Compression set

Abstract

To provide shaped hot-cure flexible PU foam articles, in particular hot-cure flexible PU foam-containing mattresses and / or cushions and the like, that have good capability of recovering their original shape after compression over a period of at least 20 hours.SOLUTION: Described herein are shaped hot-cure flexible PU foam articles, preferably mattresses and / or cushions, where the hot-cure flexible 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), at least one compound of formula (1b), at least one blowing agent and at least one catalyst.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Molded thermoset flexible PU foam articles, such as thermoset flexible PU foam-containing mattresses and / or cushions, have long been known in the art and are used worldwide. Attempts to achieve greater improvements have never been exhausted. The need for optimization has not been fully met to date.

[0003] One problem with molded thermoset flexible PU foam articles is their transportation and storage. Molded thermoset flexible 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 particularly common for mattresses. In vacuum packaging, the mattress is placed in a bag, for example made of plastic. The pre-packaged 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. The resulting vacuum package is then rolled up and placed inside an outer bag. The outer bag keeps the mattress in its rolled form so that it cannot be re-inflated.

[0005] Flattening a 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 weight exerted by a mass of 4 to 25 tonnes.

[0006] As will be readily apparent, such forces associated with compressing a molded thermoset flexible PU foam article can result in material fatigue. Providing a molded thermoset flexible PU foam article that can recover to its original dimensions even after extended compression is a very important issue. Summary of the Invention [Problem to be solved by the invention]

[0007] Against this background, it is an explicit object of the present invention to provide a molded thermoset flexible PU foam article, in particular a thermoset flexible PU foam-containing mattress and / or cushion, etc., that has an excellent ability to recover its original shape after being compressed for a period of at least 20 hours. [Means for solving the problem]

[0008] In the context of 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 provides a molded thermoset flexible PU foam article, preferably a mattress and / or cushion, the thermoset flexible PU foam being obtainable by reaction of at least one compound of formula (1a) and at least one compound of formula (1b) with 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), at least one blowing agent and at least one catalyst; where: Formula (1a):[R 1 Me2SiO 1 / 2 ] a [MeSiO 2 / 2 ] b [R 2 MeSiO 2 / 2 ] c [MeSiO 3 / 2 ] d [SiO 4 / 2 ] e [In the formula, a=2 to 10, preferably 2 to 8, more preferably 2 to 5; b=25 to 200, preferably 40 to 150, more preferably 45 to 120, c=2 to 40, preferably 2 to 30, more preferably 3 to 20; d=0 to 10, preferably 0 to 8, more preferably 0 to 5; e=0 to 5, preferably 0 to 3, more preferably 0 to 2, however, a+b+c+d+e>48 R 1 =Me or R 2 R 2 = identical or different polyethers resulting from the polymerization of ethylene oxide, propylene oxide and / or other alkylene oxides (such as butylene oxide or styrene oxide), preferably polyethers of general formula (c) [ka] [In the formula, f=0 to 6, preferably 0 to 4, more preferably 0 or 3; g=0 to 150, preferably 3 to 100, more preferably 3 to 70, h=0 to 150, preferably 0 to 100, more preferably 0 to 80; however, g+h>0, R 3 =OH, alkyl or acetyl, preferably OH, C1-C6-alkyl or acetyl, more preferably OH, methyl, acetyl or butyl]. and, Formula (1b):[R 4 Me2SiO 1 / 2 ] i [MeSiO 2 / 2 ] j [R 5 MeSiO 2 / 2 ] k [MeSiO 3 / 2 ] l [SiO 4 / 2 ] m [In the formula, i=2 to 10, preferably 2 to 8, more preferably 2 to 5, j=0 to 20, preferably 0 to 18, more preferably 0 to 15, k=0 to 20, preferably 0 to 15, more preferably 0 to 10; l=0 to 10, preferably 0 to 8, more preferably 0 to 5, m=0 to 5, preferably 0 to 3, more preferably 0 to 2; however, i+j+k+l+m<20 R 4 =Me or R 5 R 5 = the same or different polyethers obtained from the polymerization of ethylene oxide, propylene oxide and / or other alkylene oxides (such as butylene oxide or styrene oxide), preferably polyethers of general formula (d) or alkyl C3-C 15 , [ka] [In the formula, n=0 to 6, preferably 0 to 4, more preferably 0 or 3; o=0 to 100, preferably 0 to 50, more preferably 0 to 25, p=0 to 100, preferably 0 to 50, more preferably 0 to 25, however, o+p>0 R 6 =OH, alkyl or acetyl, preferably OH, C1-C6-alkyl or acetyl, more preferably OH, methyl, acetyl or butyl.

[0010] Equations (1a) and (1b) should be considered as average empirical formulas. [Brief explanation of the drawings]

[0011] [Figure 1] 1 shows the results of a roll deformation test when air permeability is changed. [Figure 2] 1 shows the results of a roll deformation test when air permeability is changed. [Figure 3]1 shows the results of a roll deformation test when air permeability is changed. DETAILED DESCRIPTION OF THE INVENTION

[0012] The roll deformation test is described in more detail below. This test allows the dimensional recovery of molded PU foams after compression to be evaluated. Air permeability is a measure of the porosity of the PU foam in question. The results of the roll deformation test are plotted on the ordinate for each case. Air permeability is plotted on the abscissa for each case. Figures 1 to 3 illustrate that the inventive use of at least one compound of formula (1a) and at least one compound of formula (1b) in the production of thermoset flexible PU foams can improve the dimensional recovery of molded PU foam articles after compression at comparable porosities.

[0013] Optionally, it is also possible to advantageously use further customary additives, active substances and auxiliaries. Mattresses are particularly highly preferred in the context of the present invention. This also applies advantageously to all of the following preferred embodiments.

[0014] Advantageously, the molded thermoset flexible PU foam articles thus provided using the compounds of formula (1a) and (1b) have an excellent ability to recover their original shape even after prolonged compression for a period of at least 20 hours.

[0015] A further advantage is that the molded thermoset flexible PU foam articles in question are particularly low-emitting with respect to emissions of low molecular weight linear and cyclic siloxanes. In the context of the present invention, "low release" in relation to low molecular weight siloxanes means more specifically that the heat-cured flexible PU foam obtained according to the present invention has a siloxane release of ≥ 0 μg / m 2 after 24 hours of laboratory loading, as determined appropriately by a laboratory method according to DIN standard DIN EN ISO 16000-9:2008-04. 3 ~≦500μg / m 3 , preferably ≦200 μg / m 3 , more preferably ≦100 μg / m 3This method is described in detail in EP 3205680 A1, particularly in paragraph

[0070] , which is incorporated herein by reference.

[0016] An additional advantage is that the molded thermoset flexible PU foam articles in question may also meet emission standards such as CertiPur. As used herein, "low emissions" according to CertiPur means total volatile organic compounds (TVOC) emissions of 500 μg / m 3 Further technical details of the requirements of the CertiPUR standard (Version 1, July 2017) can be found at https: / / www.europur.org / images / CertiPUR_Technical_Paper_-_Full_Version_-_2017.pdf. The latter document (Version 1, July 2017) can also be ordered directly from EUROPUR, Avenue de Cortenbergh 71, B-1000 Brussels, Belgium.

[0017] PU foams (polyurethane foams) and their products are well known to those skilled in the art and do not require further explanation per se. In the context of the present invention, molded articles are molded bodies of different shapes. Preferred shapes in the context of the present invention are geometric shapes such as, for example, spherical, cubic, cylindrical, etc. Molded PU foam articles in the context of the present invention are thus molded bodies made of polyurethane foam. Particularly preferred molded thermoset flexible PU foam articles in the context of the present invention are mattresses and / or cushions, as well as foam blocks in general.

[0018] Mattresses themselves and their manufacture are known. Mattresses usually consist of a mattress and / or spring core, which may contain, for example, foam, latex, or natural products, and a cover that surrounds the mattress. A corresponding structure applies to cushions. 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 flexible thermoset PU foam is present in the mattress and / or cushion. This preferably means that at least a portion of the mattress and / or cushion consists of flexible thermoset PU foam. This portion may account for at least 1% by weight, 5% by weight, or 25% by weight, preferably at least 50% by weight, and more preferably at least 75% by weight, based on the total weight of the mattress and / or cushion. It is also possible for the mattress and / or cushion to consist entirely of flexible thermoset PU foam, except for the cover.

[0019] The production of polyurethane foams in general is known per se. Polyurethane foams are formed by the tried and tested reaction of at least one polyol component with at least one isocyanate component in a polyaddition reaction in the presence of at least one blowing agent (for example, water). It is essential for the present invention that the foam is a flexible thermoset PU foam and 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), in each case as defined above.

