Molded PU foam articles

Abstract

To provide shaped PU foam articles suited very well to recover their original shape after compression over a period of at least 20 hours.SOLUTION: Described herein are shaped PU foam articles, preferably mattresses and / or cushions, where the polyurethane foam is obtained by reaction of at least one polyol component and at least one isocyanate component in the presence of at least one compound of formula (1a) and at least one compound of formula (1b) and at least one blowing agent.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to the field of polyurethane (PU) foams. In particular, the present invention relates to the provision of molded PU foam articles, such as mattresses and / or cushions. [Background technology]

[0002] Molded PU foam articles, such as polyurethane foam-containing mattresses and / or cushions, have been known in the prior art for a long time and are used worldwide. Attempts to achieve greater improvements are ever-present. The need for optimization has not been fully met up to now.

[0003] One problem with molded PU foam articles is their transportation and storage. Molded PU foam articles, such as mattresses, are very bulky and therefore, due to space considerations, are often compressed, and particularly compressed and vacuum packed, for storage and transportation. Large distributors are increasingly shipping mattresses in a compressed, rolled form.

[0004] Such packaging is widely used, especially for mattresses. In vacuum packaging, the mattress is placed in a bag, for example made of plastic. This prepackaged mattress is then placed in a press and compressed with one end of the bag open. The air is released. The open end of the bag is then hermetically sealed by welding. The resulting vacuum package is then rolled up and placed in an outer bag. The outer bag keeps the mattress in the rolled state so that it cannot be re-inflated.

[0005] Flattening the mattress to the degree achieved by the machine during rolling requires a force of, for example, 40,000 to 250,000 N depending on the mattress, which corresponds to the gravitational force exerted by a mass of 4 to 25 tonnes.

[0006] As will be readily apparent, such forces associated with compression of a molded PU foam article can result in material fatigue. Providing a molded PU foam article that can recover to its original dimensions even after extended periods of compression is of great importance. Summary of the Invention

[0007] Against this background, it is an explicit object of the present invention to provide molded PU foam articles, in particular mattresses and / or cushions etc. comprising polyurethane foam, which are highly suitable for regaining their original shape after compression over a period of at least 20 hours.

[0008] In accordance with the present invention, it has surprisingly been found that this object can be achieved by the subject matter of the present invention.

[0009] The present invention relates to a molded PU foam article, preferably a mattress and / or cushion, characterized in that the polyurethane foam is obtained by reaction of at least one polyol component and at least one isocyanate component in the presence of at least one compound of formula (1a) and at least one compound of formula (1b) and at least one blowing agent, where equations (1a) and (1b) are defined as follows:

[0010] [ka]

[0011] [In formula (1a): X is oxygen, nitrogen or amine (NR 3 or NR 3 R 4 ), specifically oxygen, Y is an amine NR 8 R 9 Or Ether OR 9 , especially amine NR 8 R 9 [In the formula, R 8 = methyl and R 9 = aminopropyl; R 1,2 represents identical or different hydrocarbon radicals having 1 to 8 carbon atoms, phenyl, cyclohexyl or hydrogen, preferably methyl, ethyl, isopropyl or hydrogen, particularly preferably methyl or hydrogen, in particular methyl, R 3~9 are identical or different hydrocarbon radicals having 1 to 8 carbon atoms, optionally carrying an NH or NH2 group, phenyl, cyclohexyl or hydrogen, preferably methyl, ethyl, isopropyl, aminoalkyl or hydrogen, particularly preferably methyl, aminopropyl or hydrogen, in particular methyl or aminopropyl, m=1 to 4, preferably 2 and 3, in particular 2; n=2, i=0 to 3, preferably 0, 1 and 2, in particular 1; However, the groups X, Y or R 1~9 at least one of them has a functional group reactive with the polyurethane matrix, preferably an isocyanate-reactive functional group, particularly preferably NH or OH,

[0012] [ka]

[0013] [In formula (1b): X is oxygen, nitrogen, hydroxyl, amine (NR 3 or NR 3 R 4 ) or urea (N(R 5 )C(O)N(R 6 ) or N(R 5 )C(O)NR 6 R 7 ), especially urea (N(R 5 )C(O)N(R 6 ) or N(R 5 )C(O)NR 6 R 7 ) or nitrogen, Y is an amine (NR 8 R 9 ) or Ether (OR 9 ), especially amines (NR8 R 9 )[R in the formula 8 and 9 = methyl], R 1,2 are identical or different hydrocarbon radicals having 1 to 8 carbon atoms, optionally carrying OH groups, phenyl, cyclohexyl or hydrogen, preferably methyl, ethyl, isopropyl, -C2H3(OH)CH3, -C2H4OH or hydrogen, particularly preferably methyl, -C2H3(OH)CH3, -C2H4OH or hydrogen, in particular methyl or hydrogen, R 3~9 are identical or different hydrocarbon radicals having 1 to 8 carbon atoms, optionally carrying OH or NH / NH groups, phenyl, cyclohexyl or hydrogen, preferably methyl, ethyl, isopropyl, -C2H3(OH)CH3, -C2H4OH, aminoalkyl or hydrogen, particularly preferably methyl, -C2H3(OH)CH3, -C2H4OH, aminopropyl or hydrogen, in particular hydrogen or methyl, m=1 to 4, preferably 2 and 3, in particular 3; n=3, i=0 to 3, preferably 0, 1 and 2, in particular 1 or 2; However, the groups X, Y or R 1~9 provided that at least one of said functional groups has a functionality reactive with the polyurethane matrix, preferably an isocyanate-reactive functionality, particularly preferably NH or OH, to provide a molded PU foam article, preferably a mattress and / or cushion.

[0014] It will be understood that further customary additives, active substances and auxiliaries may also be used advantageously if desired. Mattresses are very particularly preferred in the context of the present invention. This also applies advantageously to all of the following preferred embodiments.

[0015] Thus, the molded PU foam articles thus provided using the compounds of formula (1a) and (1b) are highly suitable to recover their original shape even after prolonged compression for a period of at least 20 hours.

[0016] A further advantage is that the associated molded PU foam articles are particularly low-emitting with respect to amine emissions.

[0017] In the context of the present invention, "low emission" in respect of amines means that in particular flexible polyurethane foams for producing mattresses and / or cushions, preferably for producing mattresses, have a specific release of ≥ 0 μg / m2 after 24 hours of loading of the laboratory, as measured suitably by a laboratory method based on DIN standard DIN EN ISO 16000-9:2008-04. 3 ~≦40μg / m 3 , preferably ≦10 μg / m 3 , particularly preferably ≦5 μg / m 3 This method is described in detail in EP 3205680 A1, specifically in paragraph

[0070] , which is incorporated herein by reference.

[0018] An additional benefit is that the associated molded PU foam article may also meet emission standards such as CertiPur and / or VDA 278. "Low Emissions" according to CertiPur means that the total volatile organic emissions are less than 500 μg / m when measured according to the ISO 16000-9 and ISO 16000-11 methods. 3 "Low emission" according to VDA278 should be understood to mean that the PU foam meets the requirements of the method of Daimler Chrysler PB VWL 709. The VDA278 requirements are also described in the examples.

[0019] PU foam (polyurethane foam) and its products are well known to those skilled in the art and do not require further explanation as such. Molded articles are molded bodies of various shapes. Preferred shapes are geometric shapes such as, for example, spherical, cubic, cylindrical, etc. Molded PU foam articles are such molded bodies made of polyurethane foam. Particularly preferred molded PU foam articles in the context of the present invention are mattresses and / or cushions, as well as foam blocks in general.

[0020] The mattress itself and its manufacture are known. The mattress usually consists of a mattress core and / or spring core, which for example comprises foam, latex, natural products, and a cover which surrounds the mattress. A corresponding construction applies to the cushion. In the context of the present application, the term mattress and / or cushion should be understood to mean that at least one section made of polyurethane foam is present in the mattress and / or cushion. This is preferably understood to mean that at least a part of the mattress and / or cushion consists of polyurethane foam or different polyurethane foams. This part can represent at least 1% or 5% or 25% by weight, preferably at least 50% by weight, in particular at least 75% by weight, based on the total weight of the mattress and / or the total weight of the cushion. It is also possible that the mattress and / or cushion consists entirely of polyurethane foam, except for the cover.

[0021] The production of polyurethane foam is known per se. Polyurethane foam is formed by the tried and tested reaction of at least one polyol component with at least one isocyanate component in the presence of at least one blowing agent (for example water) in a polyaddition reaction. It is essential for the present invention that this reaction is carried out in the presence of at least one compound of formula (1a) and at least one compound of formula (1b) as defined above in each case.

[0022] In a preferred embodiment of the present invention, the polyurethane foam according to the present invention is preferably a flexible polyurethane foam, such as a hot-cure flexible polyurethane foam, a cold-cure flexible polyurethane foam or a viscoelastic flexible polyurethane foam, or a combination of these flexible foams, for example two or three of these flexible foams, are used. The distinction between each of the above types of flexible foam is known per se to the person skilled in the art; it is a well-known technical term that is appropriately established in the field, but will nevertheless be briefly explained here.

