DE2147481A1 - Flame-proofing wool materials - by impregnation with amides of phosphorus acids and aminoplast precondensates - Google Patents

Abstract

Materials consisting of is not 50% wool are rendered flame-proof by impregnating the material with a compsn. contg. (a) the (substd.) amide of an acid of formula: where R1 and R2 are is not >4 C (halo)alkyl or alkenyl residues, X is CH3 or H (pref.) and Z is S or O (pref.), (b) an aminoplast precondensate, (c) a hardening catalyst and possibly (d) a wetting agent, drying the impregnated material and hardening the impregnant. Permanent flame-resistance is achieved. If the treated material do burn, there is little development of smoke. The wool materials are esp. thin fabrics and furnishing materials.

Description

Process for flame retarding materials containing wool.

The invention relates to a process for making vcn materials flame-resistant which consist of at least 50% wool, characterized in that these materials are impregnated with a preparation which a) the amide or a further substituted amide of a phosphorus-containing carboxylic acid of the formula where R1 and R2 each represent an alkyl, alkenyl or haloalkyl radical with a maximum of 4 carbon atoms, X a methyl group or preferably a hydrogen atom and r sulfur or preferably oxygen, b) an aminoplast precondensate (aminoplast former) c) a curing catalyst and optionally d) a wetting agent contains, the materials impregnated in this way dries and the impregnation hardens.

A large number of phosphorus-containing compounds can be used as component a). Important further substituted amides of the formula (1) are those of the formulas (2) to (10): wherein R is a hydrogen atom, an allyl radical or an alkyl radical with up to 6 carbon atoms, and X, R1 and R2 have the meaning given, where A stands for -CONH2 or -CONHCH20R't, R 'and R "each represent hydrogen or methyl, R"' represents hydrogen or alkyl having 1 to 4 carbon atoms, and n and p each represent the number 1 or 2 and R1 and R2 are the ones indicated Have meaning in which A1 and A2 each represent a hydrogen atom or an alkyl radical and X, R1 and R2 have the meaning given, where R3 stands for a hydrogen atom, an alkyl radical with a maximum of 4 carbon atoms or an alkenyl radical with a maximum of 4 carbon atoms and X, R1, R2 and n have the meaning given, where Ri> R2 'each represents an alkyl, haloalkyl or alkenyl radical with at most 4 carbon atoms each and X' represents a methyl radical or preferably a hydrogen atom and R1, R2 and X have the meaning given, wherein Y and Y 'each represent an alkyl radical with a maximum of 4 carbon atoms or a hydrogen atom and 4 is an alkyl radical with 1 to 22 carbon atoms, a haloalkyl radical with a maximum of 4 carbon atoms, a hydroxyalkyl radical with a maximum of 4 carbon atoms, an alkenyl radical with 2 to 22 carbon atoms or an optionally halogenated one Represent a benzene or benzyl radical and R1, R2, R1 ', R2, X and X' have the meaning given where A 'stands for an alkylene radical with 2 to 3 carbon atoms which is optionally substituted by lower alkyl-lower alkoxy or hydroxyl groups and R1, R2, R1', R2, X, X ', Y and Z have the meaning given, in which Q is a radical of the formula -CO-, -CS-, SO, -, -CNH- or -CO-NE-CO-, in which E is a hydrogen atom or a radical of the formula -CH2-OY and R1, R2 , Ri, R2, X, X 'and Y have the meaning given, where R4 is an optionally substituted aryl or alkyl radical and X, 7, R1 and R2 have the meaning given.

The compounds of the formulas (2) to (9) are known. For example, the compounds of formula (2) in French patent specification 1 395 178 (Case ARL 104) are those of formula (3) in French patent specification 1 422 893 (Case 5361 / E), those of formula (4) in Swiss patent specification 475 408 (Case 61 57), those of formula (5) in French patent specification 1 577 573 (Case 6226 / E), those of formula (6) in DOS 1 961 884 (Case 6626 / E), those of the formula (7) in DOS 1 962 644 (Case 6633 / E), those of the formula (8) in the Belgian patent 744 081 (Case 6637 / E), those of the formula (9) in the Belgian patent 744 082 ( Case 6638/6816). The compounds of the formula (10) (Case 7132) can be prepared in a manner known per se from phosphonopropionic acid-a-hydroxy-trichlorethylene amides and isocyanates according to the reaction equation can be obtained. Here, too, R1, R2, R4, X and Z have the meaning given. The reaction is expediently carried out at a moderately elevated temperature, in the presence of an inert solvent, such as dimethylformamide, and using at least approximately equivalent amounts of the two starting materials, optionally with the addition of a catalyst. The compounds obtainable in this way can generally be easily isolated by distilling off the solvent and can be purified by recrystallization.

