Polyurethane composition with excellent adhesion to plastic

Abstract

The present invention comprises (i) at least one linear polymer P1 having isocyanate groups and an NCO content in the range of 0.3 wt% to 3.3 wt%, obtained from the reaction of at least one monomeric aromatic diisocyanate and a polyether diol having an OH value in the range of 5 mg to 37 mg KOH / g; (ii) at least one branched polymer P2 having isocyanate groups and an NCO content in the range of 1 wt% to 10 wt%, obtained from the reaction of at least one monomeric aromatic diisocyanate and at least one polyether triol having an average number of OH functional groups of at least 2.2 and an OH value in the range of 16 mg to 380 mg KOH / g; and (iii) a plasticizer having an amount of 15 wt% or less based on the total composition, wherein polymer P1 and polymer P2 are present in a weight ratio in the range of 80 / 20 to 95 / 5, characterized by being a moisture-curing type The present invention relates to a polyurethane composition and the use of the composition as an elastic adhesive, elastic sealant, or elastic coating agent. The composition of the present invention has high elongation, surprisingly high strength, and surprisingly excellent adhesion to plastic substrates, even when the composition is formulated to have an attractive EHS classification due to a very low content of monomeric diisocyanate.

Description

Technology Field

[0001] The present invention relates to a moisture-curing polyurethane composition having excellent adhesion to a plastic substrate and to the use thereof as an elastic adhesive. Background Technology

[0002] Polyurethane compositions that provide an elastomer by crosslinking and curing through the reaction of isocyanate groups with moisture or water are used, for example, as elastic adhesives or sealants for joining or filling joints of assembled parts, particularly in the construction and manufacturing industries. Due to their adhesive strength and elasticity, they can gently dampen and cushion forces acting on a substrate, for example, triggered by vibration or temperature changes. In this specification, plasticizers support high flexibility but are disadvantageous for the development of excellent adhesion to plastic substrates.

[0003] Polyurethane compositions comprise a polymer containing isocyanate groups as a binder, prepared by reacting a polyol with a monomeric diisocyanate. The polymer thus obtained typically contains a residual monomeric diisocyanate content in the range of 1% to 3% by weight due to chain extension reactions. Monomeric diisocyanates can be potentially harmful to health. In particular, formulations containing monomeric diisocyanates at concentrations greater than 0.1% by weight must provide hazard symbols and warning messages on labels and data sheets, and may be subject to regulations regarding sale and use in some countries. Therefore, there is interest in polyurethane compositions having low monomer content, particularly less than 0.1% by weight.

[0004] An attractive approach for polymers containing isocyanate groups with low monomeric diisocyanate content is to use an excess of monomeric diisocyanate in the production of the polymer and then remove most of the unconverted monomeric diisocyanate through distillation. This approach is particularly feasible with low molecular weight and volatile monomeric diisocyanates, such as hexane diisocyanate. However, polymers based on this exhibit slow curing and low mechanical strength. Diphenylmethane 4,4'-Diisocyanate (4,4'-MDI)-based polymers enable rapid and reliable curing as well as high strength and elasticity. However, regarding the distillation removal of monomeric diisocyanate, production is significantly more challenging due to the low volatility of 4,4'-MDI.

[0005] For example, there is an increasing demand in industry for elastic adhesives for bonding plastic substrates, such as for vehicle headlamp housings or panoramic roofs, organic glass for ships or trains, or various components of caravans. These adhesives are required to cure quickly and reliably, possess high strength and high elasticity, and exhibit high adhesive strength to plastic substrates even under thermal and moisture stress without complex pretreatment. However, polymer-based adhesives with low monomeric levels show weaknesses in forming adhesion to plastic substrates, particularly because they substantially lack monomeric diisocyanates.

[0006] Accordingly, the object of the present invention is to provide a moisture-curing polyurethane composition that cures rapidly and reliably and establishes excellent adhesion to a plastic substrate with high elongation and strength, even in the case of a low content of monomeric diisocyanate. This object is achieved by a composition as described in claim 1. This comprises a linear long-chain polymer in a weight ratio ranging from 80 / 20 to 95 / 5. P1 class Branched polymer P2 It includes a combination of and a plasticizer content of 15 weight percent or less. Surprisingly, the polymer P1 class P2 The composition of the weight ratio of the present invention exhibits excellent adhesion to the substrate, particularly polycarbonate, even after heat and moisture stress. Branched polymer P2 While corresponding compositions with a higher proportion of clearly exhibit poorer adhesion, branched polymer P2 When the content is much lower, the tensile strength of the cured composition decreases sharply and significantly and is insufficient. A particularly surprising feature of the composition of the present invention is the branched polymer P2 Despite the low content The fact is that even when the diisocyanate monomer content is extremely low, a product with high strength (tensile strength and elastic modulus) is produced as a result.

[0007] The composition of the present invention enables an elastic adhesive having excellent storage stability with moisture-free plastic substrates, rapid curing, a long tack retention time combined with high elongation, surprisingly high strength, and surprisingly excellent adhesion, even in attractive EHS classifications.

[0008] Further aspects of the present invention are the subject of additional independent claims. Particularly preferred embodiments of the present invention are the subject of dependent claims. Specific details for implementing the invention

[0009] The present invention is,

[0010] (i) at least one linear polymer comprising isocyanate groups and having an NCO content in the range of 0.3 wt% to 3.3 wt%, obtained from the reaction of at least one monomeric aromatic diisocyanate and a polyether diol having an OH number in the range of 5 mg to 37 mg KOH / g. P1 ,

[0011] (ii) at least one branched polymer comprising isocyanate groups and having an NCO content in the range of 1 wt% to 10 wt%, obtained from the reaction of at least one monomeric aromatic diisocyanate and at least one polyether triol having an average number of OH functional groups of at least 2.2 and an OH value in the range of 16 mg to 380 mg KOH / g. P2 , and

[0012] (iii) Content of plasticizer of 15% by weight or less based on the total composition

[0013] Includes, polymer P1 and polymer P2 A moisture-curing polyurethane composition is provided, characterized by having a weight ratio in the range of 80 / 20 to 95 / 5.

[0014] "Monomer diisocyanate" refers to an organic compound having two isocyanate groups separated by a divalent hydrocarbyl radical having 4 to 15 carbon atoms.

[0015] "Aromatic" isocyanate groups refer to those directly bonded to aromatic carbon atoms. Isocyanates having only aromatic isocyanate groups are correspondingly referred to as "aromatic isocyanates."

[0016] "Aliphatic" isocyanate groups refer to those directly bonded to aliphatic or alicyclic carbon atoms. Isocyanates having only aliphatic isocyanate groups are correspondingly referred to as "aliphatic isocyanates."

[0017] "Monomeric aromatic diisocyanate" refers to a monomeric diisocyanate having an aromatic isocyanate group.

[0018] "NCO content" refers to the content of isocyanate groups (weight%).

[0019] "Plasticizer" refers to a substance that is liquid at room temperature, remains unchanged in the composition after curing, and plasticizes the cured composition.

[0020] "Molecular weight" refers to the molar mass (in grams per mole) of a molecule or molecular residue. "Average molecular weight" refers to the number-average molecular weight (M) of a polydisperse mixture of oligomeric or polymeric molecules or molecular residues. n It refers to ). This is determined by gel-permeation chromatography (GPC) on polystyrene as a standard material.

