MOISTURE-CURING COMPOSITION WITH GOOD ADHESION PROPERTIES

Description

Technical field

[0001] The invention relates to moisture-curing polyurethane compositions and their use as elastic adhesives and / or sealants for construction and industrial applications, in particular for the replacement glazing of vehicles. State of the art

[0002] Curable polyurethane-based adhesives are often used as adhesives for elastic bonding, for example, in automotive construction. Good properties are required, particularly with regard to storage stability, applicability, open time, curing speed, adhesion, strength, elasticity, weather resistance, and hazardous substance classification.

[0003] Single-component, moisture-curing systems are popular, primarily due to their ease of use. These systems generally exhibit good adhesion properties. However, there are applications on specific substrates where achieving good adhesion is difficult. One example is the bonding of replacement windshields in vehicles, where the body flange as a substrate contains both areas of exposed paint and areas with residues of the old adhesive adhering to the paint, which has not been completely removed or left as a primer ("residual adhesive bead"). If the new adhesive does not fully adhere to the residual adhesive bead, unwanted water ingress or wind noise can occur, and even the windshield may detach.Today's moisture-curing adhesives often exhibit insufficient adhesion to residual adhesive beads without appropriate pretreatment, especially if the old adhesive has aged significantly and thus become hard or brittle. To improve adhesion to residual adhesive beads, known adhesion promoters such as diisocyanate oligomers or derivatives thereof can be used; however, this leads to a loss of elasticity of the adhesive after curing.

[0004] Hydrophobic diols are typically used in two-component polyurethanes, particularly to improve cold flexibility or weathering stability. However, they are rarely used in one-component moisture-curing polyurethanes. WO2017 / 103070 describes a moisture-curing polyurethane adhesive with high early strength that is heated for application. It contains a polymer containing isocyanate groups, which is a multi-stage reaction product of a polyol mixture with, among other things, a dimer fatty acid-based polyol. This reaction product is very viscous and complex to produce. Due to its poor extrusion properties, it is unsuitable for adhesives that are intended to be applied at room temperature, and it does not enable the desired adhesion to residual adhesive bead. Description of the invention

[0005] The object of the present invention is to provide single-component moisture-curing polyurethane compositions with good adhesion to difficult-to-bond substrates such as residual adhesive beads, which do not have any disadvantages in other relevant product properties, in particular storage stability, applicability, curing speed, weather resistance, blistering, strength, extensibility, elasticity and hazardous substance classification.

[0006] This object is achieved with a moisture-curing composition as described in claim 1. The composition contains an isocyanate-containing polyetherurethane polymer P1 containing at least 80% by weight of 1,2-propyleneoxy units in the polyether segment and a hydrophobic polymer containing isocyanate groups P2based on a hydrophobic diol with an OH number in the range of 28 to 120 mg KOH / g, selected from a dimer fatty acid-based polyester diol or a poly(1,2-butylene glycol). The polymers P1 and P2 are prepared separately and are present in a weight ratio ranging from 70 / 30 to 98 / 2. They preferably each contain a small amount of monomeric diisocyanates.

[0007] The composition according to the invention is easy to process at room temperature, has a surprisingly long open time, surprisingly good adhesion to residual adhesive bead and a particularly high weather resistance, without any loss of curing speed, strength, extensibility or other relevant product properties compared to corresponding compositions without polymer P2Furthermore, carbon black-filled compositions according to the invention exhibit surprisingly low sooting efflorescence, preventing soiling of the substrates even after prolonged use. Furthermore, the composition according to the invention has a matte surface, which is highly desirable for many users in the case of visible adhesive joints.

[0008] Particularly surprising is the fact that the composition according to the invention has unexpectedly good processing properties. Even with a low content of hydrophobic polymer, it P2 Can be pressed out of the container with very little force at room temperature and at low temperatures, with unchanged good stability and short thread tension compared to corresponding compositions without polymer P2.

[0009] To improve initial strength, sag resistance, and stringing resistance, moisture-curing polyurethane adhesives, particularly for automotive applications, often also contain a melt component, typically a small amount of a room-temperature solid polyurethane polymer based on a crystalline polyester polyol. However, the melt component increases the adhesive's extrusion force at room temperature and in cold conditions, and the extrusion strength is highly shear-dependent, which can lead to problems during production and application. Surprisingly, the composition according to the invention is surprisingly easy to extrude even when it also contains a melt component, with the rheological properties being significantly less shear-dependent. In particular, the composition according to the invention enables adhesives in which the melt component can be used in significantly lower amounts or omitted entirely.

[0010] The composition according to the invention enables moisture-curing elastic polyurethane sealants and adhesives that can be applied at room temperature and have improved adhesion properties with a long open time, in particular on special substrates such as residual adhesive beads, improved application properties, in particular particularly good extrusion properties, even at cool temperatures, with the increase in extrusion force between room temperature and 5°C being particularly low, a matt surface and particularly good weather resistance, with unchanged good properties in terms of storage stability, curing speed, blistering, strength, extensibility, elasticity and hazardous substance classification compared to corresponding compositions without polymer. P2. This makes the composition particularly suitable as an elastic adhesive in vehicle construction, especially for replacing defective, elastically bonded windshields on automobiles.

[0011] Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims. Ways to implement the invention

[0012] The invention relates to a moisture-curing composition which is liquid at room temperature and optionally pasty and contains at least one polyetherurethane polymer containing isocyanate groups P1 containing at least 80% by weight of 1,2-propyleneoxy units in the polyether segment, and at least one hydrophobic, isocyanate-containing polymer which is liquid at room temperature P2, obtained from the reaction of at least one monomeric diisocyanate and a hydrophobic diol having an OH number in the range of 28 to 120 mg KOH / g, where the polymers P1 and P2 are produced separately and the polymer P1 and the polymer P2in a weight ratio in the range of 70 / 30 to 98 / 2, characterized in that the hydrophobic diol for the preparation of the polymer P2 is selected from the group consisting of dimer fatty acid-based polyester diols and poly(1,2-butylene glycol).

[0013] A "monomeric diisocyanate" is an organic compound with two isocyanate groups separated by a divalent hydrocarbon radical with 4 to 15 carbon atoms.

[0014] A "polyetherurethane polymer" is a polymer that has ether groups as repeating units and additionally contains urethane groups.

[0015] A "dimer fatty acid-based polyester diol" is a polyester diol that has been produced from a dimer fatty acid and / or a dimer fatty alcohol.

[0016] The "NCO content" refers to the content of isocyanate groups in weight percent based on the total polymer.

[0017] "Molecular weight" refers to the molar mass (in grams per mole) of a molecule or moiety. "Mean molecular weight" is the number average molecular weight (M n ) of a polydisperse mixture of oligomeric or polymeric molecules or moieties. It is determined by gel permeation chromatography (GPC) using polystyrene as a standard.

[0018] A substance or composition is described as "storage-stable" or "storable" if it can be stored at room temperature in a suitable container for a prolonged period of time, typically for at least 3 months up to 6 months or more, without its application or use properties being changed by storage to an extent relevant to its use.

[0019] A composition is called "one-component" if all components of the composition are present in the same container and which, as such, is storage-stable.

[0020] A temperature of 23°C is referred to as “room temperature”.

[0021] All industry standards and norms mentioned in this document refer to the versions valid at the time of filing the initial application.

[0022] Weight percentages (wt%) indicate the mass fraction of a component of a composition or molecule relative to the total composition or molecule, unless otherwise stated. The terms "mass" and "weight" are used synonymously in this document.

[0023] The moisture-curing composition contains at least one isocyanate-containing polyetherurethane polymer P1with a content of at least 80% by weight of 1,2-propyleneoxy units in the polyether segment. Preferably, the polyetherurethane polymer contains P1 80 to 100 wt% 1,2-propyleneoxy units and 0 to 20 wt% 1,2-ethyleneoxy units in the polyether segment.

[0024] Preferably, the polyetherurethane polymer P1 an average NCO functionality in the range of 1.8 to 3.5, preferably 2 to 3.

[0025] Preferably, the polyetherurethane polymer P1 an NCO content in the range of 1 to 5% by weight, in particular 1 to 3% by weight.

[0026] Preferably, the polyetherurethane polymer P1 an average molecular weight M n in the range of 2,000 to 20,000 g / mol, preferably 3,000 to 15,000 g / mol.

[0027] Preferably, the polyetherurethane polymer P1a viscosity at 20°C in the range from 5 to 300 Pa·s, particularly preferably 5 to 200 Pa·s, in particular 5 to 100 Pa·s. The viscosity is determined using a cone-plate viscometer with a cone diameter of 25 mm, cone angle of 1°, cone tip-to-plate distance of 0.5 mm at a shear rate of 50 s -1< .