[0020] The polyurethane foam according to the present invention is a thermoset flexible polyurethane foam. Alternatively, a combination of several of these flexible PU foams, for example two of these flexible PU foams, is used. The term "flexible thermoset PU foam" is a well-established and well-established term of art known to those skilled in the art, but will nevertheless be briefly explained here.

[0021] Flexible PU foams are elastic and deformable, typically with open cells. As a result, air can easily escape when compressed. In addition, rigid PU foams exist that are inelastic and typically have closed cells. These are used for thermal insulation purposes and are not the subject of the present invention. A wide variety of flexible PU foams exist. For example, those skilled in the art are aware of, among others, ester foams (made from polyester polyols), flexible thermoset PU foams, and cold-cure PU foams. Viscoelastic flexible PU foams are a relatively new type and are classified as thermoset flexible PU foams. Therefore, in the context of the present invention, viscoelastic flexible PU foams are also included in the term "flexible thermoset PU foam." The crucial difference between thermoset flexible PU foams and cold-cure PU foams lies in their mechanical properties. Flexible thermoset PU foams and soft cold-cure PU foams can be distinguished, in particular, by their rebound resilience (also called "ball rebound" (BR) or "elasticity"). Methods for measuring rebound resilience are described, for example, in DIN EN ISO 8307:2008-03. In this test, a steel ball with a certain mass is dropped onto the test specimen from a specific height, and the rebound height is then measured in % relative to the drop height. For cold-cure flexible PU foams, this value is preferably in the range of >50%. Cold-cure flexible PU foams are therefore often referred to as high-resilience (HR) foams (HR: High Resilience). In comparison, heat-cure flexible PU foams preferably have a rebound value of 1% to 50% or less. In a preferred embodiment of the present invention, the heat-cure flexible PU foams of the present invention preferably have a rebound value of 1% to 50% or less, as measured according to DIN EN ISO 8307:2008-03. A further mechanical criterion is the deflection or comfort factor. In this case, foam samples are compressed according to DIN EN ISO 2439, and the ratio of the compressive stress at 65% compression to that at 25% compression is measured. Cold-cure flexible PU foams preferably have a deflection or comfort factor of >2.5. The thermoset flexible PU phos preferably has a value of <2.5.Thus, in a preferred embodiment of the present invention, the thermoset flexible PU foams of the present invention have a deflection or comfort factor, measurable as described above, preferably <2.5.

[0022] The exact definition of the properties can also be taken from the data sheet "PUR-Kaltschaum" [Cold-Cure PU Foams] of Fachverband Schaumkunststoffe und Polyurethane eV [Association of Foam Plastics and Polyurethanes Specialists] (reference number KAL20160323, last update 23.03.2016) (https: / / www.fsk-vsv.de / wp-content / uploads / 2017 / 03 / Produktbeschreibung-PUR-Kaltschaum.pdf). This data sheet can also be ordered directly from Fachverband Schaumkunststoffe und Polyurethane eV (FSK), Stammheimerstr. 35, D-70435 Stuttgart.

[0023] The two names, hot-cure flexible PU foam and cold-cure flexible PU foam, are explained by the history of the development of PU technology and do not necessarily refer to the difference in temperatures that occur during the foaming process.

[0024] The different mechanical properties of hot-cure and cold-cure PU foams result from the differences in the formulations used to produce them. For cold-cure flexible PU foams, primarily highly reactive polyols with primary OH groups and average molar masses >4000 g / mol are typically used. Optionally, a low-molecular-weight crosslinker is also used, which is assumed to function via a high-functionality isocyanate. For hot-cure flexible PU foams, relatively unreactive polyols with secondary OH groups and average molar masses <4000 g / mol are typically used. For cold-cure flexible PU foams, the reaction between isocyanate groups and hydroxyl groups occurs as early as the foam expansion stage (CO2 generation from -NCO and HO). This rapid polyurethane reaction typically results in a viscosity increase, resulting in a relatively high inherent stability of the foam during the foaming process. Consequently, other foam stabilizers with different siloxane structures are required compared to hot-cure flexible PU foams. For this reason, the scope of this invention does not extend to cold-cure flexible PU foams. Cold-cure flexible PU foams are usually high-resilience foams. Due to their high inherent stability, the cells are generally not fully opened at the end of the foaming operation, and further mechanical crushing of the cell structure is required to open them. In contrast, crushing is usually not required for heat-cure flexible PU foams. The significant stabilization provided by the high molecular weight polyether siloxane structure is important here. The corresponding highly active stabilizer is defined by formula (1a). In the case of the heat-cure flexible PU foams of the present invention, in addition to the stabilizer of formula (1a), a silicone compound of formula (1b) is additionally used in the production.

[0025] The open-cell thermoset flexible PU foam preferably has a gas permeability (also called "porosity") in the range of 1 to 6.5 scfm. This is measured according to ASTM D 3574 (2011-00) by applying a differential pressure and measuring the volume of air passing through. This method is explained in detail in the Examples (see Porosity Measurement by Flow Method in the Examples). Scfm (standard cubic feet per minute) is measured under standard conditions (23°C, 100 kPa).

[0026] The thermosetting flexible PU foam is preferably 8 to 80 kg / m depending on the application. 3 In particular, when such thermoset flexible PU foams are used as mattresses, mattress components, and / or cushions, the foams can be differentiated according to the regional demands and needs, requirements, and preferences of consumers. Preferred thermoset flexible PU foams for mattress applications preferably have a foam density of 25 to 3 kg / m. 3 The foam density is

[0027] A unique class of thermoset flexible PU foams are the viscoelastic PU 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 flexible foams usually have low porosity and high density (or high foam density (FD)) compared to other thermoset flexible PU foams. The foam density of the cushion is preferably between 30 and 50 kg / m. 3 and is therefore at the lower end of the typical density scale for viscoelastic foams, whereas the density of viscoelastic PU foams for mattresses is preferably between 50 and 130 kg / m 3 is.

[0028] In thermoset flexible PU foams, hard (high glass transition temperature) and soft (low glass transition temperature) segments orient with each other during the reaction and then spontaneously separate from each other to form morphologically distinct phases within the "bulk polymer." Such materials are also referred to as "phase-separated." For viscoelastic foams, the glass transition temperature is preferably between -20°C and +15°C. In contrast, the glass transition temperatures of other thermoset flexible PU foams and cold-cure flexible PU foams are typically below -35°C. This "structural viscoelasticity" in the case of open-cell viscoelastic thermoset flexible PU foams is essentially based on the polymer's glass transition temperature and should be distinguished from gas behavior. In the latter case, the cell structure is relatively closed (low porosity). This low porosity allows air to return only gradually after compression, resulting in slow recovery.

[0029] Regarding the foam stabilizer used, in the present invention, a compound of formula (1a) is used in the viscoelastic PU foam. The addition of a compound having formula (1b) particularly leads to an improvement in roll compaction according to the present invention. Hereinafter, when flexible thermoset PU foam is mentioned, it also includes viscoelastic flexible PU foam, even if not otherwise specified.

[0030] Various thermoset flexible PU foams are classified not only according to foam density, but also often according to their compressive strength, also called load-bearing capacity for specific applications. For example, the compressive strength at 40% CLD (Compressive Load Deflection) according to DIN EN ISO 3386-1:2015-10 is preferably in the range of 2.0 to 8.0 kPa for thermoset flexible PU foams; viscoelastic polyurethane foams preferably have values ​​of 0.1 to 5.0 kPa, more preferably 0.5 to 2.5 kPa.

[0031] In a preferred embodiment of the present invention, the thermoset flexible PU foams used according to the present invention have the following preferred properties with respect to rebound resilience, foam density and / or porosity: rebound resilience of 1% to 50% (measured in accordance with DIN EN ISO 8307:2008-03), and / or foam density of 5 to 150 kg / m3 and / or a porosity of 1 to 6 scfm, preferably 1.5 to 4.5 scfm, more preferably 1.75 to 4.25 scfm. As mentioned above, it is particularly preferred that all three criteria regarding impact resilience, foam density, and / or porosity are met. In particular, the thermoset flexible PU foam used according to the present invention has a compressive strength at 40% CLD according to DIN EN ISO 3386-1:2015-10 of 0.1 to 8.0 kPa.

[0032] Thermoset flexible PU foams and their production are known per se. For the purposes of the present invention, in a preferred embodiment, the thermoset flexible PU foam has, in particular, a compressive strength at 40% CLD 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 1 to 50% and / or a foam density of 8 to 80 kg / m 3 and / or a porosity of 1 to 6 scfm, preferably 1.5 to 4.5 scfm, more preferably 1.75 to 4.25 scfm. Possible production methods are described, for example, in EP 2 481 770 A2 or EP 2 182 020 A1. For the purposes of the present invention, in a preferred embodiment, the viscoelastic flexible PU foam has, in particular, a glass transition temperature of -20°C to +15°C, and / or a compressive strength at 40% CLD according to DIN EN ISO 3386-1:2015-10 of 0.1 to 5.0 kPa, preferably 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 3and / or a porosity (after crushing the foam) of 1 to 6 scfm, preferably 1.5 to 4.5 scfm, more preferably 1.75 to 4.25 scfm. Possible 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 specific temperature range. Therefore, the reported values ​​are average values.

