1000, PolyTHF 1400, PolyTHF 1800 or PolyTHF 2000 (all from BASF).

[0104] Suitable monomeric diisocyanates for the polymer P3 are the commercially available aromatic, aliphatic or cycloaliphatic diisocyanates already mentioned.

[0105] The monomeric diisocyanates used in the reaction are preferably diphenylmethane 4,4'-diisocyanate (4,4'-MDI), diphenylmethane 2,4'-diisocyanate (2,4'-MDI), tolylene 2,4-diisocyanate or its mixture with tolylene 2,6-diisocyanate (TDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI) or hexane 1,6-diisocyanate (HDI). These diisocyanates are readily available, inexpensive and allow good mechanical strength. It is also possible to use a combination of two or more of these monomeric diisocyanates.

[0106] A particularly preferred monomeric diisocyanate is IPDI.Such polymers P3 are particularly suitable for moisture-curable compositions having a particularly high light stability.

[0107] The most preferred monomeric diisocyanate for the polymer P3 is 4,4'-MDI, in particular those qualities which contain only small amounts of diphenylmethane 2,4'- and / or 2,2'-diisocyanate and are solid at room temperature. Such polymers P3 allow particularly rapid curing and high strength.

[0108] The reaction of at least one monomeric diisocyanate and a polyether diol for the preparation of the polymer P3 is preferably carried out with the exclusion of moisture at a temperature in the range from 20 to 160° C., in particular from 40 to 140° C., optionally in the presence of a suitable catalyst.

[0109] The NCO / OH ratio is preferably in the range from 1.3 / 1 to 10 / 1. The monomeric diisocyanates remaining in the reaction mixture after reaction of the OH groups can be removed in particular by distillation.

[0110] If excess monomeric diisocyanates are removed by distillation, the NCO / OH ratio in the reaction is preferably in the range from 3 / 1 to 10 / 1, in particular from 4 / 1 to 7 / 1, and the resulting polymer P3 containing isocyanate groups after distillation preferably contains not more than 0.5% by weight, more preferably not more than 0.3% by weight, of monomeric diisocyanates.

[0111] If excess monomeric diisocyanates are not removed from the polymer, the NCO / OH ratio in the reaction is preferably in the range from 1.3 / 1 to 2.5 / 1. Such polymers in particular contain not more than 3% by weight, preferably not more than 2% by weight, of monomeric diisocyanates.

[0112] The polymer P3 preferably has a viscosity at 20° C. of not more than 1000 Pa·s, in particular not more than 500 Pa·s. The viscosity at 20° C. is preferably in the range of 10 to 1000 Pa·s, in particular 10 to 500 Pa·s. The viscosity is measured here as a viscosity of 50 s in a cone-plate viscometer having a cone diameter of 25 mm, a cone angle of 1°, and a cone tip-plate distance of 0.5 mm. -1 is determined at a shear rate of

[0113] Polymer P3 preferably has an NCO content in the range from 3% to 12% by weight, more preferably from 3.5% to 10% by weight, particularly preferably from 4% to 9.5% by weight, in particular from 4.5% to 9% by weight.

[0114] The polymer P3 preferably has a monomeric diisocyanate content of less than or equal to 0.5% by weight and is obtained from the reaction of at least one monomeric diisocyanate with a polyether diol having an NCO / OH ratio of at least 3 / 1, followed by removal of the majority of the monomeric diisocyanate by suitable separation methods.

[0115] Such polymers P3 are of particularly low viscosity, which makes them easier to handle, which is particularly suitable for use in compositions having less than 0.1% by weight of monomeric diisocyanates; they are safe to handle without special safety precautions and can be sold in many countries without being classified as hazardous materials.

[0116] The NCO / OH ratio in the reaction is preferably in the range of 3 / 1 to 10 / 1, more preferably 3 / 1 to 8 / 1, and particularly preferably 4 / 1 to 7 / 1.

[0117] The monomeric diisocyanate content is preferably not more than 0.3% by weight, in particular not more than 0.2% by weight.

[0118] A preferred separation method for removing the monomeric diisocyanates is a distillation method, in particular thin film distillation or short path distillation, preferably applying reduced pressure.

[0119] Particularly preferred is a multi-stage process in which the monomeric diisocyanates are removed in a short-path still with a jacket temperature in the range of 120° C. to 200° C. and a pressure of 0.001 to 0.5 mbar.

[0120] Preference is given to reacting the monomeric diisocyanates with the hydrophobic diols followed by removal of most of the monomeric diisocyanates remaining in the reaction mixture without the use of a solvent or entrainer.

[0121] The monomeric diisocyanates removed after the reaction are preferably subsequently reused, i.e. used again in the preparation of polymers containing isocyanate groups.

[0122] The polyetherurethane polymer P1 and any polyurethane polymer P2 and any polyetherurethane polymer P3 present are prepared separately from one another and are therefore only mixed with one another after preparation, in particular in the moisture-curable composition of the invention.

[0123] The moisture-curable composition preferably comprises, in addition to the polymer P1 and optionally P2 and P3, a very small amount of a further polymer containing isocyanate groups, in particular not more than 20 parts by weight, preferably not more than 15 parts by weight, in particular not more than 10 parts by weight and most preferably not more than 5 parts by weight of a further polymer containing isocyanate groups, based on 100 parts by weight of the sum of the polymers P1, P2 and P3.

[0124] A moisture-curing composition as claimed in claim 11 or 12, characterized in that it contains at least 0.5% by weight of polymer P2 and / or at least 0.5% by weight of polymer P3, based on the total composition.

[0125] The moisture-curable composition contains more than 20% by weight of carbon black based on the entire composition, preferably 20.5% to 25% by weight of carbon black, particularly 21% to 24% by weight of carbon black based on the entire composition.

[0126] Suitable carbon blacks are all those which are industrially produced and normally used in polyurethane compositions.

[0127] Carbon black is a reinforcing filler that improves early strength and mechanical properties and provides additional light and oxidative stability.

