CS105091A2 - Cloth finishing - Google Patents

Description

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9 JUDr. MiloS VŠETEČKAadvokát PRAHA 1, Žitná 25 Fabric modification

Technical field

trj.

The present invention relates to the treatment of fabrics, whereby an organo- / phosphorous compound provides a fabric with increased fire resistance.

BACKGROUND OF THE INVENTION Treatment of flame retardant fabrics with tetrakis (hydroxymethyl) phosphonium compounds, hereinafter referred to as THP compounds, or their urea precondensates has been described in U.S. Pat. Nos. 2,983,623, 4,068,026, 4,078,101, 4,145,463 and 4,494. The procedures comprise impregnating the fabric with aqueous chemicals, then drying, treating with ammonia to vulcanize phosphorous compounds to prevent solubility of the phosphorus compounds on the fabric, finally oxidizing and washing the fabric to form a fabric that retains fire resistance after many washing in use. The effectiveness of the vulcanization is measured by the degree of insolubility of the phosphorus compound on the substance, the efficiency is not always sufficient and part of the expensive phosphorus compound used in the impregnation step is not vulcanized and after the vulcanization the fabric is washed out. The vulcanization efficiency for cotton fabrics is higher than for cotton polyester fabrics and, in particular, for cotton-polyester fabrics, the THP flame resistance is difficult to achieve. Further, although some processes allow for sufficient fire resistance, this property is significantly lost by repeated washing. - 2

SUMMARY OF THE INVENTION

The above drawbacks are largely eliminated by the impregnation of fabrics according to the invention. Using the process of the present invention, the amount of phosphorus compound bound to the material that does not contain cellulosic fibers is increased, and the necessary resistance to burning of the fabric, which does not contain cellulose fibers, such as cotton / polyester blend, can be achieved.

SUMMARY OF THE INVENTION The subject matter of the invention is that the organic fiber material containing reactive groups is impregnated with a nitrogen-containing polymer or a precursor thereof and an aqueous solution of the organophosphorus compound to form an impregnated material which is dried and vulcanized to form a treated material. material.

The nitrogen-containing polymer can be applied to the material simultaneously with the organophosphorous compound, but preferably the polymer or precursor is deposited in the first stage when the first impregnated material is formed, and then the organo-phosphorous compound is applied in the second stage. Typically, the material after the first impregnation is allowed to stand still for some time to react with the material before the second stage.

The nitrogen-containing polymer preferably does not contain phosphorus atoms and reacts with cellulose at temperatures up to 150 ° C. It is preferably a polyelectrolyte containing a number of nitrogen atoms, especially in the tertiary or quaternary form, which may be included in the carbon polymer chain, but are preferably in groups bonded to the polymeric hydrocarbon chain. The hydrocarbon polymer backbone is preferably formed by structural units derived from mono- or di-ethylene unsaturated compounds containing one or more nitrogen atoms. Examples of mono-ethylenically unsaturated-3-compounds are heterocyclic nitrogen ring vinyl compounds such as N-vinylpyridine, N-vinylpyrrolidine, N-vinylpyrrolidone and their carbon ring derivatives, as well as acrylic and methacrylic compounds with amide. or an amine group such as acrylamide, methacrylamide, acrylate and ammonium methacrylate and their mono, di, trine or tetra-N-alkyl derivatives, especially those wherein the alkyl group thereof contains 1 to 6 carbon atoms, for example methyl or ethyl. The polymer may be a homo- or copolymer of monomers each containing a nitrogen atom or atoms, or it may be a copolymer with other ethylenically unsaturated monomers that do not contain nitrogen atoms, such as acrylic or methacrylic acid or the appropriate esters, e.g. 1 to 6 carbon atoms.

The proportion by weight of nitrogen-containing monomer to nitrogen monomer is usually 50 to 100: 5 to 0, preferably 80 to 100: 20 to 0, preferably 80 to 95: 20 to 5. Examples of di-ethylenic unsaturated compounds are diallylamines, especially quaternized diallylamines, for example N, N-dialkyl-N, N, di-allylammonium halides, wherein each alkyl group contains 1 to 6 carbon atoms such as ethyl, isopropyl, propyl or butyl, preferably methyl. Examples of copolymers are acrylic acids and acrylamide and acrylamide and dialkyldiallylammonium chloride. Polymeric dialkyldiallylammonium chlorides can be prepared as described in U.S. Patent 3,472,740 which is exemplified. Polymers of ethylene unsaturated compounds can be prepared in a conventional manner, such as radical polymerization, especially in aqueous solutions or aqueous emulsions.

