Process for the preparation of polyurethane foams

The invention relates to a process for the production of polyurethane foams by reacting<sl><li>a) organic and / or modified organic di- and / or polyisocyanates with</li><li>b) at least one higher molecular weight compound having at least two reactive hydrogen atoms and a combination of</li><li>c) at least one compound having three to eight, preferably three to six reactive hydrogen atoms and</li><li>d) low molecular weight chain extenders and / or crosslinkers having at least two reactive hydrogen atoms in the presence of</li><li>e) blowing agents</li><li>f) catalysts and optionally</li><li>g) further auxiliaries and additives.</li></sl>

According to this method, in particular, polyurethane foams with improved hardness and increased resistance to a Wet-heat aging made.

The preparation of polyurethanes by reacting organic Di- and / or polyisocyanates with compounds having at least two reactive hydrogen atoms, for example, polyoxyalkylene and / or preferably organic polyhydroxyl compounds, in particular polyetherols having molecular weights of, for example, 300 to 6,000, and optionally chain extenders and / or crosslinkers with molecular weights up to about 400 in the presence of of catalysts, blowing agents, flame retardants, auxiliaries and / or additives is known and has been widely described. A summary overview of the preparation of Polyurethane foams, for example, in Kunststoff-Handbuch, Volume VII, "Polyurethane", 1st edition 1966, edited by Dr. R. Vieweg and Dr. A. Hoechtlen and 2nd edition, 1983, and 3rd edition, 1993, edited by Dr. G. Oertel (Carl Hanser if Verlag, Munich).

In order to obtain foams sufficient hardness, which also are resistant to a wet-heat aging, it has been numerous publications.

Thus EP-A-449 609 describes a highly elastic flexible foam, a property improvements, especially in the compression set to be achieved through increased 2.4 TDI units. This offers the possibility to reduce the amounts of polymer polyol.

In EP-A-346 670 block foams of very low density are at a low figure produced. Here is an admixed six functional short-chain crosslinker polyol for the required Foam stabilizer used.

In EP-A-496420 flexible foams flame retardant will be described. Here is a combination of short-chain nitrogenous Vernetzerpolyolen and a trifunctional polyol having at least comprises two secondary OH groups claimed.

WO 95/15990 describes the use of high-functionality, in particular six functional, polyols for high resilient flexible foams. Diethanolamine as chain extender / crosslinker is in Proportions of up to 5 parts by weight given as an example.

In EP-A-704 468 are highly functional polymer polyols for flexible foams used. The related formulas are based in particular the inventive use of higher levels of diols as chain extenders.

In EP-A-350 868 is a highly functional high molecular weight polymer polyol claimed. As a supporting Poyol is a polyetherol having a molecular weight from 450 to 3000 and an ethylene oxide called&gt; 30%. Crosslinkers are ethanolamine species called and sugar.

In EP-A-406702 are used as ethylene oxide adducts of Vernetzerpoylole Glycerol called, said crosslinking agent having a functionality 2-8 are claimed. Here are combinations with diethanolamine claimed. By Zellöffnerpolyole used to in the index range 105-120 a very closed cell foam result.

In EP-A-731 120 are foams with verbessserter wet-heat aging mentioned, which use a polyol mixture consisting of at least one polyol of functionality from 3.5 to 8 with a Ethylene oxide content 10-30% and at least one polyetherol functionality 2 - 8 with an ethylene oxide content 50-95% consists. Crosslinkers alkanolamine derivatives are mentioned. to Hardness increase can be fillers with use.

The present invention had the object of polyurethane foams with improved hardness and increased wet-heat resistance create, with the remaining properties of the Foam should not be degraded.

Surprisingly, this object was achieved in that in addition to the usual, at least one high molecular weight compound with at least two reactive hydrogen atoms containing component (B) a special combination of at least one compound having three to eight, preferably three to six, reactive Hydrogen atoms (c) and low molecular weight chain extenders and / or Crosslinking agents having at least two reactive hydrogen atoms (D) is used, wherein the components (c) ethylenoxidreiche Adducts having an ethylene oxide content of more than 50 Wt .-% and an OH number of 200 to 800 mg KOH / g, and (d) multi-functional Chain extenders and / or crosslinking agent having an OH number of more than 700 mg KOH / g.