[0021] A substance or composition is referred to as "storage-safe" or "storability" if it can be stored in a suitable container at room temperature for an extended period, typically at least 3 months, preferably up to 6 months or more, without causing any change in application or use characteristics within the scope related to the intended use.

[0022] "Plastic" refers to an organic material based on macromolecules.

[0023] "Room temperature" refers to a temperature of 23℃.

[0024] All industry standards and norms mentioned in this specification relate to the versions valid as of the first filing date.

[0025] Weight percentage (wt%), abbreviated as wt%, refers to the mass ratio of a component of a composition or molecule relative to the total composition or total molecule, unless otherwise noted. The terms “mass” and “weight” are used as synonyms in this specification.

[0026] polymer P1 It preferably has an NCO content in the range of 0.5% to 2.6% by weight, particularly 0.7% to 2.0% by weight, and more preferably 0.9% to 2.0% by weight.

[0027] Suitable monomeric aromatic diisocyanates are particularly diphenylmethane 4,4'-diisocyanate, and optionally have fractions of diphenylmethane 2,4'- and / or 2,2'-diisocyanate (MDI), tolylene 2,4-diisocyanate or a mixture of this with tolylene 2,6-diisocyanate (TDI), phenylene 1,4-diisocyanate (PDI), 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene 1,5-diisocyanate (NDI), or 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TODI).

[0028] Among these, diphenylmethane 4,4'-diisocyanate, tolylene 2,4-diisocyanate, or phenylene 1,4-diisocyanate is preferred.

[0029] A particularly desirable monomeric aromatic diisocyanate is diphenylmethane 4,4'-diisocyanate (4,4'-MDI). This 4,4'-MDI contains only a small amount of diphenylmethane 2,4'- and / or 2,2'-diisocyanate and has the quality of being solid at room temperature. This enables polyurethane compositions with high strength, particularly associated with rapid curing and high elongation and elasticity.

[0030] 4,4'-MDI is preferably distilled and has a purity of at least 95%, particularly at least 97.5%.

[0031] Commercially available diphenylmethane 4,4'-diisocyanate of this quality is, for example, Desmodur ® 44 MC (Covestro product) or Lupranat ® MRS or ME (BASF product) or Suprasec ® It is 1400 (a Huntsman product).

[0032] The polyether diol preferably comprises a repeating unit selected from the group consisting of 1,2-ethyleneoxy, 1,2-propyleneoxy, 1,3-propyleneoxy, 1,2-butyleneoxy, and 1,4-butyleneoxy. A predetermined proportion of 1,2-propyleneoxy groups with or without 1,2-ethyleneoxy groups is preferred.

[0033] More specifically, the polyether diol comprises 80% to 100% by weight of 1,2-propylene oxygen groups and 0% to 20% by weight of 1,2-ethylene oxygen groups.

[0034] When a polyether diol contains 1,2-ethyleneoxy groups, it is desirable that the 1,2-propyleneoxy groups and 1,2-ethyleneoxy groups each form a homogeneous block, and the poly(1,2-ethyleneoxy) block is at the chain end.

[0035] Polyether diols preferably have an OH value in the range of 6 mg to 33 mg KOH / g, particularly 9 mg to 30 mg KOH / g, particularly 12 mg to 30 mg KOH / g.

[0036] The polyether diol preferably has an average molecular weight M in the range of 3,000 to 20,000 g / mol, more preferably 3,500 to 18,000 g / mol, particularly 4,000 to 12,000 g / mol, and most preferably 4,000 to 9,000 g / mol. n has

[0037] Polyether diols preferably have an average number of OH functional groups of at least 1.8, particularly at least 1.9. As a result of production, commercial polyether diols contain a specified amount of monool, and as a result, the average number of OH functional groups is typically slightly lower than 2.

[0038] Polyether diols preferably have an unsaturation level of less than 0.02 meq / g, particularly less than 0.01 meq / g, as measured according to ASTM D-2849-69. Polyether diols with an unsaturation level of less than 0.01 meq / g were prepared particularly with the help of a bimetallic cyanide complex catalyst (DMC catalyst).

[0039] Polyether diols more preferably have an OH value in the range of 6 mg to 33 mg KOH / g, preferably 9 mg to 30 mg KOH / g, particularly 12 mg to 30 mg KOH / g, and an average OH functional group number of at least 1.9.

[0040] Suitable polyether diols are, for example, Acclaim ® Polyol 4200, Acclaim ® Polyol 8200 N, Acclaim ® Polyol 12200 N or Acclaim ® Polyol 18200 N (all Covestro products), Lupranol ® 1005 / 1 (BASF product), Voranol ® P 4000 (Dow product) or Preminol ® It is commercially available, such as S 4013 F (a product of Asahi Glass).

[0041] Preferably, the polymer P1 The average molecular weight M in the range of 4,000 to 40,000 g / mol measured by gel permeation chromatography (GPC) and a refractive index detector for tetrahydrofuran as the mobile phase and polystyrene as the standard. n has

[0042] More preferably, average molecular weight M n The range is 4,500 to 30,000 g / mol, particularly 5,000 to 25,000 g / mol, more preferably 5,000 to 15,000 g / mol.

[0043] linear polymer P1 The reaction of monomeric aromatic diisocyanate and polyether diol for the production of is preferably carried out without moisture at a temperature of 20°C to 160°C, particularly in the range of 40°C to 140°C, in the presence of a suitable catalyst, optionally.

[0044] The reaction is preferably carried out at an NCO / OH ratio in the range of 1.3 / 1 to 20 / 1. Monomeric diisocyanates remaining in the reaction mixture after the reaction of the OH groups can be removed, in particular, by distillation.

[0045] In one embodiment of the present invention, the monomeric diisocyanate is not removed from the polymer. In this case, the NCO / OH ratio in the reaction is preferably in the range of 1.3 / 1 to 2.5 / 1. Such a polymer P1 It preferably contains 3.5% by weight or less of monomeric diisocyanate.

[0046] Preferably, the polymer P1 In the reaction, the NCO / OH ratio is prepared to be at least 4 / 1, and most monomeric aromatic diisocyanates are produced polymers containing isocyanate groups. P1 After this distillation, monomeric diisocyanates are subsequently removed by a suitable separation process to contain 0.5 wt% or less, particularly 0.3 wt% or less. These polymers P1 It enables polyurethane compositions having a particularly attractive EHS classification.

[0047] The NCO / OH ratio is preferably in the range of 5 / 1 to 15 / 1.

[0048] A preferred separation method for removing aromatic monomeric diisocyanates is a distillation method, particularly preferably thin-film distillation or short-path distillation under reduced pressure.

[0049] A multi-stage method in which monomeric aromatic diisocyanates are removed in a short-path evaporator having a jacket temperature in the range of 120°C to 200°C and a pressure of 0.001 mbar to 0.5 mbar is particularly preferred.

[0050] For 4,4'-MDI, which is preferred as a monomeric aromatic diisocyanate, distillation removal is particularly difficult. For example, condensate must not solidify and must not clog the system. It is preferable to operate at a jacket temperature in the range of 160°C to 200°C at 0.001 mbar to 0.5 mbar, and to condense the removed monomer at a temperature in the range of 40°C to 60°C.

