DE102013217395A1 - Use of mixtures of organofunctionally modified polysiloxanes with amides in the production of flexible polyurethane foams - Google Patents

Abstract

The invention relates to mixtures comprising (a) organofunctionally modified polysiloxane and (b) amide compounds and (c) organic solvent, optionally in combination with other blending components, as well as their use in the production of flexible polyurethane foams and a process for the preparation of flexible polyurethane foams.

Description

The invention is in the field of polyurethanes, in particular polyurethane flexible foams. It relates in particular to the use of mixtures of organofunctionally modified polysiloxanes with amides and organic solvent in the production of flexible polyurethane foams and to a process for the production of flexible polyurethane foams.

Polysiloxane-polyoxyalkylene block copolymers, referred to below as polyethersiloxanes, are used in the production of polyurethane foams. They allow the formation of a uniform, fine pore structure and stabilize the foam during the manufacturing process. Depending on the manufacturing process and depending on which other raw materials are used, however, one obtains in some cases only an insufficient cell fineness. For example, the use of highly polypropylene oxide-containing polyols often leads to a more coarse cell structure. Even machine conditions can lead to an irregular or coarse cell structure, for example, when using low-pressure mixing heads or even with simple stirring of the raw materials at atmospheric pressure.

The use of certain blowing agents, such as in particular liquid CO ₂ or methylene chloride, places particularly high demands on the polyethersiloxane with regard to achieving a fine-pored cell structure. Due to its favorable eco-balance, so-called liquid CO ₂ technology has become increasingly important in western countries in recent years. In this method, pressurized CO ₂ - used as a blowing gas - in addition to the benefits generated by a chemical reaction of the isocyanates used with water CO _2.

The introduction of this technology has shown, however, that the spontaneous onset of foaming of the pressurized CO ₂ in the discharge of the reaction mixture makes increased demands on the cell formation characteristics of the components used in the foam formulation. This is also explainable, since the isocyanate-water reaction, which began earlier in the period of several seconds, only led to a slow gas saturation of the liquid phase and thus the slow formation of gas bubbles - the so-called creaming of the foam.

The use of highly volatile methylene chloride can also lead to cell coarsening. In particular, the production of low-density foams, primarily these are produced more in Asia, makes high demands on the stabilizing properties of siloxane. At high amounts of blowing agent, the reaction mixture is increasingly low viscosity, therefore the reaction mixture strong gel catalysts and high amounts of stabilizers are added to achieve sufficient cell stabilization.

The normally slow (without CO ₂ / methylene chloride) foaming process, which lays the foundation for the morphological properties - cell number and cell size distribution of the resulting foam - shrinks to fractions of a second, the time frame required for the raw materials to dissipate pressurized mixing head of a foaming machine and the subsequent application device to reach the ambient pressures of one atmosphere. In the case of CO ₂ foaming, similar to a shaving foam from a spray can, a foam forms spontaneously by evaporating liquid CO ₂ . The occurring defect in such foams are uneven, partially coarsened cells within the foam structure, wherein the use of suitable foam stabilizers can be quite helpful in minimizing these defects. However, there is often the problem that, in particular as a function of environmental parameters (such as pressure, raw material temperatures, use of solids in the formulation), even in the current state of the art otherwise well suitable stabilizers, which eg US-A-5,357,018 or US-A-5,321,051 described, do not produce completely flawless foams.

Although a refinement of the cell structure is basically possible by increasing the amount of polyethersiloxane used, the scope for increasing is limited, on the one hand because of the then occurring concomitant phenomenon of overstabilization, which can lead to too high closed cell density, in extreme cases even to shrinkage of the foam. on the other hand because of the associated unfavorable economy.

The principal use of additives to form polyether siloxanes or flexible foam formulations for cell refining is already known per se.

So describes EP-A-0 900 811 the use of cyclic carbonates in flexible foam formulations as cell refining agents. However, the cyclic carbonates are effective only in amounts of the order of the polyethersiloxane and also have the disadvantage of thinning volatile components from the finished foam.

EP-A-0 976 781 describes the combined use of polyether siloxanes with salts of organic acids. Cell refining occurs at low concentrations, but the solubility of the salts is relatively limited, requiring the use of water as a cosolvent. The application is therefore limited only to hydrolysis-stable polyether siloxanes. Furthermore, water contributes to the blowing reaction with isocyanate and must be taken into account, depending on the use concentration, if appropriate, in the formulation calculation.

The EP-A-1 029 878 relates to the use of improved polysiloxane-polyoxyalkylene block copolymers as additives in the preparation of polyurethane foams, the improvement being that by using both Si-C and Si-OC linked silicone polyether block copolymers in a blend, particular property combinations of Activity and cell fineness are made possible.

US-A-4 520 160 describes a process for the preparation of polyethersiloxanes in the presence of fatty alcohols. The latter prevent gelation during manufacture. The resulting products are preferably used as emulsifiers in cosmetic applications or as stabilizers in the production of elastomers, but not for the production of x-mas foam.

US-A-1,132,867 involves the use of fatty alcohols as a blending component of the polyethersiloxane. These are branched alcohols which are selected from Guerbet and Ziegler alcohols, in particular branched oxo and Isotridecylalkohole. However, the use of amide-containing compounds is not mentioned there.

The information in US-A-1,132,867 according to the experiments described using a mixture of a polyethersiloxane and isostearyl alcohol and other fatty alcohols an open-cell foam is obtained, which is equal to or better in its cell structure, as a foam resulting from a comparative experiment.

The object of the present invention was to allow an effective influence name on the cell refining in the production of flexible polyurethane foam.

Surprisingly, it has now been found that mixtures of certain polyether siloxanes with certain amide group-containing compounds and organic solvent in the production of flexible polyurethane foams have a significantly more effective effect on cell refining than the corresponding polyether siloxanes alone or with conventional blending components. The mixtures according to the invention enable the production of flexible polyurethane foams having a particularly regular cell structure and increased cell fineness.

The object of the invention is achieved by the subject matter of the invention. This is a
Mixture suitable as an additive in the production of flexible polyurethane foams, comprising

wobei die Reste
R¹, unabhängig voneinander, Alkylreste oder Arylreste sind, R², unabhängig voneinander, gleich R¹ und/oder R³ sind, mit der Maßgabe, dass mindestens ein Rest R² die Bedeutung R³ hat,
R³, unabhängig voneinander, ein Polyetherrest der Formel II -(Y)_e[O(C₂H_4-dR'_dO)_m(C_xH_2xO)_pZ]_w (II) ist, mit der Maßgabe, dass
e = 0 bis 1,
w = 1 bis 3,
d = 1 bis 3,
m ≥ 0,
x = 2 bis 4, insbesondere erhältlich durch Einsatz von C₂H₄O-, C₃H₆O- und C₄H₈O-Einheiten entweder einzeln oder in Kombination, und
p ≥ 0 sind, und
Y ein Kohlenwasserstoffrest ist, der gegebenenfalls verzweigt ist,
R' ausgewählt aus der Gruppe der einwertigen, gegebenenfalls aromatischen Kohlenwasserstoffreste von C₁ bis C₁₈ ist,
Z ein Wasserstoffrest oder ein einwertiger organischer Rest einschließlich eines Acylrestes ist,
die Summe m + p = 1 bis 200 ist, wobei p- und m-Bausteine in beliebiger Reihenfolge angeordnet sein können,
a eine Zahl von 1 bis 100 ist, wenn b eine Zahl von > 6 bis 8 ist,
a eine Zahl von 1 bis 200 ist, wenn b eine Zahl von > 3 bis 6 ist,
a eine Zahl von 1 bis 300 ist, wenn b eine Zahl von 0 bis 3 ist,
b = 0 bis 8, z.B. 1 bis 8,
sowie (b) zumindest eine Verbindung der Formel (III)

mit
R einem m-bindigen organischen Rest, vorzugsweise Kohlenwasserstoffrest,
bevorzugt Kohlenwasserstoffrest mit 1 bis 30 Kohlenstoffatomen, vorzugsweise mit 8 bis 20 Kohlenstoffatomen, wenn m = 1 und 1 bis 7, vorzugsweise 2 bis 6 Kohlenstoffatomen, wenn m = 2 oder 3 ist, besonders bevorzugt gesättigter Kohlenwasserstoffrest,
R' gleich oder verschieden H oder organischer Rest, vorzugsweise C₁-C₁₂-Alkyl-, Aryl-, Alkylaryl-Rest-, der ggf. Sauerstoff- oder Stickstoffatome, insbesondere Hydroxy- oder Amino-Gruppen aufweisen kann, oder ein Rest -X-Z,
m = 1 bis 5, vorzugsweise m = 1, 2 oder 3,
Z gleich oder verschieden OH oder NHR'', mit R'' = H oder Alkyl, insbesondere Alkyl mit 1 bis 30 Kohlenstoffatomen, vorzugsweise H, und
X gleich oder verschieden ein zweibindiger organischer Rest mit mindestens zwei Kohlenstoffatomen, vorzugsweise ein Kohlenwasserstoffrest, bevorzugt ein Rest -(CH2)_w- mit w = 2 bis 5, besonders bevorzugt ein Ethylen -Rest,
sowie (c) organisches Lösungsmittel, vorzugsweise Dipropylenglykol und/oder Propylenglykol,
wobei das Massenverhältnis von Siloxanverbindungen zu Verbindungen der Formel (III) größer 1 zu 10 ist, vorzugsweise größer-gleich 1 zu 4, besonders bevorzugt größer oder gleich 1 zu 2 und besonders bevorzugt von 1 zu 1.5 bis 1 zu 0.125 beträgt.(A) organofunctionally modified polysiloxane of the general formula I.