The invention accordingly provides a process for preparing of polyurethane foams by reacting<sl><li>a) organic and / or modified organic di- and / or polyisocyanates with</li><li>b) at least one higher molecular weight compound having at least two reactive hydrogen atoms,</li><li>c) at least one compound having three to eight, preferably three to six reactive hydrogen atoms and</li><li>d) low molecular weight chain extenders and / or crosslinkers having at least two reactive hydrogen atoms in the presence of</li><li>e) blowing agents</li><li>f) catalysts and optionally </li><li>g) further auxiliaries and additives,</li></sl>characterized in that (c) ethylenoxidreiche adducts with an ethylene oxide content of more than 50 wt .-% and an OH number from 200 to 800 mg KOH / g, and (d) polyfunctional chain extenders and / or crosslinking agent having an OH number of more than 700 mg KOH / g.

The invention also continue the process after this molded polyurethane foam and its use as a cushioning material.

According to the invention in the implementation of the method for producing the polyurethane foams, in addition to conventional components a special combination of at least one compound three to eight, preferably three to six, reactive hydrogen atoms, (C) and low molecular weight chain extenders and / or Crosslinking agents having at least two reactive hydrogen atoms (D).

As component (c) ethylenoxidreiche adducts are used preferably ethylene oxide adducts of glycerol, trimethylolpropane, Pentaerythritol or any desired mixtures thereof. As initiators for the Ethylene oxide come alongside and as a mixture with the abovementioned Compounds other higher functional starters in question, for example sorbitol, ditrimethylolpropane, triethanolamine, Diethanolamine and mixtures thereof. Also useful are further starter having a functionality of 3 to 8

The ethylene oxide is the initiator or initiator mixture in the usual Way implemented.

The OHN of such ethylene oxide is in the range between 200 and 800 mg KOH / g, preferably 400 to 700 and in particular 500 and 700 mg KOH / g.

The ethylene oxide content of component c) is at least 50 wt .-%, preferably more than 90 wt .-%.

The more functional compounds (c) are preferably in Levels of from 0.5 to 10 wt .-%, in particular in proportions of from 1 to 8 wt .-%, based on the weight of components (b) to (G) used.

As component (d) are polyfunctional chain extenders and / or Crosslinking agent having an OH number of more than 700 mg KOH / g, preferably glycerol, are used. In addition, are also trimethylolpropane, Pentaerythritol or mixtures of the stated compounds usable. Besides these inventively employed can to a lesser extent those listed below conventional chain extenders and / or crosslinking agents added will.

The component (d) is preferably in proportions of from 0.5 to 6 wt .-%, particularly preferably in proportions of from 0.5 to 4 wt .-%, based on the weight of components (b) to (g), used.

The molar ratio of (c) to (d) is preferably in the range 10 to 0.3, in particular 3.0 to 0.3.

In a particularly preferred embodiment, the component (C) a trifunctional polyol based on ethylene oxide with an OH number of 530 mg KOH / g (Lupranol® VP 9209) in a Amount of from 5 to 6 wt .-%, and as component (d) glycerin in an Amount of 3 wt .-% is used.