[0051] It is desirable to react a monomeric aromatic diisocyanate with a polyether diol and subsequently remove most of the monomeric diisocyanate remaining in the reaction mixture without using a solvent or entraining agent.

[0052] It is desirable to subsequently reuse the aromatic monomeric diisocyanate removed after the reaction, that is, to reuse it for the production of polymers containing isocyanate groups.

[0053] linear polymer P1 It is a liquid at room temperature and has relatively low viscosity. Its viscosity at 20°C is 60 Pa . s or less, more preferably 45 Pa . s or less, especially 30 Pa . It is preferable that it be s or less. The viscosity is 10 s in this specification. -1 It is determined by a conical viscometer at the shear rate.

[0054] In the reaction, the OH groups of the polyether diol react with the isocyanate groups of the monomeric aromatic diisocyanate. This also results in a chain extension reaction, in that there is a reaction between the OH groups and / or isocyanate groups of the reaction product between the diol and the monomeric diisocyanate. The higher the selected NCO / OH ratio, the lower the level of the chain extension reaction occurring and the lower the polydispersity, and thus the lower the viscosity of the obtained polymer. Measures of the chain extension ratio are the average molecular weight of the polymer or the peak width and distribution in GPC analysis. If the unconverted monomeric diisocyanate is removed from the polymer by distillation, the effective NCO content of the polymer relative to the theoretical NCO content calculated from the reaction of all OH groups with the monomeric aromatic diisocyanate is an additional measure of the chain extension ratio.

[0055] Preferably, a polymer without diisocyanate monomers by distillation P1 It contains only a low content of chain extension components. Its NCO content is preferably at least 90%, particularly at least 95%, of the theoretical NCO content calculated from the addition of 1 mole of monomeric diisocyanate per 1 mole of OH groups of the polyether diol.

[0056] polymer P2 It preferably has an NCO content in the range of 1.2% to 7% by weight, particularly 1.4% to 3.5%.

[0057] Suitable monomeric aromatic diisocyanates are particularly diphenylmethane 4,4'-diisocyanate, and optionally have fractions of diphenylmethane 2,4'- and / or 2,2'-diisocyanate (MDI), tolylene 2,4-diisocyanate or a mixture of this and tolylene 2,6-diisocyanate (TDI), phenylene 1,4-diisocyanate (PDI), 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene 1,5-diisocyanate (NDI) or 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TODI).

[0058] Among these, diphenylmethane 4,4'-diisocyanate, tolylene 2,4-diisocyanate, or phenylene 1,4-diisocyanate is preferred.

[0059] A particularly desirable monomeric aromatic diisocyanate is diphenylmethane 4,4'-diisocyanate (4,4'-MDI).

[0060] 4,4'-MDI is preferably distilled and has a purity of at least 95%, particularly at least 97.5%.

[0061] The polyether triol preferably comprises a repeating unit selected from the group consisting of 1,2-ethyleneoxy, 1,2-propyleneoxy, 1,3-propyleneoxy, 1,2-butyleneoxy, and 1,4-butyleneoxy. A predetermined proportion of 1,2-propyleneoxy groups, with or without 1,2-ethyleneoxy groups, is preferred.

[0062] More specifically, the polyether triol has 80% to 100% by weight of 1,2-propyleneoxy groups and 0% to 20% by weight of 1,2-ethyleneoxy groups based on all repeating units.

[0063] Polyether triols preferably have an OH value in the range of 21 mg to 160 mg KOH / g, particularly in the range of 25 mg to 60 mg KOH / g.

[0064] Polyether triols preferably have an average number of OH functional groups in the range of 2.3 to 3. As a result of these production, commercial polyether triols contain a specified amount of monool, and as a result, their average number of OH functional groups is typically somewhat lower than 3. Accordingly, they typically contain trifunctional and monofunctional components.

[0065] The polyether triol preferably has an average molecular weight M in the range of 450 to 10,000 g / mol, more preferably 1,000 to 8,000 g / mol, and particularly 2,800 to 6,500 g / mol. n has

[0066] Polyether triols are preferably initiated by trimethylolpropane or, in particular, glycerol.

[0067] Suitable polyether triols are, for example, Desmophen ® 3061 BT, Desmophen ® 4042 BT, Desmophen ® 5031 BT, Desmophen ® 5034 BT or Acclaim ® Polyol 6300 (all Covestro products), Lupranol ® 2004 / 1 or Lupranol ® 2095 (BASF product), Voranol ® CP 450, Voranol ® CP 755, Voranol ® CP Voranol ® CP 1050, Voranol ® CP 3055, Voranol ® CP 4755, Voranol ® 5815 or Voranol ® CP 6001 (Dow product), Caradol ® ET34-08 or Caradol ® ET28-03 (Shell product) or Preminol ®7001 K or Preminol ® It is commercially available, such as S 3011 (Asahi Glass Co. product).

[0068] Preferably, the polymer P2 is an average molecular weight M in the range of 1,200 to 40,000 g / mol determined by gel permeation chromatography (GPC) and refractive index detector for tetrahydrofuran as the mobile phase and polystyrene as the standard. n has

[0069] More preferably, average molecular weight M n The range is 2,000 to 30,000 g / mol, particularly 4,000 to 20,000 g / mol.

[0070] Branched polymer P2 The reaction of a monomeric aromatic diisocyanate and a polyether triol for the production of is preferably carried out without moisture at a temperature of 20°C to 160°C, particularly in the range of 40°C to 140°C, in the presence of a suitable catalyst, optionally.

[0071] The reaction is preferably carried out at an NCO / OH ratio in the range of 1.7 / 1 to 20 / 1. Monomeric diisocyanates remaining in the reaction mixture after the reaction of the OH groups can be removed, in particular, by distillation.

[0072] In a preferred embodiment of the present invention, the monomeric diisocyanate is not removed from the polymer. In this case, the NCO / OH ratio in the reaction is preferably in the range of 1.9 / 1 to 2.5 / 1. Such a polymer P2 It preferably contains 3.5% by weight or less of monomeric diisocyanate.

[0073] These polymers P2In the manufacture of, a polyether diol in a predetermined proportion having an OH value in the range of 25 mg to 115 mg KOH / g, particularly 25 mg to 60 mg KOH / g, may be used together with the polyether triol. The ratio between the polyether triol and the polyether diol is preferably... in this specification... polymer P2 The average number of NCO functional groups is ultimately selected so that it is at least 2.2.

[0074] More preferably, the polymer P2 It is prepared such that the NCO / OH ratio in the reaction is at least 4 / 1, particularly in the range of 5 / 1 to 10 / 1, and most monomeric aromatic diisocyanates subsequently produce a resulting polymer containing isocyanate groups. P2 After distillation, monomeric diisocyanate is removed by a suitable separation process to contain 0.5 wt% or less, particularly 0.3 wt% or less. This polymer P2 It has particularly low viscosity and contributes to an attractive EHS classification for polyurethane compositions.

[0075] Preferably, two polymers P1 and P2 The monomeric aromatic diisocyanate for the manufacture of is the same monomeric aromatic diisocyanate.

[0076] Preferably, two polymers P1 and P2 The monomeric aromatic diisocyanate for is 4,4'-MDI.

[0077] The desirable polymer enables a polyurethane composition having a particularly advantageous combination of high strength and excellent adhesion to plastic substrates.