[0023] In the production of cold-cure flexible foams, the crucial difference from hot-cure flexible foams is the use of highly reactive polyols and, optionally, low molecular weight crosslinkers, which are assumed to function via highly functional isocyanates. The reaction of isocyanate groups with hydroxyl groups therefore occurs as early as the foam expansion stage (CO2 production from -NCO and H2O). This rapid polyurethane reaction usually results in a relatively high inherent stability of the foam during the foaming process, as a result of the viscosity increase. Cold-cure flexible polyurethane foams are usually high-resilience foams, where the stabilization of their outer zones plays an important role. Due to their high inherent stability, the cells are generally not fully open at the end of the foaming operation and require further mechanical crushing. The force required for crushing ("force to crush" (FTC)) gives an indication of the open cell content. Foams with a high open cell content and requiring low crushing forces are generally desirable. In mold foaming, cold cure flexible polyurethane foams, in contrast to hot cure flexible polyurethane foams, are produced at lower temperatures, for example temperatures ≦90° C.

[0024] Open-cell flexible polyurethane foams usually have a gas permeability (also called "porosity") in the range of 1 to 250 mm water column, in particular in the range of 1 to 50 mm water column (preferably determined by measuring the pressure difference when passing through a foam sample). For this purpose, for example, a foam disk with a thickness of 5 cm is placed on a smooth base. On this foam plate, a plate with a weight of 800 g (10 cm x 10 cm) and a central hole (diameter 2 cm) and a hose connection is placed. A constant air flow of 8 L / min is made to flow through the central hole to the foam sample. The more closed cells in the foam, the higher the pressure, which pushes the water column surface downwards and the larger the measured value.

[0025] Thermosetting flexible foams are usually available in a range of 8 to 80 kg / m depending on the application. 3 The foam density of low-temperature curing soft foams, especially for the production of high-quality mattresses, is usually 25-80 kg / m 3 The foams are manufactured in a range of densities ranging from 0.1 to 100%. Particularly when such foams are used as mattresses, mattress components, and / or cushions, the foams are differentiated according to the local demands and needs, wants and preferences of the consumer.

[0026] An important feature of cold-curing flexible foams is their high resilience (also called "ball rebound" (BR) or "resilience"). Methods for measuring resilience are described, for example, in DIN EN ISO 8307:2008-03. In this test, a steel ball with a certain mass is dropped from a certain height onto the test specimen, and then the rebound height is measured in % relative to the drop height. For cold-curing flexible foams, typical values ​​are usually in the range of ≧55%. Cold-curing flexible foams are therefore often also called HR foams (HR: High Resilience). In comparison, heat-curing flexible polyurethane foams usually have rebound values ​​of 15% to 60% or less.

[0027] A unique class of polyurethane foams are the viscoelastic polyurethane foams. These are also known as "memory foams" and exhibit both low resilience (preferably <10%) and slow recovery after compression (preferably recovery times of 2-10 seconds). Materials of this type are well known in the art and are particularly valued for their energy absorption and sound absorption properties. Typical viscoelastic foams usually have lower porosity and higher density (or higher foam density (FD)) compared to conventional flexible polyurethane foams. The foam density of the cushion is usually between 30 and 50 kg / m 3 and is therefore at the lower end of the typical density scale for viscoelastic foams, whereas mattress densities are typically between 40 and 130 kg / m 3 It is.

[0028] In conventional polyurethane foams, hard and soft phases (low glass transition temperature) are arranged alternately during polymerization and spontaneously separate from each other to form morphologically distinct phases in the "bulk polymer". Such materials are also called "phase separated" materials. In this context, viscoelastic polyurethane foams are a special case in which the above-mentioned phase separation, if it occurs at all, is only incomplete. For viscoelastic foams, the glass transition temperature is preferably in the range of -20°C to +15°C, while the glass transition temperatures of hot-cure and cold-cure flexible polyurethane foams, in contrast, are usually below -35°C. Such "structural viscoelasticity", which is mainly based on the glass transition temperature of the polymer, should be distinguished from the viscoelasticity of polyurethane foams with (mainly) open cells, which is due to the effect of compressed air. This is because in the latter case, substantially closed cells, i.e. cells with only small openings, are present in the foam material. Due to the small size of the openings, the air returns only gradually after compression, resulting in a slow recovery.

[0029] The various flexible polyurethane foams are not only classified according to the foam density, but also according to their compressive strength, often also called load-bearing capacity for specific applications. Thus, the compressive strength at 40% CLD (compressive load deflection) according to DIN EN ISO 3386-1:2015-10 for hot-cure flexible polyurethane foams is usually in the range of 2.0-8.0 kPa. Cold-cure flexible foams generally have values ​​of 2.0-5.0 kPa, more specifically 2.5-4.5 kPa, whereas viscoelastic polyurethane foams usually have values ​​of 0.1-5.0 kPa, more specifically 0.5-3.0 kPa.

[0030] In a preferred embodiment of the invention, the polyurethane foams used according to the invention, in particular flexible polyurethane foams, have the following preferred properties in terms of rebound resilience, foam density and / or porosity (optionally after foam crushing, in particular in the case of cold-curing flexible polyurethane foams): a rebound resilience measured in accordance with DIN EN ISO 8307:2008-03 of 1 to 80% and / or a foam density of 5 to 150 kg / m 3 and / or a porosity of 1 to 250 mm water column, in particular 1 to 50 mm water column. As mentioned above, it is particularly preferred to fulfill all three criteria regarding rebound resilience, foam density and / or porosity. In particular, the flexible polyurethane foam used according to the present invention has a compressive strength at CLD 40% according to DIN EN ISO 3386-1:2015-10 of 0.1 to 8.0 kPa.

[0031] Hot-cure flexible polyurethane foams, cold-cure flexible polyurethane foams and viscoelastic flexible polyurethane foams, as well as their production, are known per se. Hot-cure flexible polyurethane foams suitable for the purposes of the present invention are in particular those having a compressive strength at CLD 40% according to DIN EN ISO 3386-1:2015-10 of 2.0 to 8.0 kPa and / or a rebound resilience measured according to DIN EN ISO 8307:2008-03 of 15 to 60% and / or a foam density of 8 to 80 kg / m 3and / or a porosity of 1 to 250 mm water column, in particular 1 to 50 mm water column. Possible production methods are described, for example, in EP 2 481 770 A2 or EP 218 2020 A1. Suitable cold-curing flexible polyurethane foams for the purposes of the present invention have in particular a compressive strength at CLD 40% according to DIN EN ISO 3386-1:2015-10 of 2.0 to 5.0 kPa, in particular 2.5 to 4.5 kPa, and / or a rebound resilience measured according to DIN EN ISO 8307:2008-03 of ≥ 55%, and / or a foam density of 25 to 80 kg / m 3 and / or a porosity (after the foam is crushed) of 1 to 250 mm water column, in particular 1 to 50 mm water column. Possible production methods are described, for example, in EP 1 777 252 (B1). Viscoelastic flexible polyurethane foams suitable for the purposes of the present invention have in particular a glass transition temperature of -20°C to +15°C, and / or a compressive strength at CLD 40% according to DIN EN ISO 3386-1:2015-10 of 0.1 to 5.0 kPa, in particular 0.5 to 3.0 kPa, and / or a rebound resilience measured according to DIN EN ISO 8307:2008-03 of <10%, and / or a foam density of 30 to 130 kg / m 3 , and / or a porosity (after crushing the foam) of 1 to 250 mm water column, in particular 1 to 50 mm water column. Applicable manufacturing methods are described, for example, in WO 2013 / 131710(A2). The glass transition temperature can be measured using dynamic mechanical analysis (DMA) (DIN 53513:1990-03) or differential scanning calorimetry (DSC) (ISO 11357-2:2013). Strictly speaking, this temperature is the glass transition region spanning a certain temperature range. The reported glass transition temperatures are average values.

[0032] In a preferred embodiment of the present invention, the molded PU foam article of the present invention, in particular the mattress of the present invention, has a height of at least 1 cm to 50 cm, a width of at least 20 cm to 300 cm, and a length of at least 20 cm to 300 cm. Preferred dimensions are, for example, in the range of 5 cm to 40 cm for the height, 70 cm to 200 cm for the width, and 150 cm to 220 cm for the length. In a preferred embodiment of the present invention, the molded PU foam article of the present invention, in particular the cushion of the present invention, has a height of at least 1 cm to 40 cm, a width of at least 15 cm to 200 cm, and a length of at least 15 cm to 200 cm, in which preferred dimensions are, for example, in the range of 2 cm to 30 cm for the height, 15 cm to 50 cm for the width, and 15 cm to 50 cm for the length.

[0033] In a further preferred embodiment of the invention, the molded PU foam article is a mattress, preferably in the form of a multi-zone mattress. The different zones differ in particular in their hardness. Such multi-zone mattresses and their manufacture are known per se. Multi-zone mattresses are widely available commercially. In particular, the mattresses have up to seven zones of different hardness extending in the longitudinal direction of the mattress and of suitable width. When the mattress has zones of different hardness distributed over its area, said zones being formed in particular by discontinuities and / or hollow spaces in the mattress, this constitutes a preferred embodiment of the invention.