The amides of the formula (11) required as starting materials are obtained by reacting acid amides containing an unsubstituted acid amide group with choral hydrate: This reaction is also advantageously carried out at an elevated temperature, for example from 50 to 1500 ° C., using equivalent amounts of the starting materials and in the presence of an inert solvent.

Aromatic hydrocarbons, for example, are used as inert solvents such as xylenes, toluene or especially benzene into consideration.

The reaction is expediently left at 70 to 1200 ° C., with advantage at the boiling point of the reaction mixture, run off and continuously removes the Reaction water.

The formula (1) further comprises phosphorus-containing curable and water-soluble aminoplasts which (a ') at least one and preferably 1 to 2 groups of the formula -CH20R5 bonded to amide nitrogen in which R5 is an alkyl radical with 1 or 2 carbon atoms or a hydrogen atom, and furthermore (b ') at least one and preferably 4 to 5 groups of the formula bonded to amide nitrogen wherein R1, R2 and X have the meaning given. These products are described, for example, in British patent specification 1,092,793 (Case 5627).

However, the formula (1) also includes phosphorus-containing reaction products from a ') at least one compound of the formula where X, R1 and R have the meaning given, 2 b ') glyoxal c') formaldehyde or a formaldehyde-releasing agent d ') optionally urea and e') optionally at least one alkyl or alkenyl alcohol.

These products are for example in the French patent 1 576 727 (Case ARL 137).

Also of interest as component a) are phosphorus-containing reaction products from a ') a condensate product from a ″) a 1,3,5-triazine substituted by at least 2 primary amino groups and at least one compound of the formula where R1 and R2 have the meaning given and where the H2N groups of one of the components a ') or b ") are methylolated and optionally etherified, with b') formaldehyde or a formaldehyde-releasing agent and c ') optionally an alkanol with at most 4 carbon atoms , the description of which can be found in DOS 1 933 444 (Case 6510 / E).

The formula (1) also includes phosphorus-containing reaction products from at 3 a condensation product from a ″) 50 to 100 mol% of at least one compound of the formula b ") 0 to 50 mol ffi of a compound of the formula where R1 and R2 have the meaning given and R1 and R2 each represent an alkyl, halogenalkyl or alkenyl radical each having a maximum of 4 carbon atoms b ') formaldehyde or a formaldehyde-releasing agent and c') optionally an alkanol having a maximum of 4 carbon atoms.

The description of these products can be found in DAS 1 933 479.

As component a), reaction products are also used which are derived from a ') a nitrogen compound which can be at least dimethylolated, b') a compound of the formula in which X, R1 and R2 have the meaning given c ') formaldehyde or a formaldehyde-releasing agent and d') optionally an alkanol having a maximum of 4 carbon atoms (Case 6707 / E).

These reaction products can by reacting the components a '), b ')> c') and optionally d ') in the most varied of orders will. For example, components a '), b') and c ') can first be used at the same time reacted with one another and then optionally with component d ') to be etherified.

Another possibility is that component a ') with the component c '), then with the component b') and then optionally can react with component d '). The conversion products a) by reacting component a ') with component c') then with the component d ') and then obtained with component b'). Furthermore, one arrives at such reaction products a), if you first consider components a ') and b') each separately with component c ') converts, then converts the two reaction products together and then possibly still implemented with component d ').

In addition, it is also possible to first use component b ') of component c ') and optionally with component d') and then the thus resulting product can react with component a ').

Suitable nitrogen compounds which can be at least dimethylolizable [= Component a?)] Are compounds that are formed by the addition of formaldehyde into so-called curable aminoplast precondensates can be transferred. 1,3,5-aminotriazines may be mentioned such as N-substituted melamines, e.g.