[0028] The preferred polyetherurethane polymers P1 enable easily processable moisture-curing compositions with high elasticity and extensibility and high strength.

[0029] The isocyanate group-containing polyetherurethane polymer P1 is obtained in particular from the reaction of at least one monomeric diisocyanate and at least one suitable polyether polyol. The reaction is preferably carried out in the absence of moisture at a temperature in the range of 20 to 160°C, in particular 40 to 140°C, optionally in the presence of suitable catalysts.

[0030] The NCO / OH ratio is preferably in the range from 1.3 / 1 to 10 / 1. The monomeric diisocyanate remaining in the reaction mixture after the reaction of the OH groups can be removed, in particular by distillation. If excess monomeric diisocyanate is removed by distillation, the NCO / OH ratio during the reaction is preferably in the range from 3 / 1 to 10 / 1, in particular 4 / 1 to 7 / 1, and the resulting isocyanate-containing polyetherurethane polymer preferably contains at most 0.5% by weight, particularly preferably at most 0.3% by weight, of monomeric diisocyanate after distillation.

[0031] If no excess monomeric diisocyanate is removed from the polyetherurethane polymer, the NCO / OH ratio during the reaction is preferably in the range of 1.3 / 1 to 2.5 / 1. Such a polyetherurethane polymer contains, in particular, at most 3% by weight, preferably at most 2% by weight, of monomeric diisocyanate.

[0032] As a monomeric diisocyanate for the production of the polyetherurethane polymer P1 Suitable are commercially available aromatic, aliphatic or cycloaliphatic diisocyanates, in particular 4,4'-diphenylmethane diisocyanate, optionally with proportions of 2,4'- and / or 2,2'-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate or mixtures thereof with 2,6-tolylene diisocyanate (TDI), 1,4-phenylene diisocyanate (PDI), naphthalene-1,5-diisocyanate (NDI), 1,6-hexane diisocyanate (HDI), 2,2(4),4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), cyclohexane-1,3- or -1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI), perhydro-2,4'- or -4,4'-diphenylmethane diisocyanate (HMDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, m- or p-xylylene diisocyanate (XDI), or mixtures thereof.

[0033] Of these, MDI, TDI, HDI, or IPDI are preferred. IPDI or MDI is particularly preferred.

[0034] Most preferred is MDI, especially 4,4'-diphenylmethane diisocyanate (4,4'-MDI). The 4,4'-MDI is particularly of a quality that contains only small amounts of 2,4'- and / or 2,2'-diphenylmethane diisocyanate and is solid at room temperature.

[0035] The isocyanate groups of the polyetherurethane polymer P1 are therefore preferably derived from 4,4'-diphenylmethane diisocyanate. Such a polymer cures particularly quickly and enables particularly high strengths.

[0036] As a polyether polyol for the production of polyether urethane polymer P1Suitable polyether polyols are those containing at least 80% by weight of 1,2-propyleneoxy units in the polyether segment, particularly polyoxypropylene diols or polyoxypropylene triols, or so-called ethylene oxide-terminated (EO-capped or EO-tipped) polyoxypropylene diols or triols. The latter are polyoxyethylene-polyoxypropylene mixed polyols obtained, in particular, by further alkoxylating polyoxypropylene diols or triols with ethylene oxide after completion of the propoxylation reaction, thus giving them primary hydroxyl groups.

[0037] Preferred polyether polyols are those having an OH number in the range from 6 to 280 mg KOH / g, in particular 7.5 to 112 mg KOH / g.

[0038] Preferred are polyether polyols having an average molecular weight M n in the range from 400 to 20,000 g / mol, preferably 1,000 to 15,000 g / mol, in particular 2,000 to 10,000 g / mol.

[0039] Polyether polyols with an average OH functionality in the range of 1.6 to 3 are preferred.

[0040] In the production of the isocyanate group-containing polyetherurethane polymer P1 Portions of di- or polyfunctional alcohols can also be used.

[0041] Particularly preferred is the polyetherurethane polymer P1 obtained from the reaction of at least one monomeric diisocyanate and 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 11 to 58 mg KOH / g.

[0042] In a preferred embodiment of the invention, the isocyanate group-containing polyetherurethane polymer contains P1only a low content of monomeric diisocyanates. It preferably contains at most 0.5% by weight, particularly preferably at most 0.3% by weight, in particular at most 0.2% by weight, of monomeric diisocyanates. Such a polyetherurethane polymer P1 enables compositions with particularly attractive hazardous substance classification.

[0043] The preferred separation process for removing monomeric diisocyanate is a distillative process, in particular thin-film distillation or short-path distillation, preferably under vacuum.

[0044] Particularly preferred is a multi-stage process in which the monomeric diisocyanate is removed in a short-path evaporator at a jacket temperature in the range of 120 to 200°C and a pressure of 0.001 to 0.5 mbar.

[0045] In the case of 4,4'-MDI, the preferred monomeric diisocyanate, distillative removal is particularly challenging. For example, care must be taken to prevent the condensate from solidifying and clogging the system. Preferably, the process is operated at a jacket temperature in the range of 160 to 200°C at 0.001 to 0.5 mbar, and the removed monomer is condensed at a temperature in the range of 40 to 60°C.

[0046] Preferably, the reaction of the monomeric diisocyanate with the polyether polyol and the subsequent removal of the majority of the monomeric diisocyanate remaining in the reaction mixture takes place without the use of solvents or entraining agents.

[0047] Preferably, the monomeric diisocyanate removed after the reaction is subsequently reused, i.e. used again for the production of polymer containing isocyanate groups.

[0048] Particularly preferred is a polyetherurethane polymer P1with 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 at most 0.3% by weight, which is obtained from the reaction of at least one monomeric diisocyanate and a polyether triol with 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 in an NCO / OH ratio of at least 3 / 1 and subsequent removal of a large portion of the monomeric diisocyanates by means of a suitable separation process. The preferred monomeric diisocyanate is IPDI or 4,4'-MDI, in particular 4,4'-MDI.

[0049] Furthermore, a linear polyetherurethane polymer is particularly preferred P1with 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 at most 0.3% by weight, obtained from the reaction of at least one monomeric diisocyanate with a polyether diol having an OH number in the range of 13 to 38 mg KOH / g, in particular 22 to 32 mg KOH / g, in an NCO / OH ratio of at least 3 / 1 and subsequent removal of a large portion of the monomeric diisocyanates by means of a suitable separation process. The preferred monomeric diisocyanate is IPDI or 4,4'-MDI, in particular 4,4'-MDI.

[0050] Furthermore, particularly preferred as polyetherurethane polymer P1 is a mixture of these two particularly preferred polyetherurethane polymers.

[0051] The moisture-curing composition preferably contains 15 to 80% by weight, in particular 20 to 60% by weight, of polyetherurethane polymer P1.

[0052] The moisture-curing composition further contains at least one hydrophobic, isocyanate-containing polymer which is liquid at room temperature P2, obtained from the reaction of at least one monomeric diisocyanate and a hydrophobic diol.

[0053] The polymer P2 preferably has a viscosity at 20°C of at most 1,000 Pa·s, in particular at most 500 Pa·s. The viscosity at 20°C is preferably in the range from 10 to 1,000 Pa·s, in particular 10 to 500 Pa·s. The viscosity is determined using a cone-plate viscometer with a cone diameter of 25 mm, cone angle of 1°, cone tip-plate distance of 0.5 mm at a shear rate of 50 s -1< .

[0054] Preferably, the polymer P2an NCO content in the range of 1.5 to 6% by weight, more preferably 1.8 to 5% by weight, particularly preferably 2 to 4% by weight, in particular 2.2 to 3.4% by weight. This enables an attractive combination of good extrusion properties, good adhesion properties, and high strength.

[0055] The hydrophobic diol is selected from the group consisting of dimer fatty acid-based polyester diols and poly(1,2-butylene glycol). These hydrophobic diols enable moisture-curing compositions with particularly good properties regarding processability, extensibility, elasticity, strength, and adhesion to residual adhesive bead.

[0056] The hydrophobic diol has an OH number in the range of 28 to 120 mg KOH / g. Such diols have an average molecular weight Mn in the range of 950 to 4,000 g / mol. They are largely linear in structure and have an average OH functionality of approximately 2.

