DE2127132C3 - Process for the production of a hydrophilic, fine-pored foam that is permeable to moisture vapor - Google Patents

Description

Synthetic, hydrophilic ₍ fine-pored foams that are permeable to moisture vapor) are mainly used for objects that come into direct or indirect contact with the human body, such as footwear or furniture upholstery. The pores allow accumulated moisture to be removed from the skin. Another advantageous property of this Synthetic fine-pored foams suitable as artificial leather are their high wear resistance, which not only extends the life of objects made from them (such as shoes) considerably, but also makes polishing easier or even superfluous high tear resistance

Nevertheless, the known hydrophilic foams have not caught on to the extent expected This is due to the high cost of the materials and the inability to use most or to achieve all the desired aesthetic and other properties of natural leather.

The well-known artificial leather is, for example, natural leather Inferior in terms of hydrophilicity, although it is often more fine-pored than natural leather has "hydrophilicity" is generally the property of having an affinity for water. "Fine pores" (»Poromerity«) is defined here as the ability of a membrane to absorb water vapor due to its presence allow fine pores to pass through.

Most types of artificial leather have two to ten times the fine pores of natural leather, while they only have about 7% of the hydrophilicity of natural leather. The latter property leads to shoes from known artificial leather have too little ability to absorb foot sweat.

Up to now it has been extremely difficult to achieve the aforementioned properties (especially fine pores and hydrophilicity) to be combined with artificial leather. It is known, for example, to convert air into a polyvinyl chloride plastisol, which contains an emulsifier, mechanically beat in and then the foam mass into one to fuse polymeric hydrophilic foam (US-PS 32 88 920, 33 01 798 and 34 32 449 and the Journal »Kunststoffe« 57 [1967], pages 28 to 31). However, these foams have one extreme low wear resistance, tensile strength and tear resistance, so they are not considered artificial leather are suitable. It is also known that polyvinyl chloride plastisols Used to impregnate fiber-containing mats, chemically foamed and then during fusing can be compacted, a fairly solid, fine-pored material is obtained (U.S. Patent 29 17 405); however, this is not material hydrophilic and has insufficient aesthetic properties in terms of deflection or Cleavage, drapery and handle to be suitable as a substitute for natural leather. In addition, it is still known. Mix water and a polyester with a vinyl chloride plastisol and mix the mass with a polyisocyanate to form a closed-cell foamed cushioning material with relatively high strength implement (US-PS 28 98 312); however, the material obtained is neither fine-pored nor hydrophilic.

The production of molding and coating compounds based on homopolymers or copolymers of Vinyl chloride is from DE-AS 11 94 138 and US-PS 32 57 261 known However, the process does not produce foams, but rather more or less solid, unfoamed foils. Also according to GB-PS 8 44 240, in which PVC is combined with polyurethanes no foams, but solid PVC compounds

It was therefore the object of the invention to provide a method for producing an artificial leather to provide suitable foam, which has excellent hydrophilicity and fine pores and therefore vapor permeability as well as good aesthetic quality and excellent physical Has properties such as wear resistance. This object is achieved by the invention

The invention thus relates to a method for producing a hydrophilic, fine-pored, for moisture vapor permeable foam in the form of coated cloth or fabric, with the foam saturated non-woven fiber mats or unsupported films or webs by coating the Liner or a removable backing or saturating the nonwoven Fiber mats with a liquid mixture foamed with a non-reactive gas to form a foam (I) from:

1) 200 parts by weight of plastisol grade polyvinyl chloride

2) between 50 to 100 parts by weight of at least one compatible liquid plasticizer,

3) a stabilizer for the polyvinyl chloride and

4) between about 10 to about 16 parts by weight of an emulsifier that:

a) between 36 to 46 wt .-% of a saturated or unsaturated fatty acid with 12 to 24 Carbon atoms and mixtures thereof,

b) between 27 and 37% by weight of an alkali salt of a saturated or unsaturated fatty acid having 12 to 24 carbon atoms and mixtures of that,

c) between 6 to 16% acidic? aluminum phthalate, sodium phthalate and / or acid sodium phthalate,

d) between 4 to 8% by weight of water,

e) between 4 to 6% by weight of a saturated aliphatic glycol,

f) between 2 to 4% by weight of a hydrocarbon oil low molecular weight and

g) has between 1.5 to 2.5% by weight of silica,

and consolidation of the foam webs under the action of heat, which is characterized in that one a liquid mixture (I) with 7 to 19 parts by weight of a liquid polyurethane precursor (II) made from a polyester polyol and / or polyether polyol and a polyisocyanate, which has 1 to 10% reactive NCO end groups, mixed and foamed to form the foam

The method of the invention provides an excellent foam suitable as artificial leather, the an unexpectedly high hydrophilicity (100% by weight and above) with excellent fine pores combined and therefore has excellent water vapor permeability. When used as a Due to the properties mentioned, the foam has a high absorption capacity for artificial leather for shoes for foot sweat, In addition, the foam produced according to the invention has exceptional properties physical and aesthetic properties such as excellent wear resistance, flexibility, Elongation, tensile strength and tear strength (including wet strength) and handling as well as one good grip, good break 'or cleavage and draping and a uniform cell size, from which Synthetic leather made of foam can only be distinguished from natural leather after a careful examination. Such artificial leather is also cheaper than most known types of artificial leather. The foam can be produced in different densities.

The method of the present invention also requires low cost and a relative cost. minor technical effort and is accessible for automatic and semi-automatic execution.

The foam produced according to the invention can be used for a large number of products, There are many items that go with the. especially where body comfort is an important factor Foam can be covered or use this material, such as furniture and furniture upholstery, Clothing, gloves, seating, pillows and beds as well as footwear. As in the following is explained, the foam can be produced alone in the form of webs and foils or the foamed Mixture is poured onto a substrate or used to impregnate fiber mats. All such uses are encompassed by the invention

The types of polyvinyl chloride used in the liquid mixture (I) in the process according to the invention are known The most important technique for the production of polyvinyl chloride of Pias dsol quality is the emulsion polymerization, which is known to employ the emulsification of the liquid vinyl monomer in water of surfactants and movement and subsequent acceleration of polymerization required by heat and / or catalysts. Emulsion polymerized Polyvinyl chloride is a fine powder with a particle size sufficient to produce a Compounding with plasticizers to form vinyl plastisols to enable. The polyvinyl chloride can also be used by other polymerization methods, e.g. B. by bulk polymerization or solution polymerization.