[0128] Normally it is difficult to introduce more than 20% by weight of carbon black into such compositions without significantly impairing the application properties, such as the required squeeze force. However, it has surprisingly been found that the use of polymer P1 allows significantly higher amounts of carbon black without impairing the application properties.

[0129] The moisture curable composition preferably additionally comprises at least one further component selected from a silane adhesion promoter, a blocked amine, a diisocyanate oligomer, a drying agent, a catalyst and a stabilizer.

[0130] In one embodiment of the present invention, the moisture-curable composition preferably additionally comprises at least one blocked amine.

[0131] Suitable blocked amines preferably have at least one aldimino or oxazolidino group, which upon contact with moisture can be hydrolyzed to release amino groups and react with available isocyanate groups, promoting rapid, blister-free curing, particularly non-stick surfaces and / or particularly good mechanical properties.

[0132] Preferred oxazolidines are mono- or bis-oxazolidines, especially those derived from isobutyraldehyde, benzaldehyde or substituted benzaldehydes, especially benzaldehydes substituted in the para position by optionally branched alkyl groups having 10 to 14 carbon atoms.

[0133] Particularly preferred are bisoxazolidines from the reaction of monooxazolidines derived from N-alkylethanolamines, such as Nn-butylethanolamine, or OH-functional monooxazolidines derived from diethanolamine, with diisocyanates, especially hexane 1,6-diisocyanate.

[0134] Suitable aldimines are in particular the di- or tri-aldimines from the reaction of commercially available primary di- or triamines with non-enolizable aldehydes, which are aldehydes that do not have a hydrogen atom alpha to the carbon atom of the aldehyde group.

[0135] Preferred blocked amines are represented by formulas (I) and (II): [ka] (In the formula, n is 2 or 3; A is an n-valent hydrocarbyl radical, optionally containing an ether oxygen, having a molecular weight in the range of 28 to 6,000 g / mol; R 1 and R 2are each independently a monovalent hydrocarbyl radical having 1 to 12 carbon atoms or, together, a divalent hydrocarbyl radical having 4 to 12 carbon atoms which is part of an optionally substituted carbocycle having 5 to 8, preferably 6, carbon atoms; R 3 is a hydrogen radical or a linear or branched alkyl, arylalkyl or alkoxycarbonyl radical having 1 to 12 carbon atoms, R 4 is a hydrogen radical or a monovalent hydrocarbyl radical having 1 to 20 carbon atoms, R 5 is an alkyl or alkoxy radical having 6 to 20 carbon atoms).

[0136] A is preferably an aliphatic, cycloaliphatic or arylaliphatic radical, in particular one having a molecular weight in the range of 28 to 500 g / mol, in particular 1,6-hexylene, (1,5,5-trimethylcyclohexan-1-yl)methane-1,3,4(2)-methyl-1,3-cyclohexylene, 1,3-cyclohexylenebis(methylene), 1,4-cyclohexylenebis(methylene), 1,3-phenylenebis(methylene), 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, methylenebis(2-methylcyclohexan-4-yl), (bicyclo[2.2.1]heptane-2,5(2,6)-diyl(dimethylene), (tricyclo[5.2.1.0 2,6 ]Decan-3(4),8(9)-diyl(dimethylene, average molecular weight M in the range of 170-500 g / mol n and an average molecular weight M in the range of 330 to 500 g / mol. n or glycerol-initiated tris(ω-polyoxypropylene) having the formula:

[0137] Preferably, R 1 and R 2 are each methyl.

[0138] Preferably, R 3 is a hydrogen radical.

[0139] Preferably, R 4 is methyl or undecyl.

[0140] Preferably, R 5 is a para-positioned, optionally branched, alkyl radical having 10 to 14 carbon atoms.

[0141] Particularly preferred blocked amines are N,N'-bis(2,2-dimethyl-3-lauroyloxypropylidene)hexylene-1,6-diamine, N,N'-bis(2,2-dimethyl-3-acetoxypropylidene)-3-aminomethyl-3,5,5-trimethylcyclohexylamine, N,N'-bis(2,2-dimethyl-3-lauroyloxypropylidene)-3-aminomethyl-3,5,5-trimethylcyclohexylamine, N,N'-bis(4-C 10~14 -alkylbenzylidene)-3-aminomethyl-3,5,5-trimethylcyclohexylamine, with average molecular weight M in the range of 450-880 g / mol n N,N'-bis(2,2-dimethyl-3-acetoxypropylidene)polyoxypropylenediamine having an average molecular weight M in the range of 750 to 1050 g / mol n N,N'-bis(2,2-dimethyl-3-lauroyloxypropylidene)polyoxypropylenediamine having an average molecular weight M in the range of 680 to 1100 g / mol n N,N'-bis(4-C 10~14 -alkylbenzylidene)polyoxypropylenediamine, with average molecular weight M in the range of 730-880 g / mol n N,N',N''-tris(2,2-dimethyl-3-acetoxypropylidene)polyoxypropylenetriamine with an average molecular weight M in the range of 1150-1300 g / mol n N,N',N''-tris(2,2-dimethyl-3-lauroyloxypropylidene)polyoxypropylenetriamine having an average molecular weight M in the range of 1000 to 1350 g / moln N,N',N''-Tris(4-C 10~14 -alkylbenzylidene)polyoxypropylenetriamines.

[0142] The composition of the invention preferably contains at least one silane adhesion promoter. Organoalkoxysilanes, especially epoxysilanes, such as in particular 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane, (meth)acrylosilanes, anhydridosilanes, carbamatosilanes, alkylsilanes or iminosilanes or oligomeric forms of these silanes are suitable for this purpose. The use of silane adhesion promoters improves adhesion, in particular to glass and ceramic substrates. The composition preferably contains 0.1% to 1.0% by weight of silane adhesion promoter, based on the total composition.