[0033] In a preferred embodiment of the present invention, the molded thermoset flexible PU foam article of the present invention, particularly the mattress of the present invention, has a height of at least 1 cm to no more than 50 cm, a width of at least 20 cm to no more than 300 cm, and a length of at least 20 cm to no more than 300 cm. Preferred dimensions include, for example, a height of 5 cm to 40 cm, a width of 70 cm to 200 cm, and a length of 150 cm to 220 cm. In a preferred embodiment of the present invention, the molded PU foam article of the present invention, particularly the cushion of the present invention, has a height of at least 1 cm to no more than 40 cm, a width of at least 15 cm to no more than 200 cm, and a length of at least 15 cm to no more than 200 cm, and preferred dimensions include, for example, a height of 2 cm to 30 cm, a width of 15 cm to 50 cm, and a length of 15 cm to 50 cm.

[0034] In a further preferred embodiment of the present invention, the molded thermoset flexible PU foam article is in the form of a mattress, preferably 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, they have seven zones of different hardness extending in the longitudinal direction of the mattress and provided with appropriate widths. When the mattress has zones of different hardness distributed over its surface, in particular formed by cuts and / or hollow spaces in the mattress, this constitutes a further preferred embodiment of the present invention.

[0035] In a further preferred embodiment of the present invention, the molded thermoset flexible PU foam article is a cold-cure PU foam mattress, a viscoelastic soft PU foam mattress, a heat-cure soft PU foam mattress, a PU gel foam mattress, a latex mattress, or a box spring mattress, each containing at least in part the thermoset flexible PU foam according to the present invention. Mattresses of the above types are known to those skilled in the art and are sold worldwide under the above names. Mattresses made solely from heat-cure flexible PU foam are usually simply referred to in the market as foam mattresses. The term mattress, as used for the purposes of the present invention, also includes corresponding mattress covers and underlays.

[0036] In a preferred embodiment of the present invention, the molded thermoset flexible PU foam article, preferably a mattress, is characterized in that the molded thermoset flexible PU foam article is compressed by at least 20%, preferably at least 30%, more preferably at least 40% based on its starting volume, and is maintained in this compressed form by auxiliary means, in particular packaging means, for at least 20 hours.

[0037] Suitable auxiliary means, in particular packaging means, are bags and / or films, such as those known in the field of roll mattresses. The bags and / or films may be sealed by any desired means, for example by clips, adhesive tape, or welding. The function of the auxiliary means is to maintain the compressed shape until the end user of the molded thermoset flexible PU foam article wishes to use the molded article again in the normal manner. After removing the auxiliary means (in particular the packaging means), the compressed molded article will re-expand and, in the best case, recover its original shape and size. The present invention allows for improved dimensional recovery after compression for a period of at least 20 hours.

[0038] In a further preferred embodiment, the molded thermoset flexible PU foam article is in a compressed and vacuum packed state, in particular a vacuum packed and compressed roll mattress.

[0039] The production of various heat-cured flexible PU foams that can be used in connection with the present invention is known per se and can be achieved by any of the proven methods, provided that the heat-cured flexible PU foams are produced in the presence of at least one compound of formula (1a) and at least one compound of formula (1b).

[0040] In principle, the production of the corresponding thermoset flexible PU foams requires no further explanation, but some preferred details for the production of PU foams used for the purposes of the present invention are given below. The subject matter of the present invention is illustrated by the following examples, without the present invention being limited to these exemplary embodiments. Where ranges, general formulas 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 that can be obtained by excluding individual values ​​(ranges) or compounds. Where documents are cited in the present description, the entire contents thereof are intended to form part of the disclosure of the present invention, particularly with regard to the subject matter forming the context in which the document is cited. Unless otherwise stated, percentages are figures 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 23°C and a pressure of 100 kPa, unless otherwise stated. Unless otherwise stated, in the context of the present invention, compressing a foam means that the foam is preferably compressed by at least 20% based on its starting volume, especially over a period of at least 20 hours.

[0041] For the purposes of this invention, polyurethanes are all reaction products derived from isocyanates, particularly polyisocyanates, with suitable isocyanate-reactive molecules. These reaction products include polyisocyanurates, polyureas, and allophanate-, biuret-, uretdione-, uretonimine-, or carbodiimide-containing isocyanate or polyisocyanate reaction products. Those skilled in the art who wish to produce different types of flexible PU foams, such as thermoset flexible PU foams, will clearly select the appropriate substances required for each purpose, such as isocyanates, polyols, stabilizers, surfactants, etc., to obtain the desired type of polyurethane, particularly the type of PU foam. Usable starting materials, catalysts, and auxiliary and additive agents are described in Kunststoffhandbuch [Plastics Handbook], Vol. 7, Polyurethane [Polyurethanes], Carl-Hanser-Verlag Munich, first edition 1966, second edition 1983, and third edition 1993. The following compounds, ingredients and additives are given by way of example only and can be substituted and / or supplemented by other substances known to those skilled in the art.

[0042] The isocyanate component used is preferably one or more organic polyisocyanates having two or more isocyanate functionalities, and the polyol component used is preferably one or more polyols having two or more isocyanate-reactive groups.

[0043] Suitable isocyanates for the isocyanate component of the present invention are all isocyanates containing at least two isocyanate groups. In general, all known aliphatic, cycloaliphatic, arylaliphatic, and preferably aromatic polyfunctional isocyanates can be used. The isocyanate is preferably used in an amount of 60 to 350 mol %, more preferably 60 to 140 mol %, based on the total amount of isocyanate-consuming components.

[0044] 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 Examples of suitable isocyanates include trimethylcyclohexane (abbreviated as 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 mixtures thereof.

[0045] It is also possible to use isocyanates that have been modified by incorporating urethane, uretdione, isocyanurate, allophanate, and other groups, referred to as modified isocyanates.

[0046] Particularly suitable organic polyisocyanates which are particularly preferred for use are therefore 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), "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, termed "pure MDI", which mainly contain a mixture of the 2,4' and 4,4' isomers, and / or prepolymers derived therefrom. Examples of particularly suitable isocyanates are detailed, for example, in EP 1712578, EP 1161474, WO 00 / 58383, U.S. Patent Application Publication No. 2007 / 0072951, EP 1678232, and WO 2005 / 085310, which are incorporated herein by reference in their entireties.

[0047] Suitable polyols for the purposes of the present invention as the polyol component are all organic substances containing two or more isocyanate-reactive groups, preferably OH groups, and their blends. Preferred polyols are all polyether polyols and / or polyurethane systems, especially hydroxy-containing aliphatic polycarbonates customarily used in the production of polyurethane foams, particularly polyether polycarbonate polyols and / or filled polyols (polymer polyols) (e.g., 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, especially amino groups, and / or naturally occurring polyols known as "natural oil-based polyols" (NOPs). Polyols for thermosetting flexible PU foams preferably have a functionality of 1.8 to 8 and a number-average molecular weight in the range of 500 to 4000 g / mol. Polyols with an OH value in the range of 25 to 400 mg KOH / g are commonly used. The number average molecular weight is typically measured by gel permeation chromatography (GPC), particularly using polypropylene glycol as a reference material and tetrahydrofuran (THF) as an eluent. The OH number can be measured, particularly according to DIN standard DIN 53240:1971-12. Depending on the properties required for the resulting foam, suitable polyols can be used, for example, as described in U.S. Patent Application Publication No. 2007 / 0072951 (A1), WO 2007 / 111828, U.S. Patent Application Publication No. 2007 / 0238800, U.S. Patent No. 6,359,022, or WO 96 / 12759. Additional polyols are known to those skilled in the art and can be found, for example, in European Patent Application Publication No. 0,380,993 or U.S. Patent No. 3,346,557.

[0048] In a preferred embodiment of the present invention, particularly for the production of flexible slabstock foams, polyether alcohols containing secondary hydroxy groups, particularly those with propylene oxide blocks at the chain ends, or random propylene oxide and ethylene oxide blocks, or those based solely on propylene oxide blocks, are used, preferably in amounts of more than 50%, more preferably more than 90%. Such polyether alcohols preferably have a functionality of 2 to 8, more preferably 2 to 4, a number average molecular weight of 500 to 4000 g / mol, preferably 800 to 4000 g / mol, more preferably 2500 to 4000 g / mol, and typically an OH number in the range of 20 to 100 mg KOH / g, preferably 40 to 60 mg KOH / g.

