Compression set

Abstract

What are described are shaped hot-cure flexible PU foam articles, preferably mattresses and/or cushions, 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) and at least one blowing agent and at least one catalyst.

Claims

1. A shaped hot-cure flexible polyurethane foam article, wherein the hot-cure flexible PU foam is obtained by reaction of at least one polyol component and at least one isocyanate component in the presence of at least one compound of formula (1a) and at least one compound of formula (1b) and at least one blowing agent and at least one catalyst, where:
[R.sup.1Me.sub.2SiO.sub.1/2].sub.a[Me.sub.2SiO.sub.2/2].sub.b[R.sup.2MeSiO.sub.2/2].sub.c[MeSiO.sub.3/2].sub.d[SiO.sub.4/2].sub.eFormula (1a) with a=2 to 10, b=25 to 200, c=2 to 40, d=0 to 10, e=0 to 5, where: a+b+c+d+e>48 R.sup.1=Me or R.sup.2 R.sup.2=identical or different polyethers obtained from the polymerization of ethylene oxide, propylene oxide and/or other alkylene oxides and where
[R.sup.4Me.sub.2SiO.sub.1/2].sub.i[Me.sub.2SiO.sub.2/2].sub.j[R.sup.5MeSiO.sub.2/2].sub.k[MeSiO.sub.3/2].sub.l[SiO.sub.4/2].sub.mFormula (1b) with i=2 to 10, j=0 to 20, k=0 to 20, l=0 to 10, m=0 to 5, where: i+j+k+l+m<20 R.sup.4=Me or R.sup.5 R.sup.5=identical or different polyethers obtained from the polymerization of ethylene oxide, propylene oxide and/or other alkylene oxides, wherein the finished polyurethane foam comprises 0.1% to 5% by weight of the at least one compound having the formula (1a) and comprises 0.1% to 5% by weight of the at least one compound of formula (1b), and wherein the finished polyurethane foam comprises the at least one compound having the formula (1a) and the at least one compound of formula (1b) in a total amount of about 1.45% to 10.0% by weight.

2. The shaped hot-cure flexible polyurethane foam article according to claim 1, wherein the hot-cure flexible polyurethane foam has a porosity of 1 to 6 scfm.

3. The shaped hot-cure flexible polyurethane foam article according to claim 1, wherein 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/m.sup.3 and/or a porosity of 1 to 6 scfm.

4. The shaped hot-cure flexible polyurethane foam article according to claim 1, wherein 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. The shaped hot-cure flexible polyurethane foam article according to claim 1, wherein 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/m.sup.3 and/or a porosity of 1 to 6 scfm.

6. The shaped hot-cure flexible polyurethane foam article according to claim 1, wherein the hot-cure flexible polyurethane foam is a viscoelastic flexible polyurethane foam and 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/m.sup.3 and/or a porosity of 1 to 6 scfm.

7. The shaped hot-cure flexible polyurethane foam article according to claim 1, wherein 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, and a length of from at least 20 cm to not more than 300 cm.

8. The shaped hot-cure flexible polyurethane foam article according to claim 1, wherein based on its starting volume the shaped PU foam article is compressed by at least 20%, and kept in compressed form by packaging means, for at least 20 hours.

9. The shaped hot-cure flexible polyurethane foam article according to claim 8, wherein the shaped hot-cure flexible polyurethane foam article is in a compressed and a vacuum-packed state, and is a roll-up mattress.

10. The shaped hot-cure flexible polyurethane foam article according to claim 1, wherein the at least one polyol component comprises recycled polyols.

11. The shaped hot-cure flexible polyurethane foam article as defined in claim 1, for improving the dimensional recovery of the shaped hot-cure flexible polyurethane foam articles after compression thereof over a period of at least 20 hours, wherein the hot-cure flexible polyurethane foam has a porosity of 1.75 to 4.25 scfm.