[0078] polymer P1 and polymer P2It is present in the moisture-curing polyurethane composition in a weight ratio ranging from 80 / 20 to 95 / 5. This weight ratio offers a remarkable combination of excellent adhesion to plastic substrates and high strength.

[0079] polymer P1 class P2 The weight ratio between them is preferably in the range of 84 / 16 to 93 / 7.

[0080] polymer P1 When the polyether diol for the manufacture of has an OH value in the range of 22 mg to 37 mg KOH / g, particularly 25 mg to 33 mg KOH / g, the polymer P1 class P2 The weight ratio between them is preferably in the range of 88 / 12 to 93 / 7.

[0081] polymer P1 When the polyether diol for the manufacture of has an OH value in the range of 5 mg to 21 mg KOH / g, particularly 6 mg to 19 mg KOH / g, the polymer P1 class P2 The weight ratio between them is preferably in the range of 84 / 16 to 91 / 9.

[0082] At a desirable weight ratio, the combination of excellent adhesion and high strength is particularly advantageous.

[0083] Preferably, the moisture-curing polyurethane composition comprises a polymer in the range of 20% to 80% by weight, particularly 30% to 70% by weight, and more preferably 40% to 60% by weight, based on the total composition. P1 perpolymer P2 It has a total content of

[0084] polymer P1 and P2 In addition, the moisture-curing polyurethane composition is a polymer P1 or P2 It may include a polymer comprising at least one additional isocyanate group that does not correspond to.

[0085] Suitable polymers are polyether-based polymers having aliphatic isocyanate groups and polymers comprising polyester polyols, polycarbonate polyols, poly(meth)acrylate polyols, polyhydroxy-functional fats or oils, polyhydrocarbon polyols, or additional polyols.

[0086] The moisture-curing polyurethane composition preferably contains a total content of less than 0.1% by weight of monomeric diisocyanate.

[0087] The moisture-curing polyurethane composition optionally includes a plasticizer, wherein the plasticizer is present in an amount of 15 weight percent or less based on the total composition. Since the plasticizer is highly likely to have a negative effect on the adhesion to the plastic substrate, an excessive amount is not used. Preferably, the moisture-curing polyurethane composition includes 10 weight percent or less, particularly 5 weight percent or less, of a plasticizer.

[0088] Suitable plasticizers are particularly carboxylic acid esters, e.g., phthalates, particularly diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) or di(2-propylheptyl)phthalate (DPHP), hydrogenated phthalates or cyclohexane-1,2-dicarboxylate esters, particularly hydrogenated diisononyl phthalate or diisononyl cyclohexane-1,2-dicarboxylate (DINCH), terephthalates, particularly bis(2-ethylhexyl) terephthalate (DOTP) or diisononyl terephthalate (DINT), hydrogenated terephthalates or cyclohexane-1,4-dicarboxylate esters, particularly hydrogenated bis(2-ethylhexyl) terephthalate or bis(2-ethylhexyl) cyclohexane-1,4-dicarboxylate or hydrogenated diisononyl It is a plasticizer having a structure of terephthalate or diisononyl cyclohexane-1,4-dicarboxylate, isophthalate, trimellitate, adipate, particularly dioctyl adipate, azelate, sebacate, benzoate, glycol ether, glycol ester, polyether, particularly polypropylene oxide monool, diol or triol, organic phosphate or sulfonic acid ester, polybutene, polyisobutene or natural fat or oil, particularly epoxidized soybean oil or linseed oil, having blocked hydroxyl groups particularly in the form of acetate groups.

[0089] A desirable plasticizer is a plasticizer having a phthalate, hydrogenated phthalate, adipate, or polyether structure.

[0090] The moisture-curing polyurethane composition preferably comprises at least one additional component selected from the group consisting of a filler, an oligomeric diisocyanate, a blocked amine, a catalyst, and a stabilizer.

[0091] Suitable fillers are coated with, in particular, ground or precipitated calcium carbonate, optionally fatty acids, in particular stearate, burrite, quartz powder, silica sand, dolomite, willastonite, calcined kaolin, sheet silicates, e.g., mica or talc, zeolite, aluminum hydroxide, magnesium hydroxide, silica including finely ground silica from a pyrolysis process, cement, gypsum, fly ash, industrially produced carbon black, graphite, metal powder of, e.g., aluminum, copper, iron, silver or steel, PVC powder or hollow beads.

[0092] Optionally, calcium carbonate coated with fatty acids, particularly stearate, calcined kaolin, or industrially produced carbon black is preferred.

[0093] Suitable oligomeric diisocyanates are particularly suitable for HDI burettes, e.g., Desmodur ® N 100 or N 3200 (Covestro product), Tolonate ® HDB or HDB-LV (Vencorex product) or Duranate ® 24A-100 (Product of Asahi Kasei); HDI isocyanurate, e.g., Desmodur ® N 3300, N 3600, or N 3790 BA (all Covestro products), Tolonate ® HDT, HDT-LV, or HDT-LV2 (Vencorex product), Duranate ® TPA-100 or THA-100 (Asahi Kasei product) or Coronate ® HX (product of Nippon Polyurethane); HDI urethane diode, e.g., Desmodur ® N 3400 (Covestro product); HDI iminooxadiazine, e.g., Desmodur ®XP 2410 (Covestro product); HDI allophanate, e.g., Desmodur ® VP LS 2102 (Covestro product); IPDI isocyanurate, e.g., Desmodur ® A solution such as Z 4470 (Covestro product) or Vestanat ® Solid form such as T1890 / 100 (Evonik product); TDI oligomers, e.g., Desmodur ® IL (Covestro product); or TDI / HDI-based mixed isocyanurates, e.g., Desmodur ® HL (a product of Covestro), where "HDI" represents hexane 1,6-diisocyanate, "IPDI" represents isophorone diisocyanate, and "TDI" represents tolylene 2,4-diisocyanate or a mixture of tolylene 2,6-diisocyanate.

[0094] Preferably, the moisture-curing polyurethane composition comprises only oligomeric diisocyanate in a low content, preferably less than 5% by weight, more preferably less than 3% by weight, and particularly less than 1% by weight, based on the total composition.

[0095] Suitable blocked amines preferably have at least one aldimino group or oxazolidinino group. Upon contact with moisture, the amino group is hydrolyzed and released, reacting with available isocyanate groups to promote rapid, blister-free curing, particularly non-stick surfaces and / or particularly excellent mechanical properties.

[0096] Preferred oxazolidins are those derived from bis-oxazolidins, in particular isobutyraldehyde, benzaldehyde or substituted benzaldehyde, in particular benzaldehyde substituted at the para position with an optionally branched alkyl group having 10 to 14 carbon atoms.

[0097] Bisoxazolidine from the reaction of OH-functional monooxazolidine with diisocyanate, particularly hexamethylene 1,6-diisocyanate, is preferred. Suitable monooxazolidine is obtained particularly from the release of diethanolamine and aldehyde and the removal of water.

[0098] Suitable aldimins are, in particular, di- or trialdimins from the reaction of commercial primary di- or triamines with non-enolable aldehydes. These are aldehydes that lack a hydrogen atom at the alpha position for the carbon atom of the aldehyde group.