[0049] In a further preferred embodiment of the present invention, di- and / or trifunctional polyether alcohols containing primary hydroxy groups, in particular those with ethylene oxide blocks at the chain ends, are additionally used, preferably in amounts of more than 50%, more preferably more than 80%. Polyols for cold-cure flexible PU foams ("HR polyols") also form part of this category if their molar mass is simultaneously >4000 g / mol. In particular for the production of the above-mentioned hot-cure flexible PU foams, in accordance with the properties required for the preferred embodiment according to the invention, it is preferred to use not only the polyether alcohols described herein but also further polyether alcohols ("hypersoft polyols") containing primary hydroxy groups and 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, more preferably 2 to 5, a number average molecular weight in the range of 500 to 8000 g / mol, preferably 500 to 7000 g / mol, and typically an OH number in the range of 5 to 100 mg KOH / g, preferably 20 to 60 mg KOH / g. In the case of the thermoset flexible PU foams of the present invention, polyols with primary OH functionality are used in a preferred embodiment not alone but in combination with polyols with secondary OH groups. Here, polyols with primary OH functionality are used in combination, in a preferred embodiment, only to the extent of <50%.

[0050] In a more preferred embodiment of the present invention, an autocatalytic polyol is used.

[0051] In a further preferred embodiment of the present invention, particularly for the production of viscoelastic flexible PU foams, it is preferred to use a mixture of various, preferably two or three, multifunctional polyether alcohols. The polyol combinations used herein typically consist of high-functionality, low-molecular-weight "crosslinker" polyols, preferably with an OH number of 100 to 400 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 of 20 to 40 mg KOH / g, which have a high proportion of ethylene oxide and cell-opening properties. When HR polyols are also used in the viscoelastic foam formulation, the weight proportion of HR polyols in the polyol mixture is <50%.

[0052] In a further preferred embodiment of the present invention, recycled polyol is used.

[0053] The molded thermoset flexible PU foam articles obtained by the additional use of recycled polyols therefore represent a preferred embodiment of the present invention. The use of recycled polyols usually leads to problems with shape recovery after roll compaction. In connection with the present invention, it has surprisingly been found that the combined use of at least one compound of formula (1a) and at least one compound of formula (1b), as explained in detail above, can alleviate this problem.

[0054] Recycled polyols are polyols obtained from PU foam waste. This can be manufacturing waste from thermoset flexible PU foam production or post-consumer thermoset flexible PU foam waste (e.g., old mattresses). In both cases, the PU foam is liquefied by a chemical process. Various processes are useful here, such as sugar decomposition, hydrolysis, or acid decomposition. The resulting liquid recycled polyol can then be reused to produce thermoset flexible PU foam. However, such thermoset flexible PU foams are often characterized by significantly unfavorable mechanical properties, such as resistance to roll compaction. One source of further information on the use of recycled polyols in thermoset flexible PU foams is the following BMBF research report: https: / / www.cleaner-production.de / fileadmin / assets / bilder / BMBF-Projekte / 01RI05070-075_-_Abschlussbericht.pdf.

[0055] In the present invention, the additional use of recycled polyol corresponds to a preferred embodiment of the present invention for each item of the claimed subject matter.

[0056] 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 50 to 140, preferably 70 to 130, and more preferably 85 to 125. An index of 100 represents a molar ratio of reactive groups of 1:1.

[0057] The heat-cured flexible PU foams according to the invention can also be produced using a catalyst. The expression "catalyst" for the purposes of the present invention includes all compounds known from the prior art that are capable of catalyzing the isocyanate reaction and / or that can be used as catalysts, cocatalysts or activators in the production of polyisocyanate reaction products, in particular polyurethane foams.

[0058] Suitable catalysts are known: in particular substances which catalyze the gelling reaction (isocyanate-polyol), the blowing reaction (isocyanate-water) and / or the dimerization or trimerization of isocyanates. Such catalysts are preferably nitrogen compounds, especially amines and ammonium salts, and / or metal compounds.

[0059] Examples of nitrogen compounds suitable as catalysts for the purposes of the present invention are the amines triethylamine, triethanolamine, diethanolamine, N,N-dimethylcyclohexylamine, N,N-dicyclohexylmethylamine, N,N-dimethylaminoethylamine, N,N,N',N'-tetramethylethane-1,2-diamine, N,N,N',N'-tetramethylpropane-1,3-diamine, N,N,N',N'-tetramethylbutane-1,4-diamine, N,N,N',N'-tetramethylhexane-1,6-diamine, N-[2-(dimethylamino)ethyl]-N,N',N'-trimethylethane-1,2-diamine, 2-[(2-(dimethylamino)ethyl)methylamino]ethanol, N',N'-dimethylpropane-1,3-diamine, N',N'-diethylpropane-1,3-diamine, 1-(2-aminoethyl)pyrrolidine Lysine, 1-(3-aminopropyl)pyrrolidine, 1-[3-(dimethylamino)propyl-(2-hydroxypropyl)amino]propan-2-ol, 2-[[3-(dimethylamino)propyl]methylamino]ethanol, 3-(2-dimethylamino)ethoxy)propylamine, N-[3-(dimethylamino)propyl]-N',N'-dimethylpropane-1,3-diamine, N'-[3-(dimethylamino)propyl]-N,N,N'-trimethylpropane-1,3-diamine, 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol, N,N-bis[3-(dimethylamino)propyl]-N',N'-dimethylpropane-1,3-diamine, 1,4-diazabicyclo[2.2.2]octane, 1,4-diazabicyclo[2.2.2]octane-2-methanol, 1,2-dimethylimidazole, N-(2-hydroxypropyl)imidazole, 2-methyl-1-(2-methylpropyl)imidazole, N-(3-aminopropyl)imidazole, N-methylimidazole, 1-(3-aminopropyl)-2-methyl-1H-imidazole, 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'-dimorpholinodiethyl ether, N,N'-dimethylpiperazine, N-(2-hydroxyethyl)piperazine, N-(2-aminoethyl)piperazine, N,N-dimethylbenzylamine, N,N-(dimethylamino)ethanol, N,N-(diethylamino)ethanol, 1-(2-hydroxyethyl)pyrrolidine, 3-dimethylamino-1-propanol, 1-(3-hydroxypropyl)pyrrolidine, 2-[2-(dimethylamino)ethoxy]ethanol, 2-[2-(diethylamino)ethoxy]ethanol, bis(2-dimethylaminoethyl)ether, 2-[[2-(2-(dimethylamino)ethoxy)ethyl]methylamino]ethanol, N-[2-[2-(dimethylamino)ethoxy]ethyl]-N-methylpropyl Pan-1,3-diamine, 1,3,5-tris[3-(dimethylamino)propyl]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]dec-5-ene.0]oct-4-ene, 1,1,3,3-tetramethylguanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine, guanidine, 1,1'-[(3-{bis[3-(dimethylamino)propyl]amino}propyl)imino]dipropan-2-ol, (3-aminopropyl)bis[3-(dimethylamino)propyl]amine, 3-(dimethylamino)propyl urea, 1,3-bis[3-(dimethylamino)propyl]urea, 3-dimethylamino-N,N-dimethylpropanamide, 6-(dimethylamino)hexan-1-ol, and 2,4,6-tris[(dimethylamino)methyl]phenol.

[0060] Catalysts and / or mixtures of this type are, for example, Jeffcat® ZF-10, Lupragen® DMEA, Lupragen® API, Toyocat® RX20 and Toyocat® RX21, DABCO® RP202, DABCO® RP204, DABCO® NE300, DABCO® NE310, DABCO® NE400, DABCO® NE500, DABCO® NE600, DABCO® NE650, DABCO® NE660, DABCO® NE700, DABCO® NE800, DABCO® NE900, DABCO® NE910, DABCO® NE920, DABCO® NE930, DABCO® NE940, DABCO® NE950, DABCO® NE960, DABCO® NE970, DABCO® NE980, DABCO® NE990, DABCO® NE1010, DABCO® NE1020, DABCO® NE1030, DABCO® NE1040, DABCO® NE1050, DABCO® NE1060, DABCO® NE1070, DABCO® NE1080, DABCO® NE1090, DABCO® NE110, DABCO® NE1110, DABCO® NE1120, DABCO® NE1130, DABCO® NE1140, DABCO® NE1150, DABCO® NE1160, DABCO® NE1170, DABCO® NE1180, DABCO® NE1190, DABCO® NE1200, DABCO® NE1210, DABCO® NE1220, DABCO and DABCO® NE2039, Niax® EF860, Niax® EF890, Niax® EF700, Niax® EF705, Niax® EF708, Niax® EF600, Niax® EF602, Kosmos® 54, Kosmos® EF, and Tegoamin® ZE1.