The nitrogen-containing polymer may also contain nitrogen atoms in the polymer chain, and may be prepared by ring opening polymerization, such as the known polymerization of ethyleneimine to produce polyethyleneimine. - 4 -

The average molecular weight of the nitrogen-containing polymer is usually 10,000 to 5,000,000, for example 100,000 to 3,000,000, and is water-soluble, for example, water solubility at 20 ° C is at least 10 g / L, or is water-dispersible.

Other polymers which are water soluble or water dispersible may also be used, which are prepared by condensation polymerization and capable of further condensation with cellulose, such as polyamino, polyamido and polyamine / polyamidoepichlorohydrin reaction products.

The nitrogen-containing polymer may be formed by heating the precursor, in particular a monomer which polymerizes to form a polymer may be used, for example, directly on the web or during time after the first stage or after two steps of impregnation or during impregnation as previously described. or particularly during thermal vulcanization. Preferably, monomers of diethylene non-saturated compounds, such as the diallylamide salts mentioned above, are useful. The monomer can also react with the material or organophosphorus compound before reacting with other monomer molecules. The precursor is preferably added in the first stage of treatment, separately from the organophosphorus agent.

The organic fibrous material preferably comprises or comprises cellulose fibers in particular. The cellulose wagons are preferably natural cotton, but may also be flax, paper or cardboard, or regenerated fibers such as viscose or copper fibers, or partially etherified or esterified cellulose, for example cellulose acetate or propionate. The material may be entirely cellulose, for example 100% cotton, or may contain both cellulose and non-cellulose fibers, or may contain only non-cellulosic fibers, for example 100% polyester fibers. Usually, inorganic fibers such as glass fibers are not present.

The non-cellulosic fibers are preferably polyester or polyamide fibers, but may also be acrylates. The polyamides may be aliphatic, such as polyamines, for example di-8min, preferably alkylenediamine, for example 4 to 12 carbon atoms, and polycarboxylic acids, for example C 4 -C 14 dicarboxylic acids such as alkylenedicarboxylic acid, for example NYLON 66 or polylactams such as jeNYLON 6. The polyamides may also be aromatic, such as dicarboxylic acid amides and phenylenediamines. The acrylic polymers may be polyacrylonitrile homopolymer or a copolymer thereof with vinyl chloride, such as modacrylic fibers. The material may comprise at least 20% cellulose fibers and up to 50% mixed fibers, for example 10 to 80%, preferably 25 to 80% mixed fibers such as polyamides. However, the material preferably consists of cellulose and polyester fibers. Typically, the material comprises up to 80%, for example, up to 70% polyester fibers and from 20%, for example 30%, of said cellulosic fibers, for example 1 to 80% or 1 to 70%, preferably 15 to 70%, more preferably 22 to 38% or 45 to 75% polyester fibers and 20 to 99% or 30 to 85%, preferably 62 to 78 or 25 to 55% cellulose fibers.

Materials containing at least 45% non-cellulosic fibers, for example polyester fibers, such as 45-100% polyester, are preferred over such materials containing 30-78% cellulose fibers and 22-70% polyester fibers, or 30-62%. % cellulose fibers and 38-70% polyester fibers. Typically, the polyester is a condensation product containing structural units of an aliphatic alcohol, for example a dialcohol, especially ethylene glycol or butanediol (or a mixture thereof) and an aromatic dicarboxylic acid, for example terephthalic acid, or - 6 - mixtures thereof with other dicarboxylic acids such as isophthalic acid or sebacic acid .

If desired, the fibrous material may be comprised of the aforementioned non-cellulosic filaments having interactions with the cationic compound. These materials may be a polyester which reacts with a cationic compound of a hydroxyl group, or a polyamide which reacts with a carboxyl group, or a polyacrylonitrile which reacts with nitrile groups. The polyester may be as described above, the polyamide may be the reaction product of a polyamine, for example a 4 to 12 carbon diamine, with a polycarboxylic acid, for example C 4 -C 14 dicarboxylic acids. The polyacrylonitrile can be a copolymer or copolymer with vinyl chloride, such as moda-crystal fibers.