For the preparation of the polyurethane foams according to the invention find next to the above-described combination of the components (C) and (d) which are customary in polyurethane chemistry starting materials Use, including by way of example the following is executed:<sl><li>a) Suitable organic and / or modified organic di- and / or Polyisocyanates are the aliphatic, cycloaliphatic araliphatic and preferably aromatic polyfunctional Isocyanates. In Specific examples are: alkylene with 4 to 12 carbon atoms in the alkylene radical, such as 1,12-dodecane diisocyanate, 2-ethyl-tetramethylenediisocyanate-1,4, 2-methylpentamethylene diisocyanate-1,5, Tetramethylene diisocyanate and 1,4- preferably hexamethylene 1,6; cycloaliphatic Diisocyanates such as cyclohexane 1,3- and 1,4-diisocyanate and any Mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4- and 2,6-hexahydrotolylene and the corresponding isomer mixtures, 4,4'-, 2,2'- and 2,4'-Dicyclohexlylmethandiisocyanat and the corresponding isomer mixtures, and preferably aromatic Di- and polyisocyanates such as 2,4- and 2,6-diisocyanate (TDI) and the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate MDI) and the corresponding Isomers, mixtures of 4,4'- and 2,2'-MDI, polyphenyl Mixtures of 4,4'-, 2,4'- and 2,2'-MDI and polyphenyl (crude MDI) and Mixtures of crude MDI and TDI. The organic di- and polyisocyanates used individually or in the form of their mixtures werden.Geeignet are also modified polyisocyanates, ie products which organic by chemical reaction Di- and / or polyisocyanates are obtained. Examples which may are ester-, urea, biuret, allophanate, isocyanurate and preferably carbodiimide, uretonimine and / or urethane groups -containing diisocyanates and / or polyisocyanates. Specifically come Examples of possible: containing urethane prepolymers having an NCO content of 14 to 2.8 wt .-%, preferably 12 to 3.5 wt .-%, or quasi-prepolymers with an NCO content 35-14 wt .-%, preferably 34-22 wt .-%, wherein urethane-modified polyisocyanates of TDI, in particular an NCO content of 43 to 28 weight .-%, and those from 4,4'-MDI, 4,4'-and 2,4'-MDI isomer mixtures or crude MDI, particular, an NCO content of 28 to 14 wt .-%, in particular preferably 28 to 22 wt .-%, based on the total weight, have and are prepared by reacting diols, Oxalkylenglykolen and / or polyoxyalkylene glycols having molecular weights 62-6000, preferably 134-4200 with TDI, 4,4'-MDI, MDI isomer mixtures and / or crude MDI, for example at temperatures from 20 to 110 ° C, preferably from 50 to 90 ° C, as where Oxyalkylene and polyoxyalkylene glycols, which individually or as mixtures can be used, may be mentioned by way of example: Diethylene, dipropylene, polyoxyethylene, polyoxypropylene and Polyoxypropylene-polyoxyethylene glycols, carbodiimide groups and / or Uretonimine containing polyisocyanates, for example based on MDI isomers and / or TDI Basis.Die modified polyisocyanates may together or with unmodified orga-African polyisocyanates such as 2,4 ', 4,4'-MDI, raw MDI, tolylene 2,4- and / or 2,6-TDI, optionally mixed proven werden.Besonders have Organic polyisocyanates and therefore preferably used are: mixtures of TDI and containing crude MDI or mixtures of modified urethane organic polyisocyanates having an NCO content of 44 to 15 wt .-%, in particular those based on TDI, 4,4'-MDI, MDI isomer mixtures or crude MDI, in particular crude MDI with an MDI isomer content of from 30 to 80 wt.%, preferably from 30 to 55 wt .-%. </li><li>b) relatively high molecular weight compounds having at least two reactive Hydrogen atoms are expediently those having a Functionality of 2 to 4, preferably 2 to 3, and a molecular weight 300-8000, preferably from 300 to 5000 used. Have proved z. B. polyether and / or preferably Polyols selected from the group of polyether polyols, polyester polyols, Polythioether, polyester hydroxyl, Polyacetals and hydroxyl-containing aliphatic Polycarbonates or mixtures of at least two of said Polyols. Preferably using polyester polyols and / or polyether polyols. The hydroxyl number of the polyhydroxyl compounds is as a rule from 20 to 80 and preferably 28 to 56.Geeignete polyester polyols can, for example, from organic Dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic Dicarboxylic acids having 4 to 6 carbon atoms, polyvalent, Alcohols, preferably diols, having 2 to 12 carbon atoms, made preferably from 2 to 6 carbon atoms, will. Suitable dicarboxylic acids are, for example, into consideration: Succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, Sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, Phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids may be both individually and in a mixture with one another be used. Instead of the free dicarboxylic acids, the corresponding dicarboxylic acid derivatives such as dicarboxylic esters of alcohols having 1 to 4 carbon atoms, or Dicarboxylic be used. Preference are dicarboxylic acid mixtures of succinic, glutaric and adipic acid in proportions of for example 20 to 35: 35 to 50: 20 till 32 weight Tei-len and in particular adipic acid. Examples of di- and polyhydric alcohols, in particular diols, are: ethanediol, diethylene glycol, 1,2- and 1,3-propanediol, Dipro-glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, glycerol and trimethylolpropane. Preferably be used ethanediol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol. also possible to use Polyester polyols from lactones, eg ε-caprolactone or hydroxycarboxylic acids, eg ω-Hydroxycapronsäure.Zur prepare the polyester polyols, the organic, for example can aromatic and preferably aliphatic, polycarboxylic and / or derivatives and polyhydric alcohols without using a catalyst or preferably in the presence of esterification, advantageously in an atmosphere of inert gas such as nitrogen, Carbon monoxide, helium, argon, etc., in the melt at Temperatures of 150 to 250 ° C, preferably 180 to 220 ° C, gegenbenfalls under reduced pressure until the desired acid number, which is advantageously less than 10, preferably less 2, is polycondensed. According to a preferred embodiment , the esterification mixture at the abovementioned Temperatures to an acid number of 80 to 30, preferably From 40 to 30, under atmospheric pressure and subsequently under a pressure of less than 500 mbar, preferably 50 to 150 mbar, is reached. Suitable esterification catalysts are, for example, Iron, cadmium, cobalt, lead, zinc, antimony, magnesium, Titanium and tin catalysts in the form of metals, metal oxides or metal salts. The polycondensation can however in the liquid phase in the presence of diluents and / or Entrainers such as benzene, toluene, xylene or chlorobenzene, by azeotropic distillation of the condensation water werden.Zur prepare the polyester polyols, the organic polycarboxylic acids and / or derivatives and polyhydric alcohols advantageously in a molar ratio of 1: 1 to 1.8, preferably 1: 1.05 to 1.2, polycondensed. The polyester polyols obtained preferably have a functionality of 2 to 4, in particular 2 to 3, and a molecular weight of 480 to 3000, However, in particular 600 to 2000.Insbesondere used as polyols, polyether polyols, prepared by known methods, for example by anionic Polymerization with alkali such as sodium or Potassium hydroxide, or alkali, such as sodium methylate, Sodium or potassium ethoxide or potassium isopropoxide, as Catalysts with addition of at least one starter molecule 2 to 4, preferably 2 to 3, reactive hydrogen atoms bound contains, or by cationic polymerization using Lewis acids, such as antimony pentachloride, boron fluoride etherate, etc., or Bleaching earth as catalysts from one or more alkylene oxides made with 2 to 4 carbon atoms in the alkylene radical werden.Für special applications can also monofunctional starter be incorporated into the polyether. Suitable alkylene oxides for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and 1,2-propylene oxide. The alkylene oxides can be used individually, alternately be used in succession or as mixtures. Starter molecules are, for example: water, organic Dicarboxylic acids such as succinic acid, adipic acid, phthalic acid and Terephthalic acid, aliphatic and aromatic, gegenbenfalls N-mono- N, N- and N, N'-dialkylated diamines having from 1 to 4 Carbon atoms in the alkyl radical, such as optionally mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexamethylenediamine, phenylenediamine, 2,3-, 2,4- and 2,6-toluenediamine and 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethane. As