12. A process for storing and/or for transporting shaped hot-cure flexible polyurethane foam articles, comprising: (a) in a first step providing a shaped hot-cure flexible polyurethane foam article as defined in claim 1, (b) in optional subsequent steps the shaped hot-cure flexible polyurethane foam article obtained is subjected to further processing, (c) and wherein in a final step the shaped hot-cure flexible polyurethane foam article is compressed by at least 20%, based on its starting volume, and optionally vacuum-packed and kept in compressed form by auxiliary means, and sent for storage and/or transport, wherein the hot-cure flexible polyurethane foam has a porosity of 1 to 6 scfm.

13. A process for producing hot-cure flexible polyurethane foam having a porosity of 1 to 6 scfm, comprising 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, where formulae (1a) and (1b) are defined below:
[R.sup.1Me.sub.2SiO.sub.1/2].sub.a[Me.sub.2SiO.sub.2/2].sub.b[R.sup.2MeSiO.sub.2/2].sub.c[MeSiO.sub.3/2].sub.d[SiO.sub.4/2].sub.eFormula (1a) with a=2 to 10, b=25 to 200, c=2 to 40, d=0 to 10, e=0 to 5, where: a+b+c+d+e>48 R.sup.1=Me or R.sup.2 R.sup.2=polyethers of the general formula (c), ##STR00005## where f=0-6, g=0 to 150, h=0 to 150, where g+h>0 R.sup.3?OH, alkyl or acetyl, and where
[R.sup.4Me.sub.2SiO.sub.1/2].sub.i[Me.sub.2SiO.sub.2/2].sub.j[R.sup.5MeSiO.sub.2/2].sub.k[MeSiO.sub.3/2].sub.l[SiO.sub.4/2].sub.mFormula (1b) with i=2 to 10, j=0 to 20, k=0 to 20, l=0 to 10, m=0 to 5, where: i+j+k+l+m<20 R.sup.4=Me or R.sup.5 R.sup.5=polyethers of the general formula (d), or alkyl C.sub.3 to C.sub.15, ##STR00006## where n=0-6, o=0 to 100, p=0 to 100, where o+p>0 R.sup.6?OH, alkyl or acetyl, wherein the finished polyurethane foam comprises the at least one compound having the formula (1a) and the at least one compound of formula (1b) in a total amount of about 1.45% to 10.0% by weight.

14. The shaped hot-cure flexible polyurethane foam article according to claim 8, which is a mattress having improved dimensional recovery after compression over a period of at least 20 hours, having improved emissions characteristics, wherein the hot-cure flexible polyurethane foam has a porosity of 1 to 6 scfm.

15. A mixture comprising at least one compound of the formula (1b) and at least one compound of the formula (1a), and optionally glycols, polyethers, organic esters and/or other solvents suitable, for the purposes of flexible polyurethane foam production, wherein
[R.sup.1Me.sub.2SiO.sub.1/2].sub.a[Me.sub.2SiO.sub.2/2].sub.b[R.sup.2MeSiO.sub.2/2].sub.c[MeSiO.sub.3/2].sub.d[SiO.sub.4/2].sub.eFormula (1a) with a=2 to 10, b=25 to 200, c=2 to 40, d=0 to 10, e=0 to 5, where: a+b+c+d+e>48 R.sup.1=Me or R.sup.2 R.sup.2=identical or different polyethers obtained from the polymerization of ethylene oxide, propylene oxide and/or other alkylene oxides, and
[R.sup.4Me.sub.2SiO.sub.1/2].sub.i[Me.sub.2SiO.sub.2/2].sub.j[R.sup.5MeSiO.sub.2/2].sub.k[MeSiO.sub.3/2].sub.l[SiO.sub.4/2].sub.mFormula (1b) with i=2 to 10, j=0 to 20, k=0 to 20, l=0 to 10, m=0 to 5, where: i+j+k+l+m<20 R.sup.4=Me or R.sup.5 R.sup.5=identical or different polyethers obtained from the polymerization of ethylene oxide, propylene oxide and/or other alkylene oxides, wherein the mixture to produce the finished polyurethane foam comprises the at least one compound having the formula (1a) and the at least one compound of formula (1b) in a total amount of about 1.45% to 10.0% by weight.