The fibers of the material may be in the form of staple or non-woven fabrics, but woven fabrics are most suitable. Mixtures of fibers, such as cellulosic and other fibers, may be known mixtures, but the fibers are preferably mixtures of cellulose and other fibers, such as polyester fibers, such as polyester-cotton blends, but may be in the form of a yarn core core of another. fibers, for example, polyester in cotton fibers. In fabrics, the warp warp is preferably of the same material but may be different, for example one may be cotton fibers and the other may be polyester-cotton fibers. Accordingly, the term " mixture " is used herein to refer to uniform and uniform substances, such as fiber with braid. Preferably, the material is a fabric having a weight of 0.05 to 1.0 kg / m 2, for example 0.150 to 0.40 kg / m 2, or 0.05 to 0.20 kg / m 2, such as polyester-cotton like shirting, bedsheet or curtain fabric. - 7 -

The nitrogen-containing polymer, or precursor thereof, is usually applied in an aqueous solution or dispersion, for example in a concentration of 0.1 to 30%, or 0.2 to 15, preferably 0.5 to 4% by weight, at a pH of 2 to 9, e.g. 4. The weight of the nitrogen-containing polymer or precursor to be used is generally 0.01 to 20, for example 0.1 to 10%, preferably 0.5 to 5%, based on the weight of the starting fabric. (or a precursor thereof) can be applied to the fabric by wetting 50 to 150%, and then after initial drying, if necessary, for example by heating the impregnated fabric at 80 to 100 ° C for 0.1 seconds. up to 5 minutes, the impregnated fabric is heated to 90-150 ° C, for example 90-130 ° C, for 0.5-10 minutes, for example 1-5 minutes. Instead of the heating step, the impregnated material may be maintained at, for example, room temperature for 10 to 60 hours, for example 10 to 30 hours, preferably at room temperature. If desired, the polymer, or a precursor thereof, can be applied in a small amount at a rate of 10 to 50%, then dried or discarded for a period of, for example, 0.2 to 24 hours before the second stage. . A foaming technique using a cationic or amphoteric foaming agent and a stabilizer may be used to apply a small amount. In this impregnation or fixing step, it is believed that the nitrogen-containing polymer is reacted with a material, that is, its hydroxyl, amide or ester groups, to form a treated material which is bound to the polymer or maintained by a cationic or ionic bond. . In the preferred process, after treatment with the nitrogen-containing polymer, the dry material is treated with an organophosphorous compound. In the case of the tetrakis (hydroxyorgone) phosphonium compound, each hydroxyorgano group is preferably a 1-to-9 carbon alpha-hydroxyorgano group. may be the same or different, hydrogen or alkyl having 1 to 4 carbon atoms, for example methyl or ethyl. Preferably R 1 is hydrogen and R 8 is methyl or hydrogen, as in tetrakis (hydroxymethyl) phosphonium (THP) compounds. The use of tetrakis hydroxyorgano phosphonium compounds will generally be exemplified herein by reference to THP compounds and the respective molar amounts of other compounds that are used outside the THP compound.

The material is treated with an impregnating solution, which is an aqueous solution of THP salt mixed with a nitrogenous compound of a water-soluble precondensate, or a solution of the preconcentrate of said salt and a nitrogenous compound, or a THPsoli solution, or a water-soluble autocondensate thereof, or an at least partially neutralized THP salt, e.g. together or without a nitrogenous compound. The impregnating solution may optionally consist of a solution of said precondensate and other nitrogenous compounds, for example urea, so that the molar ratio of total nitrogen, i.e. free bound, free to bound THP group is 0.8 to 2: 1, e.g. 8 to 1.5: 1. The nitrogen compound is preferably one which has at least two NH groups, for example 2 to 4, but preferably contains two NH or more preferably two N 2 groups. The compound is usually double-functional and may be amine, but more preferably an amide. Examples of useful nitrogen compounds are biuret, guanidine, melamine and methylated melamine, but urea is most suitable for use in the invention, especially in the absence of melamine or methylolhomelamine. The nitrogenous compound is preferably urea as used in the precondensate. In an embodiment of the invention, the THP precondensate solution comprises a salt, for example a chloride or sulfate, and a nitrogenous compound at a molar ratio of nitrogen compound to THP of 0.05 to 0.8: 1, for example 0.05 to 0.06: 1, 9 or 0.22 to 0.8: 1, i.e. 0.25 to 0.6: 1, preferably 0.4 to 0.6: 1. 5 for example 4 to 5. The atomic ratio of the total amount of nitrogen atoms in the nitrogen compound or condensate to the total amount of phosphorus atoms in the THP compound or condensate in the impregnating solution is usually not more than 4: 1, for example 1: 3: 1.