where the radicals
R ¹ , independently of one another, are alkyl radicals or aryl radicals, R ² , independently of one another, are identical to R ¹ and / or R ³ , with the proviso that at least one radical R ^{2 has} the meaning R ³ ,
R ³ , independently of one another, a polyether radical of the formula II - (Y) _e [O (C ₂ H _4-d R ' _d O) _m (C _x H _2x O) _p Z] _w (II) is, with the proviso that
e = 0 to 1,
w = 1 to 3,
d = 1 to 3,
m ≥ 0,
x = 2 to 4, in particular obtainable by using C ₂ H ₄ O, C ₃ H ₆ O and C ₄ H ₈ O units either individually or in combination, and
p ≥ 0, and
Y is a hydrocarbon radical which is optionally branched,
R 'is selected from the group of monovalent, optionally aromatic hydrocarbon radicals of C ₁ to C ₁₈ ,
Z is a hydrogen radical or a monovalent organic radical including an acyl radical,
the sum m + p = 1 to 200, where p and m blocks can be arranged in any order,
a is a number from 1 to 100, if b is a number from> 6 to 8,
a is a number from 1 to 200, when b is a number from> 3 to 6,
a is a number from 1 to 300, when b is a number from 0 to 3,
b = 0 to 8, eg 1 to 8,
and (b) at least one compound of the formula (III)

With
R is an m-bonded organic radical, preferably hydrocarbon radical,
preferably hydrocarbon radical having 1 to 30 carbon atoms, preferably having 8 to 20 carbon atoms, when m = 1 and 1 to 7, preferably 2 to 6 carbon atoms, when m = 2 or 3, particularly preferably saturated hydrocarbon radical,
R 'is identical or different and is H or organic radical, preferably C ₁ -C ₁₂ -alkyl, aryl, alkylaryl radical, which may optionally contain oxygen or nitrogen atoms, in particular hydroxyl or amino groups, or a radical - XZ,
m = 1 to 5, preferably m = 1, 2 or 3,
Z is the same or different OH or NHR '', with R '' = H or alkyl, in particular alkyl having 1 to 30 carbon atoms, preferably H, and
X is identically or differently a divalent organic radical having at least two carbon atoms, preferably a hydrocarbon radical, preferably a radical - (CH 2) _w - where w = 2 to 5, particularly preferably an ethylene radical,
and (c) organic solvent, preferably dipropylene glycol and / or propylene glycol,
wherein the mass ratio of siloxane compounds to compounds of formula (III) is greater than 1 to 10, preferably greater than or equal to 1 to 4, more preferably greater than or equal to 1 to 2, and most preferably from 1 to 1.5 to 1 to 0.125.

Polysiloxanes of general formula I which are characterized in that the index e = 1 and b = 0 are particularly preferred for the purposes of the present invention. Accordingly, these are SiC structures. Alternatively, it is equally preferable to use polysiloxanes of the general formula I, which are characterized in that the index e = 0. These are accordingly SiOC structures.

Suitable amides of the formula (III) may preferably be obtained by reacting a fatty acid or a fatty acid ester with an alkanolamine.

In the production of flexible polyurethane foam, the mixtures according to the invention allow a particularly effective influence name on the cell refining. In particular, they allow a significantly more effective influence on the cell refinement than the corresponding polyether siloxanes alone or with the usual blending components. These advantages also arise when using certain blowing agents, such as in particular liquid CO ₂ or methylene chloride, which usually make particularly high demands on the polyether siloxane with regard to achieving a fine-pored cell structure.

For the purposes of the invention, the simultaneous use of the components (a) to (c) as a mixture is particularly advantageous, since this leads to a significantly better effect on cell refining than a separate addition, such as e.g. the addition of the amide compound (b) via the polyol component. For the purposes of the invention, therefore, a mixture comprising constituents (a) to (c) should be used.

It is preferred that the mixtures according to the invention comprising components (a) to (c) consist of at least 40% by weight, preferably 50% by weight, of the abovementioned components (a) and (b). In addition, they may contain other ingredients, such as preferably water and additional surfactants. They can also be free of water and additional surfactants.

Preferred mixtures according to the invention may optionally contain water in addition to the components (a) to (c).

Particularly preferred mixtures according to the invention comprise, in addition to components (a) and (b) as component (c), dipropylene glycol and / or propylene glycol, and optionally water and optionally at least one additional surfactant. In particular, it may be preferred that as component (c) dipropylene glycol and / or propylene glycol are included, but no water and no additional surfactant are included.

Other preferred mixtures according to the invention comprise, in addition to components (a) and (b) as component (c), dipropylene glycol and / or propylene glycol, as well as water and at least one additional surfactant.

It is also possible to use non-reactive polyethers, preferably of higher molecular weight, phthalates, animal and vegetable oils and / or antifreeze in liquid form, as additional mixing component in the mixture.

• – ≥ 30 Gew.-% bis ≤ 68 Gew.-%, vorzugsweise ≥ 35 Gew.-% bis ≤ 65 Gew.-% und bevorzugt ≥ 40 Gew.-% bis ≤ 62 Gew.-% Polyethersiloxan gemäß Formel (I), wobei ein Polyethersiloxangehalt von 40 Gew.-% bis 60 Gew.-% besonders bevorzugt ist,
• – ≥ 1 Gew.-% bis ≤ 70 Gew.-%, vorzugsweise ≥ 2 Gew.-% bis ≤ 50 Gew.-% und bevorzugt ≥ 5 Gew.-% bis ≤ 40 Gew.-% Amidgruppen-haltiger Verbindung gemäß Formel (III), wobei Verbindungen der Formel (IV) besonders bevorzugt sind,
• – ≥ 1 Gew.-% bis ≤ 70 Gew.-%, vorzugsweise ≥ 10 Gew.-% bis ≤ 60 Gew.-% und bevorzugt ≥ 20 Gew.-% bis ≤ 55 Gew.-% organische Lösungsmittel, vorzugsweise Propylen- und/oder Dipropylenglykol, insbesondere Dipropylenglykol,
• – vorteilhafterweise ≥ 1 Gew.-% bis ≤ 70 Gew.-%, vorzugsweise ≥ 10 Gew.-% bis ≤ 60 Gew.-% und bevorzugt ≥ 20 Gew.-% bis ≤ 55 Gew.-% Wasser
• – vorteilhafterweise ≥ 1 Gew.-% bis ≤ 10 Gew.-%, vorzugsweise ≥ 2 Gew.-% bis ≤ 8 Gew.-% und bevorzugt ≥ 4 Gew.-% bis ≤ 6 Gew.-% zusätzliches organisches Tensid, wie vorzugsweise Alkylbenzolsulfonat, insbesondere beim Einsatz von Wasser-haltigen Lösemittelkombinationen oder einem Anteil an Amid-gruppenhaltigen Verbindungen gemäß Formel (III) > 60 Gew-%. Eine erfindungsgemäße Mischung kann auch frei sein von Wasser und zusätzlichem organischen Tensid.

For use in the production of flexible polyurethane hot foams, the mixtures according to the invention are particularly well suited. A preferred mixture according to the invention which can be used, in particular, as a flexible polyurethane foam stabilizer solution comprises:

• - ≥ 30 wt .-% to ≤ 68 wt .-%, preferably ≥ 35 wt .-% to ≤ 65 wt .-% and preferably ≥ 40 wt .-% to ≤ 62 wt .-% polyether siloxane according to formula (I) where a polyether siloxane content of from 40% to 60% by weight is particularly preferred,
• - ≥ 1 wt .-% to ≤ 70 wt .-%, preferably ≥ 2 wt .-% to ≤ 50 wt .-% and preferably ≥ 5 wt .-% to ≤ 40 wt .-% amide group-containing compound according to formula (III), compounds of the formula (IV) being particularly preferred,
• - ≥ 1 wt .-% to ≤ 70 wt .-%, preferably ≥ 10 wt .-% to ≤ 60 wt .-% and preferably ≥ 20 wt .-% to ≤ 55 wt .-% organic solvent, preferably propylene and / or dipropylene glycol, especially dipropylene glycol,
• - Advantageously, ≥ 1 wt .-% to ≤ 70 wt .-%, preferably ≥ 10 wt .-% to ≤ 60 wt .-% and preferably ≥ 20 wt .-% to ≤ 55 wt .-% water
• - Advantageously, ≥ 1 wt .-% to ≤ 10 wt .-%, preferably ≥ 2 wt .-% to ≤ 8 wt .-% and preferably ≥ 4 wt .-% to ≤ 6 wt .-% additional organic surfactant, such as preferably alkylbenzenesulfonate, in particular when using water-containing solvent combinations or a proportion of amide-containing compounds of formula (III)> 60% by weight. A mixture according to the invention may also be free of water and additional organic surfactant.

Optionally, the mixture according to the invention, which is in particular a Polyurethanheißweichschaumstabilisatorlösung, as additional components have further additives. The proportion of the components used is in each case selected so that the total content of the components does not exceed 100% by weight.

• – ≥ 35 Gew.-% bis ≤ 65 Gew.-%, vorzugsweise 40–50 Gew.-% Polyethersiloxan gemäß Formel (I),
• – ≥ 1 Gew.-% bis ≤ 50 Gew.-% Amidgruppen-haltiger Verbindung gemäß Formel (III), wobei Verbindungen der Formel (IV) besonders bevorzugt sind,
• – ≥ 1 Gew.-% bis ≤ 10 Gew.-%, vorzugsweise ≥ 2 Gew.-% bis ≤ 8 Gew.-% und bevorzugt 5 Gew.-% Alkylbenzolsulfonat,
• – ≥ 30 Gew.-% bis ≤ 50 Gew.-%, vorzugsweise ≥ 35 Gew.-% bis ≤ 45 Gew.-% und bevorzugt 40 Gew.-% Wasser, und
• – ≥ 1 Gew.-% bis ≤ 20 Gew.-%, vorzugsweise ≥ 3 Gew.-% bis ≤ 15 Gew.-% organische Lösungsmittel, vorzugsweise Propylen- und/oder Dipropylenglykol, insbesondere Dipropylenglykol.