initiator molecules are in Alkanolamines, such as ethanolamine, N-methyl and N-ethylethanolamine, dialkanolamines such as diethanolamine, N-methyl- and N-ethyldiethanolamine, and trialkanolamines such as Triethanolamine, and ammonia. Polyhydric, in particular dihydric and / or trihydric alcohols such as Ethanediol, 1,2-propanediol and 2,3, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane and Pentaerythrit.Die polyether polyols, preferably polyoxypropylene and Polyoxypropylenpoly-oxyethylenpolyole, have a functionality of preferably from 2 to 4 and in particular 2 to 3 and molecular weights 300-8000, preferably 300 to 6000, in particular 1000 to 5000, and suitable polyoxytetramethylene glycols have a molecular weight to about 3500.Als polyether polyols are also suitable polymer-modified polyether polyols, preferably graft, especially those based on styrene and / or acrylonitrile, which are prepared by in situ Polymerization of acrylonitrile, styrene or preferably mixtures of styrene and acrylonitrile, eg in a weight ratio of 90:10 to 10:90, preferably 70:30 to 30:70, in expediently to aforementioned polyether similar to that of the German Patents 1111394, 1222669 (US-A-3304273, 3383351, 3523093), 1152536 (GB 1040452) and 1152537 (GB 987 618) produced be, and also polyether polyol as the disperse Phase, usually, in an amount of 1 to 50 wt .-% preferably 2 to 25 wt .-%, include: for example, polyureas, Polyhydrazides bound tert-amino-containing polyurethanes and / or melamine and are described, for example, in the EP-B-011,752 (US-A-4,304,708), US-A-4,374,209 and DE-A-3231497.Die polyether polyols can be polyester polyols as well as the single or used in the form of mixtures. Further, them with the graft polyether polyols or polyester polyols and the hydroxyl-containing polyesteramides, polyacetals, polycarbonates Polyether polyamines are mixed and / or. As hydroxyl-containing polyacetals are, for example from the Glycols, such as diethylene glycol, triethylene glycol, 4,4'-dihydroxyethoxydiphenyldimethylmethane, Hexanediol and formaldehyde Compounds. Also cyclic by polymerizing Acetals Suitable polyacetals herstellen.Als hydroxyl-containing polycarbonates are those of the per se known type into consideration, for example, by reacting diols such as 1,3-propanediol, 1,4-butanediol and / or 1,6-hexanediol, diethylene glycol, triethylene glycol or tetraethylene glycol with diaryl carbonates, for example diphenyl carbonate, or Phosgene are produced können.Zu The polyesteramides include, for example, polyvalent consisting saturated and / or unsaturated carboxylic acids or their anhydrides and polyfunctional saturated and / or unsaturated amino alcohols or mixtures of polyhydric alcohols and amino alcohols and / or polyamines derived predominantly linear Kondensate.Geeignete polyether can be prepared from the abovementioned polyether polyols be prepared by known methods. exemplary called The cyanoalkylation of polyoxyalkylene and subsequent hydrogenation of the nitrile formed (US Patent 3,267,050) or the partial or complete amination of polyoxyalkylene polyols with amines or ammonia in the presence of hydrogen and catalysts (DE-A-1215373).</li><li>c) According to the invention in the preparation of the polyurethane foams three to eight, preferably three to six, reactive hydrogen atoms containing compounds ethylenoxidreiche Adducts, as described above, are used.</li><li>d) For the production of the polyurethane foams according to the invention are the chain extenders described above and / or Crosslinking agent used. For modifying the mechanical However, properties can be the addition of other chain extenders, Crosslinking agent or optionally also prove mixtures thereof to be advantageous. be used as a further chain extender and / or crosslinking agents diols and / or triols having molecular weights of less than 400, preferably 60 to 300. For example, aliphatic, cycloaliphatic and / or araliphatic diols having 2 to 14, preferably 4 to 10 carbon atoms, such as ethylene glycol, 1,3-propanediol, 1,10-decanediol, o-, m-, p-dihydroxycyclohexane, Diethylene glycol, dipropylene glycol and preferably butanediol-1,4, Hexanediol-1,6 and bis- (2-hydroxyethyl) hydroquinone, triols such as 1,2,4 and 1,3,5-trihydroxycyclohexane, and low molecular weight hydroxyl-containing polyalkylene oxides based on ethylene oxide and / or 1,2-propylene oxide and the abovementioned diols and / or Triols as initiator molecules. further provided for the preparation of the polyurethane foams Chain extenders, crosslinkers or mixtures thereof are used, they come in an amount of 0 to 20 wt .-% before.</li><li>e) As blowing agent can generally from polyurethane chemistry known chlorofluorocarbon (CFC), and upload and / or perfluorinated carbons water detergents are used. The use these substances is greatly ecological reasons restricted or completely stopped. In addition to HCFCs and HFCs provide in particular aliphatic and / or cycloaliphatic Hydrocarbons, in particular pentane and cyclopentane, or Acetals such. B. methylal as alternative blowing agents. These Physical blowing agents are typically the polyol component the system added. However, you can also in the Isocyanate component or a combination of both the polyol component and the isocyanate component are added. They can also be used together with highly and / or perfluorinated hydrocarbons in form of an emulsion of Polyol. If emulsifiers they apply Oligomeric acrylates are typically used as the containing side groups bonded polyoxyalkylene and fluoroalkane radicals and having a fluorine content of ungefährt 5 to 30 wt .-%. Such products are sufficiently from plastics chemistry known, for example EP-A 351,614th The amount of blowing agent or blowing agent mixture In this case is 1 to 25 wt .-%, preferably 1 to 15 Wt .-%, each based on the components (b) to (g) .Weiterhin it is possible and common, as blowing agent, the structure component (B) water in an amount of 0.5 to 15 wt .-%, preferably 1 to 5 wt .-%, based on the structural components (B) to (g), add. The addition of water can with combined the use of other blowing agents described occur.</li><li>f) as catalysts for preparing polyurethane foams in particular, compounds which reaction the the reactive hydrogen atoms, in particular hydroxyl-containing Compounds of components (b), (c) and (d) with the organic, modified or unmodified polyisocyanates (A) strongly accelerate. Examples include organic metal compounds, preferably organic tin compounds such as Tin (II) salts of organic carboxylic acids, for example Tin (II) acetate, tin (II) octoate, tin (II) ethylhexanoate and Tin (II) laurate, and the dialkyltin (IV) salts of organic Carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, Dibutyltin and dioctyltin. The organic Metal compounds are used alone or preferably in combination used with strongly basic amines. Mention may be made, for example, Amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary Amines such as triethylamine, tributylamine, dimethylbenzylamine, N-methyl-, N-ethyl-, N-cyclohexylmorpholine, N, N, N ', N'-tetra-methylethylendiamn, N, N, N ', N'-tetramethylbutanediamine, N, N, N', N'-tetramethyl-1,6-hexanediamine, Pentamethyldiethylentriamine, Tetramethyldiaminoethylether, Bis- (dimethylaminopropyl) -urea, Dimethylpiperazine, 1,2-dimethylimidazole, 1-aza-bicyclo- (3,3,0) -octane and preferably 1,4-diazabicyclo (2,2,2) -octane, and alkanol amine compounds, such as triethanolamine, triisopropanolamine, N-methyl- and N-ethyldiethanolamine and dimethylethanolamine. Other suitable catalysts are: tris (dialkylaminoalkyl) -s-hexahydrotriazines, in particular tris (N, N-dimethylaminopropyl) -s-hexahydrotriazine, Tetraalkylammonium how Tetramethylammonium hydroxide, alkali metal hydroxide such as sodium hydroxide and alkali metal such as sodium and potassium isopropoxide, and alkali metal salts of long chain fatty acids having 10 to 20 carbon atoms and possibly lateral OH groups. Preferably be employed 0.001 to 5 wt .-%, especially 0.05 to 2 wt .-% of catalyst or catalyst combination, based on the Weight of starting components (b) to (g).</li><li>g) the reaction mixture for producing the polyurethane foams can optionally further auxiliaries and / or additives be incorporated. Mention may be made, for example, Flame retardants, surface-active substances, foam stabilizers, Cell regulators, fillers, dyes, pigments, hydrolysis, fungistatic and bacteriostatic substances.</li></sl>

