COMPRESSION SET

Description

[0001] The present invention lies in the field of polyurethane (PU) foams. It particularly relates to the provision of PU hot-cure flexible foam moldings, such as mattresses and / or pillows.

[0002] Molded PU hot-curing foam bodies, such as mattresses and / or pillows containing PU hot-curing foam, have long been known in the art and are widely used worldwide. There has been no shortage of attempts to continually improve such items. The need for optimization has not been extinguished to this day. DE102006038661A1 and EP2481770A2 disclose compositions for PU hot-curing foam bodies containing polyether siloxanes.

[0003] One problem associated with PU hot-curing flexible foam moldings is their transport and storage. PU hot-curing flexible foam moldings, such as mattresses, are very bulky and are therefore often compressed, especially compressed and vacuum-packed, for storage and transport purposes to save space. Large distributors are increasingly shipping certain mattresses in compressed and rolled form.

[0004] Such packaging is particularly common for mattresses. Vacuum packaging involves placing the mattress in a plastic bag, for example. The pre-packaged mattress is then placed in a press and compressed with the bag open. The air escapes. The open end of the bag is then sealed airtight. The resulting vacuum pack is then rolled up and placed in an outer bag. The mattress cannot expand again because the outer bag holds it in its rolled shape.

[0005] For example, to flatten a mattress as much as a machine can when rolling, you need between 40,000 and 250,000 Newtons, depending on the mattress. This corresponds to the weight of a mass of 4 to 25 tons.

[0006] As is immediately apparent, such a force applied during compression of PU hot-cure flexible foam moldings can lead to material fatigue. It is a very relevant problem to provide PU hot-cure flexible foam moldings that are capable of regaining their original dimensions even after prolonged compression.

[0007] Against this background, the specific object of the present invention was to provide PU hot-curing flexible foam molded bodies, such as in particular mattresses and / or pillows containing PU hot-curing flexible foam, which are well suited to regaining their original shape after compression over a period of at least 20 hours.

[0008] It was surprisingly found within the scope of this invention that the solution to this problem is made possible by the subject matter of the invention.

[0009] The subject of this invention is a PU hot-curing flexible foam molded body, preferably a mattress and / or pillow, wherein the PU hot-curing flexible foam was 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) and at least one blowing agent and at least one catalyst, wherein formula (1a): [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 with a= 2 to 10, preferably 2 to 8, particularly preferably 2 to 5 b= 25 to 200, preferably 40 to 150, particularly preferably 45 to 120 c= 2 to 40, preferably 2 to 30, particularly preferably 3 to 20 d= 0 to 10, preferably 0 to 8, particularly preferably 0 to 5 e= 0 to 5, preferably 0 to 3, particularly preferably 0 to 2 where: a + b + c + d + e > 48 R 1< = Me or R 2< R 2< = identical or different polyethers obtainable from the polymerization of ethylene oxide, propylene oxide and / or other alkylene oxides such as butylene oxide or styrene oxide, preferably polyethers of the general formula (c), where f = 0 - 6, preferably 0 - 4, particularly preferably 0 or 3 g = 0 to 150, preferably 3 to 100, particularly preferably 3 to 70 h = 0 to 150, preferably 0 to 100, particularly preferably 0 to 80 where g + h > 0 R 3< = OH, alkyl or acetyl, preferably OH, C 1 to C 6 alkyl or acetyl, particularly preferably OH, methyl, acetyl or butyl and where Formula (1b): [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 with i= 2 to 10, preferably 2 to 8, particularly preferably 2 to 5 j= 0 to 20, preferably 0 to 18, particularly preferably 0 to 15 k= 0 to 20, preferably 0 to 15, particularly preferably 0 to 10 l= 0 to 10, preferably 0 to 8, particularly preferably 0 to 5 m= 0 to 5, preferably 0 to 3, particularly preferably 0 to 2 where: i + j + k + l + m < 20 R 4< = Me or R 5< R 5< = identical or different polyethers obtainable from the polymerization of ethylene oxide, propylene oxide and / or other alkylene oxides such as butylene oxide or styrene oxide, preferably polyethers of the general formula (d), or alkyl C 3 to C 15 , where n = 0 - 6, preferably 0 - 4, particularly preferably 0 or 3 o = 0 to 100, preferably 0 to 50, particularly preferably 0 to 25 p = 0 to 100, preferably 0 to 50, particularly preferably 0 to 25 where o + p > 0 R 6< = OH, alkyl or acetyl, preferably OH, C 1 to C 6 alkyl or acetyl, particularly preferably OH, methyl, acetyl or butyl.

[0010] Formulas (1a) and (1b) are to be understood as average molecular formulas.

[0011] The illustrations Fig. 1 to 3show the results of roll deformation tests as a function of air permeability. The roll deformation test is explained in detail below. It allows the assessment of the dimensional recovery of the PU foam molded article after compression. 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. The air permeability is plotted on the abscissa. The figures Fig. 1 to Fig. 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 PU hot-cure flexible foam enables improved dimensional recovery of the PU foam molding after compression with comparable porosity.

[0012] Optionally, other conventional additives, active substances, and excipients can also be advantageously used. Mattresses are particularly preferred within the meaning of this invention. This also advantageously applies to all of the following preferred embodiments.

[0013] Advantageously, the PU hot-cure flexible foam molded body thus provided using the compounds of formula (1a) and (1b) is well suited to regain its original shape even after prolonged compression over a period of at least 20 hours.

[0014] A further advantage is that the PU hot-cure flexible foam moldings in question are particularly low in emissions with regard to low-molecular-weight linear and cyclic siloxanes.

[0015] For the purposes of the present invention, "low emissions" with regard to low-molecular-weight siloxanes particularly encompasses that the PU hot-cure flexible foam resulting from the invention has a siloxane emission of ≥ 0 µg / m 3 and ≤ 500 µg / m 3 , preferably ≤ 200 µg / m 3 , particularly preferably ≤ 100 µg / m 3 , determined accordingly using the test chamber method based on DIN standard DIN EN ISO 16000-9:2008-04, 24 hours after test chamber loading. This method is described in detail in EP 3205680A1, paragraph

[0070] , which is hereby incorporated by reference.

[0016] A further advantage is that the PU hot-cure flexible foam moldings in question can also meet emission specifications such as CertiPur. Low emissions according to CertiPur means that the total emissions of volatile organic compounds (TVOC) are less than 500 µg / m³. Further technical information on the requirements for the CertiPUR standard (version 1 July 2017) can be found at: https: / / www.europur.org / images / CertiPUR_Technical_Paper_-_Full_Version_-_2017.pdf. This latter document (version 1 July 2017) can also be requested directly from EUROPUR, Avenue de Cortenbergh 71, B-1000 Brussels, Belgium.

[0017] PU foams (polyurethane foams) and their production are well known to those skilled in the art and require no further explanation. Molded bodies within the meaning of the invention are shaped bodies of various shapes. Preferred shapes within the meaning of the invention include geometries such as spheres, cuboids, cylinders, etc. PU foam molded bodies within the meaning of the invention are therefore shaped bodies made of polyurethane foam. Particularly preferred PU hot-cure flexible foam molded bodies within the meaning of this invention are mattresses and / or pillows, as well as foam blocks in general.

[0018] Mattresses themselves and their production are well known. They usually consist of a mattress core, e.g. comprising foam, latex, natural products and / or spring core, and a cover surrounding the mattress. The same applies to pillows. Mattress and / or pillow within the meaning of this application means that at least one section made of PU hot-cure flexible foam is contained in the mattress and / or pillow. Preferably, it means that at least part of the mattress and / or pillow is made of PU hot-cure flexible foam. Based on the total weight of the mattress and / or pillow, this part can make up at least 1% by weight, 5% by weight, or 25% by weight, preferably at least 50% by weight, in particular at least 75% by weight. It is also possible for the mattress and / or pillow, apart from the cover, to be made entirely of PU hot-cure flexible foam.

[0019] The production of polyurethane foam is generally known per se. It is produced by the well-proven reaction of at least one polyol component and at least one isocyanate component in the presence of at least one blowing agent (e.g., water) in a polyaddition reaction. For the present invention, it is essential that the foam is a hot-cure flexible PU foam, and that this reaction takes place in the presence of at least one compound of formula (1a) and at least one compound of formula (1b), as defined above.

[0020] The polyurethane foam according to the invention is a polyurethane hot-cure flexible foam, or a combination of these PU flexible foams is used, e.g., two of these PU flexible foams. The term "PU hot-cure flexible foam" is known per se to those skilled in the art; it is a well-established technical term that is accordingly established in the specialist world, but it will nevertheless be briefly explained here.

[0021] Flexible PU foams are elastic and deformable, and usually open-celled. This allows air to escape easily upon compression. There are also rigid PU foams, which are inelastic and usually closed-celled, used for insulation purposes and are not the focus of the present invention. A wide variety of flexible PU foams exist. Ester foams (made from polyester polyols), hot-cure PU foams, and cold-cure PU foams are known to those skilled in the art. Viscoelastic flexible PU foams represent a relatively new type that falls under the category of hot-cure PU foams. For the purposes of the present invention, viscoelastic flexible PU foams are therefore encompassed by the term "hot-cure PU foams." The key difference between hot-cure PU foam and cold-cure PU foam lies in their different mechanical properties.The differentiation between PU hot-cure flexible foams and PU cold-cure flexible foams can be made primarily by their rebound resilience, also known as "ball rebound" (BR) or "resilience." One method for determining rebound resilience is described, for example, in DIN EN ISO 8307:2008-03. A steel ball of a specified mass is dropped onto the specimen from a specific height, and the rebound height is then measured as a percentage of the drop height. The relevant values ​​for PU cold-cure flexible foams are preferably in the range of > 50%. PU cold-cure flexible foams are therefore often referred to as HR foams (HR = High Resilience). In contrast, PU hot-cure flexible foams exhibit rebound values ​​of preferably 1% to a maximum of 50%.Therefore, within the scope of a preferred embodiment of the invention, the PU hot-cure flexible foams according to the invention have rebound values ​​of preferably 1% to a maximum of 50%, determinable according to DIN EN ISO 8307:2008-03. A further mechanical criterion is the SAG or comfort factor. Here, a foam sample is compressed according to DIN EN ISO 2439, and the ratio of the compressive stress at 65% and 25% compression is measured. PU cold-cure flexible foams have a SAG or comfort factor of preferably > 2.5. PU hot-cure flexible foams have one of preferably < 2.5. Therefore, within the scope of a preferred embodiment of the invention, the PU hot-cure flexible foams according to the invention have a SAG or comfort factor of preferably < 2.5, determinable as previously stated.

[0022] A precise definition of the properties can also be found in the "PUR Cold Foam" data sheet of the German Foamed Plastics and Polyurethane Association, reference KAL20160323, dated March 23, 2016. (https: / / www.fsk-vsv.de / wpcontent / uploads / 2017 / 03 / Produktbeschreibunq-PUR-Kaltschaum.pdf ).

[0023] The two names PU hot-cure flexible foam and PU cold-cure flexible foam are explained by the historical development of PU technology and do not necessarily mean that different temperatures occur during the foaming process.