N-butylmelamine, as well as ammeline, guanamines, e.g. formoguanamine, benzoguanamine, Acetoguanamine or Diguanamine.

Also possible are: biuret, guanidine, thiourea, alkyl or aryl ureas and thioureas, alkylene ureas or diureas, e.g. Ethylene urea, propylene urea or acetylenediurea; 4,5-dihydroxy-imidazolidone-2 and derivatives thereof, e.g.

the 4> 5-dihydroxyimidazolidone-2 substituted in the 4-position on the hydroxyl group by the radical -CH2CH2CO-NH-CH2-OH. There are also cyclic nitrogen compounds, for example of the formulas into consideration.

Finally, as component a) encompassed by formula (1), there may be mentioned reaction products which are obtained when an anhydrous N-methylolamide of the formula.

where R1 and R2 have the meaning given, in an anhydrous medium, optionally using an acidic catalyst in the presence of an inert one organic solvent at 70 to 1800 C condensed with itself, whereby the condensation is continued until 1 mol of N-methylolamide used about 0.7 to 1 mol of water are deposited.

Appropriate procedures are used to prepare these reaction products so that the N-methylolamide of the formula (I) is already prepared in an anhydrous medium, i.e. the methylolation is carried out with the aid of paraformaldehyde. Preferably will a catalyst such as NaOCH3 or MgO is also used. The methyl emptying takes place preferably at 80 to 1200 C, in particular at 95 to 1050 C and takes 15 to 60 minutes, preferably 25 to 30 minutes. Optionally, in Methylolated in the presence of an inert solvent or suspension medium such as toluene but it is preferable to work without a solvent.

The self-condensation of the N-methylolamides obtained in this way works one in turn by methods known per se. Appropriately, one proceeds in such a way that at least one N-methylolamide of the formula i), which is in anhydrous form must, in an anhydrous medium, if necessary using an acidic catalyst, in the presence of an organic solvent with heating to the boiling point of the solvent in question condenses with itself. The reaction will be like this Long continued until 1 mol of N-methylolamide was used in the water separator about 0.7 to 1, preferably about 0.9 to 1 or especially about 1 mol of water are deposited. Organic solvents suitable for the reaction are e.g. Toluene, benzene or xylene. The condensation temperature is preferably 80 up to 1400 C. After the reaction has ended, a maximum of 25 % of the formaldehyde bound as methylol groups in the starting product as well can be detected as bound formaldehyde. By boiling in water or by Splitting with phosphoric acid can restore the original amount as practically -CH20H bound formaldehyde can be found.

These reaction products are a mixture of Self-condensation products of the compound of the formula (1)> which as a rule contain no more than 15 structural elements of a compound of formula (I) per molecule, the individual polycondensed products being linear, branched or unbranched or can also have a cyclic structure. Because of the great complexity of the reaction product mixtures, however, it is not possible to determine the composition of the Reaction products or self-condensation products to be used according to the invention to be precisely defined using the usual examination methods.

Of the products which can be considered as component a) above, those of the formulas are wherein R6 is an ethyl or preferably methyl group and r is the number 1 or 2 and of particular practical interest.

The compounds of the formulas should also be emphasized Aminoplast precondensates [component b)] are taken to mean addition products of formaldehyde with methylolatable nitrogen compounds. Mention may be made of 1,3,5-aminotriazines such as N-substituted melamine, for example dimethylol melamine, pentamethylol melamine, hexamethylol melamine, N-butyl melamine, N-terthalomethyl melamine, further triazones, for example hydroxyethyl triazon and urone, ammeline, guanamines, for example benzoguanamines, acetoguanamines or else.

The following are also possible: alkyl or aryl ureas and thioureas, Alkylene ureas or diureas, e.g. ethylene urea, dimethyloldihydroxyethylene urea, Propylene urea, 5,5-dimethyl-4-methoxy-propylene urea, acetylenediurea or in particular 4,5-dihydroxyimidazolidone-2 and derivatives thereof, e.g. the in 4,5-Dihydroxyimidazolidon-2-substituted 4-position on the hydroxyl group with the radical -CH2CH2CO-NH-CH20H. The methylol compounds of a urea, an ethylene urea, a propylene urea or especially melamine is used. As aminoplast precondensates Both predominantly monomolecular and highly precondensed aminoplasts are suitable.