Suitable flame retardants are, for example, tricresyl phosphate, Tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, Tetrakis- (2-chloroethyl) -ethylendi-phosphate, Dimethylmethanephosphonate, diethanolaminomethylphosphonate and commercially available halogen-containing Flammschutzpolyole. Apart from the abovementioned halogen-substituted phosphates may also contain inorganic or organic flame retardants, as red phosphorus, Aliumiumoxidhydrat, antimony trioxide, Arsenic oxide, ammonium polyphosphate and calcium sulfate, expandable graphite or cyanuric acid derivatives such as melamine, or mixtures of at least two flame retardants such as ammonium polyphosphates and melamine and optionally cornstarch or Ammonium polyphosphate, melamine, and expandable graphite and / or optionally aromatic polyesters for making the polyisocyanate polyaddition products flame resistant be used. particularly effective prove Additions of melamine. It is generally proved expedient, 5 to 50 parts by weight, preferably 5 to 25 parts by weight, of said flameproofing agents per to use 100 parts by weight of the formative components (b) to (g).

As surface-active substances such as compounds come into consideration, which support the homogenization of the starting materials are used and may also be suitable, the to regulate the cell structure of the plastics. Mention may be made, for example, Emulsifiers such as the sodium salts of castor oil, or of fatty acids and salts of fatty acids, for example diethylamine oleate, diethanolamine stearate, ricinoleic acid with diethanolamine, salts of sulfonic acids, eg alkali metal or Ammonium salts of dodecyl benzene or dinaphthylmethanedisulfonic and ricinoleic acid; Foam stabilizers such as Siloxane-oxyalkylene copolymers and other organopolysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oils, Castor oil or ricinoleic esters, Turkey and Peanut oil and cell regulators such as Parafffine, fatty alcohols and Dimethylpolysiloxanes. For improving the emulsifying action, the Cell structure and / or stabilizing the foam are further oligomeric acrylates described above having polyoxyalkylene and fluoroalkane radicals as side groups. The surface-active Are usually used in amounts of 0.01 to 5 parts by weight, based on 100 parts by weight of the formative components (B) to (g) used.