[0099] Particularly desirable 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(benzylidene)-3-aminomethyl-3,5,5-trimethylcyclohexylamine, N,N'-bis(4-C 10-14 -alkylbenzylidene)-3-aminomethyl-3,5,5-trimethylcyclohexylamine, average molecular weight M in the range of 450 to 750 g / mol n N,N'-bis(2,2-dimethyl-3-acetoxypropylidene)polyoxypropylenediamine having an average molecular weight M in the range of 750 to 1,050 g / mol n N,N'-bis(2,2-dimethyl-3-lauroyloxypropylidene)polyoxypropylenediamine having an average molecular weight M in the range of 380 to 680 g / mol n N,N'-bis(benzylidene)polyoxypropylenediamine having, average molecular weight M in the range of 680 to 1,100 g / mol n N,N'-bis(4-C) having 10-14 -alkylbenzylidene)polyoxypropylenediamine, average molecular weight M in the range of 730 to 880 g / mol nN,N',N''-tris(2,2-dimethyl-3-acetoxypropylidene)polyoxypropylene lyamine having and an average molecular weight M in the range of 1,150 to 1,300 g / mol n It is selected from the group consisting of N,N',N''-tris(2,2-dimethyl-3-lauroyloxypropylidene)polyoxypropylene lyamine having

[0100] A suitable catalyst is a catalyst for accelerating the reaction of a compound comprising an isocyanate group, particularly an organotin (IV) compound, e.g., particularly dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetylacetonate, dimethyltin dilaurate, dioctyltin diacetate, dioctyltin dilaurate or dioctyltin diacetylacetonate, bismuth (III) or zirconium (IV) and a complex of a ligand selected from alkoxide, carboxylate, 1,3-diketonate, oxynate, 1,3-ketoesterate and 1,3-ketoamidate, or a tertiary amino group, e.g., particularly 2,2'-dimopolynodiethyl ether (DMDEE).

[0101] When a moisture-curing polyurethane composition contains a blocked amine, a suitable catalyst is also a catalyst for the hydrolysis of the blocked amino group, particularly organic acids, particularly aromatic carboxylic acids, such as benzoic acid, 2-nitrobenzoic acid or salicylic acid.

[0102] In addition, a combination of different catalysts is particularly suitable.

[0103] Suitable stabilizers are stabilizers, in particular, for oxidation, heat, light, or UV radiation. The composition preferably includes at least one UV stabilizer.

[0104] The moisture-curing polyurethane composition may particularly include the following additional additives:

[0105] - Inorganic or organic pigments, especially titanium dioxide, chromium oxide, or iron oxide;

[0106] - Fibers, particularly glass fibers, carbon fibers, metal fibers, ceramic fibers, polymer fibers, e.g., polyamide fibers or polyethylene fibers, or natural fibers, e.g., wool, cellulose, hemp, or sisal;

[0107] - Nanofillers, e.g., graphene or carbon nanotubes;

[0108] - Dye;

[0109] - Drying agents, particularly molecular sieve powders, calcium oxide, highly reactive isocyanates, e.g., p-tosyl isocyanate, monooxazolidine, e.g., Incozol ® 2 (Incorez product) or orthoformic acid ester;

[0110] - Adhesion promoters, particularly organoalkoxysilanes, particularly epoxysilanes, e.g., particularly 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane, (meth)acrylosilane, anhydridosilane, carbamatosilane, alkylsilane or iminosilane, or oligomeric forms of these silanes or titanates;

[0111] - Additional catalyst to accelerate the reaction of isocyanate groups;

[0112] - Flow modifiers, particularly thickeners, particularly sheet silicates, e.g., bentonite, derivatives of castor oil, hydrogenated castor oil, polyamides, polyamide waxes, polyurethanes, urea compounds, fumed silica, cellulose ethers, or hydrophobically modified polyoxyethylene;

[0113] - 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, e.g., propylal, butylal, 2-ethylhexylal, dioxolene, glycerol formal or 2,5,7,10-tetraoxaundecaene (TOU), toluene, xylene, heptane, octane, naphtha, white oil, petroleum ether or gasoline, in particular Solvesso™ grade (Exxon products) and propylene carbonate, dimethyl carbonate, butyrolactone, N-methylpyrrolidone, N-ethylpyrrolidone, p-chlorobenzotrifluoride or benzotrifluoride;

[0114] - Natural resins, fats, or oils, e.g., pine resin, shellac, linseed oil, castor oil, or soybean oil;

[0115] - A non-reactive polymer, in particular a homopolymer or copolymer of an unsaturated monomer derived from a group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate, or alkyl (meth)acrylate, in particular polyethylene (PE), polypropylene (PP), polyisobutylene, ethylene / vinyl acetate copolymer (EVA), or atactic poly-α-olefin (APAO);

[0116] - Flame-retardant materials, in particular the previously mentioned fillers aluminum hydroxide or magnesium hydroxide or organophosphate esters;

[0117] - Additives, in particular wetting agents, leveling agents, antifoaming agents, degassing agents, or biocides;

[0118] Or additional materials commonly used in moisture-curing polyurethane compositions.

[0119] It may be recommended to chemically or physically dry the specified material before mixing it into the composition.

[0120] When a polymer containing isocyanate groups is mixed with additional components of the composition, particularly fillers, the content of monomeric diisocyanate may be further reduced by reaction with present moisture.

[0121] The moisture-curing polyurethane composition preferably comprises the following:

[0122] - A polymer comprising 30% to 70% by weight of isocyanate groups,

[0123] - 20% to 60% by weight of filler,

[0124] - 0% to 15% by weight, particularly 0% to 5% by weight of a plasticizer,

[0125] and optionally additional components, in particular blocked amines or catalysts.

[0126] After curing, the moisture-curing polyurethane composition has high strength and high elongation.

[0127] The tensile strength determined as described in the examples is preferably at least 1.5 MPa, more preferably at least 2 MPa, and particularly at least 3 MPa.

[0128] As described in the example, the elastic modulus of the elongation in the range of 0.05% to 5% determined is preferably in the range of 2.5MPa to 20MPa, particularly in the range of 3MPa to 15MPa.

[0129] As described in the examples, the elongation at break determined is preferably at least 300%, particularly at least 500%.

[0130] Moisture-curing polyurethane compositions are manufactured particularly without moisture and stored at ambient temperature in moisture-tight containers. Suitable moisture-tight containers are made of metal and / or plastic, particularly optionally coated, and are drums, transport boxes, hobbocks, buckets, canisters, cans, bags, tubular bags, cartridges, or tubes.

[0131] The moisture-curing polyurethane composition may be in the form of a one-component composition or a multi-component, particularly a two-component composition.

[0132] A composition referred to as a "one-component" composition is one in which all components of the composition are contained within the same container and are stable in storage.

[0133] A composition referred to as a "2-component" composition is a composition consisting of two different components that are stored in separate containers and are not mixed with other components immediately before or during use.

[0134] The moisture-curing polyurethane composition is preferably a one-component composition. Considering suitable packaging and storage, it is typically stable for storage from several months to up to one year or longer.

[0135] When a moisture-curing polyurethane composition is applied, a curing process is initiated. This produces a cured composition.

[0136] In the case of a 1-component composition, it is applied as is and then begins to cure under the influence of moisture or water. To accelerate curing, an accelerator component containing or releasing water and / or a catalyst and / or curing agent may be mixed into the composition at the time of application or may come into contact with such accelerator component after the application of the composition.