[0034] In a further preferred embodiment of the present invention, the molded PU foam article is a cold cure polyurethane foam mattress, a viscoelastic soft polyurethane foam mattress, a hot cure polyurethane foam mattress, a polyurethane gel foam mattress, a latex mattress, or a box spring mattress. These types of mattresses are known to those skilled in the art and are sold worldwide under the above names. Hot cure foam mattresses are usually called foam mattresses in the market for simplicity. The term mattress used for the purposes of the present invention also encompasses the corresponding mattress covers and underlays.

[0035] In a preferred embodiment of the present invention, the molded PU foam article, preferably a mattress, is characterized in that the molded PU foam article is compressed by at least 20%, preferably at least 30%, in particular at least 60%, based on its starting volume, and maintains this compressed form by auxiliary means, in particular packaging means, for at least 20 hours.

[0036] Suitable auxiliary means, in particular packaging means, are bags and / or films, for example bags and / or films known in the field of rolled mattresses. The bags and / or films may be sealed by any desired means, for example by clips or by adhesive tape or by welding. The function of the auxiliary means is to maintain the compressed shape until the end user of the molded PU foam article wishes to use said molded article again in the normal way. After removing the auxiliary means, in particular the packaging means, the compressed molded article expands again and in the best case recovers its original shape and size. The invention allows an improvement of the dimensional recovery after compression over a period of at least 20 hours.

[0037] In a further preferred embodiment, the molded PU foam article is in a compressed and vacuum packed state, in particular a vacuum packed and compressed rolled mattress.

[0038] The provision of the various PU foams which can be used in connection with the present invention is known per se and all proven processes can be utilized, provided that the PU foam is produced in the presence of at least one compound of formula (1a) and at least one compound of formula (1b).

[0039] In principle, the production of the corresponding PU foams does not require further explanation, but some preferred details are given below for the production of the PU foams used for the purposes of the present invention. The subject matter of the present invention is illustrated by the following examples, without the invention being limited to these exemplary embodiments. Where ranges of compounds, general formulae or classes of compounds are specified below, these include not only the corresponding ranges or groups of compounds explicitly mentioned, but also all subranges and subgroups of compounds which can be obtained by excluding individual values ​​(ranges) or compounds. Where documents are cited in the description of this application, their entire contents are intended to form part of the disclosure of the present invention, in particular with regard to the subject matter which forms the context in which the documents are cited. Unless otherwise stated, percentages are numerical values ​​in weight percent. Where average values ​​are reported below, the values ​​in question are weight averages, unless otherwise stated. Where parameters determined by measurement are reported below, the measurements were taken at a temperature of 25° C. and a pressure of 101,325 Pa, unless otherwise stated. Unless otherwise stated, compression of a foam in the context of the present invention means that the foam is compressed by at least 20%, preferably at least 30%, in particular at least 60%, based on its starting volume, preferably over a period of at least 20 hours.

[0040] For the purposes of the present invention, polyurethanes are all reaction products derived from isocyanates, in particular polyisocyanates, and suitable isocyanate-reactive molecules. These reaction products include polyisocyanurates, polyureas, and allophanate-, biuret-, uretdione-, uretonimine- or carbodiimide-containing isocyanate or polyisocyanate reaction products. It goes without saying that a person skilled in the art who wishes to produce various flexible polyurethane foams, for example hot-cure, cold-cure or viscoelastic flexible polyurethane foams, can appropriately select the substances required for the purpose in each case, such as isocyanates, polyols, stabilizers, surfactants, etc., in order to obtain the respectively desired type of polyurethane, in particular type of polyurethane foam. The starting materials, catalysts, and the auxiliaries and additives used are described, for example, in Kunststoffhandbuch [Plastics Handbook], Volume 7, Polyurethane [Polyurethanes], Carl-Hanser-Verlag Munich, 1st edition 1966, 2nd edition 1983 and 3rd edition 1993. The following compounds, components and additives are given by way of example only and can be replaced and / or supplemented by other substances known to those skilled in the art.

[0041] The isocyanate component used is preferably one or more organic polyisocyanates having two or more isocyanate functional groups. The polyol component used is preferably one or more polyols having two or more isocyanate-reactive groups.

[0042] Suitable isocyanates as isocyanate components for the purposes of the present invention are all isocyanates having at least two isocyanate groups. All aliphatic, cycloaliphatic, arylaliphatic and preferably aromatic polyfunctional isocyanates known per se can generally be used. The isocyanates are preferably used in the range of 60 to 350 mol%, more preferably 60 to 140 mol%, based on the total of the isocyanate consuming components.

[0043] Specific examples include alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene group, such as dodecane 1,12-diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, tetramethylene 1,4-diisocyanate and preferably hexamethylene 1,6-diisocyanate (HMDI), alicyclic diisocyanates (e.g. cyclohexane 1,3- and 1,4-diisocyanate, etc.) and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanato trimethylcyclohexane (abbreviated isophorone diisocyanate or IPDI), hexahydrotolylene 2,4- and 2,6-diisocyanate and the corresponding isomer mixtures, and preferably aromatic diisocyanates and polyisocyanates, such as tolylene 2,4- and 2,6-diisocyanate (TDI) and the corresponding isomer mixtures, mixtures of diphenylmethane 2,4'- and 2,2'-diisocyanate (MDI) and polyphenylpolymethylene polyisocyanate (crude MDI) and mixtures of crude MDI and tolylene diisocyanate (TDI). The organic diisocyanates and polyisocyanates can be used individually or in the form of their mixtures.

[0044] It is also possible to use isocyanates that have been modified by the incorporation of urethane, uretdione, isocyanurate, allophanate, and other groups, referred to as modified isocyanates.

[0045] Thus, organic polyisocyanates which are particularly preferably used are the various isomers of tolylene diisocyanate (tolylene 2,4- and 2,6-diisocyanate (TDI) in pure form or as isomeric mixtures of various compositions), diphenylmethane 4,4'-diisocyanate (MDI), known as "crude MDI" or "polymeric MDI", which includes not only the 4,4' isomer of MDI but also the 2,4' and 2,2' isomers and products with more than one ring, and the two-ring products, called "pure MDI", which consist mainly of the 2,4' and 4,4' isomer mixtures and / or their prepolymers. Examples of particularly suitable isocyanates are detailed, for example, in EP 1 712 578, EP 1 161 474, WO 00 / 58383, U.S. Patent Application Publication No. 2007 / 0072951, EP 1 678 232, and WO 2005 / 085310, which are incorporated herein by reference in their entireties.

[0046] Suitable polyols as polyol component for the purposes of the present invention are all organic substances having two or more isocyanate-reactive groups, preferably OH groups, and blends thereof. Preferred polyols are all polyether polyols and / or polyester polyols, and / or polyurethane systems, in particular the hydroxyl-containing aliphatic polycarbonates customarily used in the production of polyurethane foams, in particular polyether polycarbonate polyols and / or filled polyols (polymer polyols), such as SAN, PHD and PIPA polyols, which contain solid organic fillers in dispersed form up to a solids content of 40% or more, and / or autocatalytic polyols containing catalytically active functional groups, in particular amino groups, and / or polyols of natural origin known as "natural oil-based polyols" (NOPs). The polyols usually have a functionality of 1.8 to 8 and a number-average molecular weight in the range of 500 to 15000 g / mol. Polyols with an OH value of 10 to 1200 mg KOH / g are usually used. The number average molecular weight is typically measured by gel permeation chromatography (GPC), in particular using polypropylene glycol as reference material and tetrahydrofuran (THF) as eluent. The OH number can be measured in particular according to DIN standard DIN53240:1971-12. Depending on the properties required for the resulting foam, suitable polyols can be used, for example, as described in US 2007 / 0072951(A1), WO 2007 / 111828, US 2007 / 0238800, US 6,359,022 or WO 96 / 12759. Further polyols are known to those skilled in the art and can be found, for example, in EP 0 380 993 or US 3,346,557.

[0047] One of the preferred embodiments herein, in particular for the production of molded highly resilient flexible foams, uses di- and / or trifunctional polyether alcohols containing primary hydroxyl groups, in particular those with ethylene oxide blocks at the chain ends, preferably in an amount of more than 50%, more preferably more than 80%. According to the properties required for this embodiment, which is particularly suitable for the production of said foams, it is preferred to use not only the polyether alcohols described herein but also further polyether alcohols which contain primary hydroxyl groups and are mainly based on ethylene oxide, in particular with a proportion of ethylene oxide blocks >70%, preferably >90%. All polyether alcohols described in this preferred embodiment preferably have a functionality of 2 to 8, particularly preferably 2 to 5, a number average molecular weight in the range of 2500 to 15,000 g / mol, preferably 4500 to 12,000 g / mol and usually an OH number in the range of 5 to 80, preferably 20 to 50 mg KOH / g.

[0048] A further preferred embodiment of the invention, in particular for the production of flexible slabstock foams, is the use of di- and / or trifunctional polyether alcohols having secondary hydroxyl groups, in particular those having propylene oxide blocks at the chain ends or random propylene oxide and ethylene oxide blocks or those based exclusively on propylene oxide blocks, preferably in amounts of more than 50%, more preferably more than 90%. Such polyether alcohols preferably have a functionality of 2-8, particularly preferably 2-4, a number-average molecular weight of 500-8000 g / mol, preferably 800-5000 g / mol, particularly preferably 2500-4500 g / mol and usually an OH number in the range of 10-100, preferably 20-60 mg KOH / g.