16. The shaped hot-cure flexible polyurethane foam article according to claim 1, wherein the hot-cure flexible polyurethane foam has a porosity of 1.5 to 4.5 scfm, wherein a=2 to 8, b=40 to 150, c=2 to 30, d=0 to 8, e=0 to 3, where: R.sup.2=polyethers of the general formula (c), ##STR00007## where f=0-4, g=3 to 100, h=0 to 100, where R.sup.3?OH, methyl, acetyl or butyl, and where i=2 to 8, j=0 to 18, k=0 to 15, l=0 to 8, m=0 to 3, where: R.sup.5=polyethers of the general formula (d), or alkyl C.sub.3 to C.sub.15, ##STR00008## where o=0 to 50.

17. The shaped hot-cure flexible polyurethane foam article according to claim 1, wherein the hot-cure flexible polyurethane foam has a porosity of 1.75 to 4.25-scfm, wherein a=2 to 5, b=40 to 150, where: R.sup.2=polyethers of the general formula (c), ##STR00009## where f=0-6, g=0 to 150, h=0 to 150, where g+h>0 R.sup.3?OH, alkyl or acetyl, and where where: R.sup.5=polyethers of the general formula (d), or alkyl C.sub.3 to C.sub.15, ##STR00010## where n=0-6, o=0 to 100, p=0 to 100, where o+p>0 R.sup.6?OH, alkyl or acetyl.

18. The shaped hot-cure flexible polyurethane foam article according to claim 1, wherein the hot-cure flexible polyurethane foam has a porosity of 1.5 to 4.5 scfm, wherein a=2 to 8, b=40 to 150, c=2 to 30, d=0 to 8, e=0 to 3, where: R.sup.2=polyethers of the general formula (c), ##STR00011## where f=0-4, g=3 to 100, h=0 to 100, where g+h>0 R.sup.3?OH, methyl, acetyl or butyl and where i=2 to 8, j=0 to 18, k=0 to 15, l=0 to 8, m=0 to 3, where: R.sup.5=polyethers of the general formula (d), or alkyl C.sub.3 to C.sub.15, ##STR00012## where n=0-4, l=0 to 50, p=0 to 50, where o+p>0 R.sup.6?OH, methyl, acetyl or butyl.

19. The shaped hot-cure flexible polyurethane foam article according to claim 1, wherein the hot-cure flexible polyurethane foam has a porosity of 1.5 to 4.5 scfm, wherein a=2 to 8, b=40 to 150, c=2 to 30, d=0 to 8, e=0 to 3, where: a+b+c+d+e>48 R.sup.1=Me or R.sup.2 R.sup.2=polyethers of the general formula (c), ##STR00013## where f=0-3, g=3 to 70, h=0 to 80, where g+h>0 R.sup.3?OH, methyl, acetyl or butyl and where i=2 to 8, j=0 to 18, k=0 to 15, l=0 to 8, m=0 to 3, where: i+j+k+l+m<20 R.sup.4=Me or R.sup.5 R.sup.5=polyethers of the general formula (d), or alkyl C.sub.3 to C.sub.15, ##STR00014## where n=0-3, o=0 to 25, p=0 to 25, where o+p>0 R.sup.6?OH, methyl, acetyl or butyl.