A preferred mixture according to the invention comprises:

• - ≥ 35 wt .-% to ≤ 65 wt .-%, preferably 40-50 wt .-% polyether siloxane according to formula (I),
• - ≥ 1 wt .-% to ≤ 50 wt .-% amide group-containing compound according to formula (III), compounds of formula (IV) are particularly preferred,
• From ≥ 1% by weight to ≦ 10% by weight, preferably ≥ 2% by weight to ≦ 8% by weight and preferably 5% by weight of alkylbenzenesulfonate,
• - ≥ 30 wt .-% to ≤ 50 wt .-%, preferably ≥ 35 wt .-% to ≤ 45 wt .-% and preferably 40 wt .-% water, and
• - ≥ 1 wt .-% to ≤ 20 wt .-%, preferably ≥ 3 wt .-% to ≤ 15 wt .-% organic solvent, preferably propylene and / or dipropylene glycol, in particular dipropylene glycol.

• – ≥ 35 Gew.-% bis ≤ 65 Gew.-%, vorzugsweise 40–50 Gew.-% Polyethersiloxan gemäß Formel (I),
• – ≥ 1 Gew.-% bis ≤ 50 Gew.-% Amidgruppen-haltiger Verbindung gemäß Formel (III), wobei Verbindungen der Formel (IV) besonders bevorzugt sind,
• – ≥ 5 Gew.-% bis ≤ 70 Gew.-%, vorzugsweise ≥ 10 Gew.-% bis ≤ 60 Gew.-% und bevorzugt 20–40 Gew.-%, organische Lösungsmittel, vorzugsweise Propylen- und/oder Dipropylenglykol, insbesondere Dipropylenglykol. Dieses bevorzugte Gemisch ist vorzugsweise frei von Wasser und zusätzlichem organischen Tensid.

Another mixture particularly preferred according to the invention comprises:

• - ≥ 35 wt .-% to ≤ 65 wt .-%, preferably 40-50 wt .-% polyether siloxane according to formula (I),
• - ≥ 1 wt .-% to ≤ 50 wt .-% amide group-containing compound according to formula (III), compounds of formula (IV) are particularly preferred,
• From ≥ 5% by weight to ≦ 70% by weight, preferably ≥ 10% by weight to ≦ 60% by weight and preferably 20-40% by weight, organic solvents, preferably propylene and / or dipropylene glycol, especially dipropylene glycol. This preferred mixture is preferably free of water and additional organic surfactant.

In the following, optionally additionally usable organic surfactants are described in more detail. These may in particular be selected from the group comprising anionic surfactants, cationic surfactants, nonionic surfactants and / or amphoteric surfactants, wherein the organic surfactant is preferably an anionic surfactant. The mixtures according to the invention may preferably contain one or more surfactants selected from anionic, nonionic, cationic, ampholytic (amphoteric, zwitterionic) surfactants and mixtures thereof.

A typical listing of anionic, cationic, nonionic and ampholytic (zwitterionic) classes and types of these surfactants is in U.S. Patent No. 3,929,678 and in U.S. Patent No. 4,259,217 which are hereby incorporated by reference and the contents of which are incorporated herein by reference.

Anionic surfactant: The compositions of the invention preferably comprise an anionic surfactant. These may include salts including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di- and triethanolamine salts of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate and sulfonate surfactants are preferred.

Highly preferred are surfactant systems comprising a sulfonate or a sulfate surfactant, preferably a linear or branched alkyl benzene sulfonate and alkyl ethoxy sulfates as described herein, optionally also combined with cationic surfactants as described herein.

Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (particularly saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinate (especially saturated and unsaturated C ₆ -C ₁₄ diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil are also suitable.

Anionic sulfate surfactant: These include the linear and branched, primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates containing C ₅ -C ₁₇ acyl-N- (C ₁ -C ₄ alkyl) and -N- (C ₁ -) C ₂ -hydroxyalkyl) glucamine sulfates, and sulfates of the alkyl polysaccharides such as the sulfates of alkyl polyglucoside (wherein the nonionic unsulfated compounds are described herein).

Alkyl sulfate surfactants are preferably selected from the linear and branched primary C ₁₀ -C ₁₈ alkyl sulfates, more preferably the branched chain C ₁₁ -C ₁₅ alkyl sulfates and the straight chain C ₁₂ -C ₁₄ alkyl sulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C ₁₀ -C ₁₈ alkyl sulfates ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C ₁₁ -C ₁₈ , most preferably C ₁₁ -C _15, alkyl sulfate ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.

Anionic Sulfonate Surfactant: Anionic sulfonate surfactants include the salts of linear C ₅ -C ₂₀ alkyl benzene sulfonates, alkyl ester sulfonates, C ₆ -C ₂₂ primary or secondary alkanesulfonates, C ₆ -C ₂₄ olefin sulfonates, aryl sulfonates (especially unsubstituted and alkyl-substituted benzene and naphthalene sulfonates ), sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acylglycerol sulfonates, monoesters of sulfosuccinate (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinate (especially saturated and unsaturated C ₆ -C ₁₄ diesters), fatty oleyl glycerol sulfonates and any mixture from that.

Anionic carboxylate surfactant: Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxypolycarboxylate surfactants and the soaps ("alkyl carboxyls"), especially certain secondary soaps as described herein.

Suitable alkyl ethoxy carboxylates include those of the formula RO (CH ₂ CH ₂ O) _x CH ₂ COO-M ^⊕ , wherein R is a C ₆ to C ₁₈ alkyl group, x is in the range of 0 to 10, and the ethoxylate distribution is the amount of material where x is 0 is less than 20% by weight and M is a cation. Suitable alkyl polyethoxypolycarboxylate surfactants include those having the formula RO (CHR ¹ -CHR ² -O) -R ³ , wherein R is a C ₆ to C ₁₈ alkyl group, x is from 1 to 25, R ¹ and R ^{2 are} selected from the group consisting of hydrogen, methyl acid residue, succinic acid residue, hydroxysuccinic acid residue and mixtures thereof, and R ^{3 is} selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include the secondary soap surfactants containing a carboxyl moiety bonded to a secondary carbon. Preferred secondary soap surfactants are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1 octanoic acid and 2-pentyl-1-heptanoic acid.

Sarcosinate surfactant: Other suitable anionic surfactants are the sarcosinates of the formula R-CON (R ¹ ) CH ₂ COOM, where R is a linear or branched C 5 -C 17 alkyl-; or alkenyl group, R ^{1 is} a C ₁ -C ₄ alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and Oleoylmethylsarcosinate in the form of their sodium salts.

The anionic surfactant may more preferably be selected from the group comprising alkyl sulfates, arylsulfonates, fatty alcohol sulfates, secondary alkyl sulfates, paraffin sulfonates, alkyl ether sulfates, alkylpolyglycol ether sulfates, fatty alcohol ethersulfates, alkylbenzenesulfonates, alkylphenol ether sulfates, alkyl phosphates, phosphoric mono-, di-, tri-esters, alkyl ether phosphates, ethoxylated Fettalkoholphosphorsäureester, Phosphonic acid esters, sulfosuccinic acid esters, sulfosuccinic acid monoesters, ethoxylated sulfosuccinic acid monoesters, sulfosuccinamides, α-olefinsulfonates, alkylcarboxylates, alkylethercarboxylates, alkylpolyglycolcarboxylates, fatty acid isethionate, fatty acid methyltauride, fatty acid sarcoside, arylsulfonates, naphthalenesulfonates, alkylglyceryl ether sulfonates, polyacrylates and / or α-sulfofatty acid esters.

Cationic surfactants: Suitable cationic surfactants which may be used as the surfactant component include quaternary ammonium surfactants. Preferably, the quaternary ammonium surfactant is a mono C ₆ -C ₁₆ , preferably C ₆ -C _10, N-alkyl or alkenyl ammonium surfactant wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Also preferred are the monoalkoxylated and bisalkoxylated amine surfactants.

Another suitable group of cationic surfactants that can be used are cationic ester surfactants.

The cationic ester surfactant is a preferably water-dispersible compound having surfactant properties comprising at least one ester (i.e., -COO) bond and at least one cationically charged group.

Suitable cationic ester surfactants, including choline ester surfactants, are described, for example, in US Pat U.S. Patents 4,282,842 . 4239660 and 4260529 disclosed.

In a preferred aspect, the ester bond and the cationically charged group in the surfactant molecule are separated by a spacer group consisting of a chain comprising at least three atoms (ie chain length of three atoms), preferably three to eight atoms, more preferably three to five atoms, most preferably three atoms. The atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in the chain is attached only to carbon atoms in the chain. Thus, spacer groups with, for example, -O- (ie peroxide), -NN and -NO bonds are excluded, while spacer groups with, for example, -CH ₂ -O-CH ₂ - and -CH ₂ -NH-CH ₂ bonds are included , In a preferred aspect, the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.

Cationic monoalkoxylated amine surfactants: Preferably usable cationic monoalkoxylated amine surfactants have the general formula V: R ¹ R ² R ³ N ^⊕ Z _n R ⁴ X ^- (V) wherein R ^{1 is} an alkyl or alkenyl moiety having 6 to 18 carbon atoms, preferably 6 to 16 carbon atoms, most preferably 6 to 14 carbon atoms; R ² and R ^{3 are} each independently alkyl groups of from one to three carbon atoms, preferably methyl, most preferably both R ² and R ^{3 are} methyl groups; R ^{4 is selected} from hydrogen (preferred), methyl and ethyl; X ^{- is} an anion such as chloride, bromide, methylsulfate, sulfate or the like to provide electrical neutrality; Z is an alkoxy group, especially an ethoxy, propoxy or butoxy group; and n is from 0 to 30, preferably 2 to 15, most preferably 2 to 8.