[0061] Metal compounds suitable as 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 charged or uncharged metal-containing coordination compounds, preferably 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 metal organic (e.g., organotin oxides, organotin chlorides, or organotin carboxylates). In the context of the present invention, the expression "organic metal salt" particularly includes the use of metal compounds that do not have a direct carbon-metal bond and are at the same time metal salts, either of whose anions or cations are organic compounds (e.g., tin(II) carboxylates). In the context of the present invention, the expression "inorganic metal salt" particularly includes the use of metal compounds or metal salts, either of whose anions or cations are not organic compounds, 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. In the context of the present invention, the expression "coordination compound" particularly includes the use of metal compounds formed from one or more central particles and one or more ligands, the central particles being charged or uncharged metals (e.g., metal- or tin-amine complexes). In the context of the present invention, the expression "metal-chelate complex" particularly includes the use of metal coordination compounds having ligands with at least two coordination or bonding sites to the metal center (e.g., metal- or tin-polyamine or metal- or tin-polyether complexes).Metal compounds suitable as catalysts in the sense of the present invention, in particular compounds according to the above definition, may be selected from all metal compounds containing, for example, 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, in particular sodium, potassium, magnesium, calcium, titanium, zirconium, molybdenum, tungsten, zinc, aluminum, tin, and / or bismuth, more preferably tin, bismuth, zinc, and / or potassium.

[0062] 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 metal-organic salts and organometallic salts, as specifically defined above, as catalysts in the present invention are, for example, organic tin, tin, zinc, bismuth and potassium salts, in particular the corresponding metal carboxylates, alkoxides, thiolates and mercaptoacetates, such as dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate (DBTDL), dioctyltin dilaurate (DOTDL), dimethyltin dineodecanoate, ate, 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 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 metal catalysts are generally and preferably selected so as to be inherently odorless, substantially toxicologically sound, and to produce the lowest possible levels of catalyst-related emissions in the resulting polyurethane system, particularly polyurethane foam.

[0063] In addition to amines and metal compounds, ammonium salts can also be used as catalysts. Suitable examples are ammonium formate and / or ammonium acetate.

[0064] Suitable 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 therein.

[0065] The suitable amount of 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).

[0066] The optional additives used may be all substances known from the prior art and used for the production of polyurethanes, in particular thermoset flexible PU foams, such as blowing agents, preferably water to generate 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, color pastes, fragrances, emulsifiers, buffer substances and / or catalytically active substances, in particular those as defined above.

[0067] Water is commonly used as a blowing agent in the production of thermoset flexible PU foams. It is preferred to use an amount of water such that the water concentration is 0.10 to 10.0 pphp (pphp = parts by weight per 100 parts by weight of polyol).

[0068] 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.

[0069] Besides water and physical blowing agents, it is also possible to use other chemical blowing agents that react with isocyanates to generate gases, such as formic acid.

[0070] The optional crosslinker and optional chain extender are low molecular weight polyfunctional compounds that are reactive with isocyanates. Suitable compounds are hydroxy- or amine-terminated materials such as glycerol, neopentyl glycol, 2-methyl-1,3-propanediol, triethanolamine (TEOA), diethanolamine (DEOA), and trimethylolpropane. The concentration used is typically 0.1 to 5 parts per 100 parts polyol, although some formulations may deviate from this range.

[0071] Suitable optional stabilizers against oxidative degradation, so-called antioxidants, preferably include all commonly used free radical scavengers, peroxide scavengers, UV absorbers, light stabilizers, and complexing agents for metal ion contaminants (metal deactivators). Preference is given to compounds from the following classes of substances or classes of substances containing the following functional groups, where the substituents on the respective parent molecules preferably have groups reactive in particular towards isocyanates: 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, benzoic acid and benzoates, phenols, especially those containing tert-butyl and / or methyl substituents in the aromatics, benzofuranones, diarylamines, triazines, 2,2,6,6-tetramethylpiperidine, hydroxylamines, alkyl and aryl phosphites, sulfides, zinc carboxylates, and diketones.

[0072] Optional flame retardants suitable for the present invention include all substances considered suitable for this purpose by the prior art. Preferred flame retardants include liquid organophosphorus compounds such as halogen-free organophosphates, e.g., triethyl phosphate (TEP), halogenated phosphates such as tris(1-chloro-2-propyl)phosphate (TCPP) and tris(2-chloroethyl)phosphate (TCEP), and solid substances such as organophosphonates, e.g., dimethylmethanephosphonate (DMMP), dimethylpropanephosphonate (DMPP), or ammonium polyphosphate (APP) and red phosphorus. Suitable flame retardants also include halogenated compounds, e.g., halogenated polyols, and solid substances such as expandable graphite and melamine.

[0073] Organo-modified siloxanes are commonly used in the production of thermoset flexible PU foams to stabilize the foam mixture during rise and to influence the foam properties of the PU foam. (Organo-modified) siloxanes suitable for this purpose are described, for example, in the following documents: EP 0839852, EP 1544235, DE 102004001408, EP 0839852, WO 2005 / 118668, U.S. Patent Application Publication No. 20070072951, DE 2533074, EP 1537159, EP 533202, U.S. Patent No. 3933695, EP 0780414, DE 4239054, DE 4229402, and EP 867465. These compounds can be prepared as described in the prior art. Suitable examples are described, for example, in U.S. Pat. No. 4,147,847, European Patent No. 0,493,836, and U.S. Pat. No. 4,855,379. Foam stabilizers for thermoset flexible PU foams are characterized by large siloxane structures with more than 50 Si units and pendant polyethers. These foam stabilizers are also called polydialkylsiloxane-polyoxyalkylene copolymers. 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 at terminal or lateral positions. The alkyl groups of the siloxane may be aliphatic, alicyclic, or aromatic. Methyl groups are particularly advantageous. The organomodified polydialkylsiloxane may be linear or branched. Suitable stabilizers, particularly foam stabilizers, are described in U.S. Patent Nos. 2,834,748, 2,917,480, and 3,629,308. The function of the foam stabilizer is to ensure the stability of the foaming reaction mixture. Here, the contribution to foam stabilization is correlated with the siloxane chain length. Without the foam stabilizer, collapse is observed, resulting in an inconsistent foam.For some flexible PU foam types not according to the present invention, which have high stability and therefore low tendency to collapse, it is possible to use low molecular weight polyether siloxanes. Low molecular weight polyether siloxanes have siloxane chain lengths much shorter than 50. For example, for low-temperature curing flexible PU foams or ester foams, unmodified or modified short-chain siloxanes are used. In contrast, when long-chain, and therefore more powerful, siloxane stabilizers are used, overstabilization and consequent shrinkage after foam production are observed in such foam types.

[0074] Foam stabilizers may in principle be selected as desired in the present invention, provided that a combination of compounds of formula (1a) and formula (1b) is used in the heat-cured flexible PU foams according to the present invention. As already explained, these are particularly useful for improving the dimensional stability of the foam body after compaction, in particular after roll compaction.

[0075] The compounds of formulas (1a) and (1b) can be used, for example, together with suitable solvents and / or further additives. As optional solvents, all suitable substances known from the prior art can be used. Depending on the application, aprotic nonpolar solvents, aprotic polar solvents, and protic solvents can be used. Suitable aprotic nonpolar solvents can be selected, for example, from the following substance classes or functional groups: aromatic hydrocarbons, aliphatic hydrocarbons (alkanes (paraffins) and olefins), carboxylic acid esters (e.g., esters of fatty acids such as isopropyl myristate, propylene glycol dioleate, and decyl cocoate), 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 functional groups: ketones, lactones, lactams, nitriles, carboxamides, sulfoxides, and / or sulfones. Suitable protic solvents can be selected, for example, from the following classes of substances or classes of substances having the following functional groups: alcohols, polyols, (poly)alkylene glycols, amines, carboxylic acids, preferably fatty acids and / or primary and secondary amides. Particularly preferred are solvents that are easy to use in the foaming operation and do not adversely affect the foam properties. For example, isocyanate-reactive compounds are preferred because they are incorporated into the polymer matrix by reaction and do not generate any emissions in the foam. Examples thereof 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 homologues, such as polyethylene glycol (PEG) with an average molecular weight of 200 g / mol to 3000 g / mol.Particularly preferred OH-functional compounds further include polyethers with an average molecular weight of 200 g / mol to 4500 g / mol, preferably 400 g / mol to 2000 g / mol, among which water-, allyl-, butyl- or nonyl-initiated polyethers are preferred, more preferably polyethers based on propylene oxide (PO) and / or ethylene oxide (EO) blocks.