Plastisol grade polyvinyl chloride as well as other vinyl chloride resins are mainly made by it average molecular weight or their »inherent viscosity« or »IV«. In general, the Intrinsic viscosity of a polyvinyl chloride from less than 0.40 to over 2.00. Polymers with these inherent viscosities can be used according to the invention, but polymers with inherent viscosities of about 0.60 to about 130 because of the simplicity of processing, des Mixing, foaming and shaping are preferred

so The plastisol quality polyvinyl chloride can be blended, thinned or with up to about 50 wt .-% Expanding resins are mixed. Expanding or filling resins are generally cheap, compatible polymers (usually vinyl polymers) whose main function is to reduce the overall material cost without adversely affect the chemical or physical properties. Examples of suitable Expanding resins are

Polyvinyl chloride vinyl acetate copolymers,

Polyvinyl chloride-vinylidene chloride copolymers,
Polyvinyl acetate, polyvinyl alcohol,
Polyvinylidene chloride and
Polyvinyl chloride ^ polybutadiene mixtures.
At least one compatible, liquid plasticizer is added to the plastisol-quality polyvinyl chloride

Mixture of polymer and plasticizer remains liquid The adsorb during the curing process Polymer particles form the plasticizer and form a mass of swollen particles. After further Heating melts the polymer particles to form a homogeneous matrix of resinous material together, in which the plasticizer is homogeneously distributed. This makes the hardened product soft and made pliable, and the product will have the desired properties such as draping or Wrinkling, flexibility or grip, conferred.

A wide variety of plasticizers can be used in accordance with the invention. They vary from simple organic compounds such as dioctyl phthalate to more highly branched compounds such as butyl cyclohexyl phthalate to reactive plasticizers containing epoxy groups or other groups such as epoxidized soybean oil. Further examples of suitable plasticizers are
Dibenzyl sebacate, dibutyl phthalate,
Dibutyl sebacate, dicapryl phthalate,
Bis- (uiäihy! Eng! Yko! Rnonoäthy! Äther) -phtha! At,
Di- (2-ethylhexyl) acetate,
Di- (2-ethylhexyl) phthalate,
Diisobutyl phthalate,
Dimethyl phthalate,

Di-2-ethylhexyl adipate, dioctyl sebacate,
thermoplastic phenol-formaldehyde resins,
aromatic hydrocarbons from petroleum,
Diisooctyl phthalate. Isooctyl isodecyl phthalate,
Diisodecyl adipate, butyl isodecyl phthalate,
Butyl octyl phthalate, dioctyl adipate,
n-octyl-n-decyl phthalate and
Diisodecyl phthalate.

The plasticizer and the polyvinyl chloride (with or without extender resins) become weaker Agitation mixed to give a flowable mixture.

As mentioned, a special emulsifier is added to the polyvinyl chloride of plastisol quality and the plasticizer, which consists of 36 to 46% by weight of a saturated or unsaturated fatty acid or mixtures thereof with 12 to ? A carbon atoms, between 27 to 37% by weight an alkali salt of a saturated or unsaturated fatty acid or mixtures thereof with 12 to 24 carbon atoms, between 6 to 16% by weight of acidic potassium phthalate, sodium phthalate and / or acidic sodium phthalate, between 4 to 8% by weight of water, between 4 to 6% by weight % of a saturated aliphatic glycol, between 2 to 4% by weight of a hydrocarbon oil of low molecular weight and between 1.5 to 2.5% by weight of silica. An emulsifier of this type is commercially available and has already been used in the production of air-permeable synthetic foam leather by the fumigation process (see "Kunststoffe" 57 [1967], page 28, right column). This emulsifier is the only type of emulsifier known to stabilize a foamed mixture of the plastisol grade polyvinyl chloride compatible liquid plasticizer and the flowable polyurethane precursor (described below) during the expansion and subsequent process steps of the invention.

There are a number of suitable emulsifier components. For example, the saturated or unsaturated acid lauric acid, myristic acid, palrriitic acid, Stearic acid, oleic acid, linoleic acid and linolenic acid, with oleic acid being preferred: the Alkali salts of a saturated or unsaturated fatty acid can be the sodium or potassium salts of the above be listed fatty acids, potassium oleate is preferred; the saturated aliphatic glycol can Polyethylene glycol, polypropylene glycol or polybutylene glycol with polyethylene glycol being preferred. The alkali salts of the saturated or unsaturated Fatty acids can be added directly to the emulsifier or prepared in situ; the production in situ takes place in the usual way, usually by adding a soap-forming base (such as sodium hydroxide or Potassium hydroxide) to the fatty acid.

This particular emulsifier has an additional unique property in that it causes a high degree of trimerization to occur between the active NCO groups in the precursor, such as when the polyurethane precursor is made with an active NCO end group on the ends of the molecules. This trimerization appears to explain, at least in part, the unexpected improvement in "" strength and other properties of foam .. nc ¹ materials made therefrom.

The liquid or flowable polyurethane precursor (II) is made by reacting a polyol with a Polyisocyanate produced The polyol can be a polyester and / or a polyether polyol. The manufacture of the Precursor can be carried out in such a way that the precursor has active NCO end groups, which are used for further Reaction are capable, or masked or blocked NCO groups, which after cleavage of the blocked Groups are also capable of further reaction, each of these types of precursors confers the Products made from the mass in question have particular advantages.

The polyether polyols and / or polyester polyols used as polyols to produce the precursor can be selected from a wide range of molecular weights, but redi. adorn the Presence of the vinyl plastisol in the liquid mixture (I) and the subsequent processing conditions the practical molecular weight range to between about 500 to about 3,000. Polyols with lower molecular weights, e.g., below about 500, have relatively more polymeric chains each Weight unit; thus there are more chain ends that react with the isocyanate. These polyols with while having a relatively low viscosity, form an extremely low molecular weight viscous extended chain precursors and make mixing and foaming of the components difficult (I) and (II). Higher molecular weight holols, for example above about 3000, are inherently viscous and bit more viscous precursors, which are the same Raise mixing and foaming problems.

The viscosity of the prepolymer can be adjusted within limits by heating or diluting with solvents be reduced. Do not heat above about 93 ° C as the gel will instantly form the Vinyl plastic isolates in the liquid mixture (I) would open. Only high-boiling solvents can be used, as they will affect the mixing of the two Components generated exothermic heat would cause the lowest ^ deride solvents to evaporate.

High-boiling solvents can adversely affect the foam, which is why their usability is also possible is severely limited. It was found to be expedient to use a proportion of the representative as a diluent.

Chen to use liquid plasticizer from the liquid mixture (I).