Preferably, the Z _n R ⁴ group in formula V has n = 1 and is a hydroxyalkyl group having not more than 6 carbon atoms wherein the -OH group is separated by not more than 3 carbon atoms from the quaternary ammonium nitrogen atom. Particularly preferred Z _n R ⁴ groups are -CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH (CH ₃ ) OH and CH (CH ₃ ) CH ₂ OH, wherein -CH ₂ CH ₂ OH is particularly preferred. Preferred R ¹ groups are linear alkyl groups. Linear R ¹ groups of 8 to 14 carbon atoms are preferred.

worin R1 C₁₀-C₁₈-Hydrocarbyl und Mischungen davon, besonders C₁₀-C₁₄-Alkyl, vorzugsweise C₁₀- und C₁₂-Alkyl ist und X jedes geeignete Anion zur Bereitstellung von Ladungsausgleich, vorzugsweise Chlorid oder Bromid, ist. Die Ethoxy-(CH₂CH₂O-)Einheiten (EO) der Formel II können auch durch Butoxy-, Isopropoxy[CH(CH₃)CH₂O]- und [CH₂CH(CH₃)O]-Einheiten (i-Pr) oder n-Propoxyeinheiten (Pr) oder Mischungen von EO- und/oder Pr- und/oder i-Pr-Einheiten ausgetauscht sein. Additionally preferably usable cationic monoalkoxylated amine surfactants have the formula VI:

wherein R 1 is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, especially C ₁₀ -C ₁₄ alkyl, preferably C ₁₀ and C ₁₂ alkyl, and X is any suitable anion for providing charge balance, preferably chloride or bromide. The ethoxy (CH ₂ CH ₂ O) units (EO) of the formula II can also be prepared by butoxy, isopropoxy [CH (CH ₃ ) CH ₂ O] - and [CH ₂ CH (CH ₃ ) O] units ( i-Pr) or n-propoxy units (Pr) or mixtures of EO and / or Pr and / or i-Pr units.

worin R¹ eine Alkyl- oder Alkenyleinheit mit 8 bis 18 Kohlenstoffatomen, vorzugsweise 10 bis 16 Kohlenstoffatomen, am meisten bevorzugt 10 bis 14 Kohlenstoffatomen ist; R² eine Alkylgruppe mit einem bis drei Kohlenstoffatomen, vorzugsweise Methyl ist; R³ und R⁴ unabhängig variieren können und aus Wasserstoff (bevorzugt), Methyl und Ethyl ausgewählt sind, X– ein Anion, wie Chlorid, Bromid, Methylsulfat, Sulfat oder dergleichen ist, das ausreicht, um elektrische Neutralität bereitzustellen. Z können unabhängig voneinander variieren und sind jeweils aus C₁-C₄-Alkoxy, besonders Ethoxy (d. h. -CH₂CH₂O-), Propoxy, Butoxy und Mischungen davon; n ist gleich oder unterschiedlich voneinander 1 bis 30, vorzugsweise 1 bis 4, und am meisten bevorzugt 1. Cationic bisalkoxylated amine surfactant: The cationic bisalkoxylated amine surfactant preferably has the general formula VII:

wherein R ^{1 is} an alkyl or alkenyl moiety having 8 to 18 carbon atoms, preferably 10 to 16 carbon atoms, most preferably 10 to 14 carbon atoms; R ^{2 is} an alkyl group having one to three carbon atoms, preferably methyl; R ³ and R ⁴ may vary independently and are selected from hydrogen (preferred), methyl and ethyl; X- is an anion such as chloride, bromide, methylsulfate, sulfate or the like sufficient to provide electrical neutrality. Z may vary independently and are each selected from C ₁ -C ₄ alkoxy, especially ethoxy (ie, -CH ₂ CH ₂ O-), propoxy, butoxy, and mixtures thereof; n is the same or different from each other 1 to 30, preferably 1 to 4, and most preferably 1.

worin R¹ C₁₀-C₁₈-Hydrocarbyl und Mischungen davon, vorzugsweise C₁₀-, C₁₂-, C₁₄-Alkyl und Mischungen davon sind. X ist jedes geeignete Anion, um Ladungsausgleich bereitzustellen, vorzugsweise Chlorid. Mit Bezugnahme auf die vorstehend angegebene allgemeine Struktur des kationischen bisalkoxylierten Amins, da in einer bevorzugten Verbindung R¹ von (Kokosnuss)-C12-C14-Alkylfettsäuren abgeleitet ist. Preferred cationic bisalkoxylated amine surfactants have the formula VIII:

wherein R ^{1 is} C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, preferably C ₁₀ , C ₁₂ , C ₁₄ alkyl and mixtures thereof. X is any suitable anion to provide charge balance, preferably chloride. With reference to the general structure of the cationic bis-alkoxylated amine given above, since in a preferred compound R ^{1 is derived} from (coconut) C 12 -C 14 alkyl fatty acids.

worin R¹ C₁₀-C₁₈-Hydrocarbyl, vorzugsweise C₁₀-C₁₄-Alkyl ist, unabhängig p 1 bis 3 und q 1 bis 3 ist, R² ist C₁-C₃-Alkyl, vorzugsweise Methyl und X ist ein Anion, vorzugsweise Chlorid oder Bromid. Further suitable cationic bisalkoxylated amine surfactants include compounds of the formula IX:

wherein R ^{1 is} C ₁₀ -C ₁₈ hydrocarbyl, preferably C ₁₀ -C ₁₄ alkyl, independently p is 1 to 3 and q is 1 to 3, R ² is C ₁ -C ₃ alkyl, preferably methyl and X is one Anion, preferably chloride or bromide.

Other compounds of the above type include those in which the ethoxy (CH ₂ CH ₂ O) units (EO) are substituted by butoxy (Bu), isopropoxy [CH (CH ₃ ) CH ₂ O] - and [CH ₂ CH (CH ₃ O) units (i-Pr) or n-propoxy units (Pr) or mixtures of EO and / or Pr and / or i-Pr units.

The cationic surfactant may more preferably be selected from the group comprising esterquats, preferably di (tallow fatty acid amidoethyl) methylpolyethoxyammonium methosulphate, Diamidoaminquats, Alkyloxyalkylquats, vorzugweise cocopentaethoxymethylammonium methosulfate and / or trialkyl quats, preferably cetyltrimethylammonium chloride.

Nonionic Surfactant: Substantially all nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants can be selected from the classes of nonionic condensates of alkylphenols, nonionic ethoxylated alcohols, nonionic ethoxylated / propoxylated fatty alcohols, nonionic ethoxylate / propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide / ethylenediamine addition products.

Nonionic surfactant of alkoxylated alcohol: The condensation products of aliphatic alcohols with 1 to 25 moles of alkylene oxide, especially ethylene oxide, propylene oxide, butylene oxide, dodecene oxide or styrene oxide are also usable according to the invention. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group of 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol.

Nonionic polyhydroxy fatty acid amide surfactant: Polyhydroxy fatty acid amides which are suitable are those having the structural formula R ² CONR ¹ Z wherein: R ^{1 is} H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl ethoxy, propoxy or a mixture thereof; preferably C ₁ -C ₄ -alkyl, more preferably C ₁ or C ₂ -alkyl, most preferably C ₁ -alkyl (ie methyl); and R ^{2 is} a C ₅ -C ₃₁ hydrocarbyl, preferably a straight chain C ₅ -C ₁₉ alkyl or alkenyl, more preferably a straight chain C ₉ -C ₁₇ alkyl or alkenyl, most preferably a straight chain C ₁₁ - C ₁₇ alkyl or alkenyl, or a mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain in which at least 3 hydroxyl groups are attached directly to the chain or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z is preferably derived from a reducing sugar in a reductive amination; more preferably, Z is a glycidyl.

Nonionic fatty acid amide surfactant: Suitable fatty acid amide surfactants include those having the formula: R ⁶ CON (R ⁷ ) ₂ wherein R is an alkyl group of 7 to 21, preferably 9 to 17 carbon atoms and each R ^{7 is selected} from the group consisting of hydrogen, C ₁ -C ₄ Alkyl, C ₁ -C ₄ hydroxyalkyl and - (C ₂ H ₄ O) _x H is selected, wherein x is in the range of 1 to 3.

Nonionic Alkyl Polysaccharide Surfactant: Suitable alkyl polysaccharides for use herein are described in U.S. Pat U.S. Patent 4,565,647 , disclosed with a hydrophobic group containing 6 to 30 carbon atoms, and a hydrophilic polysaccharide, e.g. B. a polyglycoside group containing 1 to 3 to 10 saccharide units.

Preferred alkyl polyglycosides have the formula: R ² O (C _n H _2n O) _t (glycosyl) _x wherein R ^{2 is} selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof in which the alkyl groups are from 10 to Contain 18 carbon atoms; n is 2 or 3; t is from 0 to 10 and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.

The nonionic surfactant may particularly preferably be selected from the group comprising alcohol ethoxylates, fatty alcohol polyglycol ethers, fatty acid ethoxylates, fatty acid polyglycol esters, glyceride monoalkoxylates, alkanolamides, fatty acid alkylolamides, ethoxylated alkanolamides, fatty acid alkylolamidoethoxylates, imidazolines, ethylene oxide-propylene oxide block copolymers, alkylphenol ethoxylates, alkylglucosides, ethoxylated sorbitan esters and / or amine alkoxylates.

Amphoteric surfactant: Suitable useful amphoteric surfactants include the amine oxide surfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds of the formula R ³ (OR ⁴ ) _x NO (R ⁵ ) ₂ wherein R ^{3 is selected} from alkyl, hydroxyalkyl, acylamidopropyl; and alkylphenyl group or mixtures thereof having from 8 to 26 carbon atoms; R ^{4 is} an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R ^{5 is} an alkyl or hydroxyalkyl group of 1 to 3 or a polyethylene oxide group of 1 to 3 ethylene oxide groups. Preference is given to C ₁₀ -C ₁₈ -alkyldimethylamine oxide and C ₁₀ -C ₁₈ -acylamidoalkyldimethylamine oxide.