[0076] When compounds of formula (1a) and (1b) are used in accordance with the present invention, or when premixed silicones combining compounds having formula (1a) and (1b) with additional carriers are used in dissolved form or in combination with a solvent, the weight ratio of the sum of all silicone components to the solvent is preferably 0.1:1 to 9:1, preferably 0.25:1 to 5:1, more preferably 0.5:1 to 4:1.

[0077] In preferred embodiments of the present invention, the two siloxane components, i.e., the compound of formula (1a) and the compound of formula (1b), may be added separately to the foam mixture, each in pure form or in a blend with a solvent, or may be mixed together before addition.

[0078] Preferably, the compound having formula (1a) may be added in a sufficient amount to the composition for producing a heat-cured flexible PU foam so that its mass proportion in the finished PU foam is 0.1 to 5 wt%, preferably 0.25 to 3.0 wt%, more preferably 0.5 to 2.0 wt%. The compound of formula (1b) is preferably used in a mass proportion in the finished polyurethane foam of 0.1 to 5 wt%, preferably 0.1 to 2.0 wt%, more preferably 0.1 to 1.5 wt%.

[0079] In the production of heat-cured flexible PU foams, it may be advantageous to prepare and / or use a composition comprising and reacting at least the inventive compounds of formulae (1a) and (1b), at least one polyol component, optionally at least one isocyanate component, and optionally one or more blowing agents.

[0080] The compounds of formula (1a) and (1b) are each preferably used in a total amount corresponding to a mass fraction of 0.1 to 5.0 parts (pphp), preferably 0.1 to 3.0 parts, more preferably 0.3 to 2.0 parts, per 100 parts (pphp) of the polyol component.

[0081] The thermoset flexible PU foams according to the invention can be produced by any method 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.

[0082] Any method known to those skilled in the art can be used to produce thermoset flexible PU foams. For example, the foaming operation can be carried out in a batch or continuous plant, either horizontally or vertically. The compositions used according to the invention can be used with CO2 technology as well. They can be used in 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 the mixing chamber and then added to the mixing chamber. Mixing in a raw material tank is also possible. Very particularly preferred thermoset flexible PU foams for the purposes of the present invention have in particular the following composition:

[0083] [Table 1]

[0084] 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), (1a) and (1b) each as defined above, in the production of a molded thermoset flexible PU foam article, the molded thermoset flexible 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, to provide a molded thermoset flexible PU foam article having improved dimensional recovery after compression for a period of at least 20 hours.

[0085] 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), (1a) and (1b) being each as defined above, for improving the dimensional recovery of a molded thermoset flexible PU foam article after compression for a period of at least 20 hours, the molded thermoset flexible 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.

[0086] The present invention further provides the use of a flexible thermoset PU foam in a mattress and / or cushion, preferably a mattress, the flexible thermoset PU foam being obtained by reacting 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 above. In this connection, particular reference is made to the above, which is also applicable to the present subject matter.

[0087] 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 improve the dimensional recovery of a mattress and / or cushion after compression over a period of at least 20 hours.

[0088] The present invention further provides 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 thermoset flexible PU foam article is provided by reacting at least one compound of formula (1a) and at least one compound of formula (1b), (1a) and (1b) each as defined above, with at least one polyol component and at least one isocyanate component in the presence of at least one blowing agent and at least one catalyst; (b) in an optional subsequent step, the resulting thermoset flexible PU foam may optionally be subjected to further processing to prepare it for application; (c) In the final step, the molded thermoset flexible PU foam article (optionally prepared for application) is compressed by at least 20%, preferably at least 30%, more preferably at least 40% based on its starting volume, optionally vacuum packed, maintained in compressed form by auxiliary means, preferably packaging means, and sent for storage and / or transportation.

[0089] The present invention further provides a process for producing a heat-cured flexible polyurethane foam having a porosity of 1 to 6 scfm, preferably 1.5 to 4.5 scfm, and more preferably 1.75 to 4.25 scfm, by reacting 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 above, with at least one blowing agent and at least one catalyst, particularly with the additional use of recycled polyol.

[0090] 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 / or glycols, polyethers, organic esters, and / or other solvents suitable for the purpose of producing thermoset flexible PU foams. [Example]

[0091] Physical properties of flexible PU foam: The produced flexible PU foams were evaluated according to the following physical properties a) to g): a) Rise time: The time from the end of mixing the reactive components to the start of polyurethane foam. b) Rise Height or Foam Height (Foam Height): The height of the free rise foam formed after 3 minutes. Foam height is reported in centimeters (cm). c) Foam sag (= retreat) at the end of the rise phase: sag can be seen from the difference in foam height immediately after foaming and after 3 minutes of 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 foam sag after foaming; positive values ​​indicate corresponding further foam rise. g) Number of cells per cm (cell count): The cell count is determined visually on a cut surface (measurement according to DIN EN 15702). e) Foam Density (FD): Determined by measuring core density as described in ASTM D 3574-11, Test A. Foam density is expressed in kg / m 3 Reported in units. f) Porosity Measured by Flow Method: The air flow method, according to ASTM D 3574(2011-00), measures the volume of air flowing through a specified foam specimen over a specified period of time when a pressure differential is applied. To do this, twelve specimens measuring 5 cm x 5 cm x 2.5 cm were cut from the finished foam transversely across the foam's rise direction and inserted sequentially into an analytical instrument configured for this method. The instrument configuration is described in ASTM D 3574(2011-00). The analytical instrument creates a pressure differential of 125 Pa between the inside of the instrument and the ambient atmosphere by drawing just enough air through the specimen to maintain a constant pressure differential. The air flow through the specimen is therefore an indicator of the foam's porosity. Values ​​ranging from 0 to 6.5 scfm (standard cubic feet per minute) were measured. Within this range, lower values ​​characterize more closed foams, while higher values ​​characterize more open foams. g) Roll Test Results This specific test is described in further detail below.

[0092] For completeness, the measurement principle of DIN EN ISO 16000-9:2008-04 is also described below.

[0093] Materials are characterized herein for the type and amount of organic substances that can outgas from the material. This analytical method serves to identify emissions from materials used in furniture and mattresses. This is done by measuring emissions using a test chamber.

[0094] analysis Test Specimens: Sample Preparation, Sample Collection, and Sample Dimensions The reaction mixture was placed in an open-top PE bag. After the foam expanded and foamed, the PE bag was closed 3 minutes after foaming. The foam was then stored at room temperature for 12 hours to complete the reaction and prevent premature release of VOCs. The PE bag was then opened, and a 7 cm x 7 cm x 7 cm cube was taken from the center of the foam block. This was immediately wrapped in aluminum foil and hermetically sealed inside the PE bag. This was then transported to the analysis laboratory, where the foam cube was placed in a cleaned 30 L glass test chamber. The test chamber conditions were controlled climatically (21°C temperature, 50% humidity). Half of the test chamber volume was replaced every hour. After 24 hours, the sample was removed from the test chamber air. A Tenax adsorption tube served to absorb the VOCs. The Tenax tube was then heated, and the evolved volatiles were cryofocused by a flow of inert gas in a cold trap in a temperature-programmable evaporator. After the heating stage is over, the cold trap is quickly heated to 280 °C. The focused material is evaporated in the process. It is then separated in a gas chromatography separation column and detected by mass spectrometry. Calibration with reference materials allows the determination of the emitted material (µg / m 3This allows for a semi-quantitative prediction of the VOC content (represented by "VOC value"). The quantitative reference substance used for VOC analysis (VOC value) is toluene. Signal peaks can be assigned to substances using mass spectra and retention indices. The following equipment was used for the analysis: Gerstel (D-45473, Mühlheim an der Ruhr, Eberhard-Gerstel-Platz 1) TDS-3 / KAS-4, Tenax® desorption tube, Agilent Technologies 7890A (GC) / 5975C (MS) column: HP Ultra2 (50 m, 0.32 mm, 0.52 μm), carrier gas: helium. A more specific description of the procedure can be found in DIN EN ISO 16000-9:2008-04.

[0095] Described below is a rolling deformation test that allows testing of dimensional recovery after compression in connection with the present invention.

[0096] Roll Deformation Test (abbreviated as "Roll Test"): the purpose: The test is designed to simulate the conditions of a rolled mattress in a laboratory setting. Since there is no meaningful industry standard for this, a new test was developed to simulate a roll of mattress foam on a small scale.

[0097] Sample preparation: Test specimens with dimensions of 12 cm (width), 16 cm (length) and 2.5 cm (thickness) are cut from the manually expanded soft PU foam block, for example using a band saw. A central position in the manually expanded foam block is selected. The specimens are cut so that the rise direction of the foam being produced is perpendicular to the length and width of the specimen. The specimens are marked with a felt-tip pen.