If the proportion of the precursor is less than about parts by weight, the polyurethane will not give any sufficient reinforcement or consolidation of the foam or improvement of other properties that are important for artificial leather. On the other hand, if more than about 19 parts by weight are used, a large Amount of resinous gel particles generated in the foaming step, which deteriorate the processing and lowered the quality of the foam.

The precursor is manufactured in a conventional manner Way. Since a polyurethane precursor with immediately reactive remaining NCO end groups is required, the amount of polyisocyanate required to produce a non-reactive polyurethane is increased were. For the preparation of a masked or blocked isocyanal group-containing polyurethane precursor you can use the polyisocyanate with a MÖCi'iiuineirisi.-iien deficiency of rviaskierungsmitiei implement, which is generally an easily dissociable polyvalent compound, e.g. B. a phenol, or kresoi Alcohol, is. The reaction product is then combined with the polyol. The remaining or not implemented NCO groups in the polyisocyanate lead to chain lengthening of the polyol; through sufficient Heating can initiate a further reaction, whereby the masking agent dissociates and the unblocked NCO groups are made reactive.

Usable polyester polyols are by condensation of at least one polyhydric alcohol and at least one polycarboxylic acid produced. Examples of suitable polyhydric alcohols are Glycerine, pentaerythritol,

Ethylene glycol, diethylene glycol, polypentaerythritol, mannitol,

Trimethylolpropane,

Sorbitol,

Methyltrimethylolmethane, 1,4,6-octanetriol, Butanediol, pentanediol, hexanediol, dodecanediol, octanediol, chloropentanediol, Glycerol monoaliyl ether,

Glycerine monoethyl ether,

Triethylene glycol, 2-ethylhexanediol-1,4, 3,3'-thiodipropanoI, 4,4'-sulfonyldihexanol, Cyclohexanediol-1,4, 1,2,6-hexanetriol, 13,5-hexanetriol, polyallyl alcohol, 13-bis (2-hydroxyethoxy) propane, 5,5'-dihydroxydiamethyl ether, tetrahydrofuran-2 ^ -dipropanol, Tetrahydrofuran-2,5-dipentanol, 2,5-dihydroxytetrahydrofuran,

55

60

65

TetrahydropyrroI-2 ^ 5-propanol, 3,4,5-hydroxytetrahydropyran, 2 ^> - dihydroxy-3,4-dihydro - !, 2-pyran, 4,4'-sulfinyldipropanol,
2 ^ -Bis- (4-hydroxyphenyl) -propane and 2 ^ '- bis- (4-hydroxyphenyl) -methane. Examples of suitable polycarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, maleic acid, dodecyl maleic acid, octadecenyl maleic acid, fumaric acid, aconitic acid, itaconic acid, trimeilitic acid, tricarballylic acid, 3,3'-thiodipropionic acid,
4.4'-sulfonyl dihexanoic acid,

3-octene-l, 7-diacid,

3-methyl-3-decenedioic acid,

Succleic acid, adipic acid,

1,4-cyclohexadiene-l ^ -dicarboxylic acid,

3-methyl-2,5-cyclohexadiene'l ^ dicarboxylic acid,

8.12-Eicosadiendic acid,

8-vinyl-10-octadecenedioic acid

and the corresponding acid anhydrides, acid chlorides and acid esters such as phthalic anhydride, phthaloyl chloride or phthalic acid dimethyl ester. Become polyether generally by reacting an alkylene oxide, for example propylene oxide, with a strong one Base such as potassium hydroxide.

The acid number of the polyester polyol should be kept at a very low level; h, below about 5, and preferably at or below about 1.0. The carboxylic acid group that provides the acid number, namely reacts with the isocyanate to form a mixed carboxylic acid-carbamic anhydride, which either Carbon dioxide is split off with the formation of an amide, which either continues with isocyanate to form a Acylurea reacts (which leads to branching and gel formation in a susceptible precursor reaction) or is disproportionated to a urea or biuret and an anhydride, the biuret the Promotes branching and gel formation and the anhydride is hydrolytically unstable and leads to degradation (depolymerization) tends to be exposed to moisture. In order to rule out these problems, it is expedient to use polyester polyols to be used with acid numbers below about 1.0.

A variety of polyisocyanate compounds can be used to prepare the precursors. Examples are

Toluene-2,4-diisocyanate,

Toluene-2,6-diisocyanate,

4,4'-diisocyanatodiphenyl methane.

1,5-naphthalene diisocyanate,

Cumene-2,4-diisocyanate,

4-methoxy-1,3-phenylene diisocyanate,

4-chloro-1,3-phenylene diisocyanate,

4-bromo-1,3-phenylene diisocyanate,

4-ethoxy-1 j-phenylenediisoeyanate,

2,4'-diisocyanate diphenyl ether,

5,6-dimethyl-13-phenylene diisocyanate,

2,4-dimethyl-1 _r 3-phenylene diisocyanate, -

4,4'-diisocyanatodiphenyl ether,

Benzidine diisocyanate,

4,6-dimethyl-1,3-phenylene diisocyanate,

9,10-anthracene diisocyanate,

4,4'-diisocyanatodibenzyl,

S ^ -DimethyM / t'-diisocyanatodiphenylmethane,

2,6-dimethyl-4,4'-diisocyanatodiphenyl,

2,4'-DiisocyanatostiIben,

33'-dimethyl-4,4'-diisocyanatodiphenyI,

S ^ '- Dimethoxy ^^' - diisocyanatodiphenyl,

1,4-anthracene diisocyanate,

2,4-fluoro diisocyanate,

1,8-naphthalene diisocyanate,

2,6-diisocyanatobenzfuran and

2,4,6-toluene tri-isocyanate L

Mixtures of two or more of these polyisocyanates can also be used. Aromatic isocyanates are preferred, especially toluylene diisoeyanate, which results in a material with extremely fine breakage and grip

When a fibrous substrate becomes saturated with the foam (e.g. the one described below

Manufacture of artificial leather), it is advisable to use a Polyurethane precursors at about 2 to 10%, especially Use 6 to 7% reactive isocyanate groups. These NCO groups presumably react to a certain extent With the fibers of the substrate and thereby - bring about a higher degree of adhesion than the hardened product has higher tensile strength, higher resistance to peeling and higher wear resistance confers

Furthermore, it was inferred from certain phenomena, that the contained in the flowable mixture (Γρ The unreacted isocyanate groups of the polyurethane precursor for trimerization to form an emulsifier causes high-strength three-dimensional crosslinked structure, which has a higher strength than that which is obtained by dimerizing the NCO groups. The noticeable belongs to these phenomena Lack of CC> 2 formation during mixing of the

liquid mixture of the plastisol resin, plasticizer and emulsifier. It is well known that the dimerization of NCO groups is under development accompanied by copious amounts of carbon dioxide, while no carbon dioxide is evolved in the trimerization reaction will.