[0143] In a preferred embodiment, the moisture-curable composition preferably contains 10% to 30% by weight of a non-thickening filler based on the total composition.

[0144] Non-thickening fillers are fillers that have essentially no effect on rheology. In contrast, carbon black and silica are counted among the thickening fillers.

[0145] Suitable non-thickening fillers are in particular powdered or precipitated calcium carbonate, optionally coated with fatty acids, in particular with stearates, barite, quartz flour, quartz sand, dolomite, wollastonite, calcined kaolin, sheet silicates, such as mica or talc, zeolites, aluminium hydroxide, magnesium hydroxide, graphite, metal powders, for example aluminium, copper, iron, silver or steel, PVC powder or lightweight fillers, such as hollow glass beads or gas-filled plastic spheres (microspheres), in particular of the type available under the trade name Expancel® (from Akzo Nobel).

[0146] Preferred are calcium carbonate and calcined kaolin, optionally coated with fatty acids, especially stearates.

[0147] In a particularly preferred embodiment, the non-thickening filler is selected from chalk and kaolin, and mixtures thereof.

[0148] Suitable plasticizers are in particular carboxylic acid esters, such as phthalates, in particular diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) or di(2-propylheptyl) phthalate (DPHP), hydrogenated phthalates or cyclohexane-1,2-dicarboxylate esters, in particular hydrogenated diisononyl phthalate or diisononyl cyclohexane-1,2-dicarboxylate (DINCH), terephthalates, in particular bis(2-ethylhexyl) terephthalate (DOTP) or diisononyl terephthalate (DINT), hydrogenated terephthalates or cyclohexane-1,4-dicarboxylate esters, in particular hydrogenated bis(2-ethylhexyl) terephthalate or bis(2-ethylhexyl) terephthalate (DOTP). (2-ethylhexyl)cyclohexane-1,4-dicarboxylate or diisononyl hydrogenated terephthalate or diisononyl cyclohexane-1,4-dicarboxylate, isophthalates, trimellitates, adipates, especially dioctyl adipate, azelates, sebacates, benzoates, glycol ethers, glycol esters, plasticizers having a polyether structure, especially polypropylene oxide mono-, di- or triols having blocked hydroxyl groups, especially those in the form of acetate groups, organic phosphoric or sulfonic acid esters, polybutenes, polyisobutenes or plasticizers derived from natural fats or oils, especially epoxidized soybean or linseed oil.

[0149] Preferred plasticizers are those having a phthalate or polyether structure.

[0150] Suitable diisocyanate oligomers are in particular HDI biurets, such as Desmodur® N100 or N3200 (from Covestro AG), Tolonate® HDB or HDB-LV (from Vencorex) or Duranate® 24A-100 (from Asahi Kasei); HDI isocyanurates, such as Desmodur® N3300, N3600 or N3790BA (all from Covestro), Tolonate® HDT, HDT-LV or HDT-LV2 (from Vencorex), Duranate® TPA-100 or THA-100 (from Asahi Kasei) or Coronate® HX (from Tosoh Corp.); HDI uretdiones, such as Desmodur® N3400 (Covestro); HDI iminooxadiazinediones, such as Desmodur® XP2410 (Covestro); HDI allophanates, such as Desmodur® VP LS2102 (Covestro); IPDI isocyanurates, such as Desmodur® Z4470 (Covestro) in solution or Vestanat® T1890 / 100 (Evonik Industries) in solid form; TDI oligomers, such as Desmodur® IL (Covestro); or mixed isocyanurates based on TDI / HDI, such as Desmodur® HL (Covestro).

[0151] Suitable catalysts are catalysts for accelerating the reaction of isocyanate groups, in particular organotin(IV) compounds, such as in particular dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetylacetonate, dimethyltin dilaurate, dioctyltin diacetate, dioctyltin dilaurate or dioctyltin diacetylacetonate, complexes of bismuth(III) or zirconium(IV) with ligands selected in particular from alkoxides, carboxylates, 1,3-diketonates, oxinates, 1,3-ketoesterates and 1,3-ketoamidates, or compounds containing tertiary amino groups, such in particular 2,2'-dimorpholinodiethyl ether (DMDEE).

[0152] If the moisture-curable composition contains a blocked amine, suitable catalysts are also catalysts for the hydrolysis of blocked amino groups, in particular organic acids, in particular carboxylic acids such as 2-ethylhexanoic acid, lauric acid, stearic acid, isostearic acid, oleic acid, neodecanoic acid, benzoic acid, salicylic acid or 2-nitrobenzoic acid, organic carboxylic acid anhydrides such as phthalic anhydride, hexahydrophthalic anhydride or methylhexahydrophthalic anhydride, silyl esters of carboxylic acids, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, sulfonic acid esters, other organic or inorganic acids or mixtures of the abovementioned acids and acid esters. Particularly preferred are carboxylic acids, in particular aromatic carboxylic acids such as benzoic acid, 2-nitrobenzoic acid or especially salicylic acid.

[0153] Combinations of different catalysts are also particularly suitable.

[0154] Suitable stabilizers are in particular stabilizers against oxidation, heat, light or UV radiation, in particular titanium dioxide, iron oxide, zinc oxide, benzophenones, benzotriazoles, compounds having a 2,6-di-tert-butylphenol group, known for example under the trade name Irganox® (BASF), compounds having a 2,2,6,6-tetramethylpiperidine group, known for example under the trade name Tinuvin® (BASF), so-called HALS (hindered amine light stabilizers), or phosphorus-containing compounds, known for example under the trade name Irgafos® (BASF).