Other suitable amphoteric surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are preferred amphoteric surfactants.

Suitable betaines are those compounds having the formula R (R ') ₂ N + R ² COO- wherein R is a C ₆ -C ₁₈ hydrocarbyl group, each R ^{1 is} typically C ₁ -C ₃ alkyl and R ^{2 is} a C ₁ -C ₅ hydrocarbyl group. Preferred betaines are C ₁₂ -C ₁₈ dimethylammonium hexanoate and the C ₁₀ -C ₁₈ acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable according to the invention.

The amphoteric surfactant may more preferably be selected from the group comprising amphoacetates, amphodiacetates, glycinates, amphopropionates, sultaines, amine oxides and / or betaines.

The mixtures according to the invention can be used for the production of flexible polyurethane foams, which include in particular (conventional) polyether soft foams, as well as polyester flexible foams, viscoelastic foams and high resilience (cold) foams, but in particular (conventional) polyether soft foams, and thereby allow a particular effective influence name on the cell refinement. These advantages also arise when using certain blowing agents, such as in particular liquid CO ₂ or methylene chloride, which usually make particularly high demands on the polyether siloxane with regard to achieving a fine-pored cell structure.

The polyether siloxanes of the general formula (I) on which this invention is based are, in particular, polysiloxane-polyoxyalkylene copolymers which contain modified polyoxyalkylene building blocks.

In principle, all those structures or mixtures of those are included, which can generally be used in the production of flexible polyurethane foams.

Particularly advantageous for the interaction of the mixture components (a) to (c) is the use of a polyether siloxane according to formula (I), which preferably has a certain nucleation support, that is, when used alone preferably already gives a satisfactory cell structure. The skilled person can find out from a few hand tests.

The polysiloxane can be varied almost arbitrarily with respect to the number of siloxane units and the number of possible connections with the polyoxyalkylene.

Polysiloxane-polyoxyalkylene block copolymers are described in numerous publications.

For example, describes DE-A-15 70 647 the so-called SiOC-linked polyether siloxanes. The preparation of this Polyethersiloxanklasse is inter alia in DE-A-10 12 602 . DE-A-10 40 251 . DE-A-11 20 147 as in US-A-3 115 512 described.

The preparation of the so-called SiC-linked polysiloxane-polyoxyalkylene block copolymers is described, for example, in US Pat USA-A-2 846 458 as well as in the layouts DE-A-12 20 615 and DE-A-11 53 166 described.

Particular preference may be given to using polyethersiloxanes of the general formula I, with the provisos that R ₂ in at least one case is R ₃ and that m> p, which corresponds to a particularly preferred embodiment.

Furthermore, it is particularly preferred if the amides of the general formula III are used in an amount of 0.1 to 200 parts by weight, in particular 10 to 150 parts by weight, based on 100 parts by weight of the polysiloxanes of the general formula I. become.

Suitable amides of the formula (III) may, for. Example by reacting alkanolamines with carboxylic acids, preferably of fatty acids or fatty acid esters are prepared.

The basic preparation of amides of the formula (III) is known per se to the person skilled in the art and can be carried out by the known processes of the prior art. For example, the production of acid amides according to those in the prior art, such. Z. in DE 1802500 ; DE 1802503 . DE 1745443 . DE 1745459 and US 3578612 take place known methods. It can be used as raw materials z. B. the corresponding carboxylic acids are used and amide formation take place with dehydration. It is likewise possible to use carboxylic esters, for example methyl esters, in which case methanol is split off. Preference is also given to glycerides. As carboxylic acids for preparing the amides of formula (III) z. As monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids are used for example based on aliphatic or aromatic hydrocarbons or derivatives thereof. Preferred acids are straight-chain saturated or unsaturated fatty acids having up to 40 carbon atoms, such as. Butyric acid (butanoic acid), caproic acid (hexanoic acid), caprylic acid (octanoic acid), capric acid (decanoic acid), lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), arachidic acid (eicosanoic acid), behenic acid (docosanoic acid ), Lignoceric acid (tetracosanoic acid), palmitoleic acid ((Z) -9-hexadecenoic acid), oleic acid ((Z) -9-hexadecenoic acid), elaidic acid ((E) -9-octadecenoic acid), cis-vaccenic acid ((Z) -11- Octadecenoic acid), linoleic acid ((9Z, 12Z) -9,12-octadecadienoic acid), alpa-linolenic acid ((9Z, 12Z, 15Z) -9,12,15-octadecatrienoic acid), gamma-linolenic acid ((6Z, 9Z, 12Z) -6,9,12-octadecatrienoic acid), di-homo-gamma-linolenic acid ((8Z, 11Z, 14Z) -8,11,14-eicosatrienoic acid), arachidonic acid ((5Z, 8Z, 11Z, 14Z) -5,8,11 , 14-eicosatetraenoic acid), erucic acid ((Z) -13-docosenoic acid), nervonic acid ((Z) -15-tetracosensic acid), ricinoleic acid, hydroxystearic acid and undecenoic acid, and mixtures thereof, such as rapeseed oil acid, soybean fatty acid sunflower fatty acid, peanut fatty acid and tall oil fatty acid. Furthermore, dimer and oligomer fatty acids, such as those resulting from the oligomerization of unsaturated fatty acids, can be used. Suitable amines for the preparation of amides of the formula (III) are those having at least one primary or secondary amine function for amidation, which may optionally have one or more hydroxyl groups. Suitable amines are, for example: ethylenediamine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenhexamine, hexapropylenepheptamine, and higher homologs based on ethylenediamine or propylenediamine, 1,2-propylenediamine, 4 4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4-methylenediphenylenediamine, isophoronediamine, trimethylhexamethylenediamine, neopentanediamine, octamethylenediamine, polyetheramines such as polyetheramine D 2000 (BASF), polyetheramine D 230 (BASF), polyetheramine T 403 (BASF), polyetheramine T 5000 (BASF) or also corresponding Jeffamine types from Huntsman, piperazine, aminoethylpiperazine, bis (aminoethyl) piperazine, 1,3-diaminopropane, 3- (cyclohexylamino) propylamine, 3- (methylamino) propylamine , N, N-bis (3-aminopropyl) methylamine, (3- (2-aminoethylamino) propylamine), dipropylene triamine, (N, N'-bis (3-aminopropyl) ethylenediamine.

Suitable hydroxylamines having at least one OH function are, for example: ethanolamine, propanolamine, alkylethanolamines, arylethanolamine, alkylpropanolamine, for example: diethanolamine, monoethanolamine, diisopropanolamine, isopropanolamine, methylisopropanolami, digylcolamine (2- (2-aminoethoxy) ethanol), dimethylethanolamine , N- (2-hydroxyethyl) aniline, 1- (2-hydroxyethyl) piperazine, 2- (2-aminoethoxy) ethanol, 3-amino-1-propanol, 5-amino-1-pentanol, butylethanolamine, ethylethanolamine, N- Methylethanolamine, aminopropylmonomethylethanolamine, 2-amino-2-methylpropanol, trishydroxymethylaminomethane (THMAM or TRIS), N- (2-aminoethyl) ethanolamine (AEEA). It is also possible to use corresponding alkoxylates, in particular ethoxylates and / or propoxylates of amines, such as e.g. Alkylamines having a hydroxyethyl or hydroxypropyl unit or for example N-hydroxyethyl-Cylohexyldiamin, N-hydroxyethyl isophoronediamine, N-hydroxyethyl piperazine, bis (hydroxyethyl) toluenediamine.

Amides of formula (III) according to the invention may also be commercially available amides having OH or NH functions, such as Evonik Industries: Rewomid ^® DC 212 S, Rewomid ^® DO 280 SE, Rewocid ^® DU 185 SE, Rewolub ^® KSM, REWOMID ^® C 212 REWOMID ^® IPP 240, REWOMID ^® SPA, Rewopon ^® IM AO, Rewopon ^® IN AN or Rewopon ^® IM R 40 and DREWPLAST ^® 154, Ninol ^® 1301 Ninol ^® 40-CO, Ninol ^® 1281, Ninol ^® COMF , Ninol ^® M-10, and ethoxylated Diethanolaminde as Ninol ^® C-4 l, Ninol ^® C-5, Ninol ^® 1301 from Stepan or DACAMID ^® MAL and DACAMID DC ^® of Sasol.

Particularly preferred according to the present invention, the mixtures according to the invention comprising (a) polysiloxane of the general formula I and (b) amide group-containing compounds according to the general formula III, and (c) at least one organic solvent, in particular dipropylene glycol, in a total amount of 0.01 to 13 wt .-%, preferably 0.1 to 13 wt .-%, based on the total polyurethane foam formulation used.

The proportion of erfindunsgemäßen mixture comprising (a) polysiloxane of the general formula I and (b) amide group-containing compounds according to the general formula III, and (c) at least one organic solvent, in particular dipropylene glycol, based on 100 parts by mass of polyol preferably from greater than 0.05 to 20 parts by mass, preferably from 0.2 to 10 parts by mass, and more preferably from 0.5 to 5 parts by mass.