[0049] In a further preferred embodiment of the present invention, particularly for the production of molded, highly resilient flexible foams, an autocatalytic polyol is used.

[0050] In a further preferred embodiment of the present invention, especially for the production of viscoelastic polyurethane foams, it is preferred to use a mixture of different, preferably two or three, polyfunctional polyester alcohols and / or polyether alcohols. The polyol combinations used here usually consist of high functionality low molecular weight "crosslinker" polymers, preferably with an OH number between 100 and 270 mg KOH / g, and / or conventional high molecular weight flexible slabstock foam polyols or HR polyols, and / or "hypersoft" polyether polyols, preferably with an OH number between 20 and 40 mg KOH / g, having a high proportion of ethylene oxide and cell opening properties.

[0051] A preferred ratio of isocyanate to polyol, when expressed as a blend index, i.e., the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (e.g., OH groups, NH groups), multiplied by 100, is in the range of 10 to 1000, preferably 40 to 350, more preferably 70 to 140. An index of 100 represents a molar ratio of reactive groups of 1:1.

[0052] In some applications it may be preferred to use in accordance with the present invention an additional catalyst in addition to the compounds of formulae (1a) and (1b) of the present invention.

[0053] The expression "additional catalyst" for the purposes of the present invention embraces all compounds known from the prior art which are capable of catalyzing the isocyanate reaction and / or which can be used as catalysts, cocatalysts or activators in the production of polyisocyanate reaction products, in particular polyurethane foams.

[0054] Additional catalysts suitable for the purposes of the present invention include, for example, substances which catalyze one of the above reactions, in particular the gelling reaction (between polyol and isocyanate), the blowing reaction (between isocyanate and water), and / or the dimerization or trimerization of isocyanates. Such catalysts are preferably nitrogen-containing compounds, more preferably amines and ammonium salts, and / or metal compounds.

[0055] Additional nitrogen-containing compounds suitable as catalysts for the purposes of the present invention are the amines triethylamine, N,N-dimethylcyclohexylamine, N,N-dicyclohexylmethylamine, N,N,N',N'-tetramethylethylene-1,2-diamine, N,N,N',N'-tetramethylpropylene-1,3-diamine, N,N,N',N'-tetramethyl-1,4-butanediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, 1-(2-aminoethyl)pyrrolidine, 1-(3-aminopropyl)pyrrolidine, N,N,N',N",N"-pentamethyldipropylenetriamine, N,N-bis[3-(dimethylamino)propyl]-N',N'-dimethylpropane-1,3-diamine, triethylenediamine, 1,4-diazabicyclo[2.2.2]Octane-2-methanol, 1,2-dimethylimidazole, N-(2-hydroxypropyl)imidazole, 1-isobutyl-2-methylimidazole, N-(3-aminopropyl)imidazole, N-methylimidazole, N-ethylmorpholine, N-methylmorpholine, 2,2,4-trimethyl-2-silamorpholine, N-ethyl-2,2-dimethyl-2-silamorpholine, N-(2-aminoethyl)morpholine, N-(2-hydroxyethyl)morpholine, 2,2'-di-morpholinodiethyl ether, N,N'-dimethylpiperazine, N-(2-hydroxyethyl)piperazine, N-(2-aminoethyl)piperazine, N,N-dimethylbenzylamine, 1-(2-hydroxyethyl)pyrrolidine, 1-(3-hydroxypropyl)pyrrolidine, bis(2- dimethylaminoethyl ether), tris(dimethylaminopropyl)hexahydro-1,3,5-triazine, 1,8-diazabicyclo[5,4,0]undec-7-ene, 1,5-diazabicyclo[4,3,0]non-5-ene, 1,5,7-triazabicyclo[4,4,0]dec-5-ene, N-methyl-1,5,7-triazabicyclo[4,4,0]dec-5-ene, 1,4,6-triazabicyclo[3,3,0]oct-4-ene, 1,1,3,3-tetramethylguanidine, tert-butyl-1,1,3,3-tetramethylguanidine, guanidine, bis-N,N-(dimethylaminoethoxyethyl)isophorone dicarbamate, 3-dimethylamino-N,N-dimethylpropionamide, and 2,4,6-tris(dimethylaminomethyl)phenol. Suitable additional nitrogen-containing catalysts known from the prior art are available, for example, from Evonik under the trade names TEGOAMIN® and DABCO®.

[0056] Metal-containing compounds suitable as additional catalysts can be selected, for example, from the group consisting of metal organic or organometallic compounds, metal organic or organometallic salts, organometallic salts, inorganic metal salts, and from the group consisting of charged or uncharged metal-containing coordination compounds, in particular metal chelate complexes. In the context of the present invention, the expression "metal organic or organometallic compounds" particularly includes the use of metal compounds having a direct carbon-metal bond, which are also referred to herein as metal organyls (e.g. tin organyls) or organometallic compounds (e.g. organotin compounds). In the context of the present invention, the expression "organometallic or metal organic salts" particularly includes the use of metal organic or organometallic compounds having salt properties, i.e. ionic compounds in which either the anion or the cation is of organometallic nature (e.g. organotin oxides, organotin chlorides or organotin carboxylates). In the context of the present invention, the expression "organometallic salts" particularly includes the use of metal compounds that do not have a direct carbon-metal bond and at the same time are metal salts, either the anion or the cation of which is an organic compound (e.g. tin(II) carboxylates). The expression "inorganic metal salts" in the context of the present invention includes in particular the use of metal compounds or metal salts in which neither the anion nor the cation is an organic compound, such as metal chlorides (e.g. tin(II) chloride), pure metal oxides (e.g. tin oxide) or mixed metal oxides (i.e. containing multiple metals), and / or metal silicates or aluminosilicates. The expression "coordination compounds" in the context of the present invention includes in particular the use of metal compounds formed from one or more central particles and one or more ligands, said central particles being charged or uncharged metals (e.g. metal- or tin-amine complexes). For the purposes of the present invention, the expression "metal-chelate complexes" includes in particular the use of metal-containing coordination compounds (e.g. metal- or tin-polyamine or metal- or tin-polyether complexes) with ligands having at least two coordination or binding sites to the metal center.Metal compounds suitable as additional catalysts for the purposes of the present invention, in particular compounds according to the above definition, may be selected from, for example, all metal compounds containing lithium, sodium, potassium, magnesium, calcium, scandium, yttrium, titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, cobalt, nickel, copper, zinc, mercury, aluminum, gallium, indium, germanium, tin, lead, and / or bismuth, preferably sodium, potassium, magnesium, calcium, titanium, zirconium, molybdenum, tungsten, zinc, aluminum, tin, and / or bismuth, more preferably tin, bismuth, zinc, and / or potassium.

[0057] Suitable metal-containing coordination compounds include, for example, any metal acetylacetonate, such as nickel(II) acetylacetonate, zinc(II) acetylacetonate, copper(II) acetylacetonate, molybdenum dioxoacetylacetonate, any iron acetylacetonate, any cobalt acetylacetonate, any zirconium acetylacetonate, any titanium acetylacetonate, any bismuth acetylacetonate, and any tin acetylacetonate.Particularly suitable organometallic salts and organometallic salts as specifically defined above as additional catalysts for the purposes of the present invention are, for example, organotin, tin, zinc, bismuth and potassium salts, in particular the corresponding metal carboxylates, alkoxides, thiolates and mercaptoacetates, such as, for example, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate (DBTDL), dioctyltin dilaurate (DOTDL), dimethyltin dineoate, dibutyltin dilaurate (DOTDL), dioctyltin dilaurate (DOTDL), diethyl ... Decanoate, dibutyltin dineodecanoate, dioctyltin dineodecanoate, dibutyltin dioleate, dibutyltin bis-n-lauryl mercaptide, dimethyltin bis-n-lauryl mercaptide, monomethyltin tris-2-ethylhexyl mercaptoacetate, dimethyltin bis-2-ethylhexyl mercaptoacetate, dibutyltin bis-2-ethylhexyl mercaptoacetate, dioctyltin bisisooctyl mercaptoacetate, tin(II) acetate, tin(II) 2-ethylhexanoate (tin(II) octoate), tin(II) isononanoate (tin(II) 3,5,5-trimethylhexanoate), tin(II) neodecanoate, tin(II) ricinoleate, zinc(II) acetate, zinc(II) 2-ethylhexanoate (zinc(II) octoate), zinc(II) isononanoate (zinc(II) 3,5,5 -trimethylhexanoate), zinc(II) neodecanoate, zinc(II) ricinoleate, bismuth acetate, bismuth 2-ethylhexanoate (bismuth octoate), bismuth isononanoate, bismuth neodecanoate, potassium formate, potassium acetate, potassium 2-ethylhexanoate (potassium octoate), potassium isononanoate, potassium neodecanoate, and / or potassium ricinoleate. Suitable additional metal catalysts are generally and preferably selected to be free of objectionable inherent odor, essentially toxicologically safe, and to provide minimal levels of catalyst-related emissions in the resulting polyurethane system, particularly polyurethane foam.