The concentration of organophosphorus compound in the aqueous solution may be 5 to 70%, for example 5 to 35%, expressed as the THP + ion, but preferably 20 to 35%.

If desired, the solution may contain a non-ionic surfactant, for example 0.05 to 0.5% by weight of impregnating solution, a fabric softener such as polyethylene at a recommended amount of 0.1 to 2% by weight and a salt of a strong acid and a weak base such as is ammonium chloride or rare earth or ammonium hydrogen phosphate as the thermal vulcanization catalyst in an amount of 0.1 to 5% by weight.

The treated substrate is impregnated to form an organophosphorus coating of up to 40%, for example 10 to 40%, i.e. 10 to 30%, preferably 20 to 30%, based on the THP ion of the starting material weight. The material may be impregnated with a solution and the wet material, for example, the fabric, may be extruded to a wetting of 50 to 130%, for example 60 to 100%, based on the starting weight of the material. Otherwise, the treated material may be impregnated with a concentrated impregnating solution in a small amount, for example by a foaming technique, starting from 10 to 50% wetting.

The organophosphate-impregnated material is then dried, for example to a moisture of 0 to 20 $, for example 5 to 15 and 10 to about 10%, for subsequent ammonia curing, and to a higher dryness for subsequent heat curing. Drying may be carried out in furnaces, or heated containers, and blanks may be heated to 80-160 ° C for 10 minutes to 10 seconds, for example 100-120 ° C for 3 minutes to 30 seconds. The dried material is then vulcanized. The vulcanization can be carried out by treatment with ammonia, usually in a gas form, which diffuses through the material and / or is passed through the material, for example by pulling the fabric over the perforated tube through which ammonia is blown. Examples of apparatus and techniques that are suitable for ammoniac vulcanization are disclosed in U.S. Pat. Nos. 4,145,463, 4,068,026 and 4,494,951, the patents being used herein for comparison. Optionally, or more preferably, the ammoniacal vulcanization site is heat curing, for example at a temperature of at least 100 ° C, such as 100 to 200 ° C, or 100 to 180 ° C, i.e. 130 to 170 ° C for 10 to 0.5 minutes, e.g. 7 to 1 minute.

Higher temperatures and longer vulcanization times cannot be used for materials with higher cellulose fiber content, especially 100% cotton. While the dried material can then be vulcanized by heat, preferably the drying and thermal vulcanization steps are combined and heated under vulcanization conditions. If the thermally vulcanized material is subsequently vulcanized with ammonia, the thermally vulcanized fabrics are allowed to level the moisture prior to ammonia treatment.

Vulcanised material usually increases in weight, depending on organophosphorus impregnation and vulcanization, by 10 to 50%, or 10 to 40%, for example 10 to 30%, ie 10 to 25% or 15 to 30%, especially 20 to 30%, based on the weight of the starting material, depending on the total wetting of the organophosphorus compound in the range of 16 to 36%, for example 20 to 28% - expressed as THP ion to the starting material.

The vulcanized material is then typically subjected to at least one of the following operations: further reducing the solubility of the vulcanized resin in the treated material, oxidizing to convert trivalent phosphorous atoms, or washing with aqueous base and water. Advantageously, the oxidation is carried out by contact with an aqueous solution of an oxidizing agent, preferably a peroxide compound, such as aqueous hydrogen peroxide, for example 0.5 to 15% concentration, preferably 1 to 5%, or a sodium perborate solution, e.g. usually used in excess, usually 0.1 to 10 minutes at 0 to 40 ° C. Otherwise, oxidation may be carried out with a gas containing molecular oxygen, preferably air, especially when the gas is purged through the material. Also, the material may, if it is a fabric, be pulled over a vacuum slit or perforated tube through which the gas is blown or aspirated.

After or during oxidation, the vulcanized material may be eluted with an aqueous composition, preferably an aqueous solution of a base such as sodium carbonate and / or washed with water. Preferably, the oxidation reduces the residual formaldehyde content of the vulcanized material.

Alternatively, the cured material may be washed with water or otherwise freed from water-soluble substances. Finally, the vulcanized fabric is dried to recover the finished material.