[0024] The different mechanical properties of PU hot-cure flexible foams and PU cold-cure flexible foams result from differences in the formulation used to manufacture the foams. In PU cold-cure flexible foams, highly reactive polyols with primary OH groups and average molecular weights > 4000 g / mol are usually used. Low molecular weight crosslinkers are also used optionally, although the function of the crosslinker can also be taken over by higher-functional isocyanates. In contrast, PU hot-cure flexible foams usually predominantly use less reactive polyols with secondary OH groups and an average molecular weight < 4000 g / mol. In PU cold-cure flexible foams, the reaction of the isocyanate groups with the hydroxyl groups already occurs during the expansion phase of the foam (CO2 formation from NCO and H2O).This rapid polyurethane reaction usually leads to a relatively high inherent stability of the foam during the foaming process via an increase in viscosity. As a result, other foam stabilizers with different siloxane structures are required compared to PU hot-cure flexible foams, which is why the present invention does not extend to PU cold-cure flexible foams. PU cold-cure flexible foams are usually highly elastic foams. Due to their high inherent stability, the cells are generally not sufficiently open at the end of the foaming process, and the cell structure still needs to be mechanically compressed. In contrast, this is normally not necessary with PU hot-cure flexible foams. Significantly stronger stabilization through high-molecular-weight polyethersiloxane structures is important here. Accordingly, highly active stabilizers are defined by formula (1a).In the case of PU hot-curing flexible foams according to the invention, in addition to a stabilizer according to formula (1a), a silicone compound of formula (1b) is also used during production.

[0025] Open-cell PU hot-cure foams preferably have a gas permeability (also called "porosity") in the range of 1 to 6.5 scfm. This is measured by applying a pressure differential and measuring the air flow volume according to ASTM D 3574 (2011-00). The method is explained in detail in the examples section (see there: Porosity determined by the flow-through method). Scfm (standard cubic feet per minute) stands for standard cubic feet per minute measured under standard conditions (23°C, 100 kPa).

[0026] Depending on the application, PU hot-cure flexible foams preferably have a density between 8 and 80 kg / m³. In particular, when using such PU hot-cure flexible foams as mattresses, mattress components, and / or pillows, a distinction is made according to regional needs, requirements, and consumer preferences. The preferred PU hot-cure flexible foam for mattress applications preferably has a density of 25–30 kg / m³.

[0027] A special class of PU hot-cure flexible foams is viscoelastic PU foams. These are also known as memory foams and are characterized by both low rebound resilience (preferably < 10%) and slow, gradual recovery after compression (recovery time preferably 2-10 seconds). Such materials are well known in the art and are particularly valued for their energy and sound-absorbing properties. Typical viscoelastic flexible foams usually have lower porosity and a high density (or high density (DV)) compared to other PU hot-cure flexible foams.Pillows, with a density of preferably 30 - 50 kg / m 3<, are at the lower end of the density scale typical for viscoelastic foams, whereas viscoelastic PU foams for mattresses preferably have a density in the range of 50 - 130 kg / m 3<.

[0028] In hot-cure flexible PU foams, the hard (high glass transition temperature) and soft (low glass transition temperature) segments orient themselves toward each other during the reaction and then spontaneously separate to form morphologically distinct phases within the bulk polymer. Such materials are also referred to as "phase-separated" materials. The glass transition temperature of viscoelastic foams is preferably between -20 and +15 °C. The glass transition temperature of other hot-cure flexible PU foams and cold-cure flexible PU foams, in contrast, is usually below -35 °C. Such "structural viscoelasticity" in open-cell viscoelastic hot-cure flexible PU foams, which is essentially based on the glass transition temperature of the polymer, must be distinguished from a pneumatic effect. In the latter case, the cell structure is relatively closed (low porosity).Due to the low air permeability, the air flows back in only slowly after compression, which results in a slower recovery.

[0029] With regard to the foam stabilizers used, compounds of formula (1a) are used for viscoelastic PU foams within the scope of the invention. Adding the compound of formula (1b) results in a particular improvement in the roll compression properties, which is in accordance with the invention. When PU hot-cure flexible foams are described below, this includes viscoelastic PU flexible foams, even if not specifically mentioned.

[0030] In addition to their density, various PU hot-curing foams are often classified for specific applications according to their compression hardness, also known as load-bearing capacity. For example, the compression hardness CLD (Compression Load Deflection), 40% according to DIN EN ISO 3386-1:2015-10, for PU hot-curing foams is preferably in the range of 2.0 - 8.0 kPa. Viscoelastic polyurethane foams preferably have values ​​of 0.1 - 5.0 kPa, especially 0.5 - 2.5 kPa.

[0031] According to a preferred embodiment of the invention, the hot-cure flexible PU foams to be used according to the invention have the following preferred properties with regard to resilience, density and / or porosity, namely a resilience of 1 to 50%, measured according to DIN EN ISO 8307:2008-03, and / or a density of 5 to 150 kg / m 3 and / or a porosity of 1 to 6 scfm, in particular 1.5 to 4.5 scfm, particularly preferably 1.75 to 4.25 scfm. Particularly preferably, all three criteria with regard to resilience, density and / or porosity, as just quantified, are met. In particular, the hot-cure flexible PU foam used according to the invention has a compression hardness CLD, 40% according to DIN EN ISO 3386-1:2015-10 of 0.1 to 8.0 kPa.

[0032] Hot-cure flexible PU foams and their production are known per se. Within the meaning of this invention, in a preferred embodiment, hot-cure flexible PU foam is characterized in particular by having a compression hardness CLD, 40% according to DIN EN ISO 3386-1:2015-10 of 2.0-8.0 kPa, and / or a rebound resilience of 1-50%, measured according to DIN EN ISO 8307:2008-03, and / or a density of 8 to 80 kg / m³ and / or a porosity of 1 to 6 scfm, in particular 1.5 to 4.5 scfm, particularly preferably 1.75 to 4.25 scfm. One possible production method is described, for example, in EP 2 481 770 A2 or EP 2 182 020 A1.Within the meaning of this invention, viscoelastic PU flexible foam is characterized in a preferred embodiment in particular by the fact that it has a glass transition temperature between -20 and +15 °C and / or a compression hardness CLD, 40% according to DIN EN ISO 3386-1:2015-10 of 0.1 - 5.0 kPa, in particular 0.5 - 2.5 kPa, and / or a rebound resilience of < 10%, measured according to DIN EN ISO 8307:2008-03, and / or a density of 30 to 130 kg / m 3< and / or a porosity (after pressing on the foam) of 1 to 6 scfm, in particular 1.5 to 4.5 scfm, particularly preferably 1.75 to 4.25 scfm. One possible production method is 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 is a glass transition region that extends over a specific temperature range.The values ​​given therefore represent averages.

[0033] Within the scope of a preferred embodiment of the invention, the PU hot-cure flexible foam molded body according to the invention, in particular the mattress according to the invention, has a height of at least 1 cm to a maximum of 50 cm, a width of at least 20 cm to a maximum of 300 cm, and a length of at least 20 cm to a maximum of 300 cm. Preferred dimensions are, for example, heights in the range of 5 cm to 40 cm, widths in the range of 70 cm to 200 cm, and lengths in the range of 150 cm to 220 cm. The PU foam molded body according to the invention, in particular the cushion according to the invention, can, within the scope of a preferred embodiment of the invention, also have a height of at least 1 cm to a maximum of 40 cm, as well as a width of at least 15 cm to a maximum of 200 cm, and a length of at least 15 cm to a maximum of 200 cm, with preferred dimensions being, for example, heights in the range from 2 cm to 30 cm, widths in the range from 15 cm to 50 cm, lengths in the range from 15 cm to 50 cm.

[0034] According to a further preferred embodiment of the invention, the PU hot-cure flexible foam molded body is a mattress and is preferably designed as a multi-zone mattress. The different zones differ in particular in their respective hardness. Such multi-zone mattresses and their production are known per se. They are widely sold commercially. In particular, the mattress has up to seven zones of different hardness, which extend across the mattress's longitudinal direction and are designed in the corresponding width. If the mattress has different hardness zones distributed over its surface, which are formed in particular by incisions and / or cavities in the mattress, this represents a further preferred embodiment of the invention.

[0035] According to a further preferred embodiment of the invention, the PU hot-cure flexible foam molded body can also be a PU cold foam mattress, a viscoelastic PU flexible foam mattress, a PU hot-cure flexible foam mattress, a PU gel foam mattress, a latex mattress, or a box spring mattress, each containing at least one part made of a PU hot-cure flexible foam according to the invention. These mattress types are known per se to those skilled in the art and are also marketed worldwide under these names. Mattresses made solely of PU hot-cure flexible foam are usually referred to simply as foam mattresses on the market. The term "mattress" according to the invention, within the meaning of this invention, also includes corresponding mattress pads and underlays.

[0036] According to a preferred embodiment of the invention, the PU hot-curing flexible foam molded body, preferably the mattress, is characterized in that the PU hot-curing flexible foam molded body has been compressed by at least 20%, preferably at least 30%, in particular at least 40%, based on its initial volume and is held in compressed form by an auxiliary means, in particular packaging means, for at least 20 hours.

[0037] Suitable aids, in particular packaging materials, are bags and / or films, such as those known from the field of rolled mattresses. The bags and / or films can be closed by any means, such as a clip, adhesive tape, or welding. The function of the aids is to be able to maintain the compressed shape until the user of the PU hot-cure flexible foam molded article wishes to use it normally again. After removal of the aid, in particular the packaging material, the compressed molded article expands again and, in the best case, regains its original shape and size. The present invention enables improved dimensional recovery after compression over a period of at least 20 hours.

[0038] According to a further preferred embodiment, the PU hot-cured flexible foam molded body is compressed and vacuumed, and in particular it is a rolled mattress that is vacuumed and compressed.

[0039] The provision of the various PU hot-curing flexible foams usable within the scope of this invention is known per se and all proven processes can be used, with the special feature that the PU hot-curing flexible foam production takes place in the presence of at least one compound of formula (1a) and at least one compound of formula (1b).

[0040] The production of corresponding hot-cure flexible PU foams requires no further explanation per se; nevertheless, some preferred details for producing the PU foam used according to the invention are mentioned below. The inventive subject matter is described below by way of example, without the invention being limited to these exemplary embodiments. Where ranges, general formulas, or classes of compounds are specified below, these are intended to encompass not only the corresponding ranges or groups of compounds explicitly mentioned, but also all subranges and subgroups of compounds that can be obtained by removing individual values ​​(ranges) or compounds.If documents are cited within the scope of this description, their content, particularly with regard to the facts in connection with which the document was cited, is intended to be fully incorporated into the disclosure of the present invention. Percentages are by weight unless otherwise stated. Mean values ​​given below are weight averages unless otherwise stated. If parameters determined by measurement are given below, the measurements were carried out at a temperature of 23°C and a pressure of 100 kPa unless otherwise stated. Unless otherwise stated, compression of the foam in the sense of this invention means that the foam is preferably compressed by at least 20%, based on its initial volume, in particular over a period of at least 20 hours.