The ethers of these aminoplast precondensates can also be used together with the conversion products are used. The ethers of alkanols, for example, are advantageous such as methanol, ethanol, n-propanol, isopropanol, n-butanol or pentanols. Appropriate However, it is when these aminoplast precondensates are water-soluble, such as the Pentamethylolmelamine dimethyl ether and hexamethylolmelamine penta methyl ether.

The preferably aqueous preparations for making the wool-containing materials usually contain such amounts of the components a) and b) that on the one hand the phosphorus content [from component a)] is at least 20 g / kg Liquor, generally 30 to 70 g / kg liquor, preferably 50 to 65 g / kg liquor and on the other hand the nitrogen content [from components a) and b)] 90 to 25 g / kg Liquor, generally 75 to 25, preferably 70 to 55 g / kg of liquor. Of the The content of component c) is strongly dependent on the type of catalyst used.

If, for example, phosphoric acid is chosen as the catalyst, then in general 10 to 100 g, preferably 20 to 50 g per kg of liquor used while for ammonium chloride mostly 2 to 50, preferably 4 to 10 g per kg of liquor and for 2-Amino-2-methylpropanol hydrochloride 4 to 80, preferably 8 to 20 g per kg of liquor suffice. Wetting agent [component d)] can be from 0 to 5, preferably from 0 to 2 g each kg of the fleet. If the preparations are watery, their pH value lies generally between 2 and 8, preferably between 3 and 7.

As component c) (curing catalyst) can be used for curing the Aminoplasts commonly used catalysts are used, such as acids and potentially acidic compounds. Preferred acids are sulfuric acid, Hydrochloric acid and especially phosphoric acid. Come as potentially acidic compounds Ammonium salts such as ammonium sulfate, ammonium dihydrogen phosphate, ammonium chloride or amine salts such as c-amino-2-methylpropanol hydrochloride are also possible the use of a wetting agent [component d)] proves to be expedient, a any wetting agent, such as the adduct of 9 molecules of ethylene oxide on nonylphenol.

In the case of the wool-containing materials to be made flame-resistant according to the invention it is preferably piece goods, such as woven and knitted fabrics. Flameproof equipment according to the present invention is in particular at relatively thin ones Fabrics and fabrics that are naturally particularly flammable are also indicated also for upholstery fabrics. The wool-containing materials are Goods made from pure wool or from blended fabrics containing at least 50% wool exist.

The preparations are now applied to the wool-containing materials, which can be carried out in a manner known per se. The piece goods are for example impregnated on a customary design foulard which is loaded with the preparation. The padding is expediently carried out in such a way that the liquor pick-up 50 to 150 %> is preferably 75 to 90 ffi. In relation to the fiber weight, that is Content of the material impregnated in this way of fixable originating from component a) Phosphorus mostly over 3%, for example between 4 and 6%> preferably between 4.5 and 5.5% of fixable nitrogen originating from components a) and b) generally between 7% and 3%, for example between 6 and 3.5%, preferably between 5.5 and 4%> while the catalyst content, for example in the case of Phosphoric acid between 0.5 and 5 J, preferably between 1.5 and 3.5%, in the case of ammonium chloride between 0.1 and 2%, preferably between 0.3 and 1.%, in the case of 2-amino-2-methylpropanol hydrochloride between 0.2 and 4, preferably between 0.6 and 1%. Under fixable phosphorus or

Nitrogen is to be understood as all phosphorus or nitrogen contained in the molecules of components a) or a) and b) is present.

The impregnated material is now dried, which is useful under Ventilation for 1 to 15 minutes at temperatures of 60 to 1200 ° C., preferably 70 to 900 C, happens. This is followed by a heat treatment to harden the equipment at temperatures above 1000 C, e.g. between 120 and 1900 C, preferably at 130 to 1700 C. The duration of the heating is of course dependent on the temperature and or depending on the type of fabric; it is generally at temperatures of 130 to 1700 C 30 to 1/2 minutes.

A rewash with an acid-binding agent, preferably with a 0> 1 to 0.5% strength aqueous sodium carbonate solution at temperatures of 20 to 500 C for 2 bits 10 minutes is appropriate.

The process according to the invention gives fiber materials with good permanent flame resistance. It should also be emphasized that that these materials, when they are burned, only a comparatively small amount Show smoke development.