[0155] The moisture-curable composition may contain further additives, in particular - inorganic or organic pigments, in particular titanium dioxide, chromium oxide or iron oxide; fibres, in particular glass fibres, carbon fibres, metal fibres, ceramic fibres, polymer fibres, for example polyamide fibres or polyethylene fibres or natural fibres, for example wool, cellulose, hemp or sisal; - nanofillers, such as graphene or carbon nanotubes; - dye; - desiccants, in particular molecular sieve powders, calcium oxide, highly reactive isocyanates, such as p-tosylisocyanate, monooxazolidines, such as Incozol® 2 (from Incorez) or orthoformates; adhesion promoters, in particular organoalkoxysilanes, in particular epoxysilanes, such as in particular 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane, (meth)acrylosilanes, anhydridosilanes, carbamatosilanes, alkylsilanes or iminosilanes or oligomeric forms or titanates of these silanes; - additional catalysts that accelerate the reaction of isocyanate groups; - rheology modifiers, in particular thickeners, in particular layered silicates, for example bentonite, derivatives of castor oil, hydrogenated castor oil, polyamides, polyamide waxes, polyurethanes, urea compounds, fumed silica, cellulose ethers or hydrophobically modified polyoxyethylenes; solvents, in particular acetone, methyl acetate, tert-butyl acetate, 1-methoxy-2-propyl acetate, ethyl 3-ethoxypropionate, diisopropyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-2-ethylhexyl ether, acetals such as propylal, butyral, 2-ethylhexylal, dioxolane, glycerol formal or 2,5,7,10-tetraoxaundecane (TOU), toluene, xylene, heptane, octane, naphtha, white spirit, petroleum ether or gasoline, in particular the Solvesso™ grades (from Exxon) and also propylene carbonate, dimethyl carbonate, butyrolactone, N-methylpyrrolidone, N-ethylpyrrolidone, p-chlorobenzotrifluoride or benzotrifluoride; natural resins, fats or oils, such as rosin, shellac, linseed oil, castor oil or soybean oil; - non-reactive polymers, in particular homo- or copolymers of unsaturated monomers, in particular those from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth)acrylates, in particular polyethylene (PE), polypropylene (PP), polyisobutylene, ethylene / vinyl acetate copolymers (EVA) or atactic poly-α-olefins (APAO); - flame retardant substances, in particular the already mentioned aluminum hydroxide or magnesium hydroxide fillers and more particularly organic phosphates, such as in particular triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenylcresyl phosphate, isodecyldiphenyl phosphate, tris(1,3-dichloro-2-propyl) phosphate, tris(2-chloroethyl) phosphate, tris(2-ethylhexyl) phosphate, tris(chloroisopropyl) phosphate, tris(chloropropyl) phosphate, isopropylated triphenyl phosphate, mono-, bis- or tris(isopropylphenyl) phosphates with different degrees of isopropylation, resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate) or ammonium polyphosphate; additives, in particular wetting agents, levelling agents, defoamers, degassing agents or biocides; or further substances customarily used in moisture-curing polyurethane compositions. may contain

[0156] It may be desirable to chemically or physically dry certain materials before incorporating them into the composition.

[0157] Preferably, the composition of the invention contains little solvent, in particular less than 5% by weight, preferably less than 2.5% by weight, of solvent. Most preferably, the composition of the invention is essentially free of solvent.

[0158] The moisture-curable composition preferably comprises - 25% to 50% by weight of polymer P1, optionally up to 1.5% by weight of polymer P2, optionally up to 2% by weight of polymer P3, - 21% to 25% by weight of carbon black, - 10% to 30% by weight of a non-thickening filler, - 10% to 20% by weight of a plasticizer, and Optionally, further components, in particular silane adhesion promoters, blocked amines, diisocyanate oligomers, drying agents, catalysts and / or stabilizers. with the proviso that at least one of the polymers P2 and P3 is present in the composition.

[0159] The moisture-curable composition preferably contains at least 0.5% by weight of polymer P2 and / or at least 0.5% by weight of polymer P3, based on the total composition.

[0160] A particularly preferred embodiment of the composition of the invention contains 0.5% to 1.5% by weight of polymer P2, based on the total composition, and does not contain polymer P3.

[0161] A further particularly preferred embodiment of the composition of the invention contains 0.5% to 2.0% by weight of polymer P3, based on the total composition, and does not contain polymer P2.

[0162] A further particularly preferred embodiment of the composition according to the invention contains from 0.5% to 1.5% by weight of polymer P2, based on the total composition, and from 0.5% to 2.0% by weight of polymer P3, based on the total composition.

[0163] In all embodiments, the moisture-curable compositions preferably contain less than 0.1% by weight of monomeric diisocyanates, and such compositions may be shipped and sold in many countries without being classified as hazardous materials.

[0164] The moisture-curable compositions are in particular produced with the exclusion of moisture and stored at ambient temperature in moisture-proof containers. Suitable moisture-proof containers are in particular made of metal and / or plastic, optionally coated, in particular drums, transport boxes, hobs, buckets, canisters, tins, bags, tubular bags, cartridges or tubes.

[0165] The moisture-curable composition is preferably a one-component composition, which, given suitable packaging and storage, is typically shelf stable for several months, up to a year or more.

[0166] Moisture-curable compositions begin to cure under the influence of moisture or water during and after application. To accelerate the cure, an accelerator component containing water and optionally a catalyst and / or a curing agent can be mixed into the composition at the time of application, or the composition can be contacted with such an accelerator component once it has been applied.

[0167] During the curing process, the isocyanate groups react with each other under the influence of moisture. If the moisture-curable composition contains a blocked amine, the isocyanate groups react additionally with the blocked amino groups as they are hydrolyzed. The totality of these reactions of the isocyanate groups that results in the curing of the composition is also referred to as crosslinking. This results in a cured composition.

[0168] The moisture required for the curing of the composition preferably flows into the composition via diffusion from air (atmospheric moisture). In this process, a solid layer ("skin") of the cured composition is formed on the surface of the composition, which is in contact with air. Curing proceeds in the direction of diffusion from the outside to the inside, and the skin gradually thickens, eventually covering the entire applied composition. Moisture can also come from the accelerator component that additionally or entirely flows into the composition from one or more substrates to which the composition is applied, and / or that is mixed into the composition during application or that comes into contact with it after application, for example by painting or spraying.