[0057] The hydrophobic diol preferably has an OH number in the range of 34 to 120 mg KOH / g, in particular 52 to 60 mg KOH / g. Such a diol has an average molecular weight M n in the range of 950 to 3,300 g / mol, in particular 1,900 to 2,200 g / mol. It enables a particularly attractive combination of good extrusion properties, good adhesion properties, and high strength.

[0058] In one embodiment of the invention, the hydrophobic diol is a dimer fatty acid-based polyester diol. It is preferably amorphous. This enables compositions with particularly good processability with respect to thread tension and particularly good hydrolysis and weathering stability, especially for carbon-filled compositions, which significantly reduce the tendency to sooting. It also enables a distinctly matte surface.

[0059] Suitable dimer fatty acid-based polyester diols are obtained in particular from the esterification of at least one dimer fatty acid and / or at least one dimer fatty alcohol with a diol, such as diethylene glycol or butanediol, and / or a dicarboxylic acid, such as adipic acid, at a stoichiometry such that the product is amorphous and liquid at room temperature and has an OH number in the range of 28 to 120 mg KOH / g.

[0060] Preferably, the dimer fatty acid-based polyester diol contains a content of carbon atoms from renewable sources according to ASTM D6866, based on the total carbon content, in the range of 50 to 100%, preferably 60 to 95%, in particular 70 to 90%. Such a polyester diol is amorphous, hydrophobic, and enables polymers P2, with particularly good compatibility with the polyetherurethane polymer P1.

[0061] Particularly suitable are commercially available amorphous dimer fatty acid-based polyester diols, especially the types Priplast ®< 1837, 1838, 3187, 3196, 3197, 3199, or 3238 (from Croda) available under the trade name Priplast ®<. Priplast ®< 1838 is preferred.

[0062] In another embodiment of the invention, the hydrophobic diol is a poly(1,2-butylene glycol). This is obtained from the polymerization of 1,2-butylene oxide. Typically, water or a small diol such as ethylene glycol or 1,2-butanediol is used as the initiator. It enables polymers P2 with a particularly low viscosity and thus particularly good handling and compositions with particularly fast curing.

[0063] Commercially available types are particularly suitable, especially Vorapel ®< D3201 (from Dow).

[0064] Suitable monomeric diisocyanates are the commercially available aromatic, aliphatic or cycloaliphatic diisocyanates already mentioned.

[0065] The monomeric diisocyanate used for the reaction is preferably 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 2,4-tolylene diisocyanate, or mixtures thereof with 2,6-tolylene diisocyanate (TDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), or 1,6-hexane diisocyanate (HDI). These diisocyanates are readily available, inexpensive, and provide good mechanical strength. A combination of two or more of these monomeric diisocyanates can also be used.

[0066] IPDI is particularly preferred as a monomeric diisocyanate. Such a polymer P2 is particularly suitable in moisture-curing compositions with particularly high light stability.

[0067] The most preferred monomeric diisocyanate is 4,4'-MDI. The 4,4'-MDI is particularly of a quality that contains only small amounts of 2,4'- and / or 2,2'-diphenylmethane diisocyanate and is solid at room temperature. Such a polymer P2 enables particularly fast curing and high strength.

[0068] The reaction of at least one monomeric diisocyanate and the hydrophobic diol to produce the polymer P2 is preferably carried out under exclusion of moisture at a temperature in the range from 20 to 160°C, in particular 40 to 140°C, optionally in the presence of suitable catalysts.

[0069] The NCO / OH ratio is preferably in the range from 1.3 / 1 to 10 / 1. The monomeric diisocyanate remaining in the reaction mixture after the conversion of the OH groups can be removed, in particular by distillation. If excess monomeric diisocyanate is removed by distillation, the NCO / OH ratio during the reaction is preferably in the range from 3 / 1 to 10 / 1, in particular 4 / 1 to 7 / 1, and the resulting isocyanate-containing polymer after distillation preferably contains at most 0.5% by weight, particularly preferably at most 0.3% by weight, of monomeric diisocyanate.

[0070] If no excess monomeric diisocyanate is removed from the polymer, the NCO / OH ratio during the reaction is preferably in the range of 1.3 / 1 to 2.5 / 1. A polymer contains, in particular, at most 3% by weight, preferably at most 2% by weight, of monomeric diisocyanate.

[0071] Preferably, the polymer P2a monomeric diisocyanate content of not more than 0.5% by weight and is obtained from the reaction of at least one monomeric diisocyanate and the hydrophobic diol in an NCO / OH ratio of at least 3 / 1 and subsequent removal of a major part of the monomeric diisocyanate by means of a suitable separation process.

[0072] Such a polymer P2 It has a particularly low viscosity, which facilitates its handling, and is particularly suitable for use in compositions containing less than 0.1% by weight of monomeric diisocyanates; these are safe to handle even without special protective measures and can be sold in many countries without classification as hazardous substances.

[0073] The NCO / OH ratio in the reaction is preferably in the range from 3 / 1 to 10 / 1, particularly preferably 3 / 1 to 8 / 1, in particular 4 / 1 to 7 / 1. The content of monomeric diisocyanates is preferably at most 0.3% by weight, in particular at most 0.2% by weight.

[0074] The preferred separation process for removing monomeric diisocyanate is a distillative process, in particular thin-film distillation or short-path distillation, preferably under vacuum.

[0075] Particularly preferred is a multi-stage process in which the monomeric diisocyanate is removed in a short-path evaporator at a jacket temperature in the range of 120 to 200°C and a pressure of 0.001 to 0.5 mbar.

[0076] Preferably, the reaction of the monomeric diisocyanate with the hydrophobic diol and the subsequent removal of the majority of the monomeric diisocyanate remaining in the reaction mixture takes place without the use of solvents or entraining agents.

[0077] Preferably, the monomeric diisocyanate removed after the reaction is subsequently reused, i.e. used again for the production of polymer containing isocyanate groups.

[0078] The moisture-curing composition according to the invention preferably contains 1 to 15% by weight, preferably 1 to 10% by weight, in particular 2 to 8% by weight, of polymer P2.

[0079] The polyetherurethane polymer P1 and the polymer P2 are manufactured separately. They are therefore only mixed together after production, in particular only in the moisture-curing composition according to the invention.

[0080] The polyetherurethane polymer P1 and the polymer P2 are present in the moisture-curing composition according to the invention in a weight ratio ranging from 70 / 30 to 98 / 2, preferably 75 / 25 to 97 / 3, in particular 80 / 20 to 95 / 5. Such a composition has particularly good processing properties, rapid curing, high extensibility with high strength, and good adhesion properties.

[0081] Preferably, the moisture-curing composition contains, in addition to the polymers P1 and P2 only a small amount of further isocyanate-containing polymers, in particular at most 20 parts by weight, preferably at most 15 parts by weight, in particular at most 10 parts by weight, of further isocyanate-containing polymers based on 100 parts by weight of the sum of polymers P1 and P2.

[0082] Preferably, the moisture-curing composition additionally contains at least one further component selected from melt components, blocked amines, fillers, plasticizers, diisocyanate oligomers, catalysts and stabilizers.

[0083] In one embodiment of the invention, the moisture-curing composition preferably additionally contains at least one melt component. A particularly suitable melt component is a room-temperature solid polyesterurethane polymer containing isocyanate groups, which is obtained from the reaction of at least one monomeric diisocyanate, in particular 4,4'-MDI, and at least one crystalline polyester or polycarbonate diol.

[0084] Particularly suitable as polyester diols are OH-functional polyesters of adipic acid or sebacic acid or dodecanedicarboxylic acid with 1,4-butanediol or 1,6-hexanediol.

[0085] OH-functional polycarbonates of 1,6-hexanediol are particularly suitable as polycarbonate diols.

[0086] Such a polymer is typically solid at room temperature and has at least partially crystalline character.

[0087] Such a hot melt component is suitable for adhesives that are applied in a heated state, for example at a temperature of around 60°C, and which very quickly achieve a high initial strength after application, so that the bonded parts are self-supporting and do not need to be fixed. The hot melt component in the heated adhesive is molten during application and crystallizes when the applied adhesive cools. Furthermore, such a hot melt component is suitable for adhesives that are applied at ambient temperature, where the hot melt component is present in crystallized form and results in increased stability. However, the hot melt component is difficult to handle and the stability achieved is highly shear-dependent, which can lead to problems during production and application.In addition, the melt component makes it difficult to extrude the adhesive at room temperature and at cold ambient or adhesive temperatures. The polymer . P2 enables compositions with a certain proportion of melt component, which are easier to press out at room temperature and in the cold.