[0058] In addition to the additional amines and metal compounds, it is also possible to use ammonium salts as additional catalysts. Suitable examples are ammonium formate and / or ammonium acetate.

[0059] Suitable additional catalysts are described, for example, in DE 102007046860, EP 1985642, EP 1985644, EP 1977825, US 2008 / 0234402, EP 0656382(B1) and US 2007 / 0282026(A1), and in the patents cited in the above mentioned patent documents.

[0060] The suitable amount of additional catalyst used depends on the type of catalyst and is preferably in the range of 0.01 to 10.0 pphp, more preferably in the range of 0.02 to 5.00 pphp (= parts by weight per 100 parts by weight of polyol), or for potassium salts, 0.10 to 10.0 pphp.

[0061] The compounds of formulae (1a) and (1b) can be used, for example, together with suitable solvents and / or further additives. As any solvent, it is possible to use all suitable substances known from the prior art. Depending on the application, it is possible to use aprotic non-polar solvents, aprotic polar solvents and protic solvents. Suitable aprotic non-polar solvents can be selected, for example, from the following substance classes or substance classes with the following functional groups: aromatic hydrocarbons, aliphatic hydrocarbons (alkanes (paraffins) and olefins), carboxylic acid esters and polyesters, (poly)ethers and / or less polar halogenated hydrocarbons. Suitable aprotic polar solvents can be selected, for example, from the following substance classes or substance classes with the following functional groups: ketones, lactones, lactams, nitriles, carboxamides, sulfoxides and / or sulfones. Suitable protic solvents can be selected, for example, from the following substance classes or substance classes with the following functional groups: alcohols, polyols, (poly)alkylene glycols, amines, carboxylic acids, in particular fatty acids and / or primary and secondary amides. Particularly preferred are solvents that can be easily used in the foaming operation and do not adversely affect the foam properties. For example, isocyanate-reactive compounds are preferred because they are reactively incorporated into the polymer matrix and do not generate any emissions in the foam. Examples are OH-functional compounds, such as (poly)alkylene glycols, preferably monoethylene glycol (MEG or EG), diethylene glycol (DEG), triethylene glycol (TEG), 1,2-propylene glycol (PG), dipropylene glycol (DPG), trimethylene glycol (propane-1,3-diol, POD), tetramethylene glycol (butanediol, BDO), butyl diglycol (BDG), neopentyl glycol, 2-methylpropane-1,3-diol (Ortegol CXT), and their higher homologs, such as polyethylene glycols (PEG) with an average molecular weight of 200 to 3000.Particularly preferred OH-functional compounds further include polyethers having an average molecular weight of 200 to 4500, in particular 400 to 2000, among which preferably water-, methyl-, ethyl-, allyl-, butyl- or nonyl-initiated polyethers, in particular polyethers based on propylene oxide (PO) and / or ethylene oxide (EO) blocks.

[0062] When compounds of formulae (1a) and (1b) are used in dissolved form or in combination with a solvent, or when a premixed catalyst combination of compounds of formulae (1a) and (1b) and additional catalyst is used in dissolved form or in combination with a solvent, the weight ratio of the total sum of all catalysts to solvent is preferably from 100:1 to 1:10, preferably from 50:1 to 1:5, more preferably from 25:1 to 1:4.

[0063] Optional additives which can be used include all substances which are known from the prior art and which find application in the production of polyurethanes, in particular polyurethane foams, such as blowing agents, preferably water for producing CO2, and, if necessary, further physical blowing agents, crosslinkers and chain extenders, stabilizers against oxidative degradation (called antioxidants), flame retardants, surfactants, biocides, cell refiners, cell openers, solid fillers, antistatic additives, nucleating agents, thickeners, dyes, pigments, colour pastes, fragrances, emulsifiers, buffer substances and / or additional catalytically active substances, in particular those as defined above.

[0064] Water is generally used as a blowing agent in the production of polyurethane foams. It is preferable to use an amount of water such that the water concentration is 0.10 to 15.0 pphp (pphp = parts by weight per 100 parts by weight of polyol).

[0065] It is also possible to use suitable physical blowing agents, such as liquefied CO2 and volatile liquids, such as hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclopentane, isopentane and n-pentane, oxygen-containing compounds, such as methyl formate, acetone and dimethoxymethane, or chlorinated hydrocarbons, preferably dichloromethane and 1,2-dichloroethane.

[0066] Besides water and physical blowing agents, it is also possible to use other chemical blowing agents which react with isocyanates to generate gases, such as formic acid.

[0067] The optional crosslinking agent and optional chain extender are low molecular weight polyfunctional compounds that are reactive towards isocyanates. Suitable compounds are hydroxyl- or amine-terminated materials such as glycerol, neopentyl glycol, 2-methyl-1,3-propanediol, triethanolamine (TEOA), diethanolamine (DEOA) and trimethylolpropane. The concentration used is usually 0.1-5 parts per 100 parts of polyol, but may deviate from the above range depending on the formulation. When crude MDI is used in the foam-in-place process, the crosslinking function is assumed as well. Thus, the content of the low molecular weight crosslinking agent may be reduced with increasing amounts of crude MDI.

[0068] Suitable optional stabilizers against oxidative degradation, so-called antioxidants, preferably include all commonly used free radical scavengers, peroxide scavengers, UV absorbers, light stabilizers, complexing agents for metal ion pollutants (metal deactivators). Preference is given to compounds of the following substance classes or substance classes containing the following functional groups, the substituents on the respective parent molecules being preferably those bearing groups which are particularly reactive towards isocyanates: 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, benzoic acid and benzoates, phenols, especially those containing tert-butyl and / or methyl substituents on the aromatics, benzofuranones, diarylamines, triazines, 2,2,6,6-tetramethylpiperidine, hydroxylamines, alkyl and aryl phosphites, sulfides, zinc carboxylates, diketones.

[0069] Any flame retardant suitable in the present invention is any material that is considered suitable for this purpose by the prior art.Preferred flame retardants are, for example, liquid organophosphorus compounds such as halogen-free organophosphates, for example triethyl phosphate (TEP), halogenated phosphates, for example tris(1-chloro-2-propyl)phosphate (TCPP) and tris(2-chloroethyl)phosphate (TCEP), and solid materials such as organophosphonates, for example dimethylmethanephosphonate (DMMP), dimethylpropanephosphonate (DMPP), or ammonium polyphosphate (APP) and red phosphorus.Suitable flame retardants further include halogenated compounds, for example halogenated polyols, and solid materials such as expandable graphite and melamine.

[0070] Since the foam properties of polyurethane foams can possibly be influenced during their production, especially using siloxanes or organomodified siloxanes, it is possible to use substances known from the prior art. It is preferable to use compounds that are particularly suitable for each foam type (rigid foams, hot-cure flexible foams, viscoelastic foams, ester foams, cold-cure flexible foams (HR foams), semi-rigid foams). Suitable (organically modified) siloxanes are described, for example, in the following documents: EP 0839852, EP 1544235, DE 102004001408, EP 0839852, WO 2005 / 118668, US 20070072951, DE 2533074, EP 1537159, EP 533202, US 393369, EP 0780414, DE 4239054, DE 4229402, EP 867465. These compounds can be prepared as described in the prior art. Suitable examples are described, for example, in US Pat. No. 4,1447,847, EP Pat. No. 0,493,836 and US Pat. No. 4,855,379.

[0071] As optional (foam) stabilizers, it is possible to use all stabilizers known from the prior art. It is preferable to use foam stabilizers based on polydialkylsiloxane-polyoxyalkylene copolymers, which are commonly used in the production of polyurethane foams. The structure of these compounds is preferably such that, for example, a long-chain copolymer of ethylene oxide and propylene oxide is bonded to a polydimethylsiloxane radical. The bond between the polydialkylsiloxane and the polyether moiety may be via a Si-C bond or a Si-O-C bond. Structurally, a polyether or different polyethers may be bonded to the polydialkylsiloxane in terminal or lateral positions. Here, the alkyl group or the different alkyl groups may be aliphatic, cycloaliphatic or aromatic. Methyl groups are particularly advantageous. The polydialkylsiloxane may be linear or may contain branches. Suitable stabilizers, especially foam stabilizers, are described in US Pat. No. 2,834,748, US Pat. No. 2,917,480 and US Pat. No. 3,629,308. Suitable stabilizers are available from Evonik Industries AG under the trade name TEGOSTAB®.

[0072] Siloxanes can also be used in the context of the present invention as part of a composition with different carrier media. Useful carrier media include, for example, glycols such as monoethylene glycol (MEG), diethylene glycol (DEG), propylene glycol (PG) or dipropylene glycol (DPG), alkoxylates, or synthetic and / or naturally derived oils.

[0073] The siloxane may be added to the composition for producing the polyurethane foam preferably in an amount such that the mass proportion of the siloxane in the finished polyurethane foam is 0.01 to 10% by weight, preferably 0.1 to 3% by weight.

[0074] In the production of flexible polyurethane foams, it may be advantageous to prepare and / or use a composition comprising at least the inventive compounds of formulas (1a) and (1b), at least one polyol component, optionally at least one isocyanate component, and optionally one or more blowing agents, and to react this composition.