The mixture (1) and the precursor (II) can contain other materials, for example dyes, Stabilizers, antioxidants, fillers, flame extinguishers or fungicides. Dyes can can be added to add a color to the final product and one that occurs below the surface Mask discoloration and other visible imperfections. They can be used in amounts from about 1 to about 30 parts by weight can be used. Examples of suitable dyes are inorganic substances such as Soot, iron oxide, manganese blue, iron oxide brown, chromium oxide green, molybdate orange, cadmium red, mercury red, aluminum, manganese violet, titanium dioxide or cadmium yellow, and organic substances such as oil black or a dispersion of aluminum powder and Styrene butadiene rubber.

Stabilizers can be added to prevent degradation of the polymer by heat or light delay. They can be used in amounts of about 1 to 30 parts by weight. Examples of usable Stabilizers are lead salts, such as basic lead carbonate, tribasic lead sulfate, dibasic lead phosphite, tribasic lead maleatate, normal lead stearate, dibasic lead stearate, dibasic lead phthalate, Lead silicate or lead salicylate; Barium-cadmium-zinc combinations, like simultaneously precipitated barium-cadmium and cadmium-zinc soaps of the lauric, Stearic or hydroxystearic acid or other fatty acids; Organotin compounds, such as dibutyltin dilaurate, Dibutyl tin maleate, dioctyl tin maleate or Dibutyl mercaptide; epoxidized oils, such as epoxidized Soybean oil or epoxidized esters of tall oil and soybean oil; Chelating agents such as tripenyl phosphite; and other stabilizers, such as benzophenones, triazo compounds, Phenylsah'cylat or Sodium Organophosphate.

Antioxidants can help regulate polymer degradation by reacting with the oxygen and ozone in the air in amounts ranging from traces up to about IO Parts are added. Examples are hydroquinone monobenzyl ether, alkylated bisphenol, tri- (nonylphenyl) phosphite and 2 £ '-dihydroxy-4,4'-dimethoxybenzophenone.

Extenders or fillers can be added to reduce costs and in some cases that Reinforce material. They can be used in amounts from about 1 to about 50 parts by weight. Examples are calcium carbonate, magnesium carbonate, aluminum silicate, Aluminum hydroxide, basic aluminum sulfate, ammonium sulfate, kaolin clay, silicon dioxide, calcium sulfate, Muscovite, diatomaceous earth, silica, amorphous silica and extender resins.

Flame extinguishers can be added to increase the fire hazard of the foams to decrease. Flame retardants, such as antimony oxide, tris (2, 3) dibromopropyl phosphate, tetrrabromophthalic anhydride, Tetrabromobisphenol, perchlorpentacyclodecane (65% chlorine) or C15CI1 jHe can be used in amounts from 1 to about 20 parts by weight can be used.

Fungicides can be added to prevent the growth of fungi and other bacteria in the

Footwear is particularly important. The fungicides can be used in amounts from 0.01 part per million to greater than 5 Parts by weight are added depending on the type of fungicide base, d. H. depending on whether the fungicide is with linked to a large molecule (e.g. a plasticizer) or whether it is added alone. to Examples of useful fungicides include arsenated epoxidized soybean oil, bis (tri-n-butyltin) sulfosalicylate, 3,5,4'-tribromomethylthiaide, N- (trichloromethylthia) -phthalimide, quaternary ammonium naphthenate, phenyl mercury acetate and copper-8-quinolinate

In the process according to the invention, the production of the components, the mixing of the Mixture (I) with the precursor (II) and the foaming of the mixture exactly and within the im The following specified limits are made so that the foam in terms of cell size, density and other properties are properly developed so that the finished Materia! the desired properties higher Has wear resistance and strength combined with hydrophilicity and fine pores

Specifically, the mixture (I) is prepared by adding 100 parts by weight of a plastisol grade polyvinyl chloride 50 to 100 parts by weight of at least one compatible liquid plasticizer, a stabilizer for the polyvinyl chloride and between about 10 to about 16 parts by weight of that described above special emulsifier. These components can be added in any desired manner are, however, for the sake of simplicity, initially the plasticizer and then the polyvinyl chloride, the stabilizer, the emulsifier and other optional additives are added and taken under slight Stir for about 5 minutes to form a low viscosity liquid (i.e. 20 to 100cP) Other ingredients such as the aforementioned dyes, flame retardants or fungicides can be used in appropriate amounts are added; all components can be in the flowable mixture be stirred in.

A flowable polyurethane precursor is separated by reacting a polyisocyanate with a Polyether or polyester polyol produced This is generally done under anhydrous and inert atmospheric conditions Conditions to avoid undesired side reactions with the isocyanate. As described above, depending on the end use of the foam (i.e., as a foam per se or as a a saturant) the remaining NCO content of the

IO

15th

20th

30th

Precursors can be varied up to 10%. The remaining NCO content is preferably 1 to 8%. The mixture (I) is then mixed with 7 to 19 parts by weight of a polyurethane precursor (II) with gentle agitation and in the absence of air or other reactive gases at room temperature to form the base material for the foam. During the mixing of the two components, a noticeable exothermic heat occurs as well as a slight surge or foaming, which is indicated by a slight degree of dimerization of the reacted NCO group with the water and other labile hydrogen-containing compounds, a nominal degree of trimerization of the same constituents (catalyzed by one or more of the components of the Emulsifiers), the mixed heat of the components or, more realistically, a combination of all three phenomena. The material obtained is a fairly viscous, flowable material. This material is then foamed with air or another non-reactive gas in a conventional foaming system to form a foam with a density of about 0.5 g / cm ³ to about 1.5 g / cm ³

Another method of mixing the flowable mixture (I) with the precursor (II) is to to bring them in separate lines to the mixing head of the foaming system, so that they are intimately mixed and foamed at the same time, the foam with the density range described above is obtained. Neither procedure seems to be better than the other, and they may vary depending on the person Process plant requirements can be exchanged and used. The viscosity of the foam will be by the speed of the foaming mixer and the amount of gas blown into the foaming head achieved and regulated

In fact, the propellant gas can be any non-reactive gas that does not harm the final foam or confers dangerous properties; Examples are air nitrogen, carbon dioxide and helium.