[0088] Furthermore, the polymer enables P2 Compositions with very good stability, in which the melting component is used in a significantly lower amount or which are completely free of melting component.

[0089] In a further embodiment of the invention, the moisture-curing composition preferably additionally contains at least one blocked amine.

[0090] A suitable blocked amine preferably has at least one aldimino or oxazolidino group. Upon contact with moisture, it reacts with existing isocyanate groups, hydrolyzing and releasing the amino group. This can promote rapid, bubble-free curing, a particularly non-tacky surface, and / or particularly good mechanical properties.

[0091] Preferred oxazolidines are mono-oxazolidines or bis-oxazolidines, in particular those derived from isobutyraldehyde, benzaldehyde or substituted benzaldehyde, in particular benzaldehyde which is substituted in the para position with an optionally branched alkyl group having 10 to 14 C atoms.

[0092] Particularly preferred are mono-oxazolidines derived from N-alkylethanolamines such as Nn-butylethanolamine, or bis-oxazolidines from the reaction of OH-functional mono-oxazolidines derived from diethanolamine with diisocyanates, in particular 1,6-hexane diisocyanate.

[0093] Suitable aldimines are, in particular, di- or trialdimines obtained from the reaction of commercially available primary di- or triamines with non-enolizable aldehydes. These are aldehydes that do not contain a hydrogen atom in the alpha position to the carbon atom of the aldehyde group.

[0094] Preferred blocked amines are selected from aldimines of formula (I) and (II), where n is 2 or 3, A is an n-valent hydrocarbon radical, optionally containing ether oxygen, having a molecular weight in the range from 28 to 6,000 g / mol, R 1< and R 2< independently of one another each represent a monovalent hydrocarbon radical having 1 to 12 C atoms or together represent a divalent hydrocarbon radical having 4 to 12 C atoms which is part of an optionally substituted, carbocyclic ring having 5 to 8, preferably 6, C atoms, R 3< represents a hydrogen radical or a linear or branched alkyl, arylalkyl or alkoxycarbonyl radical having 1 to 12 C atoms, R 4< represents a hydrogen radical or a monovalent hydrocarbon radical having 1 to 20 C atoms, and R 5< represents an alkyl or alkoxy radical having 6 to 20 C atoms.

[0095] Preferably, A represents an aliphatic, cycloaliphatic or arylaliphatic radical, in particular having a molecular weight in the range from 28 to 500 g / mol, in particular a radical selected from the group consisting of 1,6-hexylene, (1,5,5-trimethylcyclohexan-1-yl)methane-1,3, 4(2)-methyl-1,3-cyclohexylene, 1,3-cyclohexylene-bis(methylene), 1,4-cyclohexylene-bis(methylene), 1,3-phenylene-bis(methylene), 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, methylene-bis(2-methylcyclohexan-4-yl), (Bicyclo[2.2.1]heptane-2,5(2,6)-diyl)dimethylene, (Tricyclo[5.2.1.0 2,6< ]decane-3(4),8(9)-diyl)dimethylene, α,ω-polyoxypropylene with an average molecular weight M n in the range of 170 to 500 g / mol and trimethylolpropane- or glycerol-initiated tris-(ω-polyoxypropylene) with an average molecular weight M n in the range of 330 to 500 g / mol.

[0096] Preferably, R 1< and R 2< each represent methyl.

[0097] Preferably, R 3< represents a hydrogen radical.

[0098] Preferably, R 4< is methyl or undecyl.

[0099] Preferably, R 5< represents an optionally branched alkyl radical having 10 to 14 C atoms in the para position.

[0100] Particularly preferred blocked amines are selected from the group consisting of 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, N,N'-bis(2,2-dimethyl-3-acetoxypropylidene)-polyoxypropylenediamine having an average molecular weight M n in the range from 450 to 880 g / mol, N,N'-bis(2,2-dimethyl-3-lauroyloxypropylidene)polyoxypropylenediamine with an average molecular weight M n in the range of 750 to 1,050 g / mol, N,N'-bis(4-C 10-14 -alkylbenzylidene)polyoxypropylenediamine with an average molecular weight M n in the range of 680 to 1,100 g / mol, N,N',N"-tris(2,2-dimethyl-3-acetoxypropylidene)polyoxypropylenetriamine with an average molecular weight M n in the range of 730 to 880 g / mol, N,N',N"-tris(2,2-dimethyl-3-lauroyloxypropylidene)polyoxypropylenetriamine with an average molecular weight M n in the range of 1,150 to 1,300 g / mol and N,N',N"-tris(4-C 10-14 -alkylbenzylidene)polyoxypropylenetriamine with an average molecular weight M n in the range of 1,000 to 1,350 g / mol.

[0101] Suitable fillers are, in particular, ground or precipitated calcium carbonates, which may be coated with fatty acids, in particular stearates, barytes (heavy spars), quartz flours, quartz sands, dolomites, wollastonites, calcined kaolins, layered silicates such as mica or talc, zeolites, aluminum hydroxides, magnesium hydroxides, silicas including highly dispersed silicas from pyrolysis processes, cements, gypsum, fly ash, industrially produced carbon black, graphite, metal powders, for example of aluminum, copper, iron, silver or steel, PVC powder or lightweight fillers such as hollow glass spheres or gas-filled plastic hollow spheres (microspheres), in particular the types available under the trade name Expancel ®< (from Akzo Nobel).

[0102] Preferred are calcium carbonates, which may be coated with fatty acids, in particular stearates, calcined kaolins, highly dispersed silicas or industrially produced carbon blacks.

[0103] 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 1,2-cyclohexanedicarboxylic acid esters, in particular hydrogenated diisononyl phthalate or diisononyl-1,2-cyclohexanedicarboxylate (DINCH), terephthalates, in particular bis(2-ethylhexyl)terephthalate (DOTP) or diisononyl terephthalate (DINT), hydrogenated terephthalates or 1,4-cyclohexanedicarboxylic acid esters, in particular hydrogenated bis(2-ethylhexyl)terephthalate or bis(2-ethylhexyl)-1,4-cyclohexanedicarboxylate or hydrogenated diisononyl terephthalate orDiisononyl 1,4-cyclohexanedicarboxylate, isophthalates, trimellitates, adipates, in particular dioctyl adipate, azelates, sebacates, benzoates, glycol ethers, glycol esters, plasticizers with a polyether structure, in particular polypropylene oxide monols, diols or triols with blocked hydroxyl groups, in particular in the form of acetate groups, organic phosphoric or sulfonic acid esters, polybutenes, polyisobutenes or plasticizers derived from natural fats or oils, in particular epoxidized soybean or linseed oil.

[0104] Preferred plasticizers are phthalates or plasticizers with a polyether structure.

[0105] Suitable diisocyanate oligomers are in particular HDI biurets such as Desmodur ®< N 100 or N 3200 (from Covestro AG), Tolonate ®< HDB or HDB-LV (from Vencorex) or Duranate ®< 24A-100 (from Asahi Kasei); HDI isocyanurates such as Desmodur ®< N 3300, N 3600 or N 3790 BA (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 ®< N 3400 (from Covestro); HDI iminooxadiazinediones such as Desmodur ®< XP 2410 (from Covestro); HDI allophanates such as Desmodur ®< VP LS 2102 (from Covestro); IPDI isocyanurates such as in solution as Desmodur ®< Z 4470 (from Covestro) or in solid form as Vestanat ®< T1890 / 100 (from Evonik Industries); TDI oligomers such as Desmodur ®< IL (from Covestro); or mixed isocyanurates based on TDI / HDI such as Desmodur ®< HL (from Covestro).

[0106] 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, complex compounds of bismuth(III) or zirconium(IV), in particular with ligands selected from alkoxides, carboxylates, 1,3-diketonates, oxinate, 1,3-ketoesterates and 1,3-ketoamidates, or compounds containing tertiary amino groups such as in particular 2,2'-dimorpholinodiethyl ether (DMDEE).

[0107] In the event that the moisture-curing composition contains blocked amines, suitable catalysts are further catalysts for the hydrolysis of the 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 hexahydromethylphthalic 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 aforementioned acids and acid esters. Particular preference is given to carboxylic acids, in particular aromatic carboxylic acids such as benzoic acid, 2-nitrobenzoic acid, or especially salicylic acid.

[0108] Combinations of different catalysts are particularly suitable.