It may be advantageous if the amides of the formula (III) are already used as solvent in the production process of the Si compounds to be used in the mixture, usually a hydrosilylation process. In this way, an additional separation step and / or the entry of undesired solvents in the compositions according to the invention are avoided.

mit m, R, R' und X wie oben bei der Formel (III) definiert. Preferably, the amide of the formula (III) is at least one compound of the formula (IIIa)

with m, R, R 'and X as defined above for the formula (III).

mit R wie oben bei Formel (III) definiert, wobei das Amid der Formel (IV) vorzugsweise durch Umsetzung einer Fettsäure mit Diethanolamin erhalten wird.The mixture according to the invention as amide of the formula (III) preferably comprises at least one compound of the formula (IV)

with R defined above for formula (III), wherein the amide of the formula (IV) is preferably obtained by reacting a fatty acid with diethanolamine.

wobei die Reste
R¹ unabhängig voneinander, Alkylreste oder Arylreste sind, R² unabhängig voneinander, gleich R¹ und/oder R³ sind, mit der Maßgabe, dass mindestens ein Rest R² die Bedeutung R³ hat,
R³ unabhängig voneinander, ein Polyetherrest der Formel II -(Y)_e[O(C₂H_4-dR'_dO)_m(C_xH_2xO)_pZ]_w (II) ist, mit der Maßgabe, dass
e = 0 bis 1,
w = 1 bis 3,
d = 1 bis 3,
m ≥ 0,
x = 2 bis 4, insbesondere erhältlich durch Einsatz von C₂H₄O-, C₃H₆O- und C₄H₈O-Einheiten entweder einzeln oder in Kombination, und
p ≥ 0 sind, und
Y ein Kohlenwasserstoffrest ist, der gegebenenfalls verzweigt ist,
R' ausgewählt aus der Gruppe der einwertigen, gegebenenfalls aromatischen Kohlenwasserstoffreste von C1 bis C18 ist,
Z ein Wasserstoffrest oder ein einwertiger organischer Rest, gegebenenfalls ein Acetylrest ist,
die Summe m + p = 1 bis 200 ist, wobei p- und m-Bausteine in beliebiger Reihenfolge angeordnet sein können,
a eine Zahl von 1 bis 100 ist, wenn b eine Zahl von > 6 bis 8 ist,
a eine Zahl von 1 bis 200 ist, wenn b eine Zahl von > 3 bis 6 ist,
a eine Zahl von 1 bis 300 ist, wenn b eine Zahl von 0 bis 3 ist,
b = 0 bis 8, z.B. 1 bis 8,
mit der Maßgabe, dass der Indix e = 0 ist wenn b ≠ 0 ist,
wobei man die Polysiloxane der allgemeinen Formel I im Gemisch mit organischem Lösungsmittel und zumindest einer Verbindung der Formel III einsetzt

mit
R einem m-bindigen organischen Rest, vorzugsweise Kohlenwasserstoffrest, bevorzugt Kohlenwasserstoffrest mit 1 bis 30 Kohlenstoffatomen, vorzugsweise mit 8 bis 20 Kohlenstoffatomen, wenn m = 1 und 1 bis 7, vorzugsweise 2 bis 6 Kohlenstoffatomen, wenn m = 2 oder 3 ist, besonders bevorzugt gesättigter Kohlenwasserstoffrest,
R' gleich oder verschieden H oder organischer Rest, vorzugsweise C₁-C₁₂-Alkyl-, Aryl-, Alkylaryl-Rest-, der ggf. Sauerstoff- oder Stickstoffatome, insbesondere Hydroxyoder Amino-Gruppen aufweisen kann, oder ein Rest -X-Z,
m = 1 bis 5, vorzugsweise m = 1, 2 oder 3,
Z gleich oder verschieden OH oder NHR'', mit R'' = H oder Alkyl, insbesondere Alkyl mit 1 bis 30 Kohlenstoffatomen, vorzugsweise H, und
X gleich oder verschieden ein zweibindiger organischer Rest mit mindestens zwei Kohlenstoffatomen, vorzugsweise ein Kohlenwasserstoffrest, bevorzugt ein Rest -(CH2)_w- mit w = 2 bis 5, besonders bevorzugt ein Ethylen -Rest, und mindest eine Siloxanverbindung aufweist, wobei das Massenverhältnis von Siloxanverbindungen zu Verbindungen der Formel (III) größer 1 zu 10 beträgt, vorzugsweise größer-gleich 1 zu 4, besonders bevorzugt größer oder gleich 1 zu 2 und besonders bevorzugt von 1 zu 1.5 bis 1 zu 0.125 beträgt. Another object of the present invention is a process for the preparation of flexible polyurethane foams using organofunctionally modified polysiloxanes of the general formula I.

where the radicals
R ^{1 are} independently of one another, alkyl radicals or aryl radicals, R ^{2 are} independently of one another, equal to R ¹ and / or R ³ , with the proviso that at least one radical R ^{2 has} the meaning R ³ ,
R ³ independently of one another, a polyether radical of the formula II - (Y) _e [O (C ₂ H _4-d R ' _d O) _m (C _x H ₂ O) _p Z] _w (II) is, with the proviso that
e = 0 to 1,
w = 1 to 3,
d = 1 to 3,
m ≥ 0,
x = 2 to 4, in particular obtainable by using C ₂ H ₄ O, C ₃ H ₆ O and C ₄ H ₈ O units either individually or in combination, and
p ≥ 0, and
Y is a hydrocarbon radical which is optionally branched,
R 'is selected from the group of monovalent, optionally aromatic hydrocarbon radicals of C1 to C18,
Z is a hydrogen radical or a monovalent organic radical, optionally an acetyl radical,
the sum m + p = 1 to 200, where p and m blocks can be arranged in any order,
a is a number from 1 to 100, if b is a number from> 6 to 8,
a is a number from 1 to 200, when b is a number from> 3 to 6,
a is a number from 1 to 300, when b is a number from 0 to 3,
b = 0 to 8, eg 1 to 8,
with the proviso that the indix e = 0 if b ≠ 0,
wherein the polysiloxanes of the general formula I are used in a mixture with organic solvent and at least one compound of the formula III

With
R is an m-bonding organic radical, preferably hydrocarbon radical, preferably hydrocarbon radical having 1 to 30 carbon atoms, preferably having 8 to 20 carbon atoms, when m = 1 and 1 to 7, preferably 2 to 6 carbon atoms, when m = 2 or 3, especially preferably saturated hydrocarbon radical,
R 'is identical or different and is H or organic radical, preferably C ₁ -C ₁₂ -alkyl, aryl, alkylaryl radical, which may optionally contain oxygen or nitrogen atoms, in particular hydroxy or amino groups, or a radical -XZ,
m = 1 to 5, preferably m = 1, 2 or 3,
Z is the same or different OH or NHR '', with R '' = H or alkyl, in particular alkyl having 1 to 30 carbon atoms, preferably H, and
X is identically or differently a divalent organic radical having at least two carbon atoms, preferably a hydrocarbon radical, preferably a radical - (CH 2) _w - where w = 2 to 5, particularly preferably an ethylene radical, and at least one siloxane compound, wherein the mass ratio of Siloxane compounds to compounds of formula (III) is greater than 1 to 10, preferably greater than or equal to 1 to 4, more preferably greater than or equal to 1 to 2 and more preferably from 1 to 1.5 to 1 to 0.125.

In the process for producing flexible polyurethane foams, the mixtures according to the invention, as described in detail above, can be used. For the purposes of the invention, it is precisely the simultaneous use of the components (a) to (c) as a mixture which is particularly advantageous, since this leads to a significantly better effect on cell refining than a separate addition, such as e.g. the addition of the amide compound (b) via the polyol component. For the purposes of the invention, therefore, a mixture comprising constituents (a) to (c) should be used.

The preparation of the flexible polyurethane foams can otherwise be carried out in the usual way and as described in the prior art. It is well known to those skilled in the art and includes in particular the Reacting at least one polyol component with at least one isocyanate component in the presence of one or more catalysts which catalyze the reactions isocyanate-polyol and / or isocyanate-water and / or the isocyanate trimerization, wherein preferably also water, physical blowing agents, flame retardants and / or Further additives can be added, and wherein the method, as stated above, according to the invention using organofunctionally modified polysiloxanes of the general formula I is carried out, wherein the polysiloxanes of general formula I in admixture with organic solvent and at least one compound of formula III ,

In the process according to the invention, particular preference is given to using liquid carbon dioxide or methylene chloride as the blowing agent. A process according to the invention in which pressurized carbon dioxide or methylene chloride is used as blowing agent therefore corresponds to a particularly preferred embodiment of the invention.

Furthermore, it is preferred in the process according to the invention, the amides of general formula III in an amount of 0.1 to 200 parts by weight, in particular 10 to 150 parts by weight, based on 100 parts by weight of the polysiloxanes of the general formula I use.

Particularly preferred are the mixtures of polysiloxane (a) and amide compound (b) and at least one organic solvent in an amount of 0.01 to 13 wt .-%, preferably 0.1 to 13 wt .-% based on the total polyurethane foam Formulation used.

The polyol component which can be used in the context of the process according to the invention is preferably different from the amide compounds of the formula (III) and the siloxane compounds (I) present in the mixture.

Suitable polyols which can advantageously be used in the context of this invention are all organic substances having a plurality of isocyanate-reactive groups and also their preparations. Preferred polyols are all for the production of polyurethane foams, in particular polyurethane or polyisocyanurate flexible foams, commonly used polyether polyols and polyester polyols. Polyether polyols are obtained by reacting polyhydric alcohols or amines with alkylene oxides. Polyester polyols are based on esters of polybasic carboxylic acids (usually phthalic acid or terephthalic acid) with polyhydric alcohols (usually glycols). According to the required properties of the foams, corresponding polyols are used, as described for example in: US 2007/0072951 A1 . WO 2007/111828 A2 . US 2007/0238800 . US 6359022 B1 or WO 96 12759 A2 , Likewise preferably usable vegetable oil-based polyols are described in various patents, such as in WO 2006/094227 . WO 2004/096882 . US 2002/0103091 . WO 2006/116456 and EP 1 678 232 and polymer polyols, such as in the publications U.S. Re. 28,715 and U.S.-A-3,346,557 . US-A-3 823 201 . US-A-3,850,861 . US-A-4 454 255 . US-A-4 458 038 . US-A-4 550 194 . US-A-4,390,645 such as U.S.-A-4,431,754 executed.