[0075] In the context of the present invention, the compounds of the invention of formulae (1a) and (1b) also explicitly include the corresponding quaternized and / or protonated compounds. However, in the context of the present invention, it is particularly preferred to use the compounds of formulae (1a) and (1b) in non-quaternized or non-protonated form. The possible quaternization of the compounds of formulae (1a) and (1b) may be carried out using any reagent known as a quaternizing agent. It is preferred to use an alkylating agent, such as dimethyl sulfate, methyl chloride or benzyl chloride, preferably a methylating agent, in particular dimethyl sulfate, as the quaternizing agent. The quaternization can likewise be carried out using an alkylene oxide, such as ethylene oxide, propylene oxide or butylene oxide, preferably followed by neutralization with an inorganic or organic acid. When quaternized, the compounds of formulae (1a) and (1b) may be quaternized at one or more positions. It is preferred that the compounds of formulae (1a) and (1b) are only quaternized at one position. In the case of being only singly quaternized, the compounds of formulae (1a) and (1b) are preferably quaternized at the nitrogen atom. The compounds of formulae (1a) and (1b) can be converted into the corresponding protonated compounds by reaction with organic or inorganic acids. These protonated compounds are preferred, for example, if a slower polyurethane reaction is to be achieved or if the flow behavior of the reaction mixture during use is to be enhanced. As organic acids, it is possible to use, for example, all the organic acids listed below, for example carboxylic acids having 1 to 36 carbon atoms (aromatic or aliphatic, linear or branched), such as formic acid, lactic acid, 2-ethylhexanoic acid, salicylic acid and neodecanoic acid, or polymeric acids, such as polyacrylic acid or polymethacrylic acid. As inorganic acids, it is possible to use, for example, phosphorus acids, sulfur acids or boron acids.

[0076] The compounds of formulae (1a) and (1b) are preferably used in a total amount corresponding to a mass fraction of 0.01 to 20.0 parts (pphp), preferably 0.01 to 5.00 parts, and particularly preferably 0.02 to 3.00 parts, per 100 parts (pphp) of the polyol component.

[0077] The production of the polyurethane foams according to the invention can be carried out by all methods familiar to those skilled in the art, for example by hand mixing or preferably by using a foaming machine, in particular a low-pressure or high-pressure foaming machine, whereby a batch or continuous process can be used.

[0078] It is possible to use all the processes for producing polyurethane foams known to those skilled in the art. For example, the foaming operation can be carried out in batch or continuous plants, either horizontally or vertically. The compositions used in the present invention are equally useful for CO2 technology. It is possible to use low and high pressure machines, and the composition to be processed can be metered directly into the mixing chamber or it can be mixed with one of the components before being fed into the mixing chamber and then into the mixing chamber. Blending in the raw material tank is also possible.

[0079] Flexible polyurethane foams which are particularly preferred for the purposes of the present invention have in particular the following composition:

[0080] [Table 1]

[0081] The present invention further provides the use of a combination of at least one compound of formula (1a) and at least one compound of formula (1b), where (1a) and (1b) are as defined above in each case, in the production of a molded PU foam article, to provide a molded PU foam article having improved dimensional recovery after compression for a period of at least 20 hours, the molded PU foam article being obtainable by reaction of at least one polyol component and at least one isocyanate component in the presence of at least one blowing agent.

[0082] The present invention further provides the use of a combination of at least one compound of formula (1a) and at least one compound of formula (1b), where (1a) and (1b) are in each case as defined above, for restoring the dimensional recovery of a molded PU foam article after compression over a period of at least 20 hours, the molded PU foam article being obtainable by reaction of at least one polyol component and at least one isocyanate component in the presence of at least one compound of formula (1a) and at least one compound of formula (1b), in the presence of at least one blowing agent.

[0083] The present invention further provides the use of a flexible polyurethane foam in a mattress and / or cushion, in particular a mattress, which is obtained by reacting at least one polyol component and at least one isocyanate component in the presence of at least one compound of formula (1a) and at least one compound of formula (1b), where (1a) and (1b) are each as defined above. In this connection, particular reference is made to the above, which is also applicable to the present subject matter.

[0084] The use according to the invention makes it possible to provide a mattress and / or cushion with improved dimensional recovery after compression over a period of at least 20 hours.The use according to the invention makes it possible to provide a mattress and / or cushion with improved dimensional recovery after compression over a period of at least 20 hours.

[0085] The present invention further relates to a method for storing and / or transporting molded PU foam articles, preferably mattresses and / or cushions, comprising the steps of: (a) in a first step, a molded PU foam article is provided by reaction of at least one polyol component and at least one isocyanate component in the presence of at least one compound of formula (1a) and at least one compound of formula (1b), where (1a) and (1b) are each as defined above, and at least one blowing agent; (b) in an optional subsequent step, the resulting molded PU foam article may be optionally subjected to further processing to prepare it for application; (c) in the final step, the molded PU foam article (optionally prepared for application) is compressed by at least 20%, preferably at least 30%, in particular at least 60%, based on its starting volume, optionally vacuum packed, maintained in the compressed form by auxiliary means, in particular packaging means, and sent for storage and / or transportation, A method is provided.

[0086] The present invention further provides a mixture comprising at least one compound of formula (1a) and at least one compound of formula (1b), where (1a) and (1b) are each as defined above, and optionally glycols, polyethers and / or other solvents suitable for the purposes of producing PU foams. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0087] Working Example: Physical properties of flexible polyurethane foam: The produced flexible polyurethane foams were evaluated according to the following physical properties a) to g):

[0088] a) Recession of the foam after the rise phase (=sag): Sag or further expansion is found from the difference in foam height immediately after foaming and 3 minutes after foaming. Foam height is measured at its maximum value in the top center of the foam using a needle fixed to a centimeter scale. Negative values ​​indicate sag of the foam after foaming; positive values ​​indicate correspondingly further rise of the foam.

[0089] b) Foam Height: The height of the free rise foam after 3 minutes. Foam height is reported in centimeters (cm).

[0090] c) Rise time: The time from the end of mixing the reactive components to the blowing of polyurethane foam.

[0091] d) Foam Density (FD): Determined by measuring the core density as described in ASTM D 3574-11, Test A. Foam density is expressed in kg / m 3 will be reported.

[0092] e) Porosity by dynamic pressure measurement: The gas permeability of the foams was measured by dynamic pressure measurement of the foams according to DIN EN ISO 4638:1993-07. The measured dynamic pressure is reported in mm water column, lower dynamic pressure values ​​represent more open foams. Values ​​were measured in the range 0-300 mm.

[0093] The dynamic pressure was measured using an apparatus that included a nitrogen source, a pressure reducing valve with pressure gauge, a flow control screw, a wash bottle, a flow meter, a T-fitting, an applicator nozzle, and a graduated glass tube filled with water. The applicator nozzle had side lengths of 100 × 100 mm, weighed 800 g, had an inner diameter of the outlet opening of 5 mm, an inner diameter of the lower applicator ring of 20 mm, and an outer diameter of the lower applicator ring of 30 mm.

[0094] The measurement is carried out by setting the nitrogen inlet pressure to 1 bar using a pressure reducing valve and the flow rate to 480 L / h. The amount of water in the graduated glass tube is set so that no pressure difference occurs and cannot be read. To measure a test piece with dimensions 250 x 250 x 50 mm, the applicator nozzle is placed on a corner of the test piece, flush with its edge, and once in the (presumed) centre of the test piece (in each case on the side with the largest surface area). The result is read off once a constant dynamic pressure has been established.

[0095] The evaluation is carried out by taking the average of the five measurements obtained.

[0096] f) Porosity by air flow method: In order to more clearly distinguish the open cell content in the range of 0-60 mm dynamic pressure, in addition to the dynamic pressure measurements, the porosity was further measured by the air flow method with reference to ASTM D 3574 (2011-00). Twelve test samples with dimensions 5 cm x 5 cm x 2.5 cm were cut from the finished foam and inserted sequentially into an analytical instrument configured for this method. The configuration of this instrument is described in ASTM D 3574 (2011-00). The analytical instrument creates a pressure difference of 125 Pa between the inside of the instrument and the surrounding atmosphere by drawing just enough air through the test specimen to keep the pressure difference constant. The air flow through the test specimen is therefore an indication of the porosity of the foam. Values ​​ranging from 0 to 6 SCFM (standard cubic feet per minute) were measured. Lower values ​​characterize more closed foams.

[0097] g) Number of cells per cm (cell count): The cell count was determined visually on a cut surface (measurement according to DIN EN 15702).

[0098] For completeness, the analytical principle of VDA278 is also described below.

[0099] VDA278 analysis principle: The materials are characterized with respect to the type and amount of organic substances that can be gaseously released from them. For this purpose, two semi-quantitative empirical values ​​are determined to estimate the emission of volatile organic compounds (VOC value) and also the proportion of condensable substances (fogging value). The individual emissions are also determined. In this analysis, the samples are thermally extracted and the emissions are separated by gas chromatography and detected by mass spectrometry. The overall concentration of the VOC fractions thus obtained is arithmetically converted into toluene equivalents, resulting in the VOC value; the FOG fraction is expressed in hexadecane equivalents, resulting in the FOG value.