[0169] The moisture-curable composition is preferably applied at ambient temperature or in slightly heated form, especially in the range of -5 to 80°C, preferably 0 to 70°C, especially 25 to 65°C.

[0170] If polymer P2 is present, the moisture-curable composition is preferably applied in the heated state, for example at a temperature of 40°C to 80°C.

[0171] Moisture curable compositions are preferably cured at ambient temperature.

[0172] Moisture curable compositions have long application times (open times) and rapid cure.

[0173] "Open time" refers to the period during which the composition can be applied or reapplied after application without any loss of its functional capacity. If the composition is used as an adhesive, the open time also refers in particular to the period during which a bond must be made after its application in order for sufficient adhesion to occur. The open time is exceeded when at least a skin is formed or when there is no longer sufficient adhesion to the substrate.

[0174] The moisture-curable composition is preferably used as an elastic adhesive and / or sealant for bonding or sealing applications, especially in the construction and manufacturing industry or in automotive assembly, in particular for parquet bonding, assembly, bonding of attachable components, module bonding, pane bonding, joint sealing, body sealing, seam sealing or cavity sealing.

[0175] Elastic connections in vehicle assembly are, for example, the bonding attachment of parts, such as plastic covers, trim strips, flanges, fenders, cabs or other mountable components to the painted body of a vehicle, or the bonding of panes into a vehicle body, said vehicle being in particular a car, truck, bus, rail car or ship.

[0176] Particularly preferred is the use as an adhesive for automotive glazing, especially for glass replacement in automobiles.

[0177] The moisture-curable composition is preferably formulated so that it has a paste-like consistency, typically free-flowing under standard squeeze pressure, and structural viscous properties at room temperature or in slightly heated form. Compositions of this type are applied by suitable equipment, for example from commercially available cartridges or drums or hobbos, in particular in the form of a bead which may have an essentially circular or triangular cross-sectional area.

[0178] Suitable substrates that can be bonded and / or sealed with the moisture-curable composition are in particular - glass, glass ceramic or screen printed ceramic coated glass or polycarbonate; - surface-finished metals or alloys, such as zinc-plated or chromium-plated metals or alloys, e.g. aluminium, copper, iron, steel, non-ferrous metals; - coated or painted substrates, in particular powder-coated metals or alloys or painted sheet metal; - paints or varnishes, in particular automotive topcoats; - cured adhesives, in particular those based on polyurethanes, silane-modified polymers or polysulfides, in particular curing adhesives (residual adhesive beads) or body flanges having residual adhesive beads at any point or in any fixed position; - plastics, such as rigid or flexible PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM, in each case untreated or surface-treated, for example by plasma, corona or flame; - Fiber reinforced plastics, such as carbon fiber reinforced plastics (CFRP), glass fiber reinforced plastics (GFRP) and sheet molding compounds (SMC); - Repair or levelling compounds based on PCC (polymer modified cement mortar) or ECC (epoxy resin modified cement mortar); - insulating foams, in particular those made of EPS, XPS, PUR, PIR, rock wool, glass wool or foamed glass; - concrete, mortar, cement screed, fibre cement, in particular fibre cement boards, bricks, tiles, gypsum, in particular gypsum boards or anhydrite screeds or natural stone, for example granite or marble, painted tiles or painted concrete, asphalt or bitumen; - leather, textiles, paper, wood, resins, e.g. wood combined with phenolic, melamine or epoxy resins, further materials called resin / textile composites or polymer composites It is.

[0179] The substrate may, if desired, be pretreated prior to application, especially by physical and / or chemical cleaning methods or by application of an activator or primer.

[0180] It is possible to bond and / or seal two identical or two different substrates.

[0181] The present invention provides a method of bonding or sealing comprising the steps of: (i) A moisture-curable composition as described above, - applying to a first substrate and contacting the composition with a second substrate during the open time of the composition; or - applying to a first and a second substrate and bonding the two substrates together within the open time of the composition; or - applying between two substrates; (ii) curing the composition by contact with moisture The present invention further provides a method comprising:

[0182] At least one of the substrates is preferably selected from the group consisting of glass, glass ceramic, screen printed ceramic coated glass or polycarbonate, metals, alloys, powder coated metals or alloys, paints and varnishes and cured adhesives, in particular sheet metal painted with residual adhesive bead and / or automotive topcoats.

[0183] The application and curing or bonding or sealing process of the moisture curable composition results in an article bonded or sealed with the composition, which may be an architectural structure or part thereof, in particular an architectural structure in civil engineering above or below ground, a bridge, a roof, a staircase or a facade, or it may be an industrial or consumer product, in particular a window, a pipe, a rotor blade of a wind turbine, a household appliance or a means of transport, such as in particular a car, a bus, a truck, a rail car, a ship, an aircraft or a helicopter or an attachable component thereof.

[0184] The present invention therefore further provides an article resulting from the bonding or sealing method described.

[0185] Particularly preferred is the use of the bonding method for elastic bonding of glass panes to automobiles, especially for glass replacement, where good adhesion to the remaining adhesive bead is particularly important.

[0186] The moisture-curing composition has advantageous properties: it has particularly good bonding properties without any tendency to peel off, particularly good application properties, particularly good crushability combined with high sag resistance and particularly good early strength without substrate displacement, and has good cure, strength, extensibility, elasticity and hazardous materials classification without change.The composition is therefore particularly suitable as an elastic adhesive in automobile assembly, particularly for the insertion of windshields in automobiles or for the repair of defective windshields in automobiles. EXAMPLES

[0187] Examples are given below, which further illustrate the invention described. It is clear that the invention is not limited to these described examples.

[0188] "Standard Climatic Conditions" ("SCC") refers to a temperature of 23±1°C and a relative air humidity (rh) of 50±5%.

[0189] Chemicals used were from Sigma-Aldrich Chemie GmbH unless otherwise stated.