[0137] During the curing process, isocyanate groups react with each other under the influence of moisture. If the moisture-curing polyurethane composition contains blocked amines, the isocyanate groups additionally react with the blocked amino groups when hydrolyzed. This overall reaction of the isocyanate groups that induces the curing of the composition is also referred to as crosslinking.

[0138] The moisture required for the curing of the moisture-curing polyurethane composition preferably reaches the composition through diffusion from the air (atmospheric moisture). In this process, a solid layer ("skin") of the cured composition is formed on the surface of the composition that comes into contact with the air. Curing proceeds in a diffusion direction from the outside inward, and the skin becomes progressively thicker and ultimately covers the entire applied composition. The moisture may also reach the composition additionally or entirely from one or more substrate(s) to which the composition is applied, and / or may originate from an accelerator component that is mixed into the composition at application or comes into contact with the composition after application, for example, by painting or spraying.

[0139] The moisture-curing polyurethane composition is preferably applied at ambient temperatures, particularly within the range of about -10°C to 50°C, preferably -5°C to 45°C, particularly within the range of 0°C to 40°C.

[0140] The moisture-curing polyurethane composition is preferably cured at ambient temperature as well.

[0141] Moisture-curing polyurethane compositions have a long processing time (adhesion retention time) and fast curing.

[0142] When a moisture-curing polyurethane composition contains blocked amines, the aldehyde used to block the amino groups is released during the crosslinking process. If this is mostly volatile, it will mostly remain in the cured composition and act as a plasticizer.

[0143] It is preferable to use a moisture-curing polyurethane composition as an elastic adhesive, elastic sealant, or elastic coating agent.

[0144] Moisture-curing polyurethane compositions as adhesives and / or sealants are particularly suitable for bonding and sealing applications in the construction and manufacturing industries or automotive manufacturing, especially for flooring bonding, assembly, bonding of installable components, module bonding, plate glass bonding, joint sealing, body sealing, seam sealing, or cavity sealing.

[0145] Elastic joining of a vehicle structure is, for example, attaching parts such as plastic covers, trim strips, flanges, fenders, driver's seats, or other installable components to the painted body of a vehicle or joining plate glass to the vehicle body, and said vehicle is particularly an automobile, truck, bus, railway vehicle, or ship.

[0146] Moisture-curing polyurethane compositions are particularly suitable as sealants for the elastic sealing of all kinds of joints, seams, or cavities, particularly structural components, such as expansion joints or connecting joints between components made of plastic, or floor joints in civil engineering. Sealants with flexible properties and high cold flexibility are particularly suitable for sealing expansion joints in building structures.

[0147] As a coating agent, moisture-curing polyurethane compositions are particularly suitable for the protection and / or sealing of building structures or parts thereof, especially for balconies, terraces, roofs, particularly flat or slightly sloped roof areas or rooftop gardens, especially in areas made of plastic materials, or inside buildings under tiles or ceramic plates in wet rooms or kitchens, or in collection fans, conduits, shafts, silos, tanks, or wastewater treatment systems.

[0148] In addition, it can be used, for example, as a sealant or coating agent for leaked roof membranes or floor coverings that are no longer suitable for repair purposes, or as a highly reactive repair compound for spray sealing.

[0149] Moisture-curing polyurethane compositions can be formulated to have a pasty consistency having structurally viscous characteristics. This type of composition is applied by a suitable device, for example, in the form of beads that may essentially have a round or triangular cross-sectional area, for example, from a commercial cartridge or keg or hopbook.

[0150] Moisture-curing polyurethane compositions can also be formulated to be fluid and "self-leveling" or only slightly thixotropic and pourable for application. As a coating agent, it can be subsequently distributed flatly and continuously to a desired layer thickness, for example, by a roller, slide bar, toothed applicator, or trowel. In one operation, a layer thickness typically ranging from 0.5 mm to 3 mm, particularly from 1 mm to 2.5 mm, is applied.

[0151] Moisture-curing polyurethane compositions are preferably used for bonding, sealing, or coating at least one type of plastic substrate.

[0152] Suitable plastic substrates are blends of polycarbonate with additional plastics, particularly rigid and flexible PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resin, phenolic resin, PUR, POM, TPO, PE, PP, EPM, EPDM, or especially ABS and / or SAN, wherein these plastics may each be untreated or, for example, surface-treated forms treated by plasma, corona, or flame, and fiber-reinforced plastics such as carbon fiber-reinforced plastic (CFRP), glass fiber-reinforced plastic (GFRP), or sheet molding compound (SMC).

[0153] Preferably, the plastic substrate is selected from the group consisting of rigid PVC, flexible PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resin, phenolic resin, PUR, POM, TPO, PE, PP, EPM, EPDM, and additional plastics such as ABS and / or SAN, and blends of polycarbonate.

[0154] Among these, rigid PVC, polycarbonate, ABS and / or SAN, PMMA, or blends of ABS and polycarbonate are preferred, in particular polycarbonate or blends of polycarbonate. These plastics are particularly important in terms of excellent adhesion without complex pretreatment, and are especially important when frequently bonded.

[0155] Suitable additional substrates that can be bonded, sealed, or coated with a moisture-curing polyurethane composition are particularly as follows:

[0156] - Aluminum, copper, iron, steel, non-ferrous metals, including metals or alloys, such as surface-finished metals or alloys like zinc-plated or chromium-plated metals;

[0157] - Coated or painted substrates, in particular painted tiles, coated concrete, powder-coated metal or alloy or painted metal sheets;

[0158] - Paint or varnish, especially automotive finishes;

[0159] - Glass, glass ceramics, concrete, mortar, cement screed, fiber cement, especially fiber cement boards, bricks, tiles, gypsum, especially gypsum boards or anhydrous gypsum screeds, or natural stone such as granite or marble;

[0160] - Repair or leveling compounds based on PCC (polymer-modified cement mortar) or ECC (epoxy resin-modified cement mortar);

[0161] - Asphalt or bitumen;

[0162] - Additional materials referred to as leather, fabric, paper, wood, wood materials, resin / fabric composites, or polymer composites bonded with a resin such as phenol, melamine, or epoxy resin;

[0163] - In particular, insulation foam made of EPS, XPS, PUR, PIR, rock wool, glass wool, or expanded glass.

[0164] If necessary, the substrate may be pretreated prior to application, particularly by physical and / or chemical cleaning methods or by the application of an activator or primer.

[0165] It is possible to bond and / or seal two identical or two different materials.

[0166] A moisture-curing polyurethane composition is preferably used in a bonding or sealing method comprising the following steps:

[0167] (i) The moisture-curing polyurethane composition described

[0168] - Apply to the first substrate and bring the composition into contact with the second substrate within the adhesive retention time of the composition, or

[0169] - Apply to the first substrate and the second substrate, and bond the two substrates within the adhesion retention time of the composition, or

[0170] - Step applied between two materials,

[0171] (ii) A step of curing the composition by contacting it with moisture.

[0172] The moisture-curing polyurethane composition is also preferably used in a coating or sealing method comprising the following steps:

[0173] (i) a step of applying the described moisture-curing polyurethane composition to a substrate,

[0174] (ii) A step of curing the composition by contacting it with moisture.