The foaming of the mixture can be carried out in many types of foaming equipment, such as a common milk shaker or similar machine. Preference is given to what is known as an "oakes mixer" Machine, i.e., a water-jacketed high-speed emulsifying beating machine, the creates a creamy, smooth foam

The foam is then shaped for the desired product. For example, the foam can be in a layer on a release paper (release or release coated with silicone or polytetrafluoroethylene Release paper) and passed through a curing oven. The foam can too to be poured in a layer over a cloth or tissue or other substrate to create one on one Create carrier-located material; Examples of usable cloths or fabrics are nylon fabrics, Cotton jersey and non-woven rayon.

The foam is then subjected to heat or some other form of energy to produce a cured foam. "Hardening" means that the plastisol, ie the flowable mixture of polyvinyl chloride in the plasticizer, is formed into the aforementioned swollen particles, which are filled with plasticizers and then ^{fuse to form a homogeneous matrix of plasticized Pc-1} J ¹ vinyl chloride. "Hardening" also includes completion of trimerization and / or others

40

45

55

60 polymerization reactions of the polyurethane. For heat curing, the material can be cured over a wide temperature range, for example 15 minutes at 232 ° C. Obviously, a lower temperature requires a slightly longer curing time, while a higher temperature requires a shorter curing time. Care should be taken that the curing temperature does not exceed the irreversible decomposition temperature of the individual components.

A fiber mat can also be saturated with the foam and the foam becomes a synthetic one leather-like material having such appearance, feel and other properties that only on closer inspection can it be determined that it is not natural leather. the Fiber mat becomes saturated with the foam by applying the foam to both surfaces of the mat is poured and the mat is guided by press rollers to bring the foam into the interior of the mat push. Other procedures include dipping the mat in a bubble bath and then doing it Passing the mat through a set of pinch rollers. The fiber mat can be made from different fibers exist, for example natural fibers, synthetic fibers and mixtures thereof. Examples are nylon, polyethylene terephthalate fibers, Copolyester fibers (polyethylene terephthalate isophthalate in a ratio of 90:10), acrylic fibers, Rayon and cotton. From all of these fiber mats you get a very high quality one Artificial leather / material that is hardened in the same way as the materials described above can.

The aforementioned synthetic leather material can be peeled off and split to produce synthetic leather types with different weights and uses. For example, a nylon staple fiber mat of three denier, 3.8 cm and 400 or 425 g / 0.8 m ² heavy needled and pressed to form a dense fiber mat (z. B. with a thickness of 2.8 mm). This mat can then be saturated according to the method of the present invention with foam, cured at 204 ⁰ C during 3> / 2 min. And then 1.13 mm diken tracks (for men's shoes), or 0.88 mm thick webs cleaved (for women's shoes) are . This material can then e.g. B. polished, embossed and printed and used as it is or provided with another finish (such as a urethane or acrylic coating) to resemble leather more closely. The material can also be coated with other foam of the same type. Typical properties of these materials are: tensile strength 80.9 kg / cm * (warp), 130 kg / cm (final), tensile strength 53 kg / cm ² (warp), 7.7 kg / cm (weft), elongation 8% ( Warp), 11% (weft) and MVT 8000 g per square meter per 24 hours.

The wear resistance of this material is assessed by a Ford Abrasion Tester and a Taber Abrasion Tester measured; however, since it is resilient foams instead of solid structures the standard abrasion test not applicable. In general, the test is performed on a foam sample performed by either or both tests up to 1000 cycles (of the abrasive device) and the surface is checked for signs of wear. If no Wear occurs, the material is rated as "acceptable", while wear and tear is rated as "not

"inceptible" is called. The water intake is done by soaking the sample in water for 24 Std. And determination of the weight gain determined.

The following examples illustrate the invention, if any Unless otherwise stated, all parts of the data are parts per 100 parts of polyvinyl chloride and all Percentages by weight.

example 1

Two liquid components (I) and (II) were prepared from the ingredients given in Table Ia. The liquid mixture (I) was made by slowly adding the plastisol grade polyvinyl chloride to the Plasticizers with gentle stirring and subsequent addition of the other ingredients. The precursor (II) was made by reaction a molar excess of tolylene diisocyanate with a polyester resin (acid number 0.50) with a Molecular weight of 1000 at 82 ° C with gentle agitation, anhydrous conditions and exclusion of air or other reactive gas for about 15 microns (or until no further exothermic heat was observed). A polyurethane was obtained which was about 6% of the original Contained NCO groups in the unreacted state.

Table Ia

Liquid mixture (I)
Commercially available PlastisoI-PVC, IV = 1.19
Plasticizer (diootyl adipate)
Plasticizer (N-trimellitate)
Plasticizer (99% epoxidized
Soybean oil with 1% 1,1-oxybisphenoxarsine
as a fungicide)

Barium-Cadmium Stabilizer
Commercial emulsifier:

1) 41 wt% oleic acid

2) 32 wt% potassium oleate

3) 11 wt% acid potassium phthalate

Table Ib

Parts

100.0

4)
5)
6)

6% by weight
5% by weight
3 wt%

7) 2% by weight

water

Low molecular weight and polyethylene glycol of a hydrocarbon oil
Silica

Precursor (II)

ίο polyester urethane (molecular weight 1000) with 6% unreacted NCO from toluene diisocyanate

Components (I) and (II) were at room temperature

Is temperature in a flask flushed with nitrogen with gentle stirring for 15 min. Mixed to a viscous liquid. The mixture was pumped into a commercially available mixer under a nitrogen blanket. A nitrogen line was connected to the mixer head and the pressure was set to 10.5 atmospheres. The mixer was set to 180 rpm and the nitrogen ^{flow was regulated so that 23 m 3 of} nitrogen per second were added Mixer were directed. After flowing out, the mixer produced a foam with a density of 0.73 to 0.7 / g / cm ³ . The foam was processed in three ways: Part of the foam was poured onto release paper treated with silicone in a thickness of 1.25 mm, and further foam was poured on with a thickness of 1.25 mm

JO poured a cotton jersey backing and a third sample of the foam was ^{saturated with a heavily needled nylon mat of approximately 400 g per 0.8 m 2} of 3 denier. All three samples were passed through the curing oven and cured at 232 ° C for 15 minutes. The saturated material was split to thicknesses of 1.13 mm (male weight) and 0.88 mm (female weight). Each disk was polished on one side. Table Ib lists the various samples made in this example and some of their physical properties.