Finished material, such as fabric, can be used to make workwear, such as overalls, insulating suits, and protective clothing, including uniforms, made of 30-70% material, such as 55-12 70% cotton and 70 up to 30%, for example 45 to 30% polyester, and household fabrics such as bed linen and curtains, containing 30 to 70%, for example 30 to 60% cotton and 40 to 70% polyester.

If the process of the invention is compared with similar processes without the use of a nitrogen-containing polymer (or a precursor thereof), a higher amount of THP compound can be applied to the material during impregnation, the vulcanization efficiency can be increased and the loss of vulcanized phosphorus compound can be reduced by washing at Therefore, with the same total amount of phosphorus-containing compound being applied to the material, in the case of the material being vulcanized according to the invention, the phosphorous content is higher and may also have better handling properties than a similar vulcanized material. which was prepared without a nitrogen-containing polymer treatment. This process also results in less loss of phosphorus compound. The flame resistance, for example the carbon length, is usually better in different flammability tests than in materials prepared without the use of a nitrogen-containing polymer or a precursor thereof.

The material obtained by the process of the invention may have a sufficient amount of vulcanized and bound phosphorus, such that it is comparable to a non-flammable standard such as BS 6249 Part 1, 1984 Part B, with which the same starting material, vulcanized without the outset, cannot be compared. impregnating with a nitrogen-containing polymer or a precursor. The material obtained by the process of the invention loses less strength than a similar material without initial treatment. Examples of Use of the Invention Example 1

An aqueous dispersion of poly-dimethyl diallylammonium chloride was obtained by reaction in which an aqueous solution of dimethyldiallylammonium chloride (50 g) in water was gradually added to the toluene (50 g) and non-ionic surfactant (15 g) at 80 ° C in a reaction vessel with agitator and agitator. 50 g) and di- (4-tert-butylcyclohexyl peroxydicarbonate (0.15 g)) The reactor contents were stirred at 80 ° C for 3 hours to form an emulsion which was then heated and the toluene was distilled off with water which was The product was a stable aqueous dispersion with an average polymer molecular weight of about 1 million a) a conventional polyester-cotton fabric (67:33) with a weight of 0.246 kg / m was impregnated with a 2% (w / w) aqueous dispersion prepared by polymeric dimethyl diallylammonium chloride. The excess water was then removed from the tissue, which was allowed to dry at room temperature overnight, to obtain a treated fabric containing approximately 1.6% polymer. b) the treated fabric was impregnated with an aqueous solution of 1: 2 molar urea condensate and tetrakis (hydroxymethyl) phosphonium chloride containing 25.2% solids, expressed as THP + ion, and excess water was extracted from the fabric. c) The material was then thermally vulcanized at 150 ° C for 3 minutes, and then the moisture content of the material was adjusted overnight in a humidity controlled space. U.S. Pat. No. 4,145,463-14 (d) after ammonia vulcanization, the substance was washed with 10% hydrogen peroxide solution, washed with water, washed with aqueous sodium carbonate solution and then washed again with water and dried to form a finished fabric.

The finished fabric was then analyzed for phosphorus and nitrogen content. It has also been tested for flame resistance prior to washing forty times at 93 ° C. Washing was performed according to the method described in DIN 53 920, Procedure No. 1, using soft water. The test method was performed according to BS 5438 (1989), test 2 A. In all cases, the fabric complied with the non-flammability requirements of the analysis: BS 6249 index B. Fabric% P% N Vulcanized (grade c) 1.94 1.56 Ready fabric (step d) 1.81 1.65 Example 2

The procedure of Example 1 was repeated with another woven, specifically a conventional polyester-cotton blend of 60:40, with a weight of 0.268 kg / m, and a different reagent, now with monomeric diallyldimethylammonium chloride, which was fed at 2%. % and 10% aqueous solutions, wherein wetting of about 70 to 90% was achieved. Flammability, phosphorus and nitrogen content were determined for the finished material as well as 20 shots. Here are the results. - 15% reagent in solution Ready-to-use fabric Substance after 20 wash% P% N Carbon length (mm)% P% N Carbon length (mm) 2 3,05 3,05 60 2,63 2,4 50 5 2,9 2 , 9 54 2.43 2.24 47 10 2.98 2.9 58 2.38 2.38 42 Examples 3-9

The procedure of Example 1 was repeated with two different titanium compounds, in Examples 3-6 with a water-soluble acrylamide-acrylic acid copolymer in a ratio of 90:10, and in Examples 7 to 9 water-soluble polyethylene-imine. Finished fabrics, new and after 20 washes, were tested for flammability. The results of the tests performed on these materials were as follows. Example 3 4 5 6 7 89% of polymer in solution length of carbonization in step (a) (mm) 1 81 2 76 5 79 10 75 0,5 90 1,5 85 2 87

Industrial usability

The method of treating fabrics according to the invention can be used wherever there is a need to produce a material with increased fire resistance, both industrial and household.