[0041] Polyurethanes are understood here to mean all reaction products derived from isocyanates, especially polyisocyanates, and corresponding isocyanate-reactive molecules. This includes, among others, polyisocyanurates, polyureas, and isocyanate or polyisocyanate reaction products containing allophanate, biuret, uretdione, uretimine, or carbodiimide. It goes without saying that the person skilled in the art will select the necessary substances, such as isocyanates, polyols, stabilizers, surfactants, etc., for the production of the various flexible polyurethane foams, for example, hot-cure flexible PU foams, in order to obtain the desired polyurethane type, especially polyurethane foam type. Further information on the starting materials, catalysts, auxiliaries, and additives that can be used can be found, for example, in the Kunststoffhandbuch, Volume 7, Polyurethane, Carl-Hanser-Verlag Munich, 1st edition 1966, 2nd edition, 1983, and 3rd edition, 1993.The following compounds, components and additives are mentioned only as examples and can be replaced and / or supplemented by other substances known to the person skilled in the art.

[0042] The isocyanate components used are preferably one or more organic polyisocyanates with two or more isocyanate functions. The polyol components used are preferably one or more polyols with two or more isocyanate-reactive groups.

[0043] Isocyanates suitable as isocyanate components within the meaning of this 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. Isocyanates are preferably used in a range of 60 to 350 mol%, particularly preferably in a range of 60 to 140 mol%, relative to the sum of the isocyanate-consuming components.

[0044] Examples which may be mentioned here are alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene radical, such as 1,12-dodecane diisocyanate, 2-ethyltetramethylene-1,4-diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, tetramethylene-1,4-diisocyanate, and preferably hexamethylene-1,6-diisocyanate (HMDI), cycloaliphatic diisocyanates such as cyclohexane-1,3- and 1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI for short), 2,4- and 2,6-hexahydrotoluene diisocyanate and the corresponding isomer mixtures, and preferably aromatic di- and polyisocyanates such as 2,4- and 2,6-toluene diisocyanate (TDI) and the corresponding isomer mixtures, Mixtures of 2,4'- and 2,2'-diphenylmethane diisocyanates (MDI) and polyphenylpolymethylene polyisocyanates (crude MDI) and mixtures of crude MDI and toluene diisocyanates (TDI).The organic di- and polyisocyanates can be used individually or in the form of their mixtures.

[0045] It is also possible to use isocyanates that have been modified by the incorporation of urethane, uretdione, isocyanurate, allophanate and other groups, so-called modified isocyanates.

[0046] Particularly suitable organic polyisocyanates and therefore particularly preferred are various isomers of toluene diisocyanate (2,4- and 2,6-toluene diisocyanate (TDI), in pure form or as isomer mixtures of different compositions), 4,4'-diphenylmethane diisocyanate (MDI), the so-called "crude MDI" or "polymeric MDI" (containing not only the 4,4'- but also the 2,4'- and 2,2'-isomers of MDI and higher-nuclear products) as well as the binuclear product known as "pure MDI" consisting predominantly of 2,4'- and 4,4'-isomer mixtures or their prepolymers. Examples of particularly suitable isocyanates are listed, for example, in EP 1712578, EP 1161474, WO 00 / 58383, US 2007 / 0072951, EP 1678232 and WO 2005 / 085310, which are incorporated herein by reference in their entirety.

[0047] Polyols suitable as polyol components within the meaning of the present invention are all organic substances containing several isocyanate-reactive groups, preferably OH groups, and preparations thereof. Preferred polyols are all polyether polyols and / or hydroxyl-containing aliphatic polycarbonates commonly used for the production of polyurethane systems, in particular polyurethane foams, especially polyether polycarbonate polyols and / or filler polyols (polymer polyols) such as SAN, PHD, and PIPA polyols, which are characterized by containing solid organic fillers up to a solids content of 40% or more in dispersed distribution, and / or autocatalytic polyols containing catalytically active functional groups, in particular amino groups, and / or polyols of natural origin, so-called "natural oil-based polyols" (NOPs).Polyols for PU hot-cure flexible foam preferably have a functionality of 1.8 to 8 and number-average molecular weights in the range of 500 to 4000 g / mol. Polyols with OH numbers in the range of 25 to 400 mg KOH / g are typically used. The number-average molecular weights are usually determined by gel permeation chromatography (GPC), particularly with polypropylene glycol as the reference substance and tetrahydrofuran (THF) as the eluent. The OH numbers can be determined, in particular, according to DIN standard DIN 53240:1971-12. Depending on the required properties of the resulting foams, appropriate polyols can be used, as described, for example, in US 2007 / 0072951 A1, WO 2007 / 111828, US 2007 / 0238800, US 6359022, or WO 96 / 12759. Further polyols are known to the person skilled in the art and can be found, for example, in EP-A-0380993 or US-A-3346557.

[0048] According to a preferred embodiment of the invention, in particular for the production of flexible slabstock foams, polyether alcohols are used which have secondary hydroxyl groups, preferably above 50%, particularly preferably above 90%, in particular those with a propylene oxide block or random propylene and ethylene oxide blocks at the chain end, or those based solely on propylene oxide blocks. Such polyether alcohols preferably have a functionality of 2 to 8, particularly preferably 2 to 4, number-average molecular weights in the range from 500 to 4000 g / mol, preferably 800 to 4000 g / mol, particularly preferably 2500 to 4000 g / mol, and typically OH numbers in the range from 20 to 100 mg KOH / g, preferably 40 to 60 mg KOH / g.

[0049] According to a further preferred embodiment of the invention, di- and / or trifunctional polyether alcohols are also used, which contain primary hydroxyl groups, preferably above 50%, particularly preferably above 80%, especially those with an ethylene oxide block at the chain end. Polyols for cold-cure flexible PU foams ("HR polyols") belong to this category if the molecular weight is > 4000 g / mol. Depending on the required properties of this preferred embodiment of the invention, in particular for the production of the above-mentioned hot-cure flexible PU foams, in addition to the polyether alcohols described here, it is preferable to use other polyether alcohols that contain primary hydroxyl groups and are predominantly based on ethylene oxide, in particular with a proportion of ethylene oxide blocks of > 70%, preferably > 90% ("hypersoft polyol").All polyether alcohols described in this preferred embodiment preferably have a functionality of 2 to 8, particularly preferably 2 to 5, number-average molecular weights in the range from 500 to 8000 g / mol, preferably 500 to 7000 g / mol, and typically OH numbers in the range from 10 to 100 mg KOH / g, preferably 20 to 60 mg KOH / g. In the preferred embodiment, polyols with primary OH functions are not used alone in the inventive hot-cure flexible PU foams, but rather in combination with polyols with secondary OH groups. In the preferred embodiment, polyols with primary OH functions are used in only <50% of the combination.

[0050] According to a further preferred embodiment of the invention, autocatalytic polyols are used.

[0051] According to a further preferred embodiment of the invention, particularly for the production of viscoelastic PU flexible foams, mixtures of various, preferably two or three, polyfunctional polyether alcohols are preferably used. The polyol combinations used here typically consist of a low-molecular-weight "crosslinker" polyol with high functionality, preferably with an OH number of 100 to 400 mg KOH / g, and / or a conventional high-molecular-weight slabstock flexible foam or HR polyol and / or a "hypersoft" polyether polyol, preferably with an OH number of 20 to 40 mg KOH / g, with a high ethylene oxide content and cell-opening properties. If HR polyols are also used in the viscoelastic foam formulation, their mass fraction of the polyol mixture is <50%.

[0052] According to a further preferred embodiment of the invention, recycled polyols are used.

[0053] A PU hot-cure flexible foam molded article obtained with the concomitant use of recycled polyols accordingly corresponds to a preferred embodiment of the invention. The use of recycled polyols normally leads to problems with regaining the shape after roll compression. Within the scope of the present invention, it was surprisingly 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, makes it possible to overcome this problem.

[0054] Recycled polyols are polyols obtained from PU foam waste. This can be production waste from PU hot-cure flexible foam production or from PU hot-cure flexible foam waste after consumer use (e.g., old mattresses). In both cases, the PU foam is liquefied through chemical processes. Various processes, such as glycolysis, hydrolysis, or acidolysis, are possible. The resulting liquid recycled polyol can then be reused to produce PU hot-cure flexible foam. However, such PU hot-cure flexible foams are often characterized by significantly disadvantageous mechanical properties, such as resistance to rolling compression. Further information on the use of recycled polyols in PU hot-cure flexible foams can be found, among others, in the following research report from the Federal Ministry of Education and Research (BMBF): https: / www.cleaner-production.de / fileadmin / assets / bilder / BMBF-Projekte / 01RI05070-075 - Final Report.pdf.

[0055] The use of recycled polyols within the scope of the invention corresponds to a preferred embodiment of the invention for all claimed subject matters.

[0056] A preferred ratio of isocyanate and polyol, expressed as an index of the formulation, ie as the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (e.g., OH groups, NH groups) multiplied by 100, is in the range from 50 to 140, preferably 70 to 130, particularly preferably 85 to 125. An index of 100 represents a molar ratio of the reactive groups of 1 to 1.

[0057] Catalysts can also be used to produce the hot-cure flexible PU foams of the invention. For the purposes of this invention, the term "catalysts" encompasses all prior art compounds that are capable of catalyzing isocyanate reactions and / or are used as catalysts, co-catalysts, or activators in the production of polyisocyanate reaction products, in particular polyurethane foams.

[0058] Suitable catalysts are known; they are, in particular, substances that catalyze the gel reaction (isocyanate-polyol), the blowing reaction (isocyanate-water), and / or the di- or trimerization of the isocyanate. Such catalysts are preferably nitrogen-containing compounds, especially amines and ammonium salts, and / or metal-containing compounds.