Strength water tensile tensile tear

recording strength voltage strength

(mm) (%) (kg / cm ² ) (%) (kg / cm)

MVT

Taber abrasion

(g / m ^2/24 hr) (1000 cycles)

Foam sheet 0.5 75 Foam sheet on cotton 0.88 80 carrier Nylon mat saturated with foam 1.14 90 (Male weight) Nylon mat saturated with foam 0.88 90 (Woman weight)

28.1
66.8 250
50 17.7
26.5 7000
6500 acceptable
acceptable 89.0 11th 39.0 8600 acceptable 70.3 13th 60.0 9600 acceptable

MVT = moisture vapor permeability.

This example shows the feasibility of the component other than the plastisol polyvinyl chloride, we-

Basic process of the invention for producing the at least one compatible liquid plasticizing agent

hydrophilic foam or synthetic leather. Can also contain 60 agents and the emulsifier, this example shows that the liquid mixture (I) other

Example 2

Two liquid components (I) and (H) were prepared from 65 The process for preparing the components that

the ingredients indicated in Taelle Ila were with the mixing and foaming of the mixture

Prepared exception that the inherent viscosity of the measures described in Example 1

Plastisol grade polyvinyl chloride was varied. identical.

15th

Table Ha

Liquid mixture \ i) 100 100 100 Plastisol quality PVC (IV = 0.75) 73.0 Plastisol quality PVC (IV = UO) 73.0 0.5 Plastisol quality PVC 15.0 (IV = 1.27) 73.0 0.5 Plasticizers 15.0 (Dios; tylphthalate) 0.5 Pigment (iron oxide brown) 15.0 Emulsifier (possibly Table Ia)

Precursor (II)

Polyester urethane (molecular weight (1000) with 6% unreacted NCO from toluene diisocyanate

15.0 15.0 15.0

Samples from a needled nylon mauve (3 den) of ίο 400 g / 0.8 m ² were separately saturated with samples A, B and C by dipping the mat into the foamed mixture of components (I) and (II) and the The wet mat was passed through a set of squeegee rollers and dried at 177 "C for 20 minutes and then split into a 1.13 mm web and polished on one surface. Table Hb shows the physical properties of these samples.

15th

Table Hb

Samples tensile strength, elongation at break MVT

strength

(kg / err ^) (kg / cm) (%) (g / mV24 h)

Water absorption

Taber abrasion Cord abrasion (lOOOCyden) (1000 cycles)

134
129
93.5

86 12th 8100 100 acceptable acceptable 71 9 9350 90 acceptable acceptable 62 20th 9600 95 acceptable acceptable

This example shows that in the plastisol quality according to the invention from materials with a broad Process the polyvinyl chloride to be used can be selected from the range of inherent viscosities.

Example 3

Two liquid components (I) and (II) were made from the ingredients given in Table HIa with the Exception formulated that a stretch resin is used in place of some of the plastisol grade polyvinyl chloride became. Components (I) and (II) were prepared in an identical manner as in Example 1, mixed and processed The nylon fiber mat was saturated with the foam according to Example 2 and 5> processed table IHb shows the physical Properties.

Table UIa Table IHb

rehearse
AWAY

Liquid mixture (I) plastisol-PVC (see Table Ia) cadmium-barium stabilizer Commercially available stretching resin pigment (iron oxide brown) plasticizer (dioctyl phthalate)
Plasticizer (epoxidized soybean oil) Emulsifier (see Table Ia)

Precursor (II)

Polyester urethane (molecular weight 1000) with 6% unreacted NCO from toluene diisocyanate

100 75 50 4.0 4.0 4.0 25th 50 0.5 0.5 0.5 44.0 44.0 44.0

29.0 29.0 29.0

15.0 15.0 15.0

15.0 15.0 15.0

Samples tensile strength tensile strength

strain

MVT water absorption

(kg / cm *)

(kg / cm)

h) Taber Abrasion Ford Abrasion (1000 Cycles) (1000 Cycles)

A. 134 86 12th 8 100 100 D. 98.4 71.5 9 9 500 95 C. 63.3 57 9 10,000 80

acceptable acceptable acceptable acceptable acceptable acceptable

809 681/155

This example shows that in the process according to the invention, the polyvinyl chloride to be used from Plastisol grade can be stretched with resins and yet make a usable product.

Example 4

Two liquid components (I) and (II) were made from the ingredients listed in Table IVa with the Manufactured exception that the type of plasticizer and the type of isocyanate was changed. The components were produced according to Example 1, mixed and foamed A nylon fiber mat was saturated with the foam according to Example 2 and processed Table IVb lists the physical properties

Table IVa

Liquid mixture (I)

Plastisol PVC (see table Ia)

Plasticizer (dioctyl adipate)

Plasticizers

(polymer, molecular weight 6000)

Plasticizers

(polymer, molecular weight 3500)

Cadmium-barium stabilizer

Emulsifier (see Table Ia)

Precursor (II)

Polyester urethane (molecular weight 1000) with 6% unreacted NCO

from 80/20 TDI)

Precursor (II)

Polyester urethane (molecular weight 1000) with 6% unreacted NCO

from MDI **)

*) 80% 2,4-tolylene diisocyanate,
20% 2,6-tolylene diisocyanate
**) 100% 4,4'-diisocyanatodiphenylmethane.

100 100 100 100 70 40 20th 30th 30th 40 20th 30th 4.0 4.0 4.0 4.0 15.0 15.0 15.0 15.0

15.0

15.0

15.0

Table IVb

(kg / cm2)

Samples tensile strength tensile strength

(kg / cm)

strain

MVT (g / m ^2/24 hr) Water absorption

Taber Abrasion Ford Abrasion (lOOOCyclen) (1000 Cycles)

A 120 to 127 97.5 to 102 80 to 90 7,000 110 acceptable acceptable

B 123 to 130 88.5 to 103 70 to 90 7 400 90 acceptable acceptable

C 105 to 141 69 to 97.5 70 to 90 9 560 85 acceptable acceptable

D 105 to 120 78 to 97.5 85 to 105 10 300 100 acceptable acceptable

This example shows that the compatible liquid plasticizers are made for the liquid mixture (I) a wide range of molecular weights and types can be selected. The example shows also that various types of isocyanates and isocyanate compositions are used to make the Precursor (II) can be used.

example

Two liquid components (I) and (II) were selected from those listed in Table Va below Ingredients except that the nature of the polyurethane prepolymer polyois was varied. The components were produced according to Example 1, mixed and foamed. A nylon fiber mat was made according to Example 2 saturated with the foam and processed. In Table Vb are the physical Properties listed.