Example A woolen fabric is made with a liquor containing 410 g / l of dimethylphosphonopropionic acid-N-methylolamide 140 g / l of the reaction product of 1 mole of melamine with 5 moles of formaldehyde and 2.5 Mol of methanol, 30 g / l phosphoric acid (85 Çig) and 1 g / l of the condensation product of 1 mole of nonylphenol with 9 moles of ethylene oxide, to an uptake of 80 ffi padded and then dried at 800 g. This is followed by 4 1/2 minutes Hardened at 1450 C. The tissue is in a solution at 400 ° C. for 5 minutes washed, which contains 2 g / l sodium carbonate.

Individual pieces of fabric are washed 2, 5 and 10 times at 400 C in a household washing machine with a solution according to SNV draft no. 198 861 washed.

The individual pieces of fabric are then tested for their flame resistance (vertical test in accordance with DIN 53906). The results of such a test are summarized in the following table: Ignition time Continued burning time burned in Sec. Sec. Zone cm after rewash 12 0 5 8 2 5 according to the invention 6 0 2 well-worn after washing twice 12 2 5.5 tissue 8 2 4.5 6 0 2 after 5 washings 12 0 7 8 0 3.5 6 2 2.5 after washing 10 times 12 3 7 8 2 4.5 6 2 3.5 untreated fabric 6 burns through

Claims (21)