[0175] In this method, preferably at least one type of substrate is a plastic substrate as described above.

[0176] The application and curing of a moisture-curing polyurethane composition provides an article bonded, sealed, or coated with the composition. Such an article may be a building structure or part thereof, particularly in civil engineering, a building structure above or below ground, a roof, stairs, or a facade, or an industrial or consumer product, particularly a window, lamp, traffic signal, household appliance, or means of transport, e.g., an automobile, bus, caravan, truck, train car, ship, aircraft, or helicopter, or an installable component thereof, e.g., a window, panoramic roof, or lamp housing made of organic glass.

[0177] The present invention further provides a cured composition obtained from a moisture-curing polyurethane composition after contact with moisture.

[0178] The present invention further provides an adhesive comprising at least one plastic substrate and a composition that is cured by contact with moisture as described above.

[0179] Even if the composition is formulated to have an attractive EHS classification with a very low content of monomeric diisocyanate, the moisture-curing polyurethane composition is characterized by excellent storage stability in the absence of moisture, a long tack retention time and rapid curing, and, after curing, exhibiting remarkable elastic properties such as high elongation, surprisingly high strength, and surprisingly excellent adhesion to plastic substrates.

[0180] Examples

[0181] Working examples for further explaining the described invention are presented below. The invention is, of course, not limited to these described working examples.

[0182] "Standard climate conditions" ("SCC") refer to a temperature of 23±1℃ and a relative air humidity of 50±5%.

[0183] Unless otherwise noted, the chemicals used were Sigma-Aldrich products.

[0184] viscosity Rheotec RC30 conical viscometer equipped with a temperature control device (cone diameter 25 mm, cone angle 1°, cone tip-plate distance 0.05 mm, shear rate 10 s -1 It was measured as ).

[0185] Monomeric diisocyanate content It was determined by HPLC (detection via photodiode array; 0.04 M sodium acetate / acetonitrile as mobile phase) after pre-derivation with N-propyl-4-nitrobenzylamine.

[0186] Polyols used:

[0187]

[0188] Monomeric diisocyanates used:

[0189]

[0190] Preparation of a polymer containing isocyanate groups:

[0191] Polymer L1 (linear):

[0192] 727g (0.36 equivalents OH) of Acclaim ® Desmodur of 4200 and 273g (2.18 equivalent NCO) ® 44 MC L was reacted at 80°C by a known method to obtain a polymer having an NCO content of 7.4 wt%, a viscosity of 5.2 Pa·s at 20°C, and a monomeric diphenylmethane 4,4'-diisocyanate content of about 17 wt%.

[0193] Subsequently, most of the volatile components, particularly monomeric diphenylmethane 4,4'-diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 180°C, pressure 0.1 mbar to 0.005 mbar, condensation temperature 47°C). The linear polymer thus obtained had an NCO content of 1.8 wt%, a viscosity of 13.3 Pa·s at 20°C, and a monomeric diphenylmethane 4,4'-diisocyanate content of 0.08 wt%.

[0194] Polymer L2 (linear):

[0195] 400g (0.20 equivalents OH) of Acclaim ® Desmodur of 4200 and 52g (0.41 equivalent NCO) ® 44 MC L was converted into an NCO-terminated polymer at 80°C by a known method. The linear polymer thus obtained had an NCO content of 1.8 wt%, a viscosity of 33 Pa·s at 20°C, and a monomeric diphenylmethane 4,4'-diisocyanate content of about 2.5 wt%.

[0196] Polymer L3 (linear):

[0197] Acclaim of 757.7g (0.19 equivalents OH) ®Desmodur of 8200N and 242.3g (1.9 equivalent NCO) ® 44 MC L was reacted at 80°C by a known method to obtain a polymer having an NCO content of 7.2 wt%, a viscosity of 6.8 Pa·s at 20°C, and a monomeric diphenylmethane 4,4'-diisocyanate content of about 20 wt%.

[0198] Subsequently, most of the volatile components, particularly monomeric diphenylmethane 4,4'-diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 180°C, pressure 0.1 mbar to 0.005 mbar, condensation temperature 47°C). The linear polymer thus obtained had an NCO content of 1.0 wt%, a viscosity of 25.0 Pa·s at 20°C, and a monomeric diphenylmethane 4,4'-diisocyanate content of 0.06 wt%.

[0199] Polymer L4 (linear):

[0200] Acclaim of 812.0g (0.15 equivalents OH) ® Desmodur of 12200N and 188.0g (1.5 equivalent NCO) ® 44 MC L was reacted at 80°C by a known method to obtain a polymer having an NCO content of 5.6 wt%, a viscosity of 13.9 Pa·s at 20°C, and a monomeric diphenylmethane 4,4'-diisocyanate content of about 14 wt%.

[0201] Subsequently, most of the volatile components, particularly monomeric diphenylmethane 4,4'-diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 180°C, pressure 0.1 mbar to 0.005 mbar, condensation temperature 47°C). The polymer thus obtained had an NCO content of 0.7 wt%, a viscosity of 29.4 Pa·s at 20°C, and a monomeric diphenylmethane 4,4'-diisocyanate content of 0.04 wt%.

[0202] Polymer C1 (branched):

[0203] 725.0 g (0.36 equivalents OH) of Desmophen ® Desmodur of 5031 BT and 275 g (2.2 equivalent NCO) ® 44 MC L was reacted at 80°C by a known method to obtain a polymer having an NCO content of 7.6 wt%, a viscosity of 6.5 Pa·s at 20°C, and a monomeric diphenylmethane 4,4'-diisocyanate content of about 20 wt%.

[0204] Subsequently, most of the volatile components, particularly monomeric diphenylmethane 4,4'-diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 180°C, pressure 0.1 mbar to 0.005 mbar, condensation temperature 47°C). The polymer thus obtained had an NCO content of 1.7 wt%, a viscosity of 19 Pa·s at 20°C, and a monomeric diphenylmethane 4,4'-diisocyanate content of 0.04 wt%.

[0205] Polymer C2 (branched):

[0206] 685g of Voranol ® CP 4755, 115g of Desmodur ® 44 MC L and 200 g of diisodecyl phthalate were reacted at 80°C by a known method to obtain a polymer having an NCO content of 2.0 wt%, a viscosity of 55 Pa·s at 20°C, and a monomeric diphenylmethane 4,4'-diisocyanate content of about 2.5 wt%.

[0207] Moisture-curing polyurethane composition:

[0208] Compositions Z1 to Z15:

[0209] For each composition, the ingredients specified in Tables 1 to 4 were mixed in the specified amounts (in parts by weight) using a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) at 3,000 rpm for 1 minute without moisture, and stored without moisture. The compositions were tested as follows:

[0210] As a measure of adhesion retention time, skin time: ST ) was determined. To this end, several grams of the composition were applied to a cardboard layer with a thickness of about 2 mm, and the time at which no residue remained on the LDPE pipette used to gently tap the surface of the composition under standard climate conditions was determined.

[0211] Shore A Hardness was determined according to DIN 53505 for test specimens cured for 14 days under standard climate conditions.