[0059] Beispiele für geeignete stickstoffhaltige Verbindungen als Katalysatoren im Sinne der vorliegenden Erfindung sind die Amine Triethylamin, Triethanolamin, Diethanolamin, N,N-Dimethylcyclohexylamin, N,N-Dicyclohexylmethylamin, N,N-Dimethylaminoethylamin, N,N,N',N'-Tetramethylethan-1,2-diamin, N,N,N',N'-Tetramethylpropan-1,3-diamin, N,N,N',N'-Tetramethylbutan-1,4-diamin, N,N,N',N'-Tetramethylhexan-1,6-diamin, N-[2-(Dimethylamino)ethyl]-N,N',N'-trimethyl-1,2-ethandiamin, 2-[(2-(Dimethylamino)ethyl)methylamino]ethanol, N',N'-Dimethylpropan-1,3-diamin, N',N'-Diethyl-propan-1,3-diamin, 1-(2-Aminoethyl)pyrrolidin, 1-(3-Aminopropyl)pyrrolidin, 1-[3-(Dimethylamino)-propyl-(2-hydroxypropyl)amino]propan-2-ol, 2-[[3-(Dimethylamino)propyl]methylamino]ethanol, 3-(2-Dimethylamino)ethoxy)propylamin, N-[3-(Dimethylamino)propyl]-N',N'-dimethylpropan-1,3-diamin, N'-[3-(Dimethylamino)propyl]-N,N,N'-trimethylpropan-1,3-diamin, 1-[Bis[3-(dimethylamino)propyl]amino]-2-propanol, N,N-Bis[3-(dimethylamino)propyl]-N',N'-dimethylpropan-1,3-diamin, 1,4-Diazabicyclo[2.2.2]octan, 1,4-Diazabicyclo[2.2.2]octan-2-methanol, 1,2-Dimethylimidazol, N-(2-Hydroxypropyl)imidazol, 2-Methyl-1-(2-methylpropyl)imidazol, N-(3-Aminopropyl)imidazol, N-Methylimidazol, 1-(3-Aminopropyl)-2-methyl-1H-imidazol, N-Ethylmorpholin, N-Methylmorpholin, 2,2,4-Trimethyl-2-silamorpholin, N-Ethyl-2,2-dimethyl-2-silamorpholin, N-(2-Aminoethyl)morpholin, N-(2-Hydroxyethyl)morpholin, 2,2'-Dimorpholinodiethylether, N,N'-Dimethylpiperazin, N-(2-Hydroxyethyl)piperazin, N-(2-Aminoethyl)piperazin, N,N-Dimethylbenzylamin, N,N-(Dimethylamino)ethanol, N,N-(Diethyl-amino)ethanol, 1-(2-Hydroxyethyl)pyrrolidin, 3-Dimethylamino-1-propanol, 1-(3-Hydroxypropyl)-pyrrolidin, 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-methyl-1,3-propandiamin, 1,3,5-Tris[3-(dimethylamino)propyl]hexahydro-1,3,5-triazin, 1,8-Diazabicyclo[5.4.0]undec-7-en, 1,5-Diazabicyclo[4.3.0]non-5-en, 1,5,7-Triazabicyclo[4.4.0]dec-5-en, N-Methyl-1,5,7-triazabicyclo[4.4.0]dec-5-en, 1,4,6-Triazabicyclo[3.3.0]oct-4-en, 1,1,3,3-Tetramethylguanidin, 2-tert-Butyl-1,1,3,3-tetramethylguanidin, Guanidin, 1,1'-[(3-{bis[3-(dimethylamino)-propyl]amino}propyl)imino]dipropan-2-ol, (3-Aminopropyl)bis[3-(dimethylamino)propyl]amin, 3-(Dimethylamino)propylharnstoff, 1,3-Bis[3-(dimethylamino)propyl]harnstoff, 3-Dimethylamino-N,N-dimethylpropanamid, 6-(Dimethylamino)hexan-1-ol und 2,4,6-Tris[(dimethylamino)methyl]phenol.,

[0060] Such catalysts and / or mixtures are sold, for example, under the name Jeffcat ®< ZF-10, Lupragen ®< DMEA, Lupragen ®< API, Toyocat ®< RX 20 and Toyocat ®< RX 21, DABCO ®< RP 202, DABCO ®< RP 204, DABCO ®< NE 300, DABCO ®< NE 310, DABCO ®< NE 400, DABCO ®< NE 500, DABCO ®< NE 600, DABCO ®< NE 650, DABCO ®< NE 660, DABCO ®< NE 740, DABCO ®< NE 750, DABCO ®< NE 1060, DABCO ®< NE 1080, DABCO ®< NE 1082 and DABCO ®< NE 2039, Niax ®< EF 860, Niax ®< EF 890, Niax ®< EF 700, Niax ®< EF 705, Niax ®< EF 708, Niax ®< EF 600, Niax ®< EF 602, Kosmos ®< 54, Kosmos ®< EF, and Tegoamin ®< ZE 1 are commercially available.

[0061] Suitable metal-containing compounds as catalysts can be selected, for example, from the group of organometallic or organometallic compounds, organometallic or organometallic salts, organic metal salts, inorganic metal salts, and from the group of charged or uncharged metal-containing coordination compounds, in particular metal chelate complexes. For the purposes of this invention, the term "organometallic or organometallic compounds" encompasses, in particular, the use of metal-containing compounds that have a direct carbon-metal bond, also referred to herein as organometallic compounds (e.g., organotin compounds) or organometallic or organometallic compounds (e.g., organotin compounds).The term "organometallic or organometallic salts" in the sense of this invention includes in particular the use of organometallic or organometallic compounds with salt character, i.e. ionic compounds in which either the anion or cation is of organometallic nature (e.g. organotin oxides,.

[0062] Organotin chlorides or organotin carboxylates). The term "organic metal salts" for the purposes of this invention particularly encompasses the use of metal-containing compounds that do not have a direct carbon-metal bond and are simultaneously metal salts in which either the anion or the cation is an organic compound (e.g., tin(II) carboxylates). The term "inorganic metal salts" for the purposes of this invention particularly encompasses the use of metal-containing compounds or metal salts in which neither the anion nor the cation is an organic compound, e.g., metal chlorides (e.g., tin(II) chloride), pure or mixed metal oxides (e.g., tin oxides) containing multiple metals, and / or metal silicates or aluminosilicates.For the purposes of this invention, the term "coordination compound" encompasses, in particular, the use of metal-containing compounds composed of one or more central particles and one or more ligands, where the central particles are charged or uncharged metals (e.g., metal or tin-amine complexes). For the purposes of this invention, the term "metal-chelate complexes" encompasses, in particular, the use of metal-containing coordination compounds that have 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).Suitable metal-containing compounds, in particular as defined above, as catalysts in the sense of the present invention can, for example, be selected from all metal-containing 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, in particular sodium, potassium, magnesium, calcium, titanium, zirconium, molybdenum, tungsten, zinc, aluminum, tin and / or bismuth, particularly preferably tin, bismuth, zinc and / or potassium.

[0063] Suitable metal-containing coordination compounds are, for example, all metal acetylacetonates such as nickel(II) acetylacetonate, zinc(II) acetylacetonate, copper(II) acetylacetonate, molybdenum dioxoacetylacetonate, all iron acetylacetonates, all cobalt acetylacetonates, all zirconium acetylacetonates, all titanium acetylacetonates, all bismuth acetylacetonates and all tin acetylacetonates. Particularly suitable organometallic salts and organic metal salts, in particular as defined above, as catalysts in the context of the present invention are, for example, organotin, tin, zinc, bismuth and potassium salts, in particular corresponding metal carboxylates, alkoxides, thiolates and mercaptoacetates, such as, for example, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate (DBTDL), dioctyltin dilaurate (DOTDL), dimethyltin dineodecanoate, dibutyltin dineodecanoate, dioctyltin dineodecanoate, dibutyltin dioleate, dibutyltin bis-n-laurylmercaptide, dimethyltin bis-n-laurylmercaptide,Monomethyltin tris-2-ethylhexyl mercaptoacetate, dimethyltin bis-2-ethylhexyl mercaptoacetate, dibutyltin bis-2-ethylhexyl mercaptoacetate, dioctyltin bis-isooctyl 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-ethyl-hexanoate (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 metal-containing catalysts are generally preferably selected so that they do not exhibit any unpleasant odor, are essentially toxicologically safe, and the resulting polyurethane systems,In particular, polyurethane foams have the lowest possible catalyst-related emissions.

[0064] In addition to amines and metal-containing compounds, ammonium salts can also be used as catalysts. Suitable catalysts include ammonium formate and / or ammonium acetate.

[0065] Suitable catalysts are mentioned, for example, in DE 102007046860, EP 1985642, EP 1985644, EP 1977825, US 2008 / 0234402, EP 0656382 B1 and US 2007 / 0282026 A1 and the patents cited therein.

[0066] Suitable amounts of catalysts used depend on the type of catalyst and are preferably in the range from 0.01 to 10.0 pphp, particularly preferably in the range from 0.02 to 5.00 pphp (= parts by weight based on 100 parts by weight of polyol).

[0067] All substances known in the art which are used in the production of polyurethanes, in particular PU hot-cure flexible foams, can be used as optional additives, such as, for example, blowing agents, preferably water to form CO2 and, if necessary, further physical blowing agents, crosslinkers and chain extenders, stabilizers against oxidative degradation (so-called antioxidants), flame retardants, surfactants, biocides, cell-refining additives, cell openers, solid fillers, antistatic additives, nucleating agents, thickeners, dyes, pigments, color pastes, fragrances, emulsifiers, buffer substances and / or catalytically active substances, in particular as defined above.

[0068] In the production of hot-cure flexible PU foams, water is typically used as a blowing agent. The preferred amount of water is 0.10 to 10.0 pphp (pphp = parts by weight based on 100 parts by weight of polyol).

[0069] Suitable physical blowing agents can also be used. These include, for example, liquefied CO2 and highly 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.

[0070] In addition to water and physical blowing agents, other chemical blowing agents can also be used that react with isocyanates to release gas, such as formic acid.

[0071] Optional crosslinkers and optional chain extenders are low-molecular-weight, multifunctional compounds that are reactive toward isocyanates. Suitable examples include hydroxyl- or amine-terminated substances such as glycerin, neopentyl glycol, 2-methyl-1,3-propanediol, triethanolamine (TEOA), diethanolamine (DEOA), and trimethylolpropane. The concentration used is typically between 0.1 and 5 parts per 100 parts of polyol, but may vary depending on the formulation.

[0072] Suitable optional stabilizers against oxidative degradation, so-called antioxidants, are preferably all common radical scavengers, peroxide scavengers, UV absorbers, light stabilizers, and complexing agents for metal ion impurities (metal deactivators). Compounds of the following substance classes, or substance classes containing the following functional groups, are preferably used, with particular preference given to those substituents on the respective parent structures that have isocyanate-reactive groups: 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, benzoic acids and benzoates, phenols, especially containing tert-butyl and / or methyl substituents on the aromatic ring, benzofuranones, diarylamines, triazines, 2,2,6,6-tetramethylpiperidines, hydroxylamines, alkyl and aryl phosphites, sulfides, zinc carboxylates, and diketones.

[0073] Suitable optional flame retardants within the meaning of this invention are all substances that are considered suitable according to the prior art. Preferred flame retardants are, for example, liquid organic phosphorus compounds, such as halogen-free organic phosphates, e.g., triethyl phosphate (TEP), halogenated phosphates, e.g., tris(1-chloro-2-propyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP), and organic phosphonates, e.g., dimethylmethanephosphonate (DMMP), dimethylpropanephosphonate (DMPP), or solids such as ammonium polyphosphate (APP) and red phosphorus. Furthermore, halogenated compounds, e.g., halogenated polyols, and solids such as expandable graphite and melamine are suitable as flame retardants.