As the isocyanate component, it is possible to use all isocyanate compounds suitable for the production of polyurethane foams, in particular polyurethane foams or polyisocyanurate foams. Preferably, one or more organic isocyanates having two or more isocyanate functions can be used. Suitable isocyanates in the context of this invention are, for. B. all polyfunctional organic isocyanates such as 4,4'-diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI) and isophorone diisocyanate (IPDI). Particularly suitable is the mixture known as "polymeric MDI"("crudeMDI") of MDI and higher condensed analogues having an average functionality of 2 to 4. Examples of suitable isocyanates are in EP 1 712 578 A1 . EP 1 161 474 . WO 058383 A1 . US 2007/0072951 A1 . EP 1 678 232 A2 and the WO 2005/085310 called.

Preferred amines which can be used to catalyze the isocyanate-water reaction are selected from triethylamine, dimethylcyclohexylamine, tetramethylethylenediamine, tetramethylhexanediamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, triethylenediamine, dimethylpiperazine, 1,2-dimethylimidazole, N, N-dimethylhexadecylamine, silamorpholine, N Ethylmorpholine, tris (dimethylaminopropyl) hexahydro-1,3,5-triazine, N, N-dimethylaminoethanol, N '(3-dimethyl-aminopropyl) -N, N-diisopropanolamine, dimethylaminoethoxyethanol and bis (dimethylamino-ethyl) ether. At Evonik Industries AG such amines or amine catalysts z. B. under the name Tegoamin ^® SMP, Tegoamin ^® 33 or Tegoamin ^® ZE 4, are obtained.

Preferably used as the metal salt of a carboxylic acid are preferably potassium, tin, zinc or bismuth salts, preferably tin (II) salts. Preferably, at least one tin (II) salt of 2- Ethylhexanoic acid, ricinoleic acid or 3,5,5, -Trimethylhexansäure be used. At Evonik Industries AG, for example, B. a stannous salt of 2-ethylhexanoic acid exhibiting catalyst under the name KOSMOS ^® 29 can be obtained. It is also possible to use organic tin compounds, such as dibutyltin dilaurate, in particular, when it comes to HR foam production.

Another object of the invention is a composition suitable for the production of flexible polyurethane foams, the at least one polyol component, a catalyst which catalyzes the formation of a urethane or isocyanurate bond, optionally a blowing agent, optionally further additives and an isocyanate component, wherein In addition, a mixture according to the invention, as described above, is included.

Another object of the invention is a flexible polyurethane foam, obtainable by a method as previously described.

These polyurethane foams or the polyurethane foams resulting in the process according to the invention can, in particular in the furniture (eg as molded foam) and mattress industry, the vehicle (eg headrests for automobile seats, automotive seat upholstery, sheeting made of soft elastic polyurethane foam for vehicle interior decoration), Täschner -, shoe and textile industry, but also in the household and in the technical sector (eg as packaging material) are used.

Another object of the invention is the use of the mixtures according to the invention for the production of flexible polyurethane foams, in particular for increasing the cell fineness in the production of flexible polyurethane foams.

embodiments

A flexible polyurethane foam was made in a 27x27 cm open crate with a wall height of 27 cm by foaming various formulations with the following ingredients. On the one hand, a formulation with a very small amount of stabilizer (formulation I: 0.6 parts), on the other hand a formulation with an extremely high amount of stabilizer (formulation II: 10 parts) and methylene chloride was chosen to create extreme conditions and to compare the cell structure under these conditions: Formulation I: trifunctional polypropylene glycol (OH number 56) 100 parts Water (when using the water-containing Polyethersiloxanabmischung accordingly fewer) 4.05 parts TEGOAMIN ^® DMEA ¹⁾ 0.2 parts TEGOSTAB ^® BF 2470 ²⁾ 0.6 parts KOSMOS ^® 29 ³⁾ 0.2 parts TDI 80 ⁴⁾ 52.5 parts index <110> Formulation II: trifunctional polypropylene glycol (OH number 56) 100 parts Water (when using the water-containing Polyethersiloxanabmischung accordingly fewer) 11 parts TEGOAMIN ^® SMP ¹⁾ 0.9 parts TEGOSTAB ^® BF 2470 ²⁾ 10 parts KOSMOS ^® 29 ³⁾ 1.0 parts methylene chloride 90 parts TDI 80 161 parts index <140> ¹⁾ TEGOAMIN ^®: amine catalysts, available from Evonik Industries
²⁾ TEGOSTAB ^® : silicone stabilizers available from Evonik Industries
³⁾ COSMOS ^®: metal catalysts available from Evonik Industries
⁴⁾ TDI 80: tolylene diisocyanate 80% 2,4-isomers and 20% 2, 6 isomer

As a foam-stabilizing agent, a silicone-polyether copolymer obtainable by hydrosilylation of Si-H-group-containing siloxanes with allyl-started polyethers under the trade name TEGOSTAB BF 2470 corresponding to a SiC-polyethersiloxane according to the formula (I) was used to stabilize the resulting foams ,

In the inventive examples II to V, VII to X and XII to XV, this stabilizer was mixed with small amounts of an amide-containing fatty alcohol of the formula IV, while in the comparative experiments I and VI no amide group-containing fatty alcohol was used. In Example XVI, the amide group-containing alcohol was not blended with the stabilizer but added separately to the formulation with the polyol. The ratio of polyethersiloxane to blending component / amide mixture was 1 to 1. After the foam had cured, the resulting foam body was cut horizontally and the cell structure found at a height of 15 cm above the foam bottom at the cut surface was evaluated. Assessment criteria were both the number of cells / cm and the regularity of the cell structure obtained. To evaluate the foams prepared according to Formulation II, a ranking was introduced which compares the cell structure with a standard foam. A ranking of 1 means a very rough, a ranking of 5 a maximum fine cell structure.

In addition, as a measure of the open-celledness of the foams obtained, the back pressure was measured, which results when flowing through the foam sample at 8 liters per minute for a 2 cm diameter circular inlet. The lower the measured dynamic pressure (measured in mm liquid column), the more open-celled is the resulting foam. Ex. formulation relationship Cell / cm ranking Porosity / mm mixing component to amide I Ia) 100 0 10 - 50 II Ia) 80 20 12.3 - 33 III Ia) 70 30 12.8 - 26 IV Ia) 60 40 13.0 - 45 V Ia) 50 50 13.4 - 30 VI IIa) 100 0 - 3 - VII IIa) 80 20 - 3.5 - VIII IIa) 70 30 - 3.5-4.0 - IX IIa) 60 40 - 3.5 - X IIa) 50 50 - 4.5 - XI IIb) 100 0 - 3 - XII IIb) 80 20 - 3.5 - XIV IIb) 60 40 - 3.5 - XV IIb) 50 50 - 4.0 - Amid in polyol XVI Ia) 50 50 10.5 - 29 a) Blending component: dipropylene glycol
b) Blending component: 75% water, 12.5% sodium alkylbenzenesulfonate, 12.5% propylene glycol
Amide = amide group-containing fatty alcohol of formula IV

It is clear that the use of amide group-containing fatty alcohols as a component of a flexible foam stabilizer has a surprisingly positive effect on the fineness of the resulting polyurethane foams. It can be seen that as the proportion of amide-group-containing fatty alcohol increases, an increased fine-celledness results. In this case, two to three cells / cm can be obtained, which corresponds to a considerable improvement. The ranking value also shows an increase of up to 1.5 points, which corresponds to a very clear refinement of the cell structure.

The experiment XVI shows that the addition of the component into the polyol also leads to a positive effect with regard to cell refining.

The cell refining effect was also in machine trials with liquid, pressurized CO ₂ as blowing agent (according to the cardio ^® -, Nova Flex ^™ or Beamech ^TM process) can be assigned.

In this case, a formulation was foamed analogously to Formulation I with 4.05 parts of water and 2 parts of CO ₂ on a Novaflek ^TM plant. As a stabilizer again the previously mentioned BF 2470 was chosen. This stabilizer is not usually recommended for CO ₂ -Verschaeumungen because it resulting insufficient cell structure. In the inventive examples (XVIII to XXI), the amide (amide group-containing fatty alcohol of formula IV) was used in different ratios to the blending component. In Comparative Example (XVII), only blending component was used. The amount of stabilizer used was 0.9 parts, including the blending component and amide. The ratio of polyethersiloxane to mixing component / amide mixture was 1 to 1. Subsequently, the obtained cell structure of the foam was examined and classified error-free, slightly disturbed, moderately disturbed, disturbed or severely disturbed. Ex. formulation Relationship cell structure mixing component to amide XVII Ia) 100 0 moderately disturbed XVIII Ia) 80 20 flawless XVIV Ia) 70 30 flawless XX Ia) 60 40 flawless XXI Ia) 50 50 flawless a) Blending component: dipropylene glycol

It was found that even under the conditions of a foaming with liquid CO ₂ as a blowing agent again the effect of improving the cell fineness when using an amide group-containing fatty alcohol corresponding to the mixture according to the invention occurs. In Examples XVIII to XXI, foams with a very fine cell structure resulted, clearly finer than that of Example XVII.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

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Claims (15)

Mixtures suitable as an additive in the production of flexible polyurethane foams, comprising (a) organofunctionally modified polysiloxane of the general formula I.