[0100] This analytical method serves to determine emissions from non-metallic materials (including foams) used in molded automotive parts.

[0101] In pyrolysis analysis (TDA) a small amount of material is heated in a defined manner in a desorption tube and the volatile substances released in the course of heating are cryofocused by a flow of inert gas in the cold trap of a temperature programmable evaporator. After the heating phase is over, the cold trap is quickly heated to 280 °C. The focused substances evaporate in the process. They are then separated in a gas chromatography separation column and detected by mass spectrometry. Calibration with reference substances allows a semi-quantitative prediction of the emissions, which are expressed in "μg / g". The quantitative reference substances used are toluene for the VOC analysis (VOC values) and n-hexadecane for the fogging values. The signal peaks can be assigned to substances using the mass spectrum and retention indices. Source: VDA 278 / 10.2011, www.vda.de

[0102] analysis: Test Specimens: Sample Preparation, Sample Collection, and Sample Dimensions: After the foam is demolded, it is stored for 24 hours at 21°C and about 50% relative humidity. Samples of the molded part are then taken at suitable and representative locations evenly distributed across the width of the (cooled) part. The foam is then wrapped in aluminum foil and sealed in a polyethylene bag. The amount of foam sample introduced into the desorption tube is in each case 10-15 mg.

[0103] Test Procedure: VOC / FOG Thermal Desorption: The sealed samples are sent directly to the measurement immediately after receipt. Before the start of the analysis, the sample is weighed on an analytical balance with an accuracy of 0.1 mg and the corresponding amount of foam is placed in the center of the desorption tube. A helium stream is passed over the sample, which is heated to 90 ° C for 30 min. All volatile substances are collected in a cold trap cooled with liquid nitrogen. After 30 min, the cold trap is heated to 280 ° C. The evaporated substances are separated from each other using the gas chromatography column described above and then analyzed by mass spectrometry.

[0104] [Table 2]

[0105] The following is a rolling deformation test which allows the testing of the dimensional recovery after compression in the context of the present invention: The rolling deformation test forms a further part of the subject matter of the present invention.

[0106] Roll Deformation Test: the purpose: The test is intended to simulate the conditions of a rolled mattress in a laboratory, and since there is no meaningful industry standard for this, a new test was developed to simulate a small scale roll of mattress foam.

[0107] Sample preparation: Test specimens with dimensions 12 cm (width), 16 cm (length) and 2.5 cm (thickness) are cut from the hand-foamed foam block, for example using a band saw. A central position in the hand-foamed foam block is selected. The test specimens are cut so that the rise direction of the foam being produced is perpendicular to the length and width of the test specimen. The test specimens are marked with a felt-tip pen.

[0108] Test procedure: The 12 cm edge of the specimen is compressed with a thin metal rod with a diameter of 5-8 mm. The foam specimen is then wrapped around the metal rod by hand. The foam is tightly compressed to form a roll with a diameter of approximately 3-4 cm. The roll is manually held in this compressed state and placed completely inside a cardboard tube, which has an internal diameter of 4 cm and a length of at least 13 cm. As soon as the roll of foam is completely inserted into the tube, the metal rod is removed. To minimize friction during removal, the metal rod may be lightly greased before rolling the foam. The foam then fills the inside of the tube. The compression of the foam is much greater in the center than at the edges of the tube. The roll is then stored under constant, controlled conditions (temperature: 21°C, ambient humidity: 60%) for 7 days. After 168 hours, the foam is manually removed from the tube, placed on a flat surface, and observed as it unfolds from the roll. The expansion of the foam should not be impeded or affected.

[0109] evaluation: The foam is left to expand for 10 minutes. The specimens are then evaluated. The most important criterion is whether the foam fully recovers to its original thickness or whether there are still compression zones (especially at the more severely compressed ends). In some cases, grooves caused by compression are still visible on the surface of the specimen. Specimens with a low rating remain rolled at the end. Slight bending of the specimens after expansion is normal and is not taken into account in the evaluation. The following scale was used for the evaluation: +++: The specimen is fully expanded, there are no compression lines or compressed appearances, the expansion occurs rapidly and is already complete after 5 minutes. ++: The specimen recovers to a thickness of 2.5 cm in all areas. After 10 minutes, no visible dents or grooves remain on the surface (especially at the more heavily compressed edges). +: The specimen has recovered to a thickness of 2.5 cm in all areas, but there are still a few visible dents and grooves in the surface (especially at the more heavily compressed edges). 0: The specimen shows slight compression at the more severely compressed end. The thickness in that area is greater than 2.0 cm but less than 2.5 cm. A dent is clearly visible at this end. -: The specimen shows slight compression at the more severely compressed end, where the specimen thickness is greater than 1 cm but still significantly less than 2.0 cm. --: The specimen shows severe compression at the more severely compressed end. The specimen thickness at this point is less than 1 cm. The specimen is still in the initial roll form at this end. ---: The specimen remains compressed in a roll at the more severely compressed end. The evaluation is preferably performed by at least two people. Documenting the results: In the context of the present invention, the evaluation was performed by four people who reached consistent results.

[0110] Testing Obstacles and Constraints: The test must ensure correct dimensions and uniform rolling of the test specimens. The foam test specimens must have consistent cell structure parameters, i.e. in particular consistent cell size and consistent air permeability. The metal bars must not be over-greased, so that the grease does not penetrate the specimen. Consistent storage conditions must be maintained. Test specimens with different evaluation ratings must be available for comparison.

[0111] Test accuracy: Performance of the test by two or more assessors usually yields consistent judgements; duplicate measurements usually give identical results; therefore, the test has proven to be very reliable.

[0112] Flexible foam - Foaming examples: Example 1: Production of flexible polyurethane foam (flexible slabstock foam) Performance testing of the compounds of the present invention of formula (1a) and (1b) was carried out using the foam formulations shown in Table 3.

[0113] [Table 3]

[0114] In the foaming procedure, 400 g of polyol was used in each case and other formulation components were recalculated accordingly. 1.00 part of an ingredient indicates that this material is, for example, 1.00 g per 100 g of polyol.

[0115] The foaming was carried out in a so-called manual mixing process. Formulation 1 was used with different amine catalysts, as shown in Table 3. For this purpose, the polyol, the respective amine catalyst mixture, the tin catalyst tin(ll) 2-ethylhexanoate, water and foam stabilizer were first placed in a paper cup and stirred for 60 seconds at 1000 rpm with a disk stirrer. After the first stirring, the isocyanate (TDI) was added to the reaction mixture, which was stirred for 7 seconds at 2500 rpm and then immediately transferred to a box (base area 30 cm x 30 cm, height 30 cm) with a paper liner. After injection, the foam was allowed to expand in this foaming box. In the ideal case, the foam erupted upon reaching the maximum rise height and then slightly receded. This opened the cell membrane of the foam bubbles and resulted in an open-cell structure of the foam. To evaluate the catalyst properties, the following characteristic parameters were determined: rise time, rise height, foam retraction (=sag) after the end of the rise phase.

[0116] From the obtained foam blocks, defined foam bodies were cut and further analyzed: the following physical properties were determined for the test specimens: cell number, porosity by dynamic pressure measurement, porosity by air flow method, foam density (FD) and roll deformation at room temperature.

[0117] The properties of the compounds according to the invention and the physical properties of the resulting flexible slabstock foams are summarized in Table 4. DABCO® DMEA was used as a comparative prior art catalyst. Except for the comparative catalyst, equimolar amounts of amine were used in each case, resulting in slightly different loading amounts, as a result of conversion to parts by weight per 100 parts by weight of polyol. For the comparative catalyst, the smallest possible molar amount was used that produced qualitatively comparable foaming results.

[0118] [Table 4]

[0119] Comparable cell counts and porosities are critical to the rigorous reproducibility of roll deformation tests. Catalyst loadings were selected so that the finished foams had a cell count of 12-14 cells / cm and a porosity of less than 30 mm water column. The air flow method is highly accurate in this open cell porosity range. For this reason, a porosity of 2.00-4.00 SCFM by this method was chosen, with a maximum difference in porosity of ±0.4 selected between individual comparable pairs.

[0120] As can be seen from Table 4, the combination of the compound of formula (1a) of the present invention (here DABCO® NE300) with the compound of formula (1b) (here DABCO® NE750 and DABCO® NE1082) shows a significant advantage in the roll deformation test compared to the catalyst combinations not of the present invention.

[0121] The shape recovery of the test specimens after roll deformation was clearly improved. Thus, all foams produced with the emission-free blowing and gelling catalyst combination of the present invention recovered their original thickness of 2.5 cm, and after a resting time of 10 minutes, there were only a few, if any, grooves on the surface. In contrast, all foam samples produced with catalysts other than the present invention showed foam compression and various degrees of inability to recover the original foam height and shape. The foams according to the present invention also proved to be particularly low-emitting in terms of amine emissions. The advantageous properties of the present invention were also confirmed in the case of other types of foams, such as low-temperature curing flexible foams (slabstock foams and molded foams) and viscoelastic foams.