[0074] To stabilize the rising foam mixture and to influence the foam properties of polyurethane foams, organomodified siloxanes are commonly used in the production of hot-cure flexible PU foams. Suitable (organomodified) 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 3933695, EP 0780414, DE 4239054, DE 4229402, EP 867465. These compounds can be prepared as described in the prior art. Suitable examples include: These are described, for example, in US 4,147,847, EP 0,493,836, and US 4,855,379. Foam stabilizers for PU hot-cure flexible foams are characterized by large siloxane structures with more than 50 Si units and attached polyethers. These foam stabilizers are also referred to as polydialkylsiloxane-polyoxyalkylene copolymers.These compounds are preferably structured such that, for example, a long-chain copolymer of ethylene and propylene oxide is bonded to a polydimethylsiloxane residue. The linkage between the polydialkylsiloxane and the polyether moiety can be via a SiC linkage or an Si-OC bond. Structurally, the different polyether(s) can be bonded to the polydialkylsiloxane terminally or laterally. The alkyl radical of the siloxane can be aliphatic, cycloaliphatic, or aromatic. Methyl groups are particularly advantageous. The organo-modified polydialkylsiloxane can be linear or contain branches. Suitable stabilizers, in particular foam stabilizers, are described, inter alia, in US 2,834,748, US 2,917,480, and US 3,629,308. The function of the foam stabilizer is to ensure the stability of the foaming reaction mixture.The contribution to foam stabilization correlates with the siloxane chain length. Without a foam stabilizer, collapse is observed, and thus a non-homogeneous foam is obtained. For some non-inventive PU flexible foam types with higher stability and thus a lower tendency to collapse, low-molecular-weight polyether siloxanes can also be used. These then have siloxane chain lengths significantly shorter than 50. For example, unmodified or modified short-chain siloxanes are used in PU cold-curing flexible foams or ester foams. However, when long-chain and thus more potent siloxane stabilizers are used, overstabilization and thus shrinkage after foam production are observed in such foam types.

[0075] Foam stabilizers can, in principle, be selected arbitrarily within the scope of the present invention, as long as combinations of compounds of formulas (1a) and (1b) are used in the PU hot-cure flexible foam according to the invention. As already explained, these serve in particular to improve the dimensional stability of the foam bodies after compression, especially after roll compression.

[0076] The compounds of formulas (1a) and (1b) can, for example, be used with suitable solvents and / or further additives. All substances suitable according to the state of the art can be used as optional solvents. Depending on the application, aprotic-nonpolar, aprotic-polar and protic solvents can be used. Suitable aprotic-nonpolar solvents can, for example, be selected from the following classes of substances or substance classes containing the following functional groups: aromatic hydrocarbons, aliphatic hydrocarbons (alkanes (paraffins) and olefins), carboxylic acid esters (e.g. isopropyl myristate, propylene glycol dioleate, decyl cocoate or other esters of fatty acids) and polyesters, (poly)ethers and / or halogenated hydrocarbons of low polarity. Suitable aprotic-polar solvents can, for example, be selected from the following classes of substances orSubstance classes containing the following functional groups: ketones, lactones, lactams, nitriles, carboxylic acid amides, sulfoxides, and / or sulfones. Suitable protic solvents can be selected, for example, from the following substance classes or substance classes containing the following functional groups: alcohols, polyols, (poly)alkylene glycols, amines, carboxylic acids, especially fatty acids, and / or primary and secondary amides. Solvents that can be easily processed during foaming and do not negatively affect the properties of the foam are particularly preferred. Isocyanate-reactive compounds, for example, are suitable because they react with the polymer matrix and do not generate 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 (1,3-propanediol PDO), tetramethylene glycol (butanediol BDO), butyldiglycol (BDG), neopentyl glycol, 2-methyl-1,3-propanediol (Ortegol CXT) and higher homologues thereof such as polyethylene glycol (PEG) with average molecular masses between 200 g / mol and 3000 g / mol. Further particularly preferred OH-functional compounds are polyethers with average molecular masses of 200 g / mol to 4500 g / mol, in particular 400 g / mol to 2000 g / mol, preferably water-, allyl-, butyl- or nonyl-initiated polyethers, in particular those based on propylene oxide (PO) and / or ethylene oxide (EO) blocks.

[0077] If the compounds according to the formulas (1a) and (1b) are used according to the invention, or premixed silicone combinations of the compounds with the formulas (1a) and (1b) with additional carriers, dissolved or used in combination with a solvent, the mass ratio of the sum of all silicone components to the solvent is preferably from 0.1 to 1 to 9 to 1, more preferably from 0.25 to 1 to 5 to 1 and particularly preferably from 0.5 to 1 to 4 to 1.

[0078] According to preferred embodiments of the invention, the two siloxane components - namely compounds of formulas (1a) and (1b) - can be added separately to the foam mixture either pure or mixed with solvents, or can also be mixed with one another before addition.

[0079] Preferably, a composition for producing PU hot-cure flexible foams can be added with sufficient compounds of formula (1a) to achieve a mass fraction of the finished polyurethane foam in the range from 0.1 to 5% by weight, preferably from 0.25 to 3.0% by weight, particularly preferably from 0.5 to 2.0% by weight. The compound of formula (1b) is preferably used in a mass fraction of the finished polyurethane foam in the range from 0.1 to 5% by weight, preferably from 0.1 to 2.0% by weight, particularly preferably from 0.1 to 1.5% by weight.

[0080] It may be advantageous if, in the production of the PU hot-cure flexible foam, a composition is produced and / or used which comprises at least the compounds according to the invention according to the formulas (1a) and (1b), at least one polyol component, optionally at least one isocyanate component and optionally one or more blowing agents, and this composition is reacted.

[0081] It is preferred that the compounds according to formulas (1a) and (1b) are each used in a total amount in a mass fraction of 0.1 to 5.0 parts (pphp), preferably 0.1 to 3.0 parts and particularly preferably 0.3 to 2.0 parts based on 100 parts (pphp) of polyol component.

[0082] The production of the PU hot-cure flexible foams according to the invention can be carried out by any process familiar to the person skilled in the art, for example, by hand mixing or, preferably, by means of foaming machines, in particular low-pressure or high-pressure foaming machines. Discontinuous or continuous processes can be used.

[0083] All processes known to those skilled in the art for producing hot-cure flexible PU foams can be used. For example, the foaming process can be carried out horizontally or vertically, in batch or continuous systems. The compositions used according to the invention can also be used for CO2 technology. Use in low-pressure and high-pressure machines is possible, with the compositions to be processed being metered directly into the mixing chamber or being mixed upstream of the mixing chamber with one of the components subsequently entering the mixing chamber. Mixing can also take place in the raw material tank.

[0084] A particularly preferred PU hot-cure flexible foam in the sense of this invention has in particular the following composition: Table 1: component Weight fractions (pphp) Polyol 100 Water 0 to < 10, preferably 0.5 to 6 (Amine) catalyst 0.05 to 5 Tin catalyst 0 to 5, preferably 0.01 to 2 Compounds of formula (1a) 0.1 to 5, preferably 0.1 to 3 Compounds of formula (1b) 0.1 to 5, preferably 0.1 to 3 Physical blowing agent 0 to 130 Flame retardants 0 to 70 Fillers 0 to 150 other additives 0 to 20 Isocyanate Index: larger than 75 and smaller than 130

[0085] A further object of the present invention lies in the use of a combination of at least one compound of the formula (1a) and at least one compound of the formula (1b), (1a) and (1b) as already defined above in each case, in the production of PU hot-cure flexible foam moldings, wherein the PU hot-cure flexible foam molding was obtained by reacting at least one polyol component and at least one isocyanate component in the presence of at least one blowing agent, for providing PU hot-cure flexible foam moldings with improved dimensional recovery after compression over a period of at least 20 hours.

[0086] A further object of the present invention lies in the use of a combination of at least one compound of the formula (1a) and at least one compound of the formula (1b), (1a) and (1b) as already defined above, for improving the dimensional recovery of PU hot-cure flexible foam moldings after their compression over a period of at least 20 hours, wherein the PU hot-cure flexible foam molding is obtainable by reacting at least one polyol component and at least one isocyanate component in the presence of at least one blowing agent in the presence of at least one compound of the formula (1a) and at least one compound of the formula (1b).

[0087] The present invention further relates to the use of hot-cure flexible PU foam in mattresses and / or pillows, in particular mattresses, wherein the hot-cure flexible PU foam was 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), (1a) and (1b), as defined above. In this regard, particular reference is made to the preceding statements, which also apply to this subject matter.

[0088] The use according to the invention enables the provision of mattresses and / or pillows with improved dimensional recovery after compression over a period of at least 20 hours. The use according to the invention enables improved dimensional recovery of mattresses and / or pillows after compression over a period of at least 20 hours.

[0089] Another object of the invention is a method for storing and / or transporting PU foam moldings, preferably mattresses and / or pillows, wherein (a) in a first step, a PU hot-cure flexible foam molded body 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) as defined above, and at least one blowing agent and at least one catalyst, (b) in optional subsequent steps, the PU hot-cure flexible foam obtained is optionally further processed so that it is made ready for the intended use, (c) and wherein the PU hot-cure flexible foam molded body (optionally made ready for the intended use) is compressed and optionally vacuumized in a final step by at least 20%, preferably at least 30%, in particular at least 40%, based on its initial volume, and is held in compressed form by an auxiliary means, in particular packaging means, and is fed for storage and / or transport.

[0090] Another object of the invention is a process for producing polyurethane hot-cure flexible foam with a porosity of 1 to 6 scfm, preferably 1.5 to 4.5 scfm, in particular 1.75 to 4.25 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) and at least one blowing agent and at least one catalyst, formulas (1a) and (1b) as defined above, in particular with the concomitant use of recycled polyols.

[0091] The invention further provides a mixture comprising at least one compound of formula (1a) and at least one compound of formula (1b), (1a) and (1b) as defined above, and optionally glycols, polyethers, organic esters and / or other solvents suitable for the purposes of PU hot-cure flexible foam production. Examples

[0092] Physical properties of the PU flexible foams: The produced PU flexible foams were assessed based on the following physical properties a) to g): a) Rise time: The time between the end of mixing the reaction components and the blowing off of the polyurethane foam. b) Rise height or foam height: This is the height of the formed, freely rising foam after 3 minutes. The foam height is given in centimeters (cm). c) Settling of the foam after the end of the rise phase (= settling back): The settling back results from the difference in foam height after direct blowing off and 3 minutes after the foam has been blown off. The foam height is measured using a needle attached to a centimeter ruler at the maximum in the center of the foam peak. A negative value describes the settling back of the foam after blowing off, a positive value describes the subsequent rise of the foam. d) Number of cells per cm (cell count): This is determined visually on a cross-sectional area (measured according to DIN EN 15702).e) Bulk density (DV): This is determined by measuring the core density as described in Test A of ASTM D 3574-11. The bulk density is given in kg / m³. f) Porosity determined by the air flow method: The air flow method, based on ASTM D 3574 (2011-00), determines the volume of air that flows through a defined foam test specimen in a specific time when a pressure difference is applied. For this purpose, 12 test specimens measuring 5 cm × 5 cm × 2.5 cm were cut from the finished foams at right angles to the foam's rise and clamped one after the other in a measuring instrument designed for this method. The design of this instrument is described in ASTM D 3574 (2011-00). The measuring device creates an air pressure differential of 125 Pa between the interior of the device and the surrounding atmosphere by sucking in just enough air through the sample body so that the differential can be set to a constant level.The air flow through the sample is therefore a measure of the foam's porosity. Values ​​measured ranged from 0 to 6.5 scfm (standard cubic feet per minute), with lower values ​​within this interval indicating a more closed foam, while higher values ​​indicate a more open foam. g) Roll test results. This specific test is described in detail below.