where the radicals R ¹ , independently of one another, are alkyl radicals or aryl radicals, R ² , independently of one another, are identical to R ¹ and / or R ³ , with the proviso that at least one radical R has the meaning R ³ , R ³ independently of one another, a polyether radical of the formula II - (Y) _e [O (C ₂ H _4-d R ' _d O) _m (C _x H _2x O) _p Z] _w (II) with the proviso that e = 0 to 1, w = 1 to 3, d = 1 to 3, m ≥ 0, x = 2 to 4, in particular obtainable by using C ₂ H ₄ O-, C ₃ H ₆ O- and C ₄ H ₈ O units either individually or in combination, and p ≥ 0, and Y is a hydrocarbon radical which is optionally branched, R 'selected from the group of monovalent, optionally aromatic hydrocarbon radicals of C ₁ to C ₁₈ is Z is a hydrogen radical or a monovalent organic radical including an acyl radical, the sum of m + p = 1 to 200, wherein the m and p blocks can be arranged arbitrarily, a is a number from 1 to 100, when b is a number from> 6 to 8, a is a number from 1 to 200, when b is a number from> 3 to 6, a is a number from 1 to 300, when b is a number from 0 to 3, b = 0 to 8, eg 1 to 8, with the proviso that the index e = 0 if b ≠ 0, and (b) at least one compound of the formula (III)

with R is an m-bonding organic radical, preferably hydrocarbon radical, preferably a hydrocarbon radical having 1 to 30 carbon atoms, preferably having 8 to 20 carbon atoms, when m = 1 and 1 to 7, preferably 2 to 6 carbon atoms, if m = 2 or 3, particularly preferably saturated hydrocarbon radical, R 'is the same or different H or organic radical, preferably C ₁ -C ₁₂ -alkyl, aryl, alkylaryl radical, which may optionally contain oxygen or nitrogen atoms, in particular hydroxy or amino groups, or a radical -XZ, m = 1 to 5, preferably m = 1, 2 or 3, Z is the same or different OH or NHR ", with R" = H or alkyl, in particular alkyl having 1 to 30 carbon atoms, preferably H, and X is identically or differently a divalent organic radical having at least two carbon atoms, preferably a hydrocarbon radical, preferably a radical - (CH 2) _w - where w = 2 to 5, particularly preferably an ethylene radical, and also (c) organic solvent The ratio by mass of siloxane compounds of the formula (I) to compounds of the formula (III) is greater than 1: 10, preferably greater than or equal to 1: 4, more preferably greater than or equal to 1: 2, and particularly preferably 1 to 1.5 to 1 to 0.125. Mixture according to Claim 1, characterized in that it comprises at least ≥ 40% by weight, preferably ≥ 50% by weight, of the abovementioned components (a) and (b). Mixture according to one of claims 1 or 2, characterized in that as the compound of formula (III) at least one compound of formula (IV) is contained,

with R defined above for formula (III), wherein the amide of the formula (IV) is preferably obtained by reacting a fatty acid with diethanolamine. Mixture according to one of claims 1 to 3, characterized in that the polyether siloxanes of the general formula I are selected from compounds, wherein R ² in at least one case is equal to R ³ , with the proviso that m> p. Mixtures according to one of claims 1 to 4, characterized in that the compounds of general formula III in an amount of 0.1 to 200 parts by weight, in particular 10 to 150 parts by weight, based on 100 parts by weight of Polysiloxanes of general formula I are included. Mixture according to one of claims 1 to 5, comprising - ≥ 30 wt .-% to ≤ 68 wt .-%, preferably ≥ 35 wt .-% to ≤ 65 wt .-% and preferably ≥ 40 wt .-% to ≤ 62 % By weight of polyethersiloxane according to formula (I), wherein a polyethersiloxane content of 40 wt.% To 60 wt.% Is particularly preferred, - ≥ 1 wt.% To ≤ 70 wt.%, Preferably ≥ 2 wt. % to ≦ 50% by weight and preferably ≥ 5% by weight to ≦ 40% by weight of amide group-containing compound according to formula (III), compounds of formula (IV) being particularly preferred, ≥1% by weight. % to ≦ 70% by weight, preferably ≥ 10% by weight to ≦ 60% by weight and preferably ≥ 20% by weight to ≦ 55% by weight of organic solvent, preferably propylene and / or dipropylene glycol, especially dipropylene glycol.  Mixture according to one of claims 1 to 6, full - ≥ 30 wt .-% to ≤ 68 wt .-%, preferably ≥ 35 wt .-% to ≤ 65 wt .-% and preferably ≥ 40 wt .-% to ≤ 62 wt .-% polyether siloxane according to formula (I) where a polyether siloxane content of from 40% to 60% by weight is particularly preferred, - ≥ 1 wt .-% to ≤ 70 wt .-%, preferably ≥ 2 wt .-% to ≤ 50 wt .-% and preferably ≥ 5 wt .-% to ≤ 40 wt .-% amide group-containing compound according to formula (III), compounds of the formula (IV) being particularly preferred, - ≥ 1 wt .-% to ≤ 70 wt .-%, preferably ≥ 10 wt .-% to ≤ 60 wt .-% and preferably ≥ 20 wt .-% to ≤ 55 wt .-% organic solvent, preferably propylene and / or dipropylene glycol, especially dipropylene glycol, - ≥ 1 wt .-% to ≤ 70 wt .-%, preferably ≥ 10 wt .-% to ≤ 60 wt .-% and in particular ≥ 20 wt .-% to ≤ 55 wt .-% water - ≥ 1 wt .-% to ≤ 10 wt .-%, preferably ≥ 2 wt .-% to ≤ 8 wt .-% and preferably ≥ 4 wt .-% to ≤ 6 wt .-% organic surfactant, when using Water-containing solvent combinations or a proportion of amide-containing compounds of formula (III)> 60% by weight.  Mixture according to one of claims 1 to 7, full - ≥ 40 wt .-% to ≤ 55 wt .-%, preferably 50 wt .-% polyether siloxane according to formula (I), - ≥ 2 wt .-% to ≤ 50 wt .-% amide-containing compound according to formula (III), compounds of formula (IV) are particularly preferred, From ≥ 1% by weight to ≦ 10% by weight, preferably ≥ 2% by weight to ≦ 8% by weight and preferably 5% by weight of alkylbenzenesulfonate, - ≥ 30 wt .-% to ≤ 50 wt .-%, preferably ≥ 35 wt .-% to ≤ 45 wt .-% and preferably 40 wt .-% water, and - ≥ 1 wt .-% to ≤ 10 wt .-%, preferably ≥ 3 wt .-% to ≤ 7 wt .-% and preferably 5 wt .-% organic solvent, preferably propylene and / or dipropylene glycol, in particular dipropylene glycol. Process for the preparation of flexible polyurethane foams using organofunctionally modified polysiloxane of the general formula I.

wherein the radicals R ^{1 are} independently of one another, alkyl radicals or aryl radicals, R ^{2 is} independently of one another, equal to R ¹ and / or R ³ , with the proviso that at least one radical R ^{2 has} the meaning R ³ , R ³ independently of one another Polyether radical of the formula II - (Y) _e [O (C ₂ H _{4 -d} R ' _d O) _m (C _x H _2x O) _p Z] _w (II) with the proviso that e = 0 to 1, w = 1 to 3, d = 1 to 3, m ≥ 0, x = 2 to 4, in particular obtainable by using C ₂ H ₄ O, C ₃ H ₆ O and C ₄ H ₈ O units either individually or in combination, and p ≥ 0, and Y is a hydrocarbon radical, which is optionally branched, R 'is selected from the group of monovalent, optionally aromatic hydrocarbon radicals of C ₁ to C ₁₈ , Z is a hydrogen radical or a monovalent organic radical, optionally acetyl radical, the sum m + p = 1 to 200, wherein the m- and p-blocks can be arranged arbitrarily. a is a number from 1 to 100 when b is a number from> 6 to 8, a is a number from 1 to 200, when b is a number from> 3 to 6, a is a number from 1 to 300, when b is a number from 0 to 3, b = 0 to 8, eg 1 to 8, with the proviso that the index e = 0 when b ≠ 0, wherein the polysiloxanes of the general formula I mixed with organic solvent , preferably dipropylene glycol and / or propylene glycol, together with at least one compound of formula III

with R is an m-bonding organic radical, preferably hydrocarbon radical, preferably a hydrocarbon radical having 1 to 30 carbon atoms, preferably having 8 to 20 carbon atoms, when m = 1 and 1 to 7, preferably 2 to 6 carbon atoms, if m = 2 or 3, particularly preferably saturated hydrocarbon radical, R 'is the same or different H or organic radical, preferably C ₁ -C ₁₂ -alkyl, aryl, alkylaryl radical, which may optionally contain oxygen or nitrogen atoms, in particular hydroxy or amino groups, or a radical -XZ, m = 1 to 5, preferably m = 1, 2 or 3, Z is the same or different OH or NHR ", with R" = H or alkyl, in particular alkyl having 1 to 30 carbon atoms, preferably H, and X is identically or differently a divalent organic radical having at least two carbon atoms, preferably a hydrocarbon radical, preferably a radical - (CH 2) _w - where w = 2 to 5, particularly preferably an ethylene radical, and at least one siloxane compound wherein the mass ratio of siloxane compounds to compounds of formula (III) is greater than 1 to 10, preferably greater than or equal to 1 to 4, more preferably greater than or equal to 1 to 2, and most preferably from 1 to 1.5 to 1 to 0.125. Process according to Claim 9, characterized in that polyethersiloxanes of general formula I are used, which are characterized in that R ² in at least one case is R ³ , with the proviso that m> p. Method according to one of claims 9 or 10, characterized in that pressurized carbon dioxide or methylene chloride is used as blowing agent. Method according to one of claims 9-11, characterized in that the mixtures of polysiloxane of the formula (I) and compounds of the formula (III), and at least one organic solvent, in particular dipropylene glycol, in an amount of 0.01 to 13 wt .-% based on the total polyurethane foam formulation. Flexible polyurethane foam, obtainable by a process according to one of claims 9 to 12. Use of mixtures according to one of Claims 1 to 8 for the production of flexible polyurethane foams. Use of mixtures according to one of Claims 1 to 8 for increasing the cell fineness in the production of flexible polyurethane foams.