Fillers, in particular reinforcing fillers, are known per se, conventional organic and inorganic Fillers, reinforcing agents, weighting agents, agents for improving the abrasion behavior in paints, coating agents etc. to understand. The following may be exemplified mentioned: inorganic fillers, such as silicate minerals, for example phyllosilicates, such as antigorite, serpentine, Hornblende, amphiboles, chrysotile, talc; Metal oxides such as kaolin, Aluminum oxides, titanium oxides and iron oxides, metal salts, such as Chalk, barite and inorganic pigments such as cadmium sulfide, Zinc sulfide, and also glass. etc. Kaolin (China clay), aluminum silicate and coprecipitates of barium sulfate and aluminum silicate and also natural and synthetic fibrous Minerals, such as wollastonite, metal, and in particular Glass fibers of different length , the settled optionally could be. Organic fillers are, for example, in : Carbon, rosin, cyclopentadienyl resins and graft polymers and cellulose fibers, polyamide, polyacrylonitrile, Polyurethane, polyester fibers based on aromatic and / or aliphatic dicarboxylic esters and in particular Carbon. The inorganic and organic fillers may be used singly or as mixtures and are of the Reaction mixture advantageously in amounts of 0.5 to 50 wt .-%, preferably 1 to 40 wt .-%, based on the weight of of components (a) incorporated to (g), although the content of mats, nonwovens and woven fabrics of natural and synthetic Fibers may reach values ​​of up to 80 wt .-%.