[0109] Suitable stabilizers are, in particular, stabilizers against oxidation, heat, light or UV radiation, in particular titanium dioxides, iron oxides, zinc oxides, benzophenones, benzotriazoles, compounds with 2,6-di-tert.butylphenol groups, such as those known under the trade name Irganox ®< (from BASF), compounds with 2,2,6,6-tetramethylpiperidine groups, so-called HALS (hindered amine light stabilizers), such as those known under the trade name Tinuvin ®< (from BASF), or phosphorus-containing compounds, such as those known under the trade name Irgafos ®< (from BASF).

[0110] The moisture-curing composition may contain further additives, in particular inorganic or organic pigments, in particular titanium dioxide, chromium oxides or iron oxides; fibers, in particular glass fibers, carbon fibers, metal fibers, ceramic fibers, plastic fibers such as polyamide fibers or polyethylene fibers, or natural fibers such as wool, cellulose, hemp or sisal; nanofillers such as graphene or carbon nanotubes; dyes; drying agents, in particular molecular sieve powder, calcium oxide, highly reactive isocyanates such as p-tosyl isocyanate, mono-oxazolidines such as Incozol ®< 2 (from Incorez) or orthoformic acid esters; adhesion promoters, in particular organoalkoxysilanes, in particular epoxysilanes such as 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane, (meth)acrylosilanes, anhydridosilanes, carbamatosilanes, alkylsilanes or iminosilanes, or oligomeric forms of these silanes, or titanates; further catalysts which accelerate the reaction of the isocyanate groups;Rheology modifiers, in particular thickeners, in particular layered silicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyamide waxes, polyurethanes, urea compounds, pyrogenic silicas, 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, butylal, 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 Solvesso™< types (from Exxon), as well as 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 from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth)acrylates, in particular polyethylenes (PE), polypropylenes (PP), polyisobutylenes, ethylene-vinyl acetate copolymers (EVA) or atactic poly-α-olefins (APAO);flame-retardant substances, in particular the fillers aluminum hydroxide or magnesium hydroxide already mentioned, and in particular organic phosphoric acid esters such as triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenyl cresyl phosphate, isodecyl diphenyl 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 varying degrees of isopropylation, resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate) or ammonium polyphosphates; additives, in particular wetting agents, leveling agents, defoamers, deaerators or biocides; ; or other substances commonly used in moisture-curing polyurethane compositions.

[0111] It may be useful to dry certain substances chemically or physically before mixing them into the composition.

[0112] The composition according to the invention preferably contains little solvent. In particular, it contains less than 5% by weight, preferably less than 2.5% by weight, of solvent. Most preferably, the composition according to the invention is substantially free of solvents.

[0113] Preferably, the moisture-curing composition contains 20 to 60% by weight polyetherurethane polymers P1, 0.5 to 10% by weight polymer P2, 0 to 5% by weight melt component, 20 to 60% by weight fillers, 0 to 35% by weight plasticizer, and optionally further components, in particular blocked amines, diisocyanate oligomers, catalysts or stabilizers.

[0114] In a preferred embodiment of the invention, the moisture-curing composition contains carbon black, in particular at least one industrially produced carbon black, in particular in an amount in the range of 5 to 40% by weight, preferably 10 to 30% by weight. Such a composition is particularly suitable for bonding panes due to its high stability, strength, and durability, and thanks to the hydrophobic polymer P2 it is particularly less prone to sooting.

[0115] Preferably, the moisture-curing composition contains less than 0.1% by weight of monomeric diisocyanates. Such a composition can be transported and sold in many countries without being classified as hazardous.

[0116] The moisture-curing composition is manufactured, in particular, in the absence of moisture and stored at ambient temperature in moisture-proof containers. A suitable moisture-proof container consists, in particular, of an optionally coated metal and / or plastic and is, in particular, a drum, container, hobbock, bucket, canister, can, bag, tubular bag, cartridge, or tube.

[0117] The moisture-curing composition is preferably a single-component product. When properly packaged and stored, it is stable over time, typically for several months to a year or more.

[0118] The moisture-curing composition begins to cure during and after application under the influence of moisture or water. To accelerate curing, an accelerator component containing water and, optionally, a catalyst and / or a hardener can be added to the composition during application, or the composition can be brought into contact with such an accelerator component after application.

[0119] During curing, the isocyanate groups react with each other under the influence of moisture. If the moisture-curing composition contains a blocked amine, the isocyanate groups also react with the hydrolyzing blocked amine groups. The entirety of these reactions of the isocyanate groups leading to the curing of the composition is also referred to as crosslinking. The resulting cured composition is the result.

[0120] The moisture required to cure the composition preferably enters the composition from the air (humidity) by diffusion. A solid layer of cured composition ("skin") forms on the surfaces of the composition in contact with air. Curing continues along the diffusion direction from the outside to the inside, with the skin becoming increasingly thicker and eventually encompassing the entire applied composition. The moisture can also enter the composition, additionally or entirely, from one or more substrates to which the composition was applied and / or from an accelerator component that is added to the composition during application or brought into contact with it after application, for example, by brushing or spraying.

[0121] The moisture-curing composition is preferably applied at ambient temperature, in particular in the range of about -10 to 50°C, preferably in the range of -5 to 45°C, in particular 0 to 40°C.

[0122] If desired, the moisture-curing composition can also be applied in a heated state, for example at a temperature of about 60°C.

[0123] The moisture-curing composition preferably cures at ambient temperature.

[0124] The moisture-curing composition has a long processing time (open time) and rapid curing.

[0125] The "open time" refers to the period of time during which the composition can be processed or reworked after application without any loss of functionality. In the case of the composition being used as an adhesive, the open time also refers in particular to the period of time within which a bond must be assembled after application in order to establish sufficient adhesion. The open time is exceeded at the latest when skin formation occurs or when sufficient adhesion to the substrates is no longer established.

[0126] The moisture-curing composition is preferably used as an elastic adhesive and / or sealant, in particular for adhesive or sealing applications in the construction and manufacturing industry or in vehicle construction, in particular for parquet bonding, assembly, attachment bonding, module bonding, window bonding, joint sealing, body sealing, seam sealing or cavity sealing.

[0127] Elastic bonding in vehicle construction includes, for example, the bonding of parts such as plastic covers, trim strips, flanges, bumpers, driver's cabs or other attachments to the painted body of a vehicle, or the bonding of windows into the body, whereby the vehicles are in particular automobiles, trucks, buses, rail vehicles or ships.

[0128] Particularly preferred is the use as an adhesive for vehicle glazing, in particular for replacement vehicle glazing.

[0129] The moisture-curing composition is preferably formulated to have a pasty consistency with pseudoplastic properties at room temperature. Such a composition is applied using a suitable device, for example, from commercially available cartridges, drums, or hobbocks, particularly in the form of a bead, which may have a substantially round or triangular cross-sectional area.

[0130] Suitable substrates which can be bonded and / or sealed with the moisture-curing composition are in particular Glass, glass ceramic or glass or polycarbonate coated with screen-printed ceramic; metals or alloys such as aluminum, copper, iron, steel, non-ferrous metals, including surface-treated metals or alloys such as galvanized or chrome-plated metals; coated or painted substrates, in particular powder-coated metals or alloys or painted sheets; paints or varnishes, in particular automotive topcoats; cured adhesives, in particular based on polyurethane, silane-modified polymer or polysulfide, in particular aged adhesives (residual adhesive bead), or body flanges which have a residual adhesive bead throughout or in places; plastics such as rigid or soft 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 means of plasma, corona or flames;Fiber-reinforced plastics, such as carbon fiber-reinforced plastics (CFRP), glass fiber-reinforced plastics (GRP) and sheet molding compounds (SMC); repair or leveling compounds based on PCC (polymer-modified cement mortar) or ECC (epoxy resin-modified cement mortar); insulating foams, in particular made of EPS, XPS, PUR, PIR, rock wool, glass wool or foamed glass (Foamglas); concrete, mortar, cement screed, fiber cement, in particular fiber cement boards, brick, tiles, gypsum, in particular gypsum boards or anhydride screed, or natural stone such as granite or marble, varnished tiles or painted concrete, asphalt or bitumen. Leather, textiles, paper, wood, wood materials bonded with resins such as phenolic, melamine or epoxy resins, resin-textile composites or other so-called polymer composites. ;

[0131] If necessary, the substrates may be pretreated before application, in particular by physical and / or chemical cleaning processes or the application of an activator or a primer.

[0132] Two similar or two different substrates can be bonded and / or sealed.

[0133] Another object of the invention is a method for bonding or sealing, comprising the steps (i) applying the described moisture-curing composition to a first substrate and contacting the composition with a second substrate within the open time of the composition, or to a first and a second substrate and joining the two substrates within the open time of the composition, or between two substrates, (ii) curing the composition by contact with moisture.