19th

20th

Table Va

Samples A

Liquid mixture (I)

Plastisol PVC (see Table Ia) 100

Plasticizer (dioctyl phthalate) 44.0

Plasticizers (polymer, molecular 25.0

weight 4500)

Plasticizer (epoxidized soybean oil) 4.0

Pigment (iron oxide brown) 0.5

Cadmium-barium stabilizer 4.0

Emulsifier (see Table Ia) 15.0

Precursor (II)

Polyester urethane (molecular weight 1000) with 15.0 6% unreacted NCO

80/20: 2,4,2,6-toluene diisocyanate

Precursor (II)

Polyether urethane (molecular weight 1000) with 6% unreacted NCO from 80/20: 2,4 / 2,6-tolylene diisocyanate

Precursor (II)

Molecular weight 1000 / molecular weight 1000 Polyester / polyether 50/50 polyurethane with 6% unreacted NCO from 80/20: 2,4 / 2,6-toluene diisocyanate

100
44.0
25.0

4.0

0.5

4.0

15.0

15.0

100 44.0 25.0

4.0

0.5

4.0

15.0

15.0

Table Vb

Samples tensile strength tensile strength

Del.tiung

Water absorption

(kg / cm2)

(kg / cm)

MVT Taber Abrasion Ford Abrasion

(g / m ² / 24h) (1000 cycles) (1000 cycles)

A 66.8 to 93.5 28.4 to 62 8 to 20 110 9

B 93.2 to 155 57 to 92 80 to 105 100 10

C 643 to 120 41.5 to 74 13 to 18 95 9

acceptable acceptable acceptable acceptable acceptable acceptable

This example shows that the polyurethane prepolymer Polyester polyols, polyether polyols and mixed polyester-polyether-polyols may contain.

Example 6

Two liquid components (I) and (II) were made from the ingredients listed in Table VIa with dör

Table VIa

Manufactured exception that the type of polyurethane precursor isocyanate was changed. The components were prepared according to Example 1, mixed and foamed. A nylon fiber mat was saturated with the foam and processed in accordance with Example 2 Table VIb are the physical properties

50 listed.

rehearse B. C. A. Liquid mixture (I) 100 100 Plastisol PVC (see table Ia) 100 44.0 44.0 Plasticizer (dioctyl phthalate) 44.0 25.0 25.0 Plasticizer (polymer, molecular *
weight 4500)
Plasticizer (epoxidized soybean oil) 25.0 4.0 4.0 pigment 4.0 0.5 0.5 CadmiunvBanum-Stabilisafor 0.5 4.0 4.0 Emulsifier (see table Ia) 4.0 15.0 15.0 15.0

continuation

Samples Λ

Precursor (II)

Polyester urethane with 6% unreacted NCO 15.0

from 80/20: 2,4 / 2,6-tolylene diisocyanate

Precursor (II)

Polyester urethane with 6% unreacted NCO from 65/35: 2,4 / 2,6-toluene diisocyanate

Precursor (II)

Polyester urelhan with 6% unreacted NCO

from 2,2'-diisocyanatodiphenyl imethane

15.0

15.0

Tabel VIb Tensile strength
strength
(kg / cm) strain
(0/0) water
recording
(%) MVT
(g / m ^ / 24 h) Taber abrasion
(lOOOCyclen) Ford Wear
(lOOOCyclen) rehearse tensile strenght
(kg / cm- ') 53 to 84
49 to 88.5
35.4 to 62 8 to 11
11 to 20
11 to 20 105
95
100 8100
9600
9600 acceptable
acceptable
acceptable acceptable
acceptable
acceptable A.
B.
C. 79.0 to 148
73.5 to 143
66.8 to 91.4

This example shows that numerous isocyanate compounds for the preparation of the invention to using polyurethane precursors can be used.

Example 7

Two liquid components (I) and (II) were made from those listed in Table VIIa below Components produced The components were produced according to Example 1, mixed and foamed.

Table VIIa

Liquid mixture (I)
Plastiboi PVC (see Table Ia)
Plasticizer (dioctyl phthalate) Plasticizer (dioctyl adipate) Plasticizer (99% epoxy plasticizer - 1% 1,10-oxybisphenoxyarsine) Barium-cadmium stabilizer

Parts

100.0

25.0

44.0

4.0

2.0

Emulsifier (see table Ia)

Precursor (II)

Polyester urethane (molecular weight 1000) with

6% unreacted NCO

80/20: 2,4 / 2,6-tolylene diisocyanate

Parts 15.0

Each component was divided into two parts. In Sample A, the appropriate proportion of the component (I) mixed with the portion of component (II), and the mixture was foamed (as in Example 1). One Nylon mat was made according to Example 2 .tiit the foam saturated. In the case of sample B, the proportions corresponding to components (I) and (II) were separated and then in the mixed heat of an Oakes mixer via separate lines from their respective containers fed into the mixer. The foam produced was then used in accordance with Example 2 a nylon mat saturated and processed.

In Table VfIb are the physical properties of the samples produced.

Table VIIb

Samples tensile strength tensile strength

(kg / cm ')

(kg / cm)

strain

(0/0)

A 70.3 to 129 46 to 80 5 to 9

B 73.8 to 129 44.3 to 71 6 to 9

Water absorption

(O/")

This example shows that components (I) and (II) can be reacted before foaming or simultaneously with foaming and that the MVT
(g / tT .- / 24 h)

100 95 9500
9350

Taber abrasion
(lOOOCyclen)

acceptable
acceptable

Ford wear (1000 cycles)

acceptable
acceptable

products obtained therefrom have the same physical Have properties.

23

example

Two liquid components (I) and (II) were made from the ingredients listed in Table Villa manufactured. The combining, mixing and foaming is carried out according to Example 1 with the

Exception that different foaming gases are used ^ del were. A nylon mat according to Example 2 was then saturated with the foams. In table The physical properties are listed in VlIIb.