Further details regarding the abovementioned other customary auxiliaries and Additives in the technical literature, for example the monograph by JH Saunders and KC Frisch "High Polymers" Volume XVI, Polyurethanes, Parts 1 and 2, Verlag Interscience Publishers 1962 and 1964, or the plastic Manual, polyurethanes, Volume VII, Hanser-Verlag Munich, Vienna, 1st, 2nd and 3rd edition, 1966, 1983 and refer 1993rd

For the preparation of the polyurethane foams, the components are (A) to (g) in such amounts to implement that the Equivalence ratio of the NCO groups of component (a) to the sum of the reactive hydrogen atoms of components (b) to (g) 0.60 to 1.25: 1, preferably from 0.90 to 1.15: 1, is.

Polyurethane foams according to the inventive method, advantageously produced by the one-shot process, for example, using the high or low pressure technique, in open or closed molds, for example metallic Molds produced. It is also common that continuous Apply the reaction mixture to suitable conveyor belts for the production of foam blocks.

Especially advantageous has proven to be the two-component method to work and the structural components (b) (C), (d), (e), (f) and optionally (G) to a so-called Polyol component, often referred to as component A unite, and as the isocyanate component, often referred to as component B refers to the structure of component (a) and optionally blowing agents (E) to be used. The starting components are mixed at Temperature of 15 to 90 ° C, preferably from 20 to 60 ° C and in particular from 20 to 35 ° C, mixed, and in the open or optionally under elevated pressure in the closed mold introduced or in a continuous workstation on a tape which receives the reaction mass, is applied. mixing can mechanically by means of a stirrer, by means of a Stirring screw or by a high-pressure mixing in a nozzle be performed. The mold temperature is expediently 20 to 110 ° C, preferably 30 to 65 ° C and in particular 35 to 65 ° C.

The polyurethane foams produced by the process of the invention have a density of 10 to 800 kg / m³. preferably from 35 to 70 kg / m³ and in particular from 25 to 50 kg / m³ on. They are particularly suitable as cushioning material in Furniture and car seat sector but also at correspondingly higher Densities as integral foam part in car safety area.

They are particularly suited for use in climates with increased humidity, where as a respective resistance is absolutely necessary. They are furthermore suitable, in produce lower densities foams, despite the lower density sufficient mechanical application level have and maintain over an extended period of time.

The present invention is intended by the examples be explained, but without thereby being restricted make.

Examples 1-4 (Comparative Examples)

<tables><table><tgroup cols="5"><tbody><row><entry align="center" /><entry align="center">example 1</entry><entry align="center">example 2</entry><entry align="center">example 3</entry><entry align="center">example 4</entry></row><row><entry align="center">Lupranol® 2042</entry><entry align="center">60,05</entry><entry align="center">57,95</entry><entry align="center">56,90</entry><entry align="center">63,10</entry></row><row><entry align="center">Lupranol® 4100</entry><entry align="center">30,00</entry><entry align="center">30,00</entry><entry align="center">30,00</entry><entry align="center">30,00</entry></row><row><entry align="center">glycerin</entry><entry align="center">1.00</entry><entry align="center">3.00</entry><entry align="center">4.00</entry></row><row><entry align="center">diethylene glycol</entry><entry align="center">2.00</entry><entry align="center">2.00</entry><entry align="center">2.00</entry></row><row><entry align="center">triethanolamine</entry><entry align="right" /><entry align="right" /><entry align="right" /><entry align="center">3.20</entry></row><row><entry align="center">Lupranol® 2047</entry><entry align="center">3.00</entry><entry align="center">3.00</entry><entry align="center">3.00</entry></row><row><entry align="center">Lupragen® N201</entry><entry align="center">0.40</entry><entry align="center">0.50</entry><entry align="center">0.55</entry><entry align="center">0.15</entry></row><row><entry align="center">Lupragen® N206</entry><entry align="center">0.25</entry><entry align="center">0.25</entry><entry align="center">0.25</entry><entry align="center">0.25</entry></row><row><entry align="center">B 8680</entry><entry align="center">0.30</entry><entry align="center">0.30</entry><entry align="center">0.30</entry><entry align="center">0.30</entry></row><row><entry align="center">water</entry><entry align="center">3.00</entry><entry align="center">3.00</entry><entry align="center">3.00</entry><entry align="center">3.00</entry></row><row><entry align="center">RD (core)</entry><entry align="center">37,00</entry><entry align="center">36,70</entry><entry align="center" /><entry align="center">36,60</entry></row><row><entry align="center">DVR, 70 ° C</entry><entry align="center">84,70</entry><entry align="center">33,40</entry><entry align="center" /><entry align="center">70,30</entry></row><row><entry align="center">DVR, 40 ° C, 98% RH.</entry><entry align="center">91,50</entry><entry align="center">70,10</entry><entry align="center" /><entry align="center">83,90</entry></row><row><entry align="center">StH, 50%</entry><entry align="center">4.20</entry><entry align="center">5.40</entry><entry align="center" /><entry align="center">4.20</entry></row><row><entry>Lupranol® 2042 OH number 28 mg KOH / g, polyetherol based Propylene oxide and ethylene oxide (BASF), Lupranol® 2047 OH number 42 mg KOH / g, polyetherol based Propylene oxide and ethylene oxide (BASF) Lupranol® 4100 OHN 24 mg KOH / g, polymer polyol based on acrylonitrile / Styrene (BASF), Lupragen® N201 amine catalyst (BASF) Lupragen® N206 amine catalyst (BASF), B 8680 silicone stabilizer (Goldschmidt) RD (core) core density in kg / m³. DRV compression set at a specified temperature, measured according to method D'Essai 1046, RH relative humidity, StH 50% compressive strength - Method D'Essai 1003</entry></row></tbody></tgroup></table></tables>