[0098] Test procedure: A 12 cm edge of the specimen is compressed with a thin metal rod (e.g., a metal ballpoint pen) with a diameter of 5–8 mm. The foam specimen is then manually wrapped around the metal rod. The foam is firmly compressed to form a roll approximately 3–4 cm in diameter. The roll is manually held in this compressed state and completely inserted into a cardboard tube. The cardboard tube has an inner diameter of 4 cm and is at least 13 cm long. As soon as the rolled 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 tube. The foam is compressed much more severely in the center than at the edges of the tube. The roll is then stored under controlled, constant 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 foam's expansion should not be impeded or affected.

[0099] evaluation: The molded flexible PU foam article is left to expand for 10 minutes. The specimens are then evaluated. The most important criterion is whether the foam has fully recovered its original thickness or whether there are still compressed zones (especially at the more heavily compressed ends). In some cases, grooves caused by the compression are still visible on the surface of the specimen. Specimens with a low rating have one end still rolled up. A slight bend in the specimen 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 appearance, and the expansion occurs rapidly and is already complete after 5 minutes. ++: The specimen has recovered 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 edge. The thickness in that area is greater than 2.0 cm but less than 2.5 cm. A dent is clearly visible at this edge. -: The specimen shows slight compression at the more severely compressed edge, 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 partially rolled at this end. ---: The specimen remains compressed in a roll with the end that is more heavily compressed. The evaluation is preferably carried out by at least two people. The results are documented. In the context of the present invention, the evaluation was carried out by four people who reached consistent results.

[0100] Test deficiencies and limitations: The test must ensure correct dimensions and uniform rolling of the specimens. Foam specimens must have consistent cell structure parameters, i.e., in particular, consistent cell size and consistent air permeability. The metal rods must not be over-greased, so that the grease does not penetrate the specimen. Consistent storage conditions must be maintained. Specimens with different evaluation grades must be kept available for comparison.

[0101] Test accuracy: Performance of the test by two or more assessors usually yields consistent judgments; duplicate measurements usually yield the same results; therefore, the test has been proven to be reliable.

[0102] Thermosetting flexible PU foam - Foaming example Example 1: Thermoset Flexible PU Foam (Flexible Slabstock Foam) The heat-cured flexible PU foam formulations shown in Table 2 were used to test the performance of the compounds of formula (1a) and (1b) of the present invention. [Table 2]

[0103] 1) Polyol 1: Voranol® CP3322, a glycerol-based polyether polyol available from Dow Chemical, with an OH number of 48 mg KOH / g, predominantly secondary OH groups, and an average molar mass = 3500 g / mol. 2) KOSMOS® 29, available from Evonik Industries: 2-ethylhexanoate of tin(II). 3) TEGOAMIN® DMEA: Dimethylethanolamine, available from Evonik Industries. Amine catalyst for polyurethane foam production. 4) Polyether-modified polysiloxanes of the following structure: Foam stabilizer 1 (corresponding to the compound of formula 1a): Polyether siloxanes of the following structure: [R 1 Me2SiO 1 / 2 ] a [MeSiO 2 / 2 ] b [R 2 MeSiO 2 / 2 ] c [MeSiO 3 / 2 ] d [SiO 4 / 2 ] e [In the formula, a=2 b=70 c=4 d=0 e=0 however, a+b+c+d+e=76, R 1 =Me R 2 = identical or different polyethers of general formula (e) obtained from the polymerization of ethylene oxide and propylene oxide Formula (e): [ka] [In the formula, f=3 g=37 h=38 however, g+h=75, statistical structure R 3 = Methyl Polyether 1 is 37.5 mol %, f=3 g=14 h=0 however, g+h=14, statistical structure R 3 = Methyl The content of polyether 2 is 62.5 mol %.

[0104] In the present experiments, a short-chain siloxane component was added to a heat-cured flexible PU foam formulation containing a high molecular weight silicone component (Formula 1a) as a foam stabilizer. Three selected silicone additives (each corresponding to a compound of Formula 1b) were characterized as follows:

[0105] 5) Silicone Additives 1 Unmodified silicone oil with the following composition: [R 4 Me2SiO 1 / 2 ] i [MeSiO 2 / 2 ] j [R 5 MeSiO 2 / 2 ] k [MeSiO 3 / 2 ] l [SiO 4 / 2 ] m [In the formula, i=2 Distributed from j=2 to 15, maximum at 9 k=0 l=0 m=0 however, Distributed between i+j+k+l+m=4 and 17, with a maximum of 11 R 4 =Me]. Silicone Additives 2 Polyether-modified polysiloxanes of the following structure: [R 4 Me2SiO 1 / 2 ] i [MeSiO 2 / 2 ] j [R 5 MeSiO 2 / 2 ] k [MeSiO 3 / 2 ] l [SiO 4 / 2 ] m [In the formula, i=2 j=4.0 k=2.0 l=0 m=0 however, i+j+k+l+m=8 R 4 =Me R 5 = polyether 1 of formula f: [ka] [In the formula, n=3 o=3.5 p=2.0 however, o+p=5.5 R 6 =OH] is]. Silicone Additives 3 The structural parameters of n-octene modified heptamethyltrisiloxane are as follows: [R 4 Me2SiO 1 / 2 ] i [MeSiO 2 / 2 ] j [R 5 MeSiO 2 / 2 ] k [MeSiO 3 / 2 ] l [SiO 4 / 2 ] m [In the formula, i=2 j=0 k=1 l=0 m=0 however, i+j+k+l+m=3 R 4 =Me R 5 = n-octyl].

[0106] 6) Tolylene diisocyanate T80 (80% 2,4 isomer, 20% 2,6 isomer), from Covestro, 3 mPa·s, 48% NCO, functionality 2.

[0107] 400 g of polyol was used for each foaming operation; 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.

[0108] Foaming was performed using a so-called manual mixing process. Formulation 1 was used, as shown in Table 2. For this purpose, the polyol, the respective amine catalyst mixture, the tin catalyst tin(II) 2-ethylhexanoate, water, foam stabilizer, and optionally additional low-molecular-weight silicone additive (compound of formula (1b)) were placed in a paper cup, and the contents were mixed for 60 seconds at 1000 rpm using a disc stirrer. After initial stirring, the isocyanate (TDI) was added to the reaction mixture, which was then stirred for 7 seconds at 2500 rpm and immediately transferred to a paper-lined box (bottom area 30 cm × 30 cm, height 30 cm). After pouring, the foam expanded within the foam box. Ideally, the foam should burst upon reaching its maximum rise height and then slightly recede. This opens the cell membranes of the foam bubbles, resulting in an open-cell structure of the foam. To evaluate the properties, the following characteristic parameters were determined: rise time, rise height, and foam recede (=sag) after the end of the rise phase.

[0109] Defined foam bodies were cut from the resulting thermoset flexible PU foam blocks and further analyzed. The following physical properties were determined for the specimens: cell count, flow porosity, foam density (FD) and roll deformation at room temperature.

[0110] The results of the influence of the compounds according to the invention on foaming and the physical properties of the resulting heat-cured flexible PU foams are summarized in the table below. For comparison, heat-cured flexible PU foams were first produced using only the standard flexible foam stabilizer (Foam Stabilizer 1) and only the silicone additives Silicone Additive 1, Silicone Additive 2, and Silicone Additive 3. All foams without foam stabilizer collapsed, and no meaningfully evaluable foams were obtained. In accordance with the present invention, combinations of Foam Stabilizer 1 with Silicone Additives 1, 2, and 3 were then used.

[0111] [Table 3]

[0112] [Table 4]

[0113] [Table 5]

[0114] [Table 6] [Table 7]

[0115] When evaluating the results, it must be taken into account that the results of the roll test depend greatly on the porosity of the foam. Foams with a more closed cell structure are generally worse than those with an open cell structure. Since the porosity during the foaming operation varies to a certain extent as a result of a wide variety of different influencing factors (temperature, air pressure, etc.), the results of the roll test must be evaluated in each case in combination with the porosity for a meaningful analysis.

[0116] For this purpose, Figures 1 to 3 plot the results of the roll test against the porosity. In each case, the values ​​for the reference (thermoset flexible PU foam using only foam stabilizer 1) and the reference plus 1 part silicone additive are plotted. To obtain thermoset flexible PU foams with different porosities, the same foaming operation was repeated on different days, varying the amount of stabilizer and the amount of tin catalyst (Kosmos 29). In particular, varying the amount of tin catalyst allowed for a wide range of desirable porosity values.

[0117] It can be seen that the roll test results depend strongly on the porosity, as observed for the reference foams. Non-inventive foams with a porosity of up to 2.3 scfm generally show very poor roll test results. Conversely, non-inventive thermoset flexible PU foams show very good roll test results when very open (scfm > 4.5). However, the majority of industrial thermoset flexible PU foams are between 1.5 and 4.5 scfm. Within this range, surprisingly, improved roll test results are observed for all foams according to the invention. Since both the porosity measurement and the measurement of the roll test results are subject to variability, there is a certain scatter of values. Nevertheless, significant improvements can be observed.