[0190] Preparation of polymers containing isocyanate groups: Viscosity was measured using a thermostatic Rheotec RC30 cone-plate viscometer (cone diameter 25 mm, cone angle 1°, cone tip-plate distance 0.5 mm, shear rate 50 s -1 ) was used for the measurements.

[0191] Monomeric diisocyanate content was determined by HPLC (detection via photodiode array; 0.04 M sodium acetate / acetonitrile as mobile phase) after prior derivatization with N-propyl-4-nitrobenzylamine.

[0192] Polymer P1-1 (Polymer P1a, invention): 727.0 g of Acclaim® 4200 (polyoxypropylene diol, OH number 28 mg KOH / g, manufactured by Covestro) and 273.0 g of diphenylmethane 4,4′-diisocyanate (Desmodur® 44MC L, manufactured by Covestro) were converted by known methods into a polyether urethane polymer having an NCO content of 7.6% by weight, a viscosity of 5.2 Pa·s at 20° C. and a diphenylmethane 4,4′-diisocyanate content of about 18% by weight.

[0193] The majority of the volatile constituents, especially the diphenylmethane 4,4'-diisocyanate, were subsequently removed as described for polymer P1-1. The polyetherurethane polymer thus obtained had an NCO content of 1.8% by weight, a viscosity of 15.2 Pa·s at 20° C. and a diphenylmethane 4,4'-diisocyanate content of 0.08% by weight.

[0194] Polymer P1-2 (Polymer P1b, invention): 725.0 g of Desmophen® 5031BT (glycerol initiated ethylene oxide terminated polyoxypropylene triol, OH number 28 mg KOH / g, ex Covestro) and 275.0 g of diphenylmethane 4,4′-diisocyanate (Desmodur® 44MC L, ex Covestro) were converted by known methods into a polyether urethane polymer having an NCO content of 7.6 wt. %, a viscosity of 6.5 Pa·s at 20° C. and a diphenylmethane 4,4′-diisocyanate content of about 20 wt. %.

[0195] The majority of the volatile components, especially diphenylmethane 4,4'-diisocyanate, were subsequently removed by distillation in a short-path still (jacket temperature 180°C, pressure 0.1-0.005 mbar, condensation temperature 47°C). The polyetherurethane polymer thus obtained had an NCO content of 1.7% by weight, a viscosity of 19 Pa·s at 20°C and a diphenylmethane 4,4'-diisocyanate content of 0.04% by weight.

[0196] Polymer P1Ra (non-inventive linear polyether urethane polymer): 400 g of polyoxypropylene diol (Acclaim® 4200, from Covestro AG; OH number 28.5 mg KOH / g) and 52 g of diphenylmethane 4,4′-diisocyanate (Desmodur® 44MC L, from Covestro AG) were reacted at 80° C. according to a known process to give an NCO-terminated polymer which was liquid at room temperature and had an isocyanate group content of 1.85% by weight and a content of monomeric diphenylmethane 4,4′-diisocyanate of about 2.1% by weight.

[0197] Polymer P1Rb (branched polyether urethane polymer not according to the invention): 685 g of Voranol® CP4755 (glycerol initiated ethylene oxide terminated polyoxypropylene triol, OH number 35.0 mg KOH / g, OH functionality about 2.4; from Dow), 115 g of diphenylmethane 4,4'-diisocyanate (Desmodur® 44MC L, from Covestro) and 200 g of diisodecyl phthalate (DIDP) were converted by known methods at 80° C. into a polyether urethane polymer with an NCO content of 1.9% by weight and a monomeric diphenylmethane 4,4'-diisocyanate content of about 2.1% by weight. Due to the high viscosity of the polymer, it contains 20% by weight of DIDP remaining from the synthesis.

[0198] Polymer P2-1 (Polymer P2, invention): 709.0 g of polyesterdiol (Dynacoll® 7360, semi-crystalline, OH number 30.5 mg KOH / g, from Evonik) and 291.0 g of diphenylmethane 4,4′-diisocyanate (Desmodur® 44MC L, from Covestro) were converted by known methods at 80° C. to a polymer with an NCO content of 7.8% by weight, a viscosity of 7.9 Pa·s at 60° C. and a content of the monomer diphenylmethane 4,4′-diisocyanate of about 16% by weight.

[0199] Subsequently, the majority of the volatile constituents, in particular the monomeric diphenylmethane 4,4'-diisocyanate, were removed by distillation in a short-path still (jacket temperature 180 °C, pressure 0.1-0.005 mbar, condensation temperature 47 °C). The room-temperature solid polymer thus obtained had an NCO content of 1.8 wt.%, a viscosity of 7.1 Pa·s at 100 °C and a monomeric diphenylmethane 4,4'-diisocyanate content of 0.2 wt.%.

[0200] Polymer P3-1 (Polymer P3, invention): 500.0 g of PTMG-650 (Terathane® 650, OH number 170-180 mg KOH / g, Invista) and 750.0 g of diphenylmethane 4,4'-diisocyanate (Desmodur® 44MC L, Covestro) were converted at 80°C by known methods to a polymer with an NCO content of 15.4 wt. % (NCO / OH approximately 4 / 1).

[0201] The majority of the volatile constituents, in particular the monomeric diphenylmethane 4,4'-diisocyanate, were subsequently removed by distillation in a short-path still (jacket temperature 180° C., pressure 0.1-0.005 mbar, condensation temperature 47° C.) The room-temperature liquid polymer thus obtained had an NCO content of 6.0% by weight and a monomeric diphenylmethane 4,4'-diisocyanate content of 0.05% by weight.

[0202] Polymer P3-2 (Polymer P3, invention): Polymer P3-2 was prepared similarly to polymer P3-1, except that 330 g of Voranol P400 (Voranol® P400, OH number 260 mg KOH / g, Dow) was used as diol instead of 500.0 g of PTMG-650. The room temperature liquid polymer thus obtained had an NCO content of 4.0% by weight and a content of the monomer diphenylmethane 4,4′-diisocyanate of 0.05% by weight.