Claims

1. A molded polyurethane (PU) foam article, preferably a mattress and / or cushion, characterized in that the polyurethane foam is obtained by reaction of at least one polyol component and at least one isocyanate component in the presence of at least one compound of formula (1a) and at least one compound of formula (1b) and at least one blowing agent, characterised in that the moulded PU foam article is compressed by at least 20%, preferably at least 30%, in particular at least 60%, based on its starting volume, and maintains the compressed form for at least 20 hours by means of auxiliary means, in particular packaging means, wherein formulas (1a) and (1b) are defined as follows: 【Chemistry 1】 [In formula (1a): X is oxygen, nitrogen or an amine (NR ３ Or NR ３ R ４ ), especially oxygen, Y is an amine NR ８ R ９ Or Ether OR ９ , especially Amine NR ８ R ９ [In the formula, R ８ = Methyl and R ９ = aminopropyl; R １，２ represents identical or different hydrocarbon radicals having 1 to 8 carbon atoms, phenyl, cyclohexyl or hydrogen, preferably methyl, ethyl, isopropyl or hydrogen, particularly preferably methyl or hydrogen, in particular methyl, R ３～９ represents identical or different hydrocarbon groups having 1 to 8 carbon atoms, optionally NH or NH ２ may contain the radical phenyl, cyclohexyl or hydrogen, preferably methyl, ethyl, isopropyl, aminoalkyl or hydrogen, particularly preferably methyl, aminopropyl or hydrogen, in particular methyl or aminopropyl, m=1 to 4, preferably 2 and 3, in particular 2; n=2, i=0 to 3, preferably 0, 1 and 2, in particular 1; However, the groups X, Y, or R １～９ at least one of them has a functional group reactive with the polyurethane matrix, preferably an isocyanate-reactive functional group, particularly preferably NH or OH; 【Chemistry 2】 [In formula (1b): X is oxygen, nitrogen, hydroxyl, amine (NR ３ Or NR ３ R ４ ) or urea (N(R ５ ) C(O)N(R ６ ) or N(R ５ )C(O)NR ６ R ７ ), especially urea (N(R ５ ) C(O)N(R ６ ) or N(R ５ )C(O)NR ６ R ７ ) or nitrogen, Y is an amine (NR ８ R ９ ) or ether (OR ９ ), especially amines (NR ８ R ９ ) [wherein R ８ and ９ = methyl; R １，２ represents identical or different hydrocarbon radicals having 1 to 8 carbon atoms, optionally carrying OH groups, phenyl, cyclohexyl or hydrogen, preferably methyl, ethyl, isopropyl, -C ２ H ３ (OH)CH ３ , -C ２ H ４ OH or hydrogen, particularly preferably methyl, -C ２ H ３ (OH)CH ３ , -C ２ H ４ represents OH or hydrogen, in particular methyl or hydrogen, R ３～９ represents identical or different hydrocarbon groups having 1 to 8 carbon atoms, optionally OH or NH / NH ２ It can have the group, phenyl, cyclohexyl or hydrogen, preferably methyl, ethyl, isopropyl, -C ２ H ３ (OH)CH ３ , -C ２ H ４ OH, aminoalkyl or hydrogen, particularly preferably methyl, -C ２ H ３ (OH)CH ３ , -C ２ H ４ represents OH, aminopropyl or hydrogen, in particular hydrogen or methyl, m=1 to 4, preferably 2 and 3, in particular 3; n=3, i=0 to 3, preferably 0, 1 and 2, in particular 1 or 2; However, the groups X, Y, or R １～９ at least one of them has a functional group reactive with the polyurethane matrix, preferably an isocyanate-reactive functional group, particularly preferably NH or OH; A molded PU foam article, preferably a mattress and / or cushion.

2. 2. The molded PU foam article, preferably a mattress and / or cushion, according to claim 1, characterized in that the PU foam is a flexible polyurethane foam, in particular a thermosetting flexible polyurethane foam, a cold-setting flexible polyurethane foam or a viscoelastic flexible polyurethane foam.

3. The flexible polyurethane foam has a rebound resilience of 1 to 80% as measured in accordance with DIN EN ISO 8307:2008-03, and / or a foam density of 5 to 150 kg / m ３ and / or the porosity is from 1 to 250 mm water column, in particular from 1 to 50 mm water column, optionally after crushing the foam.

4. The molded PU foam article, preferably a mattress and / or cushion, according to any one of claims 2 to 3, wherein the flexible polyurethane foam has a compressive strength at CLD 40% according to DIN EN ISO 3386-1:2015-10 of 0.1 to 8.0 kPa.

5. The flexible polyurethane foam is a thermoset flexible polyurethane foam, preferably having a compressive strength at CLD 40% according to DIN EN ISO 3386-1: 2015-10 of 2.0 to 8.0 kPa, and / or a rebound resilience measured according to DIN EN ISO 8307: 2008-03 of 15 to 60%, and / or a foam density of 8 to 80 kg / m ３ 5. The molded PU foam article, preferably a mattress and / or cushion, according to any one of claims 2 to 4, characterized in that it has a porosity of 1 to 250 mm water column, in particular 1 to 50 mm water column.

6. The flexible polyurethane foam is a cold-curing flexible polyurethane foam, preferably having a compressive strength at CLD 40% according to DIN EN ISO 3386-1: 2015-10 of 2.0 to 5.0 kPa, in particular 2.5 to 4.5 kPa, and / or a rebound resilience measured according to DIN EN ISO 8307: 2008-03 of ≥ 55%, and / or a foam density of 25 to 80 kg / m ３ and / or a porosity of 1 to 250 mm water column, in particular 1 to 50 mm water column, preferably after crushing the foam.

7. The flexible polyurethane foam is a viscoelastic flexible polyurethane foam, preferably having a glass transition temperature of -20°C to +15°C, and / or a compressive strength at CLD 40% according to DIN EN ISO 3386-1:2015-10 of 0.1 to 5.0 kPa, in particular 0.5 to 3.0 kPa, and / or a rebound resilience measured according to DIN EN ISO 8307:2008-03 of <10%, and / or a foam density of 30 to 130 kg / m ３ 5. The moulded PU foam article, preferably a mattress and / or cushion, according to any one of claims 2 to 4, characterized in that it has a porosity of 1 to 250 mm water column, in particular 1 to 50 mm, preferably after crushing the foam.

8. 8. The molded PU foam article, preferably a mattress, according to any one of claims 1 to 7, characterized in that the molded PU foam article has a height of at least 1 cm and no more than 50 cm, a width of at least 20 cm and no more than 300 cm, preferably at least 70 cm and no more than 200 cm, and a length of at least 20 cm and no more than 300 cm, preferably at least 150 cm and no more than 220 cm.

9. 10. The molded PU foam article, preferably a mattress, according to claim 1, characterized in that the molded PU foam article is in a compressed and preferably vacuum packed state.

10. 10. The molded PU foam article of claim 9, wherein the molded PU foam article is a rolled mattress.

11. 1. Use of a combination of at least one compound of formula (1a) and at least one compound of formula (1b), wherein (1a) and (1b) are each as defined in claim 1, for improving dimensional recovery of a molded PU foam article after compression for a period of at least 20 hours, wherein the molded PU foam article is obtained by reaction of at least one polyol component and at least one isocyanate component in the presence of at least one compound of formula (1a) and at least one compound of formula (1b), in the presence of at least one blowing agent.

12. 1. A method for storing and / or transporting molded PU foam articles, preferably mattresses and / or cushions, comprising: (d) in a first step, a molded PU foam article is provided by reaction of at least one polyol component and at least one isocyanate component in the presence of at least one compound of formula (1a) and at least one compound of formula (1b), where (1a) and (1b) are each as defined in claim 1, and at least one blowing agent; (e) in an optional subsequent step, the resulting molded PU foam article may be optionally subjected to further processing to prepare the article for application; (f) in a final step, said molded PU foam article (optionally prepared for application) is compressed by at least 20%, preferably at least 30%, in particular at least 60% based on its starting volume, optionally vacuum packed by auxiliary means, in particular packaging means, stored in the compressed state, maintained in compressed form and sent for storage and / or transportation. method.

13. 1. Use of a flexible polyurethane foam in a mattress and / or cushion, in particular a mattress, to provide a (preferably compressed) mattress and / or cushion having improved dimensional recovery after compression for a period of at least 20 hours, in particular improved release properties, said flexible polyurethane foam being obtainable by reaction of at least one polyol component with at least one isocyanate component in the presence of at least one compound of formula (1a) and at least one compound of formula (1b), where (1a) and (1b) are each as defined in claim 1.

14. 1. A mixture comprising at least one compound of formula (1a) and at least one compound of formula (1b), wherein (1a) and (1b) are each as defined in claim 1, and optionally glycols, polyethers and / or other solvents suitable for the purposes of producing PU foams, wherein when said compounds of formula (1a) and (1b) are used in dissolved form or in combination with a solvent, or when a premixed catalyst combination of said compounds of formula (1a) and (1b) and additional catalyst is used in dissolved form or in combination with a solvent, the weight ratio of the total amount of all catalysts to the solvent is preferably from 100:1 to 1:10, more preferably from 50:1 to 1:5, even more preferably from 25:1 to 1:4.

Images