[0093] For the sake of completeness, the measurement principle of DIN EN ISO 16000-9:2008-04 is also explained below.

[0094] The materials are characterized with regard to the type and quantity of organic substances that can be released from them. This analytical method is used to determine emissions from materials used in furniture and mattresses. Test chambers are used to measure the emissions. Analytics Test specimen: sample preparation, sampling and specimen dimensions

[0095] The reaction mixture is placed in a top-open PE plastic bag. After the foam has risen and deflated, the PE bag is closed 3 minutes after deflation. The foam is stored at room temperature for 12 hours to allow for complete reaction while preventing premature release of VOCs. The PE bag is then opened, and a 7 cm x 7 cm x 7 cm cube is removed from the center of the foam block. It is immediately wrapped in aluminum foil and hermetically sealed in a PE bag. It is then transported to the analytical laboratory, and the foam cube is placed in a cleaned 30 L glass test chamber. The test chamber operates under controlled climatic conditions (temperature 21°C, humidity 50%). Half the test chamber volume is flowed through the test chamber every hour. After 24 hours, samples are taken from the test chamber air.Tenax adsorption tubes are used to absorb VOCs. The Tenax tube is then heated, and the released volatile substances are cryofocused using an inert gas stream in a cold trap of a temperature-programmable evaporator. After the annealing phase, the cold trap is rapidly heated to 280°C. This evaporates the focused substances. They are then separated in the gas chromatographic separation column and detected by mass spectrometry. Calibration with reference substances allows a semi-quantitative estimate of emissions, expressed in "µg / m³<". Toluene is used as a quantitative reference substance for VOC analysis (VOC value). Signal peaks can be assigned to substances based on their mass spectra and retention indices. The following device is used for the analysis: Fa.Gerstel, D-45473 Mühlheim an der Ruhr, Eberhard-Gerstel-Platz 1, TDS-3 / KAS-4, Tenax® desorption tubes, Agilent Technologies 7890A (GC) / 5975C (MS), Column: HP Ultra2 (50 m, 0.32 mm, 0.52 µm), Carrier gas: Helium. Detailed specifications can be found in DIN EN ISO 16000-9:2008-04.

[0096] The following describes the rolling deformation test, which can be used to check the dimensional recovery after compression in the sense of this invention. Roll deformation test (short "roll test") Objective:

[0097] The purpose of the test is to simulate the conditions of rolled mattresses in the laboratory. Since there is no definitive industry standard for this, a new test was developed that replicates the rolling of mattress foam on a small scale. Sample preparation:

[0098] From the PU flexible foam blocks, such as those obtained by hand foaming, sample specimens measuring 12 cm (width), 16 cm (length), and 2.5 cm (thickness) are cut using a knife band saw. A central position is selected within the foam blocks from hand foaming. The sample specimen is cut out such that the direction of rise of the foam during production is perpendicular to the length and width of the sample specimen. Sample specimens are marked with a felt-tip pen. Test implementation:

[0099] The sample body is pressed together along a 12 cm edge using a thin metal rod with a 5 - 8 mm diameter (e.g. a metal ballpoint pen). The foam sample body is then rolled up by hand around this metal rod. The foam is strongly compressed, forming a roll with a diameter of approximately 3 - 4 cm. This roll is held in place by hand in this compressed state and pushed completely 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 inside the tube, the metal rod is pulled out. To reduce friction during removal, the metal rod can be lightly greased before rolling the foam. The foam then fills the volume of the tube. The compression of the foam is much greater in the center than at the edges towards the tube.The roll is then stored for 7 days under controlled and constant conditions (temperature: 21°C, humidity: 60%). After 168 hours, the foam is pulled out of the tube with the fingers, placed on a flat surface, and observed as it unrolls. The foam's expansion must not be disturbed or influenced. Evaluation:

[0100] The PU flexible foam body is allowed 10 minutes to expand. The specimens are then evaluated. The most important criterion is whether the foam has fully recovered its original thickness or, especially at the more heavily compressed edge, whether there are still compression zones. Sometimes, a groove from the compression is still visible on the surface of the specimen. Very poor specimens remain rolled up at one end. Slight bending of the specimen after expansion is normal and is not included in the evaluation. The following grading was used for the evaluation: +++ : The specimen has completely unrolled, no compression lines or compaction is visible at all, expansion is rapid and is complete after just 5 minutes. ++ : The specimen has regained a thickness of 2.5 cm in all places. After 10 minutes, no indentations or grooves are visible on the surface (especially at the more heavily compressed end). + : The specimen has regained a thickness of 2.5 cm in all places. However, slight indentations and grooves are still visible on the surface (especially at the more heavily compressed end). 0 : The specimen shows slight compaction at the more heavily compressed end. The thickness there is more than 2.0 cm but less than 2.5 cm. A notch is clearly visible at this end. - : The specimen shows slight compaction at the more heavily compressed end. The thickness of the specimen is more than 1 cm but still significantly less than 2.0 cm.- - : The specimen exhibits strong compaction at the more heavily compressed end. The thickness of the specimen there is less than 1 cm. The specimen is still partially curled at this end. - - - : The specimen is still curled and compressed at the more heavily compressed end.

[0101] The evaluation is preferably carried out by at least two people. The results are documented. In the present invention, the evaluation was carried out by four people, who reached consistent results.

[0102] Disturbances and boundary conditions of the test:During the test, care must be taken to ensure the correct dimensions of the specimen and consistent rolling. The foam specimen must exhibit consistent cell structure parameters, specifically, a consistent cell size and consistent air permeability. The metal pin must not be over-greased to prevent grease from penetrating the specimen. Consistent storage conditions must be maintained. Specimens from the various evaluation levels must be kept available for comparison. Accuracy of the test:

[0103] Conducting the test with multiple people for evaluation regularly results in consistent assessments. Repeated measurements have also consistently confirmed the same results, proving the test to be reliable. PU hot-cure flexible foam - foaming examples Example 1: Production of PU hot-cure flexible foams (flexible block foam)

[0104] For the application testing of the compounds of formulas (1a) and (1b) according to the invention, the PU hot-curing flexible foam formulation given in Table 2 was used. Table 2: Formulation 1 for PU hot-cure flexible foam production. Formulation 1 Mass parts (pphp) Polyol 1 1)< 100 pieces Water 4.00 pieces Tin catalyst 2)< 0.20 - 0.28 parts TEGOAMIN ®< DMEA 3)< 0.15 parts FOAM STABILIZER 1 4)< 0.40 or 0.45 parts if necessary, silicone additives 5)< 1.0 parts Desmodur ®< T 80 6)< 50.0 parts 1)< Polyol 1: Voranol ®< CP 3322, available from Dow Chemical. This is a glycerin-based polyether polyol with an OH number of 48 mg KOH / g and predominantly secondary OH groups, average molecular weight = 3500 g / mol. 2)< KOSMOS ®< 29, available from Evonik Industries: Tin(II) salt of 2-ethylhexanoic acid. 3)< TEGOAMIN ®< DMEA: Dimethylethanolamine, available from Evonik Industries. Amine catalyst for the production of polyurethane foams. 4)< Polyether-modified polysiloxane according to the following structure: Foam stabilizer 1 (corresponds to compound of formula 1a):

[0105] Polyethersiloxane of the following structure [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 where a= 2 b= 70 c= 4 d= 0 e= 0 with: a + b + c + d + e = 76 R 1< = Me R 2< = identical or different polyethers of the general formula (e), obtainable from the polymerization of ethylene oxide and propylene oxide, with: 37.5 mol% polyether 1, where f = 3 g= 37 h= 38 where g + h = 75 , statistically constructed R 3< = methyl and 62.5 mol% polyether 2, where f = 3 g= 14 h= 0 where g + h = 14 , statistically constructed R 3< = methyl.

[0106] In the experiments according to the invention, short-chain siloxane components were added to a PU hot-cure flexible foam formulation containing a high-molecular-weight silicone component (according to formula 1a) as a foam stabilizer. The three selected silicone additives (each corresponding to compounds of formula 1b) are characterized below: 5) < Silicone Additive 1

[0107] Unmodified silicone oil with the following composition [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 where i= 2 j= distribution 2 to 15, maximum at 9 k= 0 l= 0 m= 0 with: i+j+k+l+m = distribution 4 to 17, maximum at 11 R 4< = Me Silicone Additive 2

[0108] Polyether-modified siloxane with the following structural parameters: [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 where i= 2 j= 4.0 k= 2.0 l= 0 m= 0 with: i + j + k + l + m = 8 R 4< = Me R 5< = Polyether 1 according to where: n = 3 o= 3.5 p= 2.0 where o + p = 5 , 5 R 6< = OH Silicone Additive 3

[0109] Heptamethyltrisiloxane modified with n-octene. Structure parameters as follows: [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 where i= 2 j= 0 k= 1 l= 0 m= 0 where: i + j + k + l + m = 3 R 4< = Me R 5< = n-octyl 6)< Toluene diisocyanate T 80 (80% 2,4-isomer, 20% 2,6-isomer) from Covestro, 3 mPa·s, 48% NCO, functionality 2.

[0110] During foaming, 400 g of polyol were used in each case; the other formulation components were converted accordingly. For example, 1.00 part of a component meant 1.00 g of this substance per 100 g of polyol.

[0111] The foaming was carried out using the so-called hand-mixing method. Formulation 1, as shown in Table 2, was used. For this purpose, polyol, the respective amine catalyst mixture, the tin catalyst tin(II) 2-ethylhexanoate, water, foam stabilizer, and optionally an additional low-molecular-weight silicone additive (compounds of formula (1b)) were placed in a paper cup and mixed with a disk stirrer for 60 s at 1000 rpm. After the initial stirring, the isocyanate (TDI) was added to the reaction mixture and stirred for 7 s at 2500 rpm. The mixture was immediately transferred to a paper-lined box (30 cm × 30 cm base area and 30 cm high). The foam rose after pouring into the foaming box. Ideally, the foam deflated upon reaching the maximum rise height and then sank back slightly. The cell membranes of the foam bubbles opened and an open-pore cell structure of the foam was obtained.To evaluate the properties, the following characteristic parameters were determined: rise time, rise height and sagging of the foam after the end of the rise phase (= relapse).

[0112] Defined foam bodies were cut from the resulting PU hot-cured flexible foam blocks and further analyzed. The following physical properties were determined on the sample bodies: cell count, porosity using the flow-through method, density (DV), and roll deformation at room temperature.