20. The shaped hot-cure flexible polyurethane foam article according to claim 1, wherein:
[R.sup.1Me.sub.2SiO.sub.1/2].sub.a[Me.sub.2SiO.sub.2/2].sub.b[R.sup.2MeSiO.sub.2/2].sub.c[MeSiO.sub.3/2].sub.d[SiO.sub.4/2].sub.eFormula (1a) with a=2 b=70 c=4 d=0 e=0 with a+b+c+d+e=76 R.sup.1=Me or R.sup.2 R.sup.2=identical or different polyethers obtained from the polymerization of ethylene oxide, propylene oxide and/or other alkylene oxides and where
[R.sup.4Me.sub.2SiO.sub.1/2].sub.i[Me.sub.2SiO.sub.2/2].sub.j[R.sup.5MeSiO.sub.2/2].sub.k[MeSiO.sub.3/2].sub.l[SiO.sub.4/2].sub.mFormula (1b) with i=2 j=0, 4 or distribution 2 to 15, maximum at 9 k=0, 1, or 2 l=0 m=0 with i+j+k+l+m=3, 8 or distribution 4 to 17, maximum at 11 R.sup.4=Me R.sup.5=n-octyl or polyether 1 of formula f: ##STR00015## where: n=3 o=3.5 p=2.0 where O+p=5.5 R.sup.6?OH.

21. The shaped hot-cure flexible polyurethane foam article according to claim 1, wherein the finished polyurethane foam comprises 0.25% to 2.0% by weight of the at least one compound having the formula (1a) and comprises 0.1% to 1.5% by weight of the at least one compound of formula (1b).

22. A shaped hot-cure flexible polyurethane foam article, wherein the hot-cure flexible PU foam is obtained by reaction of at least one polyol component and at least one isocyanate component in the presence of at least one compound of formula (1a) and at least one compound of formula (1b) and at least one blowing agent and at least one catalyst, where:
[R.sup.1Me.sub.2SiO.sub.1/2].sub.a[Me.sub.2SiO.sub.2/2].sub.b[R.sup.2MeSiO.sub.2/2].sub.c[MeSiO.sub.3/2].sub.d[SiO.sub.4/2].sub.eFormula (1a) with a=2 to 10, b=25 to 200, c=2 to 40, d=0 to 10 e=0 to 5, where: a+b+c+d+e>48 R.sup.1=Me or R.sup.2 R.sup.2=identical or different polyethers obtained from the polymerization of ethylene oxide propylene oxide and/or other alkylene oxides and where
[R.sup.4Me.sub.2SiO.sub.1/2].sub.i[Me.sub.2SiO.sub.2/2].sub.j[R.sup.5MeSiO.sub.2/2].sub.k[MeSiO.sub.3/2].sub.l[SiO.sub.4/2].sub.mFormula (1b) with i=2 to 10, j=0 to 20 k=0 to 20 l=0 to 10, m=0 to 5, where: i+j+k+l+m<20 R.sup.4=Me or R.sup.5 R.sup.5=identical or different polyethers obtained from the polymerization of ethylene oxide, propylene oxide and/or other alkylene oxides, which does not comprise a surfactant other than compounds of formula (1a) and formula (1b).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 the result of the rolling test for silicone additive 1 is plotted against the porosity.

(2) FIG. 2 the result of the rolling test for silicone additive 2 is plotted against the porosity.

(3) FIG. 3 the result of the rolling test for silicone additive 3 is plotted against the porosity.

(4) For this purpose, in the figures FIG. 1 to FIG. 3, the result of the rolling test is plotted against porosity. In each case, the values for the reference (hot-cure flexible PU foam with foam stabilizer 1 only) and reference+1 part silicone additive are plotted. In order to obtain hot-cure flexible PU foams having different porosity, the same foaming operations were repeated on different days, the amount of stabilizer was varied and the amount of tin catalyst (Kosmos 29) was altered. Particularly the variation of the tin catalyst shows the desirably broad spectrum of porosity values.

(5) It is found that significant dependence of the result of the rolling test on porosity is observed for the reference foams. Non-inventive foams having porosities up to 2.3 scfm are generally very poor in the rolling test. Conversely, non-inventive hot-cure flexible PU foams are very good in the rolling test when they are very open (scfm>4.5). Most of the industrial hot-cure flexible PU foams, however, are between 1.5 and 4.5 scfm. Within this range, significantly improved results have surprisingly been found for all foams according to the invention in the rolling test. There is generally a certain degree of scatter in the values since both the measurement of porosity and the measurement of the results of the rolling test are subject to variations. Nevertheless, a significant improvement can be discerned.