[0134] Preferably, at least one of the substrates is selected from the group consisting of glass, glass ceramic, glass or polycarbonate coated with screen-printed ceramic, metals, alloys, powder-coated metals or alloys, paints and varnishes and cured adhesive, in particular residual adhesive bead and / or sheets painted with automotive topcoats.

[0135] The application and curing of the moisture-curing composition or the bonding or sealing process results in an article bonded or sealed with the composition. This article may be a building or a part thereof, in particular a civil engineering structure, a bridge, a roof, a staircase, or a facade, or it may be an industrial or consumer good, in particular a window, a pipe, a wind turbine rotor blade, a household appliance, or a means of transport, such as, in particular, an automobile, a bus, a truck, a rail vehicle, a ship, an aircraft, or a helicopter, or an attachment thereof.

[0136] A further subject of the invention is thus an article obtained from the described method for bonding or sealing.

[0137] The bonding process is particularly preferably used for the elastic bonding of windows on vehicles, in particular for replacement glazing, where good adhesion to residual adhesive bead is particularly important.

[0138] The moisture-curing composition exhibits advantageous properties. It features particularly good adhesion properties with a long open time, especially on residual adhesive beads, particularly good application properties, particularly particularly good extrusion properties with high stability, a matte surface, and particularly good weather resistance, while maintaining consistently good curing, strength, extensibility, elasticity, and hazardous substance classification. This makes the composition particularly suitable as an elastic adhesive in vehicle construction, especially for replacing defective, elastically bonded windshields on automobiles. Examples

[0139] The following are exemplary embodiments intended to illustrate the described invention in more detail. Of course, the invention is not limited to these described exemplary embodiments.

[0140] The "standard climate" (NK) is defined as a temperature of 23±1°C and a relative humidity of 50±5%.

[0141] Unless otherwise stated, the chemicals used were from Sigma-Aldrich Chemie GmbH. polyols used:

[0142] Desmophen ®< 5031 BT: Glycerin-initiated ethylene oxide-terminated polyoxypropylenetriol, OH number 28 mg KOH / g (from Covestro) Acclaim ®< 4200: Polyoxypropylenediol, OH number 28 mg KOH / g (from Covestro) Priplast ®< 1838: Dimer fatty acid-based amorphous polyesterdiol, OH number 56 mg KOH / g, liquid at room temperature (from Croda) (=hydrophobic diol) Priplast ®< 1837: Dimer fatty acid-based amorphous polyesterdiol, OH number 110 mg KOH / g, liquid at room temperature (from Croda) (=hydrophobic diol) Priplast ®< 3196: Dimer fatty acid-based amorphous polyesterdiol, OH number 37 mg KOH / g, liquid at room temperature (from Croda) (=hydrophobic diol) Priplast ®< 3197: Dimer fatty acid-based amorphous polyesterdiol, OH number 56 mg KOH / g, liquid at room temperature (from Croda) (=hydrophobic diol) Vorapel ®< D3201: Poly(1,2-butylene glycol), OH number 56 mg KOH / g, liquid at room temperature (from Dow) (=hydrophobic diol) Dynacoll ®< 7360 Solid, semi-crystalline polyesterdiol at room temperature, OH number 34 mg KOH / g (from Evonik) Production of polymers containing isocyanate groups:

[0143] The viscositywas measured with a thermostatted cone-plate viscometer Rheotec RC30 (cone diameter 25 mm, cone angle 1°, cone tip-plate distance 0.5 mm, shear rate 50 s -1< ).

[0144] The Content of monomeric diisocyanate was determined by HPLC (detection via photodiode array; 0.04 M sodium acetate / acetonitrile as mobile phase) after prior derivatization using N-propyl-4-nitrobenzylamine. Polymer P1-1:

[0145] 725.0 g of Desmophen ®< 5031 BT and 275.0 g of 4,4'-diphenylmethane diisocyanate (Desmodur ®< 44 MC L, from Covestro) were reacted according to a known process to form a polyetherurethane polymer with an NCO content of 7.6 wt.%, a viscosity of 6.5 Pa·s at 20°C and a 4,4'-diphenylmethane diisocyanate content of approximately 20 wt.%.

[0146] The volatile components, particularly a large portion of the 4,4'-diphenylmethane diisocyanate, were then removed by distillation in a short-path evaporator (jacket temperature 180°C, pressure 0.1 to 0.005 mbar, condensation temperature 47°C). The resulting polyetherurethane polymer had an NCO content of 1.7% by weight, a viscosity of 19 Pa s at 20°C, and a 4,4'-diphenylmethane diisocyanate content of 0.04% by weight. Polymers P1-2:

[0147] 727.0 g of Acclaim ®< 4200 and 273.0 g of 4,4'-diphenylmethane diisocyanate (Desmodur ®< 44 MC L, from Covestro) were reacted according to a known process to form a polyetherurethane polymer with an NCO content of 7.6% by weight, a viscosity of 5.2 Pa s at 20°C and a content of 4,4'-diphenylmethane diisocyanate of approximately 18% by weight.

[0148] Subsequently, the volatile components, in particular a large part of the 4,4'-diphenylmethane diisocyanate, were removed as for polymer P1-1The resulting polyetherurethane polymer had an NCO content of 1.8% by weight, a viscosity of 15.2 Pa s at 20°C, and a 4,4'-diphenylmethane diisocyanate content of 0.08% by weight. Polymer P2-1:

[0149] 597.5 g of Priplast ®< 1838 and 402.5 g of 4,4'-diphenylmethane diisocyanate (Desmodur ®< 44 MC L, from Covestro) were reacted at 80 °C to form a polymer with an NCO content of 11.0 wt.%, a viscosity of 36 Pa s at 20 °C and a 4,4'-diphenylmethane diisocyanate content of approximately 26 wt.%.

[0150] Subsequently, the volatile components, in particular a large part of the 4,4'-diphenylmethane diisocyanate, were removed as for polymer P1-1The resulting polymer was slightly cloudy and had a liquid, viscous consistency at room temperature. It had an NCO content of 2.8% by weight, a viscosity of 312 Pa s at 20°C and 11.5 Pa s at 60°C, and a 4,4'-diphenylmethane diisocyanate content of 0.09% by weight. Polymer P2-2:

[0151] 445.0 g of Priplast ®< 1837 and 555.0 g of 4,4'-diphenylmethane diisocyanate (Desmodur ®< 44 MC L, from Covestro) were reacted at 80°C to form a polymer with an NCO content of 14.8 wt%, a viscosity of 6.5 Pa s at 20°C and a 4,4'-diphenylmethane diisocyanate content of approximately 35 wt%.

[0152] Subsequently, the volatile components, in particular a large part of the 4,4'-diphenylmethane diisocyanate, were removed as for polymer P1-1The resulting polymer was slightly cloudy and had a liquid, viscous consistency at room temperature. It had an NCO content of 4.8 wt.%, a viscosity of 11 Pa s at 60°C, and a 4,4'-diphenylmethane diisocyanate content of 0.06 wt.%. Polymer P2-3:

[0153] 663.0 g of Priplast ®< 3196 and 337.0 g of 4,4'-diphenylmethane diisocyanate (Desmodur ®< 44 MC L, from Covestro) were reacted at 80°C to form a polymer with an NCO content of 9.4 wt%, a viscosity of 57 Pa s at 20°C and a 4,4'-diphenylmethane diisocyanate content of approximately 23 wt%.

[0154] Subsequently, the volatile components, in particular a large part of the 4,4'-diphenylmethane diisocyanate, were removed as for polymer P1-1The resulting polymer was slightly cloudy and had a liquid, viscous consistency at room temperature. It had an NCO content of 2.2% by weight, a viscosity of 17 Pa s at 60°C, and a 4,4'-diphenylmethane diisocyanate content of 0.06% by weight. Polymer P2-4:

[0155] 600.0 g of Priplast ®< 3197 and 400.0 g of 4,4'-diphenylmethane diisocyanate (Desmodur ®< 44 MC L, from Covestro) were reacted at 80°C to form a polymer with an NCO content of 10.7 wt%, a viscosity of 28 Pa s at 20°C and a 4,4'-diphenylmethane diisocyanate content of approximately 25 wt%.