Examples 5-8 (Invention)

<tables><table><tgroup cols="5"><tbody><row><entry align="center" /><entry align="center">example 5</entry><entry align="center">example 6</entry><entry align="center">example 7</entry><entry align="center">example 8</entry></row><row><entry align="center">Lupranol® 2042</entry><entry align="center">53,30</entry><entry align="center">53,30</entry><entry align="center">77.05</entry><entry align="center">55,05</entry></row><row><entry align="center">Lupranol® 4100</entry><entry align="center">30,00</entry><entry align="center">30,00</entry><entry align="center">10,00</entry><entry align="center">30,00</entry></row><row><entry align="center">glycerin</entry><entry align="center">0.60</entry><entry align="center">0.60</entry><entry align="center">3.00</entry><entry align="center">3.00</entry></row><row><entry align="center">Lupranol® 2047</entry><entry align="center">4.00</entry><entry align="center">4.00</entry></row><row><entry align="center">Lupranol® VP 9236</entry><entry align="center">8.50</entry><entry align="center">8.50</entry></row><row><entry align="center">Lupranol® VP 9209</entry><entry align="right" /><entry align="right" /><entry align="center">5.00</entry><entry align="center">7.00</entry></row><row><entry align="center">Lupragen® N201</entry><entry align="center">0.15</entry><entry align="center">0.15</entry><entry align="center">0.30</entry><entry align="center">0.40</entry></row><row><entry align="center">Lupragen® N206</entry><entry align="center">0.15</entry><entry align="center">0.15</entry><entry align="center">0.25</entry><entry align="center">0.25</entry></row><row><entry align="center">XFH 2584</entry><entry align="right" /><entry align="right" /><entry align="right" /><entry align="center">0.30</entry></row><row><entry align="center">B 8680</entry><entry align="center">0.30</entry><entry align="center">0.30</entry><entry align="center">0.40</entry></row><row><entry align="center">water</entry><entry align="center">3.00</entry><entry align="center">3.00</entry><entry align="center">4.00</entry><entry align="center">3.00</entry></row><row><entry align="center">RD</entry><entry align="center">40,00</entry><entry align="center">40,00</entry><entry align="center">37,00</entry><entry align="center">36,00</entry></row><row><entry align="center">DVR, 70 ° C</entry><entry align="center">18,20</entry><entry align="center">25,40</entry><entry align="center">17,50</entry><entry align="center">16,00</entry></row><row><entry align="center">DVR, 40 ° C, 98% RH.</entry><entry align="center">30,60</entry><entry align="center">36,40</entry><entry align="center">21,80</entry><entry align="center">23,90</entry></row><row><entry align="center">StH, 50%</entry><entry align="center">8.00</entry><entry align="center">11,20</entry><entry align="center">4.70</entry><entry align="center">5.70</entry></row><row><entry>Lupranol® VP 9209 OHZ 530 mg KOH / g, three functional polyol based on ethylene oxide (BASF), Lupranol® VP 9236 OHZ 605 mg KOH / g, three functional polyol based on ethylene oxide (BASF), XFH 2584 Dabco XFH 2584 - silicone stabilizer (Air Products)</entry></row></tbody></tgroup></table></tables>