Table villa

Parts

Liquid mixture (I)

Plastisol PVC (see Table Ia) 100.0

Plasticizer (dioctyl phthalate) 25.0

Plasticizer (polymer, molecular 44.0

weight 3500)

Plasticizer (99% epoxy plasticizer- 4.0

medium - 1% 1,10-oxybisphenoxarsine)

Barium Cadmium Stabilizer 2.0

Emulsifier (see Table Ia) 15.0

Precursor (II)

Polyester urethane (molecular weight 1000) at 15.0

6% unreacted NCO

80/20: 2,4 / 2,6-tolylene diisocyanate

Table VIIIb

rehearse

Tensile strength tear strength

Elongation water MVT
recording

(kg / cm *)

(kg / cm)

Taber abrasion Ford wear (g / m ² / 24h) (1000 cycles) (1000 cycles)

A foamed with air 70.3 to 127 443 to 71 5 to 9 100 9350

B with nitrogen '73.8 to 129 46 to 71 5 to 9 100 9400

C foamed with CO ₂ 73.8 to 130 35.4 to 74.3 5 to 9 105 9200

acceptable acceptable acceptable acceptable acceptable acceptable

example

Two liquid components (I) and (II) were made from 45 needled fiber mats made from different fibers those listed in the following Table IXa were prepared according to Example 2 with the Ingredients Manufactured Combining, Vermi-Foam Saturated and Processed are in Table IXb see and foaming was carried out according to Example 1. the physical properties listed

Table IXa

Parts

Liquid mixture (I)

Plastisol PVC (see Table Ia) 100.0

Plasticizer (dioctyl phthalate) 25.0

Plasticizer (polymer, molecular 44.0

weight 4500)

Plasticizer (99% epoxy plasticizer- 4.0

medium - 1% 1,10-oxybisphenoxarsine)
Barium Cadmium Stabilizer 2.0

Emulsifier (see Table Ia) 15.0

Forerunner (Π)

Polyester urethane (10000 molecular weight) 15.0

with 6% unreacted NCO

80/20: 2,4 / 2,6-tolylene diisocyanate

Table IXb

material

Tensile Strength Ford Wear

(kg / cm *)

Tensile strength

(1000 cycles) (kg / cm) Taber abrasion elongation water MVT recording

(1000 Cycles) (%)

(g / mV24 h)

70% nylon
30% Ray £ h
100% polyethylene terephthalate
100% copolyester »)

59.8 to 98.4 acceptable
58.4 to 98.4 acceptable
74.2 to 118 acceptable to 66 acceptable 45 to 75 110

up to 65.5 acceptable 40 to 60 105

100% acrylic compound 14.4 to 30.2 acceptable to 66 acceptable
12.4 to 19.5 acceptable

100% rayon

43.9 to 70.3 acceptable 26.6 to 32 acceptable

70 to 100 110 45 to 85 100 40 to 80 95

9700 Π 700

10,000

10 400

9 600

') Polyethylene terephthalate / isophthalate (90:10).

This example shows that a large number of fiber mats according to the invention with foam to achieve a fine-pored, hydrophilic foam can be saturated with high strength.

Comparative experiment I

A liquid mixture was prepared from the ingredients listed in Table X. The polyvinyl chloride and the plasticizer were mixed with gentle stirring. Then it became Water, a polyester and the vinyl stabilizer are added and mixed in. For this mixture 5 Parts of a mixture (ratio 80:20) of 2,4 / 2,6 isomers of tolylene diisocyanate added. To

Table X

Upon addition of the isocyanate, the mixture began to vigorously due to the reaction of the isocyanate with water foam. Attempts have been made to mix this mixture in an Oakes mixer with nitrogen foam, but the mixer was blocked with gel so quickly that no foam is produced could.

Components parts

Plastisol grade polyvinyl chloride (IV = 1.20) 100.00

Plasticizer (dioctyl phthalate) 75.00

Water 5.00

Polyester (molecular weight 1000, 11.00 Acid number 0.6)

Vinyl stabilizer (barium-cadmium compound) 2.00

Tolylene diisocyanate 5.00

This example shows that if only a polyol, water and an isocyanate were added to one Vinyl plastisol no fine-pored, hydrophilic foam is obtained.

Comparative experiment II

A mixture of 100 parts of a plastisol grade polyvinyl chloride, 70 parts of a compatible liquid plasticizer, 4 parts a barium-cadmium stabilizer and 15 parts of potassium oleate. This mixture was made into a Mixer and mix with air to a density of

Table XI

1.1 g / cm ³ foamed Then a nylon mat was saturated with part of the foam in this way and processed according to Example 2. The other part of the foam was poured onto release paper and cured. Table XI shows the physical properties

material

Ford Abrasion Taber Abrasion Water Absorption

tensile strenght

Elongation tensile strength

MVT

(kg / cm) (g / mV24 h)

With foam
saturated mat

foam

1000 cycles 1000 cycles

not acceptable not acceptable

17 Cycien not
acceptable

25 cycles not acceptable

59.8 45 133 8500

4.9 200 1.77 8500

This Example 2 shows that a polyurethane precursor free polyvinyl chloride plastisol foam does not have the properties of the foam produced according to the invention results

Claims (4)

Patent claims: 1. Process for the production of a hydrophilic, fine-pored, permeable to moisture vapor , Foam in the form of coated cloth or fabric, with the foam saturated non-woven Fiber mats or unsupported films or webs by coating the fiber base material or a removable backing or saturating the nonwoven fiber matites with one with non-reactive gas to form a foam foamed liquid mixture (I) of: 1) 100 parts by weight of a polyvinyl chloride of Plastisol quality, 2) between 50 to 100 parts by weight of at least one compatible liquid plasticizer, 3) a stabilizer for the polyvinyl chloride and 4) between 10 and 16 parts by weight of an emulsifier that: a) between 36 to 46 wt .-% of a saturated or unsaturated fatty acid with 12 to 24 carbon atoms and mixtures thereof, b) between 27 and 37% by weight of an alkali metal salt of a saturated or unsaturated one Fatty acids with 12 to 24 carbon atoms and mixtures thereof, c) between 6 to 16% acid chewing phthalate. Sodium phthalate and / or acid sodium phthalate, d) between 4 to 8% by weight of water, e) between 4 to 6% by weight of a saturated aliphatic glycol, f) between 2 to 4% by weight of a hydrocarbon oil low molecular weight and g) between 1.5 to 2.5% by weight of silica having, and solidifying the foam webs under the action of heat, characterized in that a liquid mixture (I) containing 7 to 19 parts by weight of a liquid polyurethane precursor (II) from a polyester polyol and / or polyether polyol and a polyisocyanate, which 1 has up to 10% reactive NCO end groups, mixed and foamed to form the foam. 2. The method according to claim 1, characterized in that the formation of the liquid mixture from the liquid mixture (I) and the liquid polyurethane precursor (II) and the foaming of the liquid mixture with a non-reactive gas to form the foam simultaneously in the Mixing head of a foaming device takes place. 3. The method according to claim 1 or 2, characterized in that there is a polyurethane precursor (II) used, that of a polyester polyol and / or polyether polyol having a molecular weight in the range between 500 and 3000 was obtained.