[0118] As can be seen, the combination of the compound of formula (1a) and the compound of formula (1b) of the present invention exhibits significant advantages in the roll deformation test for heat-cured flexible PU foams compared to the use of a single high molecular weight silicone component as the foam stabilizer. The shape recovery of the specimens after roll deformation is improved to a very significant extent. The use of the low molecular weight silicone additive (compound of formula (1b)) alone leads to the collapse of the heat-cured flexible PU foam formulation. The combination of the high molecular weight foam stabilizer (compound of formula (1a)) and the low molecular weight silicone component (compound of formula (1b)) still exhibits sufficient stabilization (sag of less than 2.0 cm) and no change in cell count (14-15 cells / cm), demonstrating a clear advantage in the roll test.

[0119] It has also been found that the thermoset flexible PU foams according to the invention have low emissions when using release-optimized additives. This can be confirmed by VOC testing according to DIN EN ISO 16000-9:2008-04. Here, in the low-emission formulations, the total emissions increase slightly when silicone additive 1 is added (40 μg / m 3 (See Table 8) to 130 μg / m 3 (See Table 9)), but nevertheless, the general limit for TVOCs is 500 μg / m 3 Therefore, Silicone Additive 1 is also very suitable for use in low release formulations.

[0120] The overall benefits of the present invention have also been confirmed in the case of viscoelastic flexible foams. [Table 8]

[0121] [Table 9]

Claims

1. A molded thermoset flexible polyurethane (PU) foam article, wherein the thermoset flexible PU foam 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), at least one blowing agent, and at least one catalyst; where: [R １ Me ２ SiO １／２ ａ [Me ２ SiO ２／２ ｂ [R ２ MeSiO ２／２ ｃ [MeSiO ３／２ ｄ [SiO ４／２ ｅ Formula (1a)​​​​​ [During the ceremony a = 2 to 10, b = 25 to 200, c=2 to 40, d=0 to 10, e=0 to 5, however, a+b+c+d+e>48, R １ = Me or R ２ R ２ = identical or different polyethers obtained from the polymerization of ethylene oxide, propylene oxide and / or other alkylene oxides, said polyethers comprising polyethers of general formula (c) 【Chemistry 1】 Formula (c) [In the formula, f=0 to 6, g = 0 to 150, h=0 to 150, however, g+h>0, R ３ =OH, alkyl or acetyl], and [R ４ Me ２ SiO １／２ ｉ [Me ２ SiO ２／２ ｊ [R ５ MeSiO ２／２ ｋ [MeSiO ３／２ ｌ [SiO ４／２ ｍ Formula (1b)​​​​​ [During the ceremony i = 2 to 10, j=0 to 20, k=0, l=0 to 10, m=0 to 5, however, i+j+k+l+m<20 R ４ = Me or R ５ R ５ = the same or different polyethers obtained from the polymerization of ethylene oxide, propylene oxide and / or other alkylene oxides, or alkyl C ３ ~C １５ wherein the polyether includes a polyether of general formula (d): 【Chemistry 2】 Formula (d) [In the formula, n=0 to 6, o=0 to 100, p=0 to 100, however, o+p>0 R ６ =OH, alkyl or acetyl], 1. A molded thermoset flexible PU foam article comprising:

2. The molded thermoset flexible PU foam article according to claim 1, wherein the thermoset flexible polyurethane foam has a porosity of 1 to 6 scfm.

3. The thermosetting flexible polyurethane foam has a rebound resilience of 1% to 50% measured in accordance with DIN EN ISO 8307:2008-03 and / or a foam density of 5 to 150 kg / m ３ and / or a porosity of 1 to 6 scfm.

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

5. The thermosetting flexible polyurethane foam has a compressive strength at 40% CLD 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 50%, and / or a foam density of 8 to 80 kg / m ３ and / or a porosity of 1 to 6 scfm.

6. The thermosetting flexible polyurethane foam is a viscoelastic flexible polyurethane foam having a glass transition temperature of -20°C to +15°C, and / or a compressive strength at 40% CLD according to DIN EN ISO 3386-1:2015-10 of 0.1 to 5.0 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 of 1 to 6 scfm.

7. 7. The molded thermoset flexible PU foam article of any one of claims 1 to 6, wherein the molded thermoset flexible 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, and a length of at least 20 cm and no more than 300 cm.

8. 8. The molded thermoset flexible PU foam article of any one of claims 1 to 7, wherein the molded thermoset flexible PU foam article is compressed by at least 20% based on its starting volume and maintained in the compressed form with an assisted means for at least 20 hours.

9. 10. The molded thermoset flexible PU foam article of claim 8, wherein the molded thermoset flexible PU foam article is in a compressed state.

10. A molded thermoset flexible PU foam article according to any one of claims 1 to 9, characterized in that it is obtained by additional use of recycled polyols.

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 thermoset flexible PU foam article after compression for a period of at least 20 hours, wherein the molded thermoset flexible PU foam article is 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 and at least one catalyst; The thermoset flexible polyurethane foam has a porosity of 1 to 6 scfm. use.

12. 1. A method for storing and / or transporting molded thermoset flexible PU foam articles, mattresses and / or cushions, comprising: (a) in a first step, a molded thermoset flexible PU foam article is provided 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), (1a) and (1b) each being as defined in claim 1, with at least one blowing agent and at least one catalyst; (b) in an optional subsequent step, the resulting molded thermoset flexible PU foam article may optionally be subjected to further processing to prepare the article for application; (c) In the final step, the molded thermosetting soft P compressing the U-foam article (optionally prepared for application) by at least 20% based on its starting volume, optionally vacuum-packing, maintaining it in a compressed form by auxiliary means, and sending it for storage and / or transportation; The thermoset flexible polyurethane foam has a porosity of 1 to 6 scfm. method.

13. 13. The method of claim 12, wherein a sufficient amount of the compound having formula (1 a) is added in step (a) to provide a mass fraction in the finished polyurethane foam of from 0.1 to 5 wt. % and a sufficient amount of the compound having formula (1 b) is added in step (a) to provide a mass fraction in the finished polyurethane foam of from 0.1 to 5 wt. %.

14. 1. A process for producing a heat-cured flexible polyurethane foam having a porosity of 1 to 6 scfm 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), at least one blowing agent, and at least one catalyst, the process comprising: Formulas (1a) and (1b) are defined as follows: [R １ Me ２ SiO １／２ ａ [Me ２ SiO ２／２ ｂ [R ２ MeSiO ２／２ ｃ [MeSiO ３／２ ｄ [SiO ４／２ ｅ Formula (1a)​​​​​ [In the formula, a = 2 to 10, b = 25 to 200, c=2 to 40, d=0 to 10, e=0 to 5, however, a+b+c+d+e>48 R １ = Me or R ２ R ２ = identical or different polyethers obtained from the polymerization of ethylene oxide, propylene oxide and / or other alkylene oxides, said polyethers including polyethers of general formula (c), 【Transformation 3】 Formula (c) [In the formula, f=0 to 6, g = 0 to 150, h=0 to 150, however, g+h>0, R ３ =OH, alkyl or acetyl], and [R ４ Me ２ SiO １／２ ｉ [Me ２ SiO ２／２ ｊ [R ５ MeSiO ２／２ ｋ [MeSiO ３／２ ｌ [SiO ４／２ ｍ Formula (1b)​​​​​ [In the formula, i = 2 to 10, j=0 to 20, k=0, l=0 to 10, m=0 to 5, however, i+j+k+l+m<20 R ４ = Me or R ５ R ５ = the same or different polyethers obtained from the polymerization of ethylene oxide, propylene oxide and / or other alkylene oxides, or alkyl C ３ ~C １５ wherein the polyether comprises a polyether of general formula (d): 【Chemistry 4】 Formula (d) [In the formula, n=0 to 6, o=0 to 100, p=0 to 100, however o+p>0 R ６ =OH, alkyl or acetyl], Use additional recycled polyols, method.

15. 1. Use of a heat-cured flexible polyurethane foam in a mattress and / or cushion to provide a mattress and / or cushion having improved dimensional recovery after compression for a period of at least 20 hours, said heat-cured flexible polyurethane foam being obtainable by reaction of at least one compound of formula (1a) and at least one compound of formula (1b), (1a) and (1b) each being as defined in claim 1, with at least one polyol component and at least one isocyanate component in the presence of at least one blowing agent and at least one catalyst; The thermoset flexible polyurethane foam has a porosity of 1 to 6 scfm. use.

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