[0203] Polymers P1-1 and P1-2 are polyetherurethane polymer P1. Polymers P1Ra and P1Rb are equivalent polyetherurethane polymers but not according to the invention (in terms of NCO / OH ratio). Polymer P2-1 is invention polymer P2. Polymers P3-1 and P3-2 are invention polymer P3.

[0204] Moisture-curing compositions: Compositions Z1~Z17: For each composition, the components specified in Tables 1 and 2 were thoroughly mixed in the amounts (parts by weight) specified in a planetary mixer under reduced pressure with the exclusion of moisture, and each composition was dispensed into aluminum cartridges with airtight seals and stored at room temperature.

[0205] The following result measurements are given in Tables 1 and 2 as well.

[0206] Compositions labeled "(Ref.)" are comparative examples.

[0207] Each composition was tested as follows: The measure determined for the workability or spreadability of the composition was the squeeze force, i.e. the force required to squeeze the composition out of the cartridge. A lower squeeze force means a higher workability or spreadability.

[0208] The squeeze force was determined at 60° C. The first closed cartridge was stored at 23° C. for 7 days and then heated at 60° C. for 2 hours. The squeeze force was then measured in each case by means of a squeezer (Zwick / Roell Z005) by screwing a nozzle with an inner diameter of 3 mm into the cartridge and then measuring the force required to squeeze the composition through the nozzle at a squeeze rate of 60 mm / min. The reported value is the average of the forces measured after squeeze distances of 22 mm, 24 mm, 26 mm and 28 mm. Values ​​below 1200 N are considered adequate and values ​​below 1100 N are considered good.

[0209] For the determination of mechanical properties, each composition was pressed between two silicone-coated release papers to obtain a thin film 2 mm thick and stored under standard climatic conditions for 14 days. After removal of the release papers, several test specimens were punched out and tested as described below:

[0210] For the determination of the tensile strength, elongation at break and modulus of elasticity at an elongation of 0.5-5%, dumbbell pieces with a length of 75 mm with a bar length of 30 mm and a bar width of 4 mm were punched out of the thin films and they were tested according to DIN EN53504 at a strain rate of 200 mm / min.

[0211] Further measurements were carried out to determine the tendency to slip (slip-off), the adhesive stability (peel-off) under compressive and tensile stresses required for bonding of substrates, and to determine the suitability of the compositions as adhesives for window adhesives in automotive manufacturing.

[0212] The measurements of the compression force were carried out with a Zwicki 1020 testing machine (Zwick Roell, Germany) and the accompanying software (TestXpert Advanced Edition; compression force test program). For this purpose, the adhesive, which had been heated in a cartridge for 2 hours at 60° C., was applied in the form of an equilateral triangular bead to a polyethylene sheet (L×W×H=100 mm×40 mm×6 mm) over its entire length. The adhesive bead had an original height of 10 mm, a base width of 8 mm and a length of 100 mm. Exactly 5 minutes after application of the adhesive bead at 23° C. and 50% rh, the sheet with the adhesive bead was inserted into the testing machine. A second test sheet of the same type was placed on the adhesive bead in such a way that the faces of the two test sheets were parallel to each other and the sheets were aligned. The sheet was then compressed at a constant speed of 200 mm / min and the required compression force was recorded until a compressed adhesive bead with a height of 4 mm and a width of 9-11 mm was obtained. Measurements made by the test program gave the compression force (N / cm) required to compress the adhesive to that thickness. Reported values ​​are the average of at least three measurements. A relatively low compression force is preferred. Values ​​below 4 N / cm are considered adequate.

[0213] The tendency of the bond to delaminate (loss of adhesion under tensile stress) with the test composition was tested as follows: the cartridge with the test composition was heated in an oven at 60° C. for 2 hours before application of the test material. During this period, two test sheets were prepared. A first test sheet (250 mm×40 mm×4 mm) made of float glass was pretreated on the air side with Sika® HydroPrep®-110 (a water-based primer available from Sika Schweiz). A second test sheet, a steel sheet coated with cathodic electrodeposition (L×W×H=120 mm×50 mm×0.8 mm), was cleaned with heptane. The coated steel sheet was clamped horizontally in a holder. A triangular bead of the adhesive to be tested, 100 mm long, was applied to the pretreated glass plate, and the plate with the bead was pressed at 23°C / 50% rh on a fixed steel plate 1 minute after application, with a spacer of 5 mm, which compressed the adhesive bead. This compressed the original triangular bead between the two plates to a size of (L x W x H =) 100 mm x 10 mm x 5 mm. After 2.5 minutes of compression, the screw started to increase the pressure on one side (width) of the glass plate, so that the distance between the plates where it was initially applied increased and spread on one side (width), thus imposing a tensile stress on the bond on one side. The dynamic increase in tensile stress resulted from a continuous increase in the distance between the two plates on one side (width) at 0.5 mm / 20 s. After 6 minutes and 20 seconds from the start of the tensile strength, an additional distance of 10 mm was thus continuously created on one side (width) of the initially parallel plates. During the measurement, the distance (0-10 mm) at which the first peeling phenomenon (detachment of the adhesive from the steel plate) was evident was continuously monitored. The evaluation was according to the following scheme: No significant peeling within a distance of 10 mm: "OK" Peeling begins at a distance of 5-10 mm: "moderate" Peeling begins before a distance of 5 mm: "High".

[0214] What is desired is a value that is classified as "OK", ie, a measurement that does not show bond delamination (loss of adhesion).