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

(7) The hot-cure flexible PU foams according to the invention are also found to have low emissions if emissions-optimized additives are used. This can be seen in the VOC tests according to DIN EN ISO 16000-9:2008-04. It is found here, in a low-emissions formulation, that total emissions are slightly increased when silicone additive 1 is added (from 40 g/m.sup.3, cf. Table 8, to 130 ?g/m.sup.3, cf. Table 9), but are nevertheless still well below the typical limits for TVOC of 500 ?g/m.sup.3. The silicone additive 1 is thus also highly suitable for use in low-emissions formulations.

(8) The overall advantageousness of the invention has also been confirmed in the case of viscoelastic flexible foams.

(9) TABLE-US-00008 TABLE 8 VOC tests according to DIN EN ISO 16000-9: 2008- 04: (reference hot-cure PU flexible foam) Sample name: Reference Instrument: 7890/5975C Sample volume: 2.000 l Mass of standard: 0.396 ?g Area of standard: 129693683 Concentration Retention time equivalent to [min] Area toluene 4.6 510950 <1 ?g/m.sup.3 5.1 593475 <1 ?g/m.sup.3 5.9 534225 <1 ?g/m.sup.3 6.4 957326 1 ?g/m.sup.3 dimethylsilanediol 22.1 3381605 5 ?g/m.sup.3 ethylhexanoic acid 23.5 2598228 4 ?g/m.sup.3 cyclic siloxane D5 25.4 940103 1 ?g/m.sup.3 29.0 8728324 13 ?g/m.sup.3 branched alkanes 29.4 4122469 6 ?g/m.sup.3 branched alkanes 29.6 3680639 6 ?g/m.sup.3 branched alkanes 29.7 2462516 4 ?g/m.sup.3 branched alkanes 41.3 542066 <1 ?g/m.sup.3 Total (TVOC) 40 ?g/m.sup.3 Siloxane emissions (total) 5 ?g/m.sup.3

(10) TABLE-US-00009 TABLE 9 VOC tests according to DIN EN ISO 16000-9: 2008-04: (reference hot-cure PU flexible foam + 1.0 part silicone additive 1) Sample name: Reference + silicone additive 1 Instrument: 7890/5975C Sample volume: 2.000 l Mass of standard: 0.396 ?g Area of standard: 117796486 Concentration Retention time equivalent to [min] Area toluene 4.3 1241210 2 ?g/m.sup.3 4.4 904874 2 ?g/m.sup.3 4.6 813896 1 ?g/m.sup.3 5.1 803280 1 ?g/m.sup.3 6.0 1775599 3 ?g/m.sup.3 benzene 6.5 1756844 3 ?g/m.sup.3 dimethylsilanediol 8.8 2026275 3 ?g/m.sup.3 17.3 1528105 3 ?g/m.sup.3 cyclic siloxane D4 20.3 1676694 3 ?g/m.sup.3 linear siloxane N4 22.1 3887341 7 ?g/m.sup.3 ethylhexanoic acid 23.5 6367115 11 ?g/m.sup.3 cyclic siloxane D5 26.5 8835334 15 ?g/m.sup.3 linear siloxane N5 29.0 11993451 20 ?g/m.sup.3 branched alkanes 29.4 5008151 8 ?g/m.sup.3 branched alkanes 29.6 4203748 7 ?g/m.sup.3 branched alkanes 29.7 2903703 5 ?g/m.sup.3 branched alkanes 31.2 3916492 7 ?g/m.sup.3 linear siloxane N6 34.3 2291055 4 ?g/m.sup.3 linear siloxane N7 36.5 7455648 13 ?g/m.sup.3 linear siloxane N8 38.4 4932388 8 ?g/m.sup.3 linear siloxane N9 42.1 1213236 2 ?g/m.sup.3 Total 130 ?g/m.sup.3 (TVOC) Siloxane 67 ?g/m.sup.3 emissions (total)