[0156] Subsequently, the volatile components, in particular a large part of the 4,4'-diphenylmethane diisocyanate, were removed as for polymer P1-1The resulting polymer was slightly cloudy and had a liquid, viscous consistency at room temperature. It had an NCO content of 2.8% by weight, a viscosity of 16 Pa s at 60°C, and a 4,4'-diphenylmethane diisocyanate content of 0.08% by weight. Polymer P2-5:

[0157] 601.1 g of Vorapel ®< D3201 and 398.9 g of 4,4'-diphenylmethane diisocyanate (Desmodur ®< 44 MC L, from Covestro) were reacted at 80°C to form a polymer with an NCO content of 10.7 wt%, a viscosity of 3.5 Pa·s at 20°C and a 4,4'-diphenylmethane diisocyanate content of approximately 24 wt%.

[0158] Subsequently, the volatile components, in particular a large part of the 4,4'-diphenylmethane diisocyanate, were removed as for polymer P1-1The polymer thus obtained had an NCO content of 3.0 wt.%, a viscosity of 26 Pa s at 20°C, and a 4,4'-diphenylmethane diisocyanate content of 0.06 wt.%. Polymer M:

[0159] 1000 g Dynacoll ®< 7360 and 142 g 4,4'-diphenylmethane diisocyanate (Desmodur ®< 44 MC L, from Covestro) were reacted at 80°C to form a polymer that was solid at room temperature and had an NCO content of 2.0 wt% and a 4,4'-diphenylmethane diisocyanate content of 2.3 wt%.

[0160] The polymers P1-1 and P1-2 are polyetherurethane polymers P1. The polymers P2-1 until P2-5 are hydrophobic polymers P2. The polymer M is a polymer that is solid at room temperature and was used as a melt component. Moisture-curing compositions: Compositions Z1 to Z6:

[0161] For each composition, the ingredients listed in Table 1 were thoroughly mixed in the specified amounts (in parts by weight) using a planetary mixer under vacuum and moisture exclusion, the composition was filled into an airtight tubular bag and stored at room temperature.

[0162] For rapid curing, a water-based accelerator component was added to the composition during application. The composition was applied using a PowerCure dispenser (available from Sika Schweiz AG), with 2% by weight of a water-based paste added to the composition during dispensing and mixed using a dynamic mixer.

[0163] The Adhesion to residual adhesive beadwas determined on a cured and aged adhesive layer. For this purpose, a commercially available polyurethane adhesive for window bonding (Sikaflex ®< -250 SV-3, from Sika Automotive Hamburg GmbH) was applied to a glass body in the form of a triangular bead approximately 8 mm wide and approximately 10 mm high. The bead was covered with a silicone-coated release paper, pressed to a layer thickness of approximately 5 mm, cured for 7 days under standard conditions, the release paper was removed, and the pressed adhesive bead was aged for 14 days at 80°C. The cured and aged adhesive bead was then cut away from the glass body to a layer thickness of approximately 1 mm.

[0164] The accelerated composition was then applied from the PowerCure dispenser in the form of a triangular bead approximately 8 mm wide and 10 mm high onto strips of silicone-coated release paper under standard conditions. After the waiting time specified in Table 1, the triangular beads applied to the release paper were turned over and placed on the residual adhesive bead remaining on the glass body, with the release paper on top and the composition in contact with the residual adhesive bead. The composition was then pressed to a layer thickness of approximately 5 mm and cured for 7 days under standard conditions. The release paper was then removed and the adhesion of the cured composition to the residual adhesive bead was tested by cutting into the cured composition at the narrow end just above the bonding surface, holding the cut end of the composition with round-nose pliers, and attempting to pull the composition away from the substrate (= residual adhesive bead).The composite was then cut again down to the substrate, the cut-out portion was rolled up with round-nose pliers, and another attempt was made to peel the composite away from the substrate. The composite was then cut away from the substrate by pulling. The adhesion was then assessed based on the fracture pattern using the following scale: . "Very good" stands for more than 95% cohesive failure, "good" stands for 75 to 95% cohesive failure, "moderate" stands for 50 to 75% cohesive failure, "poor" stands for less than 50% cohesive failure, and "no adhesion" stands for 0% cohesive failure or 100% adhesive failure.

[0165] The results are shown in Table 1.

[0166] Compositions marked "(Ref.)" are comparative examples. Z1 Z6. Table 1: Composition (in parts by weight) and properties of up to 1< 2,2'-Dimorpholinodiethyl ether composition Z1 Z2 Z3 Z4 Z5 Z6 (Ref.) Polymer P1-1 36.8 36.8 36.8 36.8 36.8 41.8 Polymer P2-1 5.0 - - - - - Polymer P2-2 - 5.0 - - - - Polymer P2-3 - - 5.0 - - - Polymer P2-4 - - - 5.0 - - Polymer P2-5 - - - - 5.0 Polymer M 2.8 2.8 2.8 2.8 2.8 2.8 Dioctyl adipate 17.1 17.1 17.1 17.1 17.1 17.1 chalk 20.0 20.0 20.0 20.0 20.0 20.0 Soot 18.0 18.0 18.0 18.0 18.0 18.0 DMDEE 1< 0.3 0.3 0.3 0.3 0.3 0.3 Adhesion to residual adhesive bead: after waiting time 0 min very good good very good very good very good moderate 5 minutes very good good very good very good very good good 7 minutes very good good very good very good very good moderate 10 minutes very good moderate very good good very good bad Compositions Z7 and Z8:

[0167] Each composition was prepared using the ingredients shown in Table 2 in the amounts indicated (in parts by weight) as for composition Z1 described, filled into an airtight aluminum cartridge and stored at room temperature.

[0168] Each composition was applied between two silicone-coated release papers, pressed into a 2 mm thick film, and stored for 14 days under standard conditions. After removing the release papers, rectangular test specimens (75 x 150 mm) were cut from the cured film, tested in a QUV weathering apparatus for the time specified in Table 2, and then the weathered surface was examined for Soot pollutionCarbon black staining was tested by first pressing a transparent adhesive tape onto the surface by hand and then adhering it to white printer paper. If a light gray color was visible, the soot contamination was rated as "no," if a dark gray color was visible, the soot contamination was rated as "medium," and if a black color was present, the soot contamination was rated as "heavy."

[0169] The results are shown in Table 2.

[0170] Compositions marked "(Ref.)" are comparative examples. Z7 Z8. Table 2: Composition (in parts by weight) and properties of and 1< Tinuvin ®< 292 (from BASF) composition Z7 Z8 (Ref.) Polymer P1-1 22.3 27.3 Polymer P1-2 10.0 10.0 Polymer P2-1 5.0 - Diisodecyl phthalate 16.6 16.6 Stabilizer 1< 1.0 1.0 chalk 25.0 25.0 Soot 20.0 20.0 2,2'-Dimorpholinodiethyl ether 0.1 0.1 Soot pollution: 200h QUV no medium 500h QUV no strong 3,000h QUV no strong Compositions Z9 to Z18:

[0171] Each composition was prepared using the ingredients shown in Tables 3 and 4 in the amounts indicated (in parts by weight) as for composition Z1 described, filled into an airtight aluminum cartridge and stored at room temperature.

[0172] Each composition was tested as follows: The extrusion force, sag resistance, and string tension were determined as measures of the composition's workability and applicability. Low extrusion force, high sag resistance, and short string tension indicate good workability and applicability.

[0173] The Extrusion forcewas determined at 23°C and at 5°C. A first sealed cartridge was stored at 23°C for 7 days, and a second was stored at 23°C for 6 days and then at 5°C for 24 hours. The extrusion force was then measured using a dispensing device (Zwick / Roell Z005). A nozzle with an inner diameter of 5 mm was screwed onto the cartridge and the force required to extrude the composition through the nozzle at an extrusion speed of 60 mm / min was measured. The stated value is an average of the forces measured after extrusion travels of 22 mm, 24 mm, 26 mm, and 28 mm.

[0174] From each composition, the StabilityThis test was carried out under standard conditions by applying a triangular bead approximately 8 mm wide and 20 mm high to a vertical cardboard surface in such a way that the triangular bead formed an 8 mm wide horizontal strip with a 20 mm protruding height (= tip). After curing under standard conditions, it was assessed whether and how the position of the applied bead had changed. In particular, the extent to which the tip had sunk downwards, measured from the horizontal position, was determined. A sinking of less than 1 mm was rated as "very good," 1 to less than 3 mm as "good," 4 to 7 mm as "medium," and 8 mm or more as "poor." A composition is referred to as "liquid" if the applied material moved downwards, i.e., ran down, not only at the tip but also at the base of the applied triangular bead.

[0175] Of some compositions, the Thread pullwas determined by measuring the length of the thread created by pulling away the application cartridge on the triangular bead that had been applied to determine the stability.