[0113] The results of the influence of the compounds according to the invention on foaming and the physical properties of the resulting hot-cure flexible PU foams are summarized in the tables below. For comparison, hot-cure flexible PU foams were produced using only a standard flexible foam stabilizer (Foam Stabilizer 1) and only the silicone additives Silicone Additive 1, Silicone Additive 2, and Silicone Additive 3. The foams without foam stabilizer consistently collapsed, and no meaningfully assessable foam was obtained. Combinations of Foam Stabilizer 1 and Silicone Additives 1, 2, and 3 were then used according to the invention. Table 3: Reference (foam stabilizer 1 only) (not according to the invention) Reference (foam stabilizer 1 only) (not according to the invention) Reference (foam stabilizer 1 only) (not according to the invention) Reference (foam stabilizer 1 only) (not according to the invention) Reference (foam stabilizer 1 only) (not according to the invention) Reference (foam stabilizer 1 only) (not according to the invention) Sn catalyst amount 0,22 0,22 0,22 0,22 0,22 0,20 Stabilizer 0.45 parts foam stabilizer 1 0.40 parts foam stabilizer 1 0.45 parts foam stabilizer 1 0.40 parts foam stabilizer 1 0.45 parts foam stabilizer 1 0.45 parts foam stabilizer 1 Additive - - - - - - a) Rise time (s) 94 94 99 99 98 105 b) Rise height (cm) 31,8 31,3 29,5 30,1 29,4 26,6 c) Relapse (cm) -0,3 -0,5 -0,1 -0,1 -0,1 -0,1 d) Cell count (per cm) 14 14 13 14 14 13 e) Density (kg / m 3< ) 24,4 24,4 25,1 24,8 24,8 27,1 f) Porosity (SCFM) 2,12 1,86 2,23 3,64 3,23 4,79 9) Rolling deformation (7 d, 21 °C) --- --- --- - 0 ++++ Table 4: Additive only (not according to the invention) Additive only (not according to the invention) Foam stabilizer 1 + silicone additive 1 (according to the invention) Foam stabilizer 1 + silicone additive 1 (according to the invention) Foam stabilizer 1 + silicone additive 1 (according to the invention) Foam stabilizer 1 + silicone additive 1 (according to the invention) Sn catalyst amount 0,20 0,22 0,22 0,22 0,24 0,26 stabilizer - - 0.45 parts foam stabilizer 1 0.45 parts foam stabilizer 1 0.45 parts foam stabilizer 1 0.45 parts foam stabilizer 1 Additive 1.0 parts silicone additive 1 1.0 parts silicone additive 1 1.0 parts silicone additive 1 1.0 parts silicone additive 1 1.0 parts silicone additive 1 1.0 parts silicone additive 1 Climbing time (s) collapse collapse 96 87 91 89 Rise height (cm) collapse collapse 27,9 27,1 28,1 28,1 Relapse (cm) collapse collapse -2,0 -1,4 -1,7 -1,6 Cells (per cm) collapse collapse 14 14 14 14-15 Density (kg / m 3< ) collapse collapse 26,8 25,2 26,3 25,8 Porosity (SCFM) collapse collapse 3,79 2,46 2,58 1,85 Rolling deformation (7 d, 21 °C) collapse collapse + + + + 0 - Table 5: Foam stabilizer 1 + silicone additive 1 (according to the invention) Additive only (not according to the invention) Additive only (not according to the invention) Foam stabilizer 1 + silicone additive 2 (according to the invention) Foam stabilizer 1 + silicone additive 2 (according to the invention) Foam stabilizer 1 + silicone additive 2 (according to the invention) Sn catalyst amount 0,28 0,20 0,22 0,20 0,22 0,24 stabilizer 0.45 parts foam stabilizer 1 - - 0.45 parts foam stabilizer or 1 0.45 parts foam stabilizer 1 0.45 parts foam stabilizer 1 Additive [parts] 1.0 parts silicone additive 1 1.0 parts silicone additive 2 1.0 parts silicone additive 2 1.0 parts silicone additive 2 1.0 parts silicone additive 2 1.0 parts silicone additive 2 Climbing time (s) 85 collapse collapse 107 102 98 Rise height (cm) 29,1 collapse collapse 26,5 26,8 27,4 Relapse (cm) -1,4 collapse collapse -0,1 0,0 -0,1 Cells (per cm) 14-15 collapse collapse 13 13 13 Density (kg / m 3< ) 25,4 collapse collapse 27,5 27,4 24,1 Porosity (SCFM) 0,99 collapse collapse 4,99 4,42 3,77 Roll deformation (7 d, 21 °C) --- collapse collapse + + + + + + + + + + + Table 6: Foam stabilizer 1 + silicone additive 2 (according to the invention) Foam stabilizer 1 + silicone additive 2 (according to the invention) Foam stabilizer 1 + silicone additive 2 (according to the invention) Additive only (not according to the invention) Additive only (not according to the invention) Foam rod iliser 1 + silicone additive 3 (according to the invention) Foam stabilizer 1 + silicone additive 3 (according to the invention) Foam stabilizer 1 + silicone additive 3 (according to the invention) Sn catalyst amount 0,26 0,22 0,28 0,20 0,22 0,20 0,22 0,24 stabilizer 0.45 parts foam stabilizer 1 0.45 parts foam stabilizer 1 0.45 parts foam stabilizer 1 - - 0.45 parts foam rod iliser 1 0.45 parts foam stabilizer 1 0.45 parts foam stabilizer 1 Additive 1.0 parts silicone additive 2 1.0 parts silicone additive 2 1.0 parts silicone additive 2 1.0 parts silicone additive 3 1.0 parts silicone additive 3 1.0 parts silicone additive 3 1.0 parts silicone additive 3 1.0 parts silicone additive 3 Climbing time (s) 93 90 89 collapse collapse 109 103 97 Rise height (cm) 27,2 28,6 27,7 collapse collapse 27,1 27,6 27,8 Relapse (cm) 0,0 -0,1 -0,2 collapse collapse -0,1 -0,1 0,0 Cells (per cm) 13 14 13 collapse collapse 13 13 13 Density (kg / m 3< ) 27,0 24,3 26,3 collapse collapse 28,1 27,6 26,7 Porosity (SCFM) 3,12 3,03 1,32 collapse collapse 5,34 4,91 3,76 Rolling deformation (7 d, 21 °C) +++ + + - - - collapse collapse + + + + + + + + + + + Table 7: Foam stabilizer 1 + silicone additive 3 (according to the invention) Foam stabilizer 1 + silicone additive 3 (according to the invention) Sn catalyst amount 0,26 0,28 stabilizer 0.45 parts foam stabilizer 1 0.45 parts foam stabilizer 1 Additive 1.0 parts silicone additive 3 1.0 parts silicone additive 3 Climbing time (s) 92 88 Rise height (cm) 27,4 28,6 Relapse (cm) 0,0 -0,1 Cells (per cm) 13 13 Density (kg / m 3< ) 26,6 25,6 Porosity (SCFM) 2,21 1,32 Rolling deformation (7 d, 21 °C) + + --

[0114] When evaluating the results, it must be considered that the roll test result depends heavily on the porosity of the foam. Foams with a more closed cell structure generally perform worse than those with an open cell structure. Since porosity varies to a certain extent during foaming due to various influencing factors (temperatures, air pressure, etc.), the roll test result must be evaluated in conjunction with the porosity for a meaningful analysis.

[0115] For this purpose, the figures FIG. 1 to FIG. 3The roll test result is plotted against porosity. The values ​​for the reference (PU hot-cure flexible foam with only foam stabilizer 1) and the reference + 1 part silicone additive are plotted. To obtain PU hot-cure flexible foams with different porosities, identical foaming processes were repeated on different days, varying the amount of stabilizer and the amount of tin catalyst (Kosmos 29). In particular, varying the tin catalyst yields the desired broad range of porosity values.

[0116] It can be seen that the roll test results for the reference foams are strongly dependent on porosity. Foams not according to the invention with porosities up to 2.3 scfm generally perform very poorly in the roll test. Conversely, non-inventive hot-cure flexible PU foams perform very well in the roll test if they are very open (scfm > 4.5). However, the majority of industrial hot-cure flexible PU foams are between 1.5 and 4.5 scfm. Surprisingly, significantly improved roll test results were found for all foams according to the invention in this range. There is generally a certain degree of scatter in the values, as both the porosity measurement and the measurement of the roll test results are subject to deviations. Nevertheless, a significant improvement can be seen.

[0117] As can be seen, the inventive combination of a compound of formula (1a) with a compound of formula (1b) shows significant advantages in roll deformation tests of PU hot-cure flexible foams compared to the sole use of a single high-molecular-weight silicone component as a foam stabilizer. The recovery of the original shape of the specimens after roll deformation was significantly improved. The use of exclusively low-molecular-weight silicone additives (compounds of formula (1b)) leads to collapse in PU hot-cure flexible foam formulations. Combinations of a high-molecular-weight foam stabilizer (compounds of formula (1a)) and low-molecular-weight silicone components (compounds of formula (1b)) still show sufficient stabilization (regression of less than 2.0 cm), unchanged cell counts (14 to 15 cells per cm), and clear advantages in the roll test.

[0118] Furthermore, the PU hot-cure flexible foams according to the invention proved to be low-emission when emission-optimized additives were used. This is evident in the VOC tests according to DIN EN ISO 16000-9:2008-04. In a low-emission formulation, it can be seen that the addition of silicone additive 1 slightly increases total emissions (from 40 µg / m 3 , see Table 8, to 130 µg / m 3 , see Table 9), but is still well below the usual TVOC limit of 500 µg / m 3 . Silicone additive 1 is therefore also ideally suited for use in low-emission formulations.

[0119] The overall advantages of the invention were also confirmed for viscoelastic flexible foams. Table 8: VOC tests according to DIN EN ISO 16000-9:2008-04: (Reference PU hot-cure flexible foam) Sample name: reference Instrument: 7890 / 5975C Sample volume: 2,000 l Standard dimensions: 0,396 µg Area Standard: 129693683 Retention time [min] Area Concentration equivalent to toluene 4,6 510950 <1 µg / m 3 < 5,1 593475 <1 µg / m 3 < 5,9 534225 <1 µg / m 3 < 6,4 957326 1 µg / m 3< Dimethylsilanediol 22,1 3381605 5 µg / m 3< Ethylhexanoic acid 23,5 2598228 4 µg / m 3< Cyclic siloxane D5 25,4 940103 1 µg / m 3< 29,0 8728324 13 µg / m 3< branched alkanes 29,4 4122469 6 µg / m 3< branched alkanes 29,6 3680639 6 µg / m 3< branched alkanes 29,7 2462516 4 µg / m 3< branched alkanes 41,3 542066 <1 µg / m 3 < Total (TVOC) 40 µg / m 3< Siloxane emissions (total) 5 µg / m 3< Table 9: VOC tests according to DIN EN ISO 16000-9:2008-04: (Reference PU hot-cure flexible foam + 1.0 parts silicone additive 1 ) Sample name: Reference + Silicone Additive 1 Instrument: 7890 / 5975C Sample volume: 2,000 l Standard dimensions: 0,396 µg Area Standard: 117796486 Retention time [min]T Area Concentration equivalent to toluene 4,3 1241210 2 µg / m 3< 4,4 904874 2 µg / m 3< 4,6 813896 1 µg / m 3< 5,1 803280 1 µg / m 3< 6,0 1775599 3 µg / m 3< benzene 6,5 1756844 3 µg / m 3< Dimethylsilanediol 8,8 2026275 3 µg / m 3< 17,3 1528105 3 µg / m 3< Cyclic siloxane D4 20,3 1676694 3 µg / m 3< Linear Siloxane N4 22,1 3887341 7 µg / m 3< Ethylhexanoic acid 23,5 6367115 11 µg / m 3< Cyclic siloxane D5 26,5 8835334 15 µg / m 3< Linear Siloxane N5 29,0 11993451 20 µg / m 3< branched alkanes 29,4 5008151 8 µg / m 3< branched alkanes 29,6 4203748 7 µg / m 3< branched alkanes 29,7 2903703 5 µg / m 3< branched alkanes 31,2 3916492 7 µg / m 3< Linear Siloxane N6 34,3 2291055 4 µg / m 3< Linear Siloxane N7 36,5 7455648 13 µg / m 3< Linear Siloxane N8 38,4 4932388 8 µg / m 3< Linear Siloxane N9 42,1 1213236 2 µg / m 3< Total (TVOC) 130 µg / m 3< Siloxane emissions (total) 67 µg / m 3<