[0212] To determine mechanical properties, the composition was applied to silicone-coated release paper to produce a 2 mm thick film, which was stored for 14 days under standard climate conditions; the film was then punched with several dumbbells, each measuring 75 mm in length, 30 mm in rod length, and 4 mm in rod width, and the tensile strength (Breaking force), Elongation at break and 5% elastic modulus Tested according to DIN EN 53504 at a strain rate of 200 mm / min for (0.5% to 5% elongation).

[0213] Regarding plastic substrates AdhesionThe adhesion was determined by applying four parallel bead-shaped compositions, each approximately 10 mm in width, 5 mm in height, and 15 mm in length, to each substrate and curing them for 7 days under standard climatic conditions. Subsequently, the first bead was cut at the narrow end just above the bonding surface, and the cut end of the bead was grasped with round tweezers and pulled from the substrate to test the adhesion of the initially cured composition. Then, the bead was cut again under the substrate, the cut portion was wrapped with round tweezers, and an attempt was made again to pull the bead from the substrate. By pulling in this manner, the entire bead was severed from the substrate. Subsequently, the adhesion was evaluated from the failure profile, which was " 7d SCC " is reported in Table 1, Table 2, or Table 3 below. Then, some of the test specimens were immersed in deionized water for 7 days and stored, followed by storage under standard climatic conditions for 2 hours; subsequently, the second bead was pulled out with rounded tweezers and cut from the substrate, and the adhesion was evaluated from the failure profile, which is " 7d H 2 O " is reported in Table 1, Table 2, or Table 3 below. Then, the test specimens were stored in an air-circulating oven at 80°C for 24 hours, followed by storage under standard climate conditions for 2 hours; then, the third bead was tested for adhesion as described, and the adhesion was evaluated from the failure profile, which is " 1d 80℃ " is reported in Table 1, Table 2, or Table 3 below. Finally, the test specimens were stored at 70°C and 100% relative humidity for 7 days, then stored for 2 hours under standard climatic conditions, and the fourth bead was tested for adhesion as described, and the adhesion was evaluated from the failure profile, which is " 7d 70℃ / 100%RH It is reported in Table 1, Table 2, or Table 3 below.

[0214] The plastic substrate used was a plastic sheet (300×200×2㎜) as follows:

[0215] PMMA : Plexiglas ® XT 0A000 (Evonik Röhm product)

[0216] PC : Makrolon ® GP clear 099 (uncoated polycarbonate, Covestro product)

[0217] ABS : Metzoplast ABS / G (Product of Metzeler Plastics GmbH)

[0218] PVC : ® ES(Komering Kunstof( Kunststoffe products

[0219] Adhesion was evaluated using the following scales:

[0220] 100 indicates more than 95% cohesive failure and signifies very excellent adhesion.

[0221] 70 to 90 indicates 70% to 90% by weight of cohesive failure and signifies excellent adhesion.

[0222] 5 indicates 5% cohesive failure and means insufficient adhesion.

[0223] 0 indicates 0% cohesive failure (100% adhesive failure) and means poor adhesion.

[0224] The results are reported in Tables 1 to 4.

[0225] Comparative example is (Ref.) It is identified as.

[0226]

[0227]

[0228]

[0229]

[0230] From Tables 1 to 4, the composition of the present invention in which linear polymers and branched polymers are present in the ratio of the present invention contains a very low amount of linear polymer ( Z1 / Z11 / Z15 Compared to each reference composition with a content of too low ), it has excellent mechanical properties and improved adhesion to plastic substrates, whereas the linear polymer ( Z7 / Z14 / Z18 It is evident that a reference composition with too high a content of ) has excellent adhesive strength but low tensile strength, making it unsuitable as an adhesive for elastic bonding.

Claims

Claim 1 A moisture-curing polyurethane composition comprising: (i) at least one linear polymer having an isocyanate group and an NCO content in the range of 0.3 wt% to 3.3 wt%, obtained from the reaction of at least one monomeric aromatic diisocyanate with a polyether diol having an OH value in the range of 5 mg to 37 mg KOH / g. P1 , (ii) at least one branched polymer comprising isocyanate groups and having an NCO content in the range of 1 wt% to 10 wt%, obtained from the reaction of at least one monomeric aromatic diisocyanate and at least one polyether triol having an average number of OH functional groups in the range of at least 2.2 and OH in the range of 16 mg to 380 mg KOH / g. P2 , and (iii) a plasticizer comprising an amount of 15% by weight or less based on the total composition, wherein the polymer P1 and polymer P2 A moisture-curing polyurethane composition characterized by having a weight ratio in the range of 80 / 20 to 95 / 5. Claim 2 In paragraph 1, the polymer P1 A moisture-curing polyurethane composition characterized by having an NCO content in the range of 0.5% to 2.6% by weight. Claim 3 In paragraph 1, the polymer P1 It is prepared such that the NCO / OH ratio in the above reaction is at least 4 / 1, and the monomeric aromatic diisocyanate is subsequently produced as a polymer containing isocyanate groups. P1 A moisture-curing polyurethane composition characterized by being removed to contain 0.5% by weight or less of monomeric diisocyanate after distillation. Claim 4 A moisture-curing polyurethane composition according to claim 1, characterized in that the polyether diol has an OH value in the range of 6 mg to 33 mg KOH / g and an average number of OH functional groups of at least 1.

9. Claim 5 In paragraph 1, two polymers P1 and P2 A moisture-curing polyurethane composition characterized in that the monomeric aromatic diisocyanate for the above is diphenylmethane 4,4'-diisocyanate. Claim 6 In claim 1, the polymer based on the total composition P1 and polymer P2 A moisture-curing polyurethane composition characterized by a total content in the range of 20% to 80% by weight. Claim 7 A moisture-curing polyurethane composition according to claim 1, characterized in that the content of monomeric diisocyanate in the composition is less than 0.1% by weight in total. Claim 8 A moisture-curing polyurethane composition according to claim 1, characterized in that at least one additional component selected from the group consisting of a filler, an oligomeric diisocyanate, a blocked amine, a catalyst, and a stabilizer is present. Claim 9 A moisture-curing polyurethane composition used as an elastic adhesive, elastic sealant, or elastic coating agent in claim 1. Claim 10 A moisture-curing polyurethane composition according to claim 9, characterized in that at least one plastic substrate is bonded, sealed, or coated. Claim 11 A moisture-curing polyurethane composition according to claim 10, wherein the plastic substrate is selected from the group consisting of rigid PVC, flexible PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resin, phenolic resin, PUR, POM, TPO, PE, PP, EPM, EPDM, and blends of polycarbonate and ABS and / or SAN. Claim 12 A bonding or sealing method comprising: (i) applying a moisture-curing polyurethane composition according to any one of claims 1 to 8 to a first substrate and bringing the composition into contact with a second substrate within the open time of the composition, or applying it to the first substrate and the second substrate and bonding the two substrates within the open time of the composition, or applying it between the two substrates; and (ii) bringing the composition into contact with moisture to cure the composition. Claim 13 A coating or sealing method comprising: (i) applying a moisture-curing polyurethane composition according to any one of claims 1 to 8 to a substrate; and (ii) curing the composition by contacting it with moisture. Claim 14 A cured composition, obtained from a moisture-curing polyurethane composition according to any one of claims 1 to 8 after contact with moisture. Claim 15 A bonded composite comprising at least one plastic substrate and a polyurethane composition according to any one of claims 1 to 8 that is cured by contact with moisture.

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