[0176] As a measure for the processing time (open time) the Skin formation time (HTZ) For this purpose, a few grams of the composition were applied to cardboard in a layer thickness of approximately 2 mm, and the time taken for the first time to leave no residue on the pipette when the surface of the composition was lightly tapped using an LDPE pipette was determined under standard conditions.

[0177] To determine the mechanical properties, each composition was pressed between two silicone-coated release papers to form a film of 2 mm thickness and stored for 14 days under standard conditions. After removing the release papers, some test specimens were punched out and tested as follows: To determine Tensile strength (tensile strength), Elongation at break (Elongation at break) and Young's modulus At 0.5-5% elongation, dumbbells with a length of 75 mm, a bar length of 30 mm and a bar width of 4 mm were punched out of the film and tested according to DIN EN 53504 at a tensile speed of 200 mm / min.

[0178] Furthermore, some test specimens were used to determine the Tear resistance punched out and tested according to DIN ISO 34 at a tensile speed of 500 mm / min.

[0179] The aspect and the Gloss level were determined visually on the film produced for the determination of mechanical properties. A "nice" film is defined as non-sticky, even, and bubble-free.

[0180] To determine the strength of an adhesive bond, the tensile shear strength of some compounds was (ZSF)on glass. For this purpose, composites were produced by bonding two glass plates that had been degreased with isopropanol and pretreated with Sika ® Aktivator-100 (from Sika Switzerland) in such a way that the overlapping adhesive bond had dimensions of 12 x 25 mm and a thickness of 4 mm and the glass plates protruded at the ends. After storing the composites for 14 days in a standard climate, the tensile shear strength was tested according to DIN EN 1465 at a tensile speed of 20 mm / min. As a measure of the heat and hydrolysis stability of the bond, additional test specimens were stored for 7 days in a circulating air oven at 100°C or 7 days at 70°C / 100% relative humidity, cooled in the standard climate and tested in the same way. The results are marked with the suffix "14d NK" or "7d 100°C" or "7d 70 / 100".

[0181] The results are shown in Tables 3 and 4.

[0182] Compositions marked "(Ref.)" are comparative examples. Z9 Z15. Table 3: Composition (in parts by weight) and properties of up to 1< 2,2'-Dimorpholinodiethylether nm stands for "not measurable" "nb" stands for "not determined" composition Z9 Z10 Z11 (Ref.) Z12 Z13 (Ref.) Z14 Z15 (Ref.) Polymer P1-1 36.8 36.8 41.8 38.2 43.2 39.6 44.6 Polymer P2-1 5.0 - - 5.0 - 5.0 - Polymer P2-5 - 5.0 - - - - - Polymer M 2.8 2.8 2.8 1.4 1.4 - - Dioctyl adipate 17.1 17.1 17.1 17.1 17.1 17.1 17.1 chalk 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Soot 18.0 18.0 18.0 18.0 18.0 18.0 18.0 DMDEE 1< 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Extrusion force [N] 23°C 809 801 919 653 616 471 249 5°C 1002 1039 1235 812 869 685 468 Stability very good very good very good very good medium very good bad, liquid Thread tension [mm] 6 14 5 8 11 12 nm HBZ [min] 17 12 17 17 18 17 22 Tensile strength [MPa] 8.4 8.6 7.7 8.3 7.6 8.6 8.2 Elongation at break [%] 502 557 487 490 466 513 477 Young's modulus [MPa] 6.1 5.7 5.8 5.5 5.2 4.6 4.0 Tear resistance [N / mm] 12.3 13.0 11.7 12.0 11.2 11.7 10.0 Aspect / gloss level beautiful / matte beautiful / slightly matte beautiful / shiny beautiful / matte beautiful / shiny beautiful / matte beautiful / shiny CSF [MPa] 14d NK 4.7 4.8 4.5 4.1 4.5 4.6 4.2 7d 100°C 5.9 nb 5.8 7.0 5.5 5.3 6.8 7d 70 / 100 5.2 nb 5.3 5.0 3.2 5.2 3.5 Z16 Z18. Table 4: Composition (in parts by weight) and properties of up to composition Z16 Z17 Z18 Polymer P1-1 36.8 36.8 36.8 Polymer P2-2 5.0 - - Polymer P2-3 - 5.0 - Polymer P2-4 - - 5.0 Polymer M 2.8 2.8 2.8 Dioctyl adipate 17.1 17.1 17.1 chalk 20.0 20.0 20.0 Soot 18.0 18.0 18.0 2,2'-Dimorpholinodiethyl ether 0.3 0.3 0.3 Extrusion force [N] 23°C 959 633 539 Stability very good very good very good Skin formation time [min] 17 16 16 Tensile strength [MPa] 7.8 6.9 7.4 Elongation at break [%] 472 493 482 Young's modulus [MPa] 8.1 5.1 5.6 Tear resistance [N / mm] 13.6 12.5 11.4 Aspect / gloss level beautiful / matte beautiful / matte beautiful / matte

Claims

1. Moisture-curing composition which is liquid or pasty at room temperature, comprising - at least one polyether urethane polymer P1 containing isocyanate groups and having a content of at least 80% by weight of 1,2-propyleneoxy units in the polyether segment, and - at least one room temperature liquid, hydrophobic polymer P2 containing isocyanate groups, obtained from the reaction of at least one monomeric diisocyanate and a hydrophobic diol having an OH number in the range from 28 to 120 mg KOH / g, wherein polymers P1 and P2 are prepared separately from one another and polymer P1 and polymer P2 are present in a weight ratio in the range from 70 / 30 to 98 / 2, characterized in that the hydrophobic diol for the preparation of polymer P2 is selected from the group consisting of dimer fatty acid-based polyester diols and poly(1,2-butylene glycol).

2. Moisture-curing composition according to Claim 1, characterized in that polymer P1 has an NCO content in the range from 1% to 5% by weight.

3. Moisture-curing composition according to either of Claims 1 and 2, characterized in that the isocyanate groups of polymer P1 are derived from diphenylmethane 4,4'-diisocyanate.

4. Moisture-curing composition according to any of Claims 1 to 3, characterized in that polymer P1 is obtained from the reaction of at least one monomeric diisocyanate and 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.

5. Moisture-curing composition according to any of Claims 1 to 4, characterized in that polymer P1 has a monomeric diisocyanate content of not more than 0.5% by weight.

6. Moisture-curing composition according to any of Claims 1 to 5, characterized in that polymer P2 has an NCO content in the range from 1.5% to 6% by weight.

7. Moisture-curing composition according to any of Claims 1 to 6, characterized in that the hydrophobic diol is an amorphous dimer fatty acid-based polyester diol.

8. Moisture-curing composition according to any of Claims 1 to 7, characterized in that polymer P2 has a monomeric diisocyanate content of not more than 0.5% by weight and is obtained from the reaction of at least one monomeric diisocyanate and the hydrophobic diol in an NCO / OH ratio of at least 3 / 1, followed by removal of a majority of the monomeric diisocyanate by means of a suitable separation method.

9. Moisture-curing composition according to any of Claims 1 to 8, characterized in that polymer P2 has a viscosity at 20°C in the range from 10 to 1000 Pa·s, determined with a cone-plate viscometer having a cone diameter 25 mm, cone angle 1°, cone tip-plate distance 0.5 mm, at a shear rate of 50 s-1.

10. Moisture-curing composition according to any of Claims 1 to 9, characterized in that at least one further constituent selected from meltable components, blocked amines, fillers, plasticizers, diisocyanate oligomers, catalysts and stabilizers is additionally present.

11. Moisture-curing composition according to Claim 10, characterized in that it comprises - 20% to 60% by weight of polymers P1, - 0.5% to 10% by weight of polymer P2, - 0% to 5% by weight of meltable component, - 20% to 60% by weight of fillers, - 0% to 35% by weight of plasticizers, and optionally further constituents, especially blocked amines, diisocyanate oligomers, catalysts or stabilizers.

12. Moisture-curing composition according to Claim 10 or 11, characterized in that it comprises carbon black.

13. Moisture-curing composition according to any of Claims 1 to 12, characterized in that it comprises less than 0.1% by weight of monomeric diisocyanates.

14. Method of bonding or sealing, comprising the steps of (i) applying the moisture-curing composition according to any of Claims 1 to 13 - to a first substrate and contacting the composition with a second substrate within the open time of the composition, or - to a first and to a second substrate and joining the two substrates within the open time of the composition, or - between two substrates, (ii) curing the composition by contact with moisture.

15. Article obtained from the method according to Claim 14.