Claims

1. Shaped hot-cure flexible PU foam article, preferably mattress and / or cushion, wherein the hot-cure flexible PU foam has been 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 and at least one catalyst, where         [R1Me2SiO1 / 2]a [Me2SiO2 / 2]b [R2MeSiO2 / 2]c [MeSiO3 / 2]d [SiO4 / 2]e     Formula (1a) with 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 where: a + b + c + d + e > 48 R1 = Me or R2 R2 = identical or different polyethers obtainable from the polymerization of ethylene oxide, propylene oxide and / or other alkylene oxides such as butylene oxide or styrene oxide, preferably polyethers of the general formula (c), where f = 0-6, preferably 0-4, 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 where g + h > 0 R3= OH, alkyl or acetyl, preferably OH, C1 to C6-alkyl or acetyl, more preferably OH, methyl, acetyl or butyl and where         [R4Me2SiO1 / 2]i [Me2SiO2 / 2]j [R5MeSiO2 / 2]k [MeSiO3 / 2]l [SiO4 / 2]m     Formula (1b) with 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 1 = 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 where: i + j + k + l + m < 20 R4 = Me or R5 R5 = identical or different polyethers obtainable from the polymerization of ethylene oxide, propylene oxide and / or other alkylene oxides such as butylene oxide or styrene oxide, preferably polyethers of the general formula (d), or alkyl C3 to C15, where n = 0-6, preferably 0-4, 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 where o + p > 0 R6= OH, alkyl or acetyl, preferably OH, C1 to C6-alkyl or acetyl, more preferably OH, methyl, acetyl or butyl.

2. Shaped hot-cure flexible PU foam article, preferably mattress and / or cushion, according to Claim 1, characterized in that the hot-cure flexible polyurethane foam has a porosity of 1.7 to 10.2 m3 / h, preferably 2.6 to 7.7 m3 / h, especially 2.97 to 7.22 m3 / h, where porosity is measured as disclosed in the description.

3. Shaped hot-cure flexible PU foam article, preferably mattress and / or cushion, according to Claim 1 or 2, characterized in that the hot-cure 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 / m3 and / or a porosity of 1.7 to 10.2 m3 / h, preferably 2.6 to 7.7 m3 / h, especially 2.97 to 7.22 m3 / h, where porosity is measured as disclosed in the description.

4. Shaped hot-cure flexible PU foam article, preferably mattress and / or cushion, according to any of Claims 1 to 3, characterized in that the hot-cure flexible polyurethane foam has a compressive strength CLD, 40% in accordance with DIN EN ISO 3386-1:2015-10, of 0.1 to 8.0 kPa.

5. Shaped hot-cure flexible PU foam article, preferably mattress and / or cushion, according to any of Claims 1 to 4, characterized in that the hot-cure flexible polyurethane foam has a compressive strength CLD, 40% in accordance with DIN EN ISO 3386-1:2015-10, of 2.0-8.0 kPa and / or a rebound resilience of 15-50%, measured in accordance with DIN EN ISO 8307:2008-03, and / or a foam density of 8 to 80 kg / m3 and / or a porosity of 1.7 to 10.2 m3 / h, preferably 2.6 to 7.7 m3 / h, especially 2.97 to 7.22 m3 / h, where porosity is measured as disclosed in the description.

6. Shaped hot-cure flexible PU foam article, preferably mattress and / or cushion, according to any of Claims 1 to 4, characterized in that the hot-cure flexible polyurethane foam is a viscoelastic flexible polyurethane foam and preferably has a glass transition temperature between -20°C and +15°C and / or a compressive strength CLD, 40% in accordance with DIN EN ISO 3386-1:2015-10, of 0.1 - 5.0 kPa, in particular 0.5 - 2.5 kPa, and / or a rebound resilience of < 10%, measured in accordance with DIN EN ISO 8307:2008-03, and / or a foam density of 30 to 130 kg / m3 and / or a porosity of 1.7 to 10.2 m3 / h, preferably 2.6 to 7.7 m3 / h, especially 2.97 to 7.22 m3 / h, where porosity is measured as disclosed in the description.

7. Shaped hot-cure flexible PU foam article, preferably mattress, according to any of Claims 1 to 6, characterized in that the shaped article has a height of from at least 1 cm to not more than 50 cm and a width of from at least 20 cm to not more than 300 cm, preferably from at least 70 cm to not more than 200 cm, and a length of from at least 20 cm to not more than 300 cm, preferably from at least 150 cm to not more than 220 cm.

8. Shaped hot-cure flexible PU foam article, preferably mattress, according to any of Claims 1 to 7, characterized in that based on its starting volume the shaped PU foam article is compressed by at least 20%, preferably 30%, especially 40%, and kept in compressed form by an auxiliary means, especially packaging means, for at least 20 hours.

9. Shaped hot-cure flexible PU foam article, preferably mattress, according to Claim 8, characterized in that the shaped hot-cure flexible PU foam article is in a compressed and preferably a vacuum-packed state, and is especially a roll-up mattress.

10. Shaped hot-cure flexible PU foam article according to any of Claims 1 to 9, characterized in that it has been obtained with additional use of recycled polyols.

11. Use of a combination of at least one compound of formula (1a) and at least one compound of formula (1b), with (1a) and (1b) each as defined in Claim 1, for improving the dimensional recovery of shaped hot-cure flexible PU foam articles after compression thereof over a period of at least 20 hours, wherein the shaped hot-cure 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 blowing agent and of at least one catalyst in the presence of at least one compound of formula (1a) and at least one compound of formula (1b), where the hot-cure flexible polyurethane foam has a porosity of 1.7 to 10.2 m3 / h, preferably 2.6 to 7.7 m3 / h, especially 2.97 to 7.22 m3 / h, where porosity is measured as disclosed in the description.

12. Process for storing and / or for transporting shaped hot-cure flexible PU foam articles, preferably mattresses and / or cushions, where (a) in a first step a shaped hot-cure flexible 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), with (1a) and (1b) each as defined in Claim 1, and of at least one blowing agent and at least one catalyst, (b) in optional subsequent steps the shaped hot-cure flexible PU foam article obtained may optionally be subjected to further processing to prepare it for the application, (c) and wherein in a final step the shaped hot-cure flexible PU foam article (optionally prepared for the application) is compressed by at least 20%, preferably 30%, especially 40%, based on its starting volume, and optionally vacuum-packed and kept in compressed form by auxiliary means, in particular packaging means, and sent for storage and / or transport, where the hot-cure flexible polyurethane foam advantageously has a porosity of 1.7 to 10.2 m3 / h, preferably 2.6 to 7.7 m3 / h, especially 2.97 to 7.22 m3 / h, where porosity is measured as disclosed in the description.

13. Process according to Claim 12, characterized in that a sufficient amount of compounds having the formula (1a) is added in step (a) that the proportion by mass thereof in the finished polyurethane foam is from 0.1% to 5% by weight, preferably from 0.25% to 3.0% by weight, more preferably 0.5% to 2.0% by weight, and a sufficient amount of compounds of formula (1b) is added in step (a) that the proportion by mass thereof in the finished polyurethane foam is from 0.1% to 5% by weight, preferably from 0.1% to 2.0% by weight, more preferably 0.1% to 1.5% by weight.

14. Process for producing hot-cure flexible polyurethane foam having a porosity of 1.7 to 10.2 m3 / h, preferably 2.6 to 7.7 m3 / h, especially 2.97 to 7.22 m3 / h, where porosity is measured as disclosed in the description, 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 and at least one catalyst, where formulae (1a) and (1b) are defined below:         [R1Me2SiO1 / 2]a [Me2SiO2 / 2]b [R2MeSiO2 / 2]c [MeSiO3 / 2]d [SiO / 4 / 2]e     Formula (1a) with 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 where: a + b + c + d + e > 48 R1 = Me or R2 R2 = identical or different polyethers obtainable from the polymerization of ethylene oxide, propylene oxide and / or other alkylene oxides such as butylene oxide or styrene oxide, preferably polyethers of the general formula (c), where f = 0-6, preferably 0-4, 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 where g + h > 0 R3= OH, alkyl or acetyl, preferably OH, C1 to C6-alkyl or acetyl, more preferably OH, methyl, acetyl or butyl and where         [R4Me2SiO1 / 2]i [Me2SiO2 / 2]j [R5MeSiO2 / 2]k [MeSiO3 / 2]l [SiO4 / 2]m     Formula (1b) with 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 where: i + j + k + l + m < 20 R4 = Me or R5 R5 = identical or different polyethers obtainable from the polymerization of ethylene oxide, propylene oxide and / or other alkylene oxides such as butylene oxide or styrene oxide, preferably polyethers of the general formula (d), or alkyl C3 to C15, where n = 0-6, preferably 0-4, 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 where o + p > 0 R6= OH, alkyl or acetyl, preferably OH, C1 to C6-alkyl or acetyl, more preferably OH, methyl, acetyl or butyl, especially with additional use of recycled polyols.

15. Use of hot-cure flexible polyurethane foam in mattresses and / or cushions, especially mattresses, wherein the hot-cure flexible polyurethane foam has been 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), with (1a) and (1b) each as defined in Claim 1, and of at least one blowing agent and at least one catalyst, preferably for provision of (preferably compressed) mattresses and / or cushions having improved dimensional recovery after compression over a period of at least 20 hours, especially having improved emissions characteristics, where the hot-cure flexible polyurethane foam advantageously has a porosity of 1.7 to 10.2 m3 / h, preferably 2.6 to 7.7 m3 / h, especially 2.97 to 7.22 m3 / h, where porosity is measured as disclosed in the description.

16. Mixture comprising at least one compound of the formula (1b) and at least one compound of the formula (1a), with (1a) and (1b) each as defined in Claim 1, and optionally glycols, polyethers, organic esters and / or other solvents suitable for the purposes of flexible PU foam production.