[0215] For the measurement of slippage (vertical slippage characteristic of the substrate in freshly applied adhesive), a square metal plate (L x W = 320 mm x 320 mm) with a weight of 4200 g was provided. Decorator adhesive tape was applied along the edge on one side of the plate. Triangular beads of the adhesive to be tested were applied to all four edges of the decorator adhesive tape while the plate was placed on a balance. It was ensured that a total of 80 g of adhesive to be tested was applied (20 g per edge per triangular bead). The triangular beads each had a base width of about 10 mm and a height of about 10 mm. The adhesive was applied directly in the warm state, having previously been subjected to a heat treatment in a cartridge at 60 ° C for 2 hours. The measurements were carried out in a climate-controlled space (23 ° C, 50% rh). 30 seconds after application of the adhesive bead, the adhesive-coated plate was pressed onto a second vertically fixed square plate (L×W=400 mm×400 mm) additionally with a spacer (5 mm) so that the two plate faces were placed parallel and the plate faces faced directly downwards. The adhesive bead between the plates was compressed to a thickness of 5 mm with the aid of the spacer, while the first non-fixed plate was first stabilized against downward slippage. After 30 seconds of compression of the adhesive between the plates (60 seconds after application of the adhesive bead), the device stabilizing the first non-fixed plate was removed and a measurement of the slippage characteristic was measured by a digital distance measuring device (Sony U30A). The distance that the non-fixed first plate subsequently slipped under its own weight is described by slippage (mm). Low slippage values ​​are desirable, values ​​of less than 0.5 mm are considered adequate and values ​​of less than 0.4 mm are considered good.

[0216] The results are reported in Tables 1 and 2.

[0217] Compositions labeled "(Ref.)" are comparative examples.

[0218] The data in Tables 1 and 2 show that only the compositions of the invention have all these properties in combination, at the same time they have good mechanical properties (tensile strength and elongation at break) and therefore optimal suitability as elastic structural adhesives.

[0219] Compositions with a squeeze force of <1200N, a compression force of <4cm, a slippage of <0.5mm and a peel classified as "OK" are optimally suitable as adhesives for the automotive industry, in particular as window adhesives. They have good application properties for automotive applications as well as good early strength and good adhesive stability.

[0220] Compositions containing less than 20% by weight carbon black exhibit too high shear-off.

[0221] [Table 1]

[0222] [Table 2]

Claims

1. A moisture-curable polyurethane composition, at least one polyetherurethane polymer P1 containing isocyanate groups and having a monomeric diisocyanate content of not more than 0.5% by weight, the at least one monomeric diisocyanate having an average molecular weight M of more than 2500 g / mol with an NCO / OH ratio of at least 3 / 1; ｎ with at least one polyether polyol having the formula: and subsequent removal of most of the monomeric diisocyanates by suitable separation methods; and more than 20% by weight of carbon black, based on the total composition; - optionally up to 2% by weight, based on the total composition, of a polyurethane polymer P2 solid at room temperature obtained from the reaction of at least one monomeric diisocyanate with at least one at least semi-crystalline polyester polyol or polycarbonate polyol, in an NCO / OH ratio of at least 1.3 / 1; optionally, at least one monomeric diisocyanate with an average molecular weight M of less than or equal to 2500 g / mol, with an NCO / OH ratio of at least 1.3 / 1; ｎ and at most 5% by weight, based on the total composition, of a polyetherurethane polymer P3 obtained from the reaction of at least one polyether diol having the formula with the proviso that at least one of said polymers P2 and P3 is present in said composition.

2. 2. The moisture-curable composition according to claim 1, wherein the at least one polymer P1 has an NCO content ranging from 1% to 5% by weight and at least 80% by weight of 1,2-propyleneoxy units in the polyether segments.

3. 3. The moisture-curable composition according to claim 1, wherein the isocyanate groups of the polymers P1, P2 and / or P3 are derived from diphenylmethane 4,4'-diisocyanate.

4. 3. The moisture-curable composition according to claim 1, wherein the polymer P1 comprises at least one polymer P1a obtained from a polyether diol and at least one polymer P1b obtained from a polyether triol.

5. 3. The moisture-curable composition according to claim 1, comprising 20.5% by weight to 25% by weight of carbon black based on the total weight of the composition.

6. 3. The moisture-curing composition according to claim 1, which contains 0.5 to 1.5% by weight of polymer P2, based on the total composition.

7. 3. The moisture-curable composition according to claim 1, which contains 0.5% to 2% by weight of polymer P3, based on the total composition.

8. 8. The moisture-curing composition according to claim 7, characterized in that the polymer P3 is based on poly(oxy-1,4-butylene)diol.

9. 3. The moisture-curable composition according to claim 1, comprising 10 to 30% by weight of a non-thickening filler based on the total weight of the composition.

10. 10. The moisture-curing composition according to claim 9, characterized in that the non-thickening filler is selected from chalk and kaolin and mixtures thereof.

11. 3. The moisture-curable composition according to claim 1 or 2, characterized in that at least one further component selected from silane adhesion promoters, blocked amines, diisocyanate oligomers, drying agents, catalysts and stabilizers is additionally present.

12. In each case based on the composition as a whole, - 25% to 50% by weight of polymer P1, optionally up to 1.5% by weight of polymer P2, optionally up to 2% by weight of polymer P3, - 21% to 25% by weight of carbon black, - 10% to 30% by weight of a non-thickening filler, - 10% to 20% by weight of a plasticizer, and Optionally, further components, in particular silane adhesion promoters, blocked amines, diisocyanate oligomers, drying agents, catalysts and / or stabilizers, 12. The moisture-curable composition according to claim 11, characterized in that it contains at least one of polymers P2 and P3, with the proviso that at least one of polymers P2 and P3 is present in the composition.

13. 12. Moisture-curing composition according to claim 11, characterized in that it contains at least 0.5% by weight of polymer P2 and / or at least 0.5% by weight of polymer P3, based on the total composition.

14. 1. A method of bonding or sealing comprising the steps of: (i) The moisture-curable composition according to claim 1 or 2, - applying to a first substrate and contacting said composition with a second substrate within the open time of said composition, or - applying to a first and a second substrate and bonding the two substrates together during the open time of the composition; or - application between two substrates; (ii) curing the composition by contact with moisture; A method comprising:

15. 15. An article obtained from the method of claim 14.

Images