Claims (20)

ĎóSr. v '; - 7' »·. 16-16 PATENT CLAIMS A process for the treatment of non-flammable organic fibrous materials containing reactive groups, characterized in that: a) the material is impregnated with a polymer containing nitrogen, or a precursor thereof, and an aqueous solution of organophosphorus compound b) the material is drying c) the material is vulcanized by heating to at least 100 ° C and / or by ammonia treatment. 2. The process of claim 1 wherein the organophosphorus compound is applied to the dry material after impregnation with a nitrogen-containing polymer or a precursor thereof. 3. A process according to claim 1 or claim 2, wherein the organic fibrous material is mainly cellulosic fibers, such as natural cotton, ramie, flax, paperboard, viscose or copper-fiber, or cellulose acetate or propionate. 4. A process according to claim 1 or claim 2 wherein the organic fibrous material is cellulosic and non-cellulosic fibers, such as polyester, polyamide or polyacrylonitrile fibers. 5. A method according to claim 1 or 2, wherein the organic fibrous material is comprised mainly of cellulose fibers. 6. The process of claims 1 to 5 wherein the nitrogen-containing polymer is a homopolymer-17- or copolymer polyelectrolyte that contains a series of ato. of nitrogen, which may be in the carbon polymer chain or may be in groups bonded to a polymeric hydrocarbon chain, especially when the nitrogen-containing polymer does not contain phosphorus atoms, especially when the nitrogen-containing polymer consists of a chain of units removed from ethylenically unsaturated compounds containing one or more nitrogen atoms, for example N-vinylpyridine, N-vinylpyrrolidine, N-vinylpyrrolidone, and their alkyl ring-carbon derivatives, or acrylamide, methacrylamide, acrylate, and ammonium methacrylate; -, tri- or tetra-N-methyl or N-ethyl derivatives, or structural units derived from diethylene unsaturated compounds that contain one or more nitrogen atoms, especially when the diethylenic unsaturated compounds are quaternized with a dialkylamine wherein each alkyl group contains 1 to 5 carbon atoms, especially when the nitrogen-containing polymer is homopoly dialkyldi-allylammonium chloride, or a copolymer of acrylamide and di-alkyldiallylammonium chloride. 7. A process as claimed in claim 1, wherein the nitrogen-containing polymer consists of a hydrocarbon polymer chain which itself consists of ethylenically unsaturated monomers, for example acrylic acid or methacrylic acid or the corresponding esters with alkanols of one to six atoms. carbon, wherein the weight ratio of nitrogen-containing monomers to nitrogen-free monomers in the polymer is 50:50 to 100: 0, preferably when the weight ratio is from 80:20 to 100: 0, especially when the polymer containing the copolymer is acrylic acid and acrylamide. 8. The process of claim 1 wherein the nitrogen-containing polymer comprises nitrogen atoms in the polymer chain, for example, said nitrogen-containing polymer is polyethylene. 18 9. The process of claim 1, wherein the nitrogen-containing polymer is prepared by condensation polymerization and the resulting nitrogen-containing polymer capable of further condensing with cellulose, for example, when said nitrogen-containing polymer is a polyamine, a polyamide or a reaction product from a polyamine reaction. polyamide and epi-chlorohydrin. 10. The process of claim 1, wherein the nitrogen-containing polymer has an average molecular weight of from 1,000 to 5,000,000, and wherein the nitrogen-containing polymer is water-soluble or water-dispersible. and wherein the nitrogen-containing polymer or precursor thereof is applied to the material during its impregnation according to (a) in an aqueous solution or dispersion wherein the aqueous solution or dispersion is from 0.1 to 30 weight percent, and wherein the weight of the polymer with the content nitrogen, or a precursor thereof, is from 0.01 to 20% based on the weight of the impregnated fabric. 11. A process according to any one of claims 1 to 10, wherein the impregnation (a) is carried out by treating the material with a solution comprising a nitrogen-containing polymer or a precursor thereof, for example a diallylamine salt, so that the wetting is in the range of 50 to 100%. 