Claims 1. A process for making materials flame-resistant which consist of at least 50% wool, characterized in that these materials are impregnated with a preparation which a) the amide or a further substituted amide of a phosphorus-containing carboxylic acid of the formula wherein R1 and R2 each represent an alkyl, alkenyl or haloalkyl radical with a maximum of 4 carbon atoms, X a methyl group or preferably a hydrogen atom and Z represent sulfur or preferably oxygen, b) an aminoplast precondensate, c) a curing catalyst and optionally d) a wetting agent which contains such impregnated materials dries and the impregnation hardens. 2. The method according to claim 1, characterized in that as component a) at least one compound of the formula wherein R is a hydrogen atom, an allyl radical or an alkyl radical having up to 6 carbon atoms and X, R1 and R2 have the meaning given in claim 1, is used. 3. The method according to claim 1, characterized in that as component a) at least one compound of the general formula where A stands for -CONH2 or -CONHCH20R "',, R' and R" each represent hydrogen or methyl, R "'represents hydrogen or alkyl having 1 to 4 carbon atoms, and n and p each represent the number 1 or 2 and R1 and R2 are the in claim 1 have given meaning is used. 4. The method according to claim 1, characterized in that as component a) at least one phosphorus-containing N, N-dimethylolcarboxamide of the formula in which A1 and A2 each represent a hydrogen atom or an alkyl radical, and @ X, R1 and R2 have the meaning given in claim 1, is used. 5. The method according to claim 1, characterized in that as component a) at least one thiophosphonocarboxamide of the formula in which X, R1, R2 and n have the meaning given in claims 1 and 3 and R3 is a hydrogen atom, an alkyl radical with at most 4 carbon atoms or an alkenyl radical with at most 4 carbon atoms. 6. The method according to claim 1, characterized in that as component a) at least one heterocyclic phosphorus compound of the formula wherein R1, R2 and X have the meaning given in claim 1; R1, R2 each represent an alkyl, haloalkyl or alkenyl radical having at most 4 carbon atoms each and X 'represents a methyl radical or preferably a hydrogen atom. 7. The method according to claim 1, characterized in that as component a) at least one phosphorus compound of the formula whereinR1, R2> R1, R2, X and X 'have the meaning given in claims 1 and 6, Y and Y' each represent an alkyl radical with at most 4 carbon atoms or a hydrogen atom and areinen alkyl radical with 1 to 22 carbon atoms, a haloalkyl radical with at most 4 carbon atoms, a hydroxyalkyl radical having a maximum of 4 carbon atoms, an alkenyl radical having 2 to 22 carbon atoms or an optionally halogenated benmol or benzyl radical is used. 8. The method according to claim 1, characterized in that as component a) at least one phosphorus compound of the formula wherein R1, R2, R1 ', R2', X, X ', Y and Z have the meaning given in claims 1, 6 and 7 and A' represents an alkylene radical with 2 which is optionally substituted by lower alkyl, lower alkoxy or hydroxyl groups to 3 carbon atoms is used. 9. The method according to claim 1, characterized in that as component a) at least one phosphorus compound of the formula wherein R1, R2> R1 ', R2 ,, X, X' and Y have the meaning given in claims 1, 6 and 7, Q is a radical of the formula -CO-, -CS-, SO2-, -CNH- or -CO-NE-CO-, in which E is a hydrogen atom or a radical of the formula -CH2-OY, is used. 10. The method according to claim 1, characterized in that as component a) at least one phosphonocarboxamide of the formula in which X, Z, R1 and R have the meaning given in claim 1 and R4 is an optionally substituted aryl or alkyl radical, is used. 11. The method according to claim 1, characterized in that as component a) at least one phosphorus-containing, curable and water-soluble aminoplast, which (a ') at least one and preferably 1 to 2 groups of the formula -CH2 0 R5 where R5 is an alkyl radical bonded to amide nitrogen with 1 or 2 carbon atoms or a hydrogen atom, and furthermore (b ') at least one and preferably 4 to 5 groups of the formula bonded to amide nitrogen contains, wherein R1, R2 and X have the meaning given in claim 1, is used. 12. The method according to claim 1, characterized in that as component a) a phosphorus-containing reaction product from a ') at least one compound of the formula wherein X, R1 and R2 have the meaning given in claim 1, b ') glyoxal ct) formaldehyde or a formaldehyde-releasing agent d') optionally urea and et) optionally at least one alkyl or alkenyl alcohol is used. 13. The method according to claim 1, characterized in that as component a) a phosphorus-containing reaction product from a ') a condensation product from a ") a 1,3,5-triazine substituted by at least 2 primary amino groups and b") at least one compound of the formula where R1 and R2 have the meaning given in claim 1 and where the H2N groups of one of the components a ") or b ') are methylolated and optionally etherified, with bt) formaldehyde or a formaldehyde-releasing agent and c') optionally with an alkanol at most 4 carbon atoms is used. 14. The method according to claim 1, characterized in that as component a) a phosphorus-containing reaction product from a ') 50 to 100 mol% of at least one compound of the formula b ") 0 to 50 mol% of a compound of the formula where R1 and R2 have the meaning given in claim 1 and Rt and R2 each represent an alkyl, halogen-12 alkyl or alkenyl radical each having at most 4 carbon atoms, b ') formaldehyde or a formaldehyde-releasing agent and c') optionally one Alkanol with a maximum of 4 carbon atoms} is used. 15. The method according to claim 1, characterized in that as component a) at least one reaction product of a ') an at least -dimethylolatable nitrogen compound, bl) a compound of the formula in which X, R1 and R2 have the meaning given in claim 1 c ') formaldehyde or a formaldehyde-releasing agent and d') optionally an alkanol having a maximum of 4 carbon atoms is used. 16. The method according to claim 1, characterized in that as component a) at least one reaction product which is obtained when using an anhydrous N-methylolamide of the formula wherein R1 and R2 have the meaning given in claim 1, condensed with themselves in an anhydrous medium, optionally using an acidic catalyst, in the presence of an inert organic solvent at 70 to 1800 C, the condensation being continued until 1 Mol N-methylolamide used are deposited about 0.7 to 1 mol of water, is used. 17. The method according to claim 1, characterized in that as component a) a phosphonopropionamide of the formula in which R6 is an ethyl or, preferably, methyl group and r is the number 1 or 2, is used. 18. The method according to claim 1, characterized in that the phosphonopropionic acid methylolamide of the formula as component a) is used. 19. The method according to any one of claims 1 to 17, characterized in, that a methyl oil melamine or an alkyl ether thereof is used as the aminoplast. 20. The method according to any one of claims 1 to 18, characterized in that that as a catalyst ammonium chloride, 2-amino-2-methylpropanol hydrochloride or preferably phosphoric acid is used. 21. The method according to any one of claims 1 to 20> in particular Claim 18, characterized in that the impregnation like that It is stated that for the wool-containing materials, based on the unfinished Fiber weight, between 4.0 and 6.0% fixable phosphorus and between 6.0 and 3.5 % fixable nitrogen is used.