150%, and the impregnated material is then subjected to one or more of the following operations: i) drying by heating to 80 to 100 ° C for 0.1 to 5 minutes ii) heating to 90 to 150 ° C for 0.5 to 10 minutes iii) maintaining at normal temperature for 10 to 60 hours, when the impregnated material is allowed to dry. 12. A process according to any one of claims 1 to 10 wherein the nitrogen-containing polymer, or a precursor thereof, e.g., a diallylamine salt, is applied to the material by impregnating it in a small amount, preferably with foaming, using a cationic or an amphoteric foaming agent and a stabilizer wherein the wetting is in the range of 10 to 50 13. A process according to any one of claims 1 to 12, wherein the impregnation (a) is carried out with tetrakis (hydroxyorgano) phosphonium compound, preferably the hydroxyorgano group is an alpha-hydroxyorgano group having 1 to 9 carbon atoms, the alpha-hydroxyorgano group having the formula (R 5 -J) wherein R 1 and R 2 are the same or different hydrogen atoms or C 1 -C 4 alkyl groups, preferably tetrakis (hydroxymethyl) phosphonium compound, THP, or a water-soluble autocondensate thereof, or a water-soluble condensate with an organic nitrogen compound, such as urea, biuret, guanidine, melamine, or methylated melamine, or a mixture of said organic nitrogen compound with a phosphonium compound or an autocondensate thereof. 14. A process according to any one of claims 1 to 13, wherein the impregnation (a) is carried out by treatment with a solution consisting of a THP salt precondensate and an organic nitrogen compound wherein the organic nitrogen compound to THP molar ratio is from 0.05 to 1. 0.8: 1, preferably from 0.25: 1 to 0.6: 1, more preferably from 0.4: 1 to 0.6: 1, and wherein the solution has a pH of from 2 to 7.5, preferably from 0.2 to 1: 0.6: 1; 4 to 5, and wherein the concentration of the organophosphorus compound expressed as THP + ion in the impregnating solution is from 5 to 70%, and the impregnating solution comprises one or more of the following additives: i) wetting agent, preferably the nonionic surfactant and preferably, the wetting agent is used in an amount of 0.05 to 0.5% by weight in the impregnating solution, 20 µl of the fabric softener, 3 preferably the plasticizer is used in an amount of 0.1 to 2% by weight in the impregnating solution iii) a catalyst, preferably the catalyst is made of soluble acids and weak bases, e.g. Preferably, the ammonium or ammonium or rare earth or ammonium hydrogen phosphate catalyst is used in an amount of from 0.1 to 5% by weight in the impregnating solution. 15. A process as claimed in claim 1, wherein the impregnation (a) is carried out by applying an impregnating solution to the material when wetting which is less than 40%, based on the THP + ion, by weight of the material, preferably from 20 to 30%. , based on the THP + ion to the weight of the material. 16. The process of claim 15 wherein the wet material is wound to a wetting of from 50 to 130% by weight of the material. 17. A process according to any one of claims 1 to 14 wherein the treated material is impregnated with a concentrated impregnating solution in a small amount, preferably by foaming, and wherein the wetting is from 10 to 50% by weight of the material. 18. A process according to any one of claims 1 to 17, wherein the thermal vulcanization (c) is at a temperature of from 100 to 180 ° C and the vulcanization time is from 10 to 0.5 minutes. 19. The process of claim 18 wherein the thermal vulcanization takes place prior to vulcanization with ammonia. 20. A process according to claim 1, wherein the vulcanized material is subjected to at least one of the following operations: i) reducing the solubility of the vulcanized resin by the treated material; ii) oxidizing; iii) washing with an aqueous base and washing with water, wherein oxidation (ii) is achieved by the action of the oxidizing agent in the form of 0.1 to 10 minutes at 0 to 40 ° C, that the oxidizing agent is an aqueous solution of hydrogen peroxide at a concentration of 0.5 to 15% by weight or an aqueous solution of sodium perborate at a concentration of 1 to 10% by weight or wherein the vulcanized material is subjected to a molecular oxygen-containing gas oxidation which is purged through the material.