AU1036000A

AU1036000A - Phosphoric acid esters

Info

Publication number: AU1036000A
Application number: AU10360/00A
Authority: AU
Inventors: Ralf Heinen; Martin Riegels; Uwe Vogt
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1998-10-23
Filing date: 1999-10-12
Publication date: 2000-05-15
Also published as: EP1123300A1; DE19848894A1; PL347412A1; HUP0103975A3; EP1123300B1; BR9914739A; DE59902788D1; CN1324362A; JP2002528457A; WO2000024749A1; CA2349580A1; KR20010075645A; ATE224398T1; NZ511231A; HUP0103975A2

Abstract

The invention relates to the preparation of novel phosphoric acid esters having general formula (1) which are obtained by reacting phosphoryl chloride with special alcohols and which can be used as leveling agents for dying fibrous materials containing nitrogen.

Description

Phosphoric esters The present invention relates to novel phosphoric esters, to a process for their 5 preparation and to their use as dyeing auxiliaries. Textiles are dyed using levelling agents as auxiliaries. These levelling agents are surface-active substances whose office it is to efficiently wet the fibre or fibre blend to be dyed, to promote the penetration of the fibres by the dye and to inhibit an 10 excessively rapid, unlevel exhaustion of the dyes during the dyeing process. The use of levelling agents thus makes it possible to obtain an even and uniform dyeing result. Nitrogenous fibre materials, especially wool, are suitably dyed with anionic dyes, for 15 example acid dyes, 1:1 metal complex dyes, 1:2 metal complex dyes, chromium dyes or mixtures thereof. The prior art discloses a wide variety of levelling agents for the dyeing of textile materials, especially wool, with the dyes mentioned. 20 DE-A-19 40 178 describes for example polyalkoxylated ethanesulphonic acid compounds or their quaternization products as levelling agents for the dyeing of nitrogenous fibre materials with acid dyes or 1:2 metal complex dyes. The polyalkoxylated ethanesulphonic acid compounds in question have the following 25 structural formula: R R'N-(CH 2 -CHR"-0)m-CH 2

-CH

2

-SO

3 M where R is a C 12

-C

22 -alkyl, a C 1 2

-C

22 -alkenyl or C 1 2

-C

22 -cycloalkyl radical, R' is CH 3 30 or one of -(CH 2 -CHR'-O-)nH or -(CH 2

-CHR"-O),-CH

2

-CH

2

-SO

3 M, R" is H, CH 3

,

-2

C

2

H

5 or phenyl, M is a cation and the sum of m+n is 5-70, at least 80% of the alkylene oxide units in the molecule being ethylene oxide units. DE-A-1 619 372 discloses the dyeing of natural and synthetic polyamide fibres, 5 cellulose or regenerated cellulose fibres in the presence of specific levelling agents as replacement for natural lecithin. These levelling agents are obtained by alkoxylation of polyalkyleneamines acylated with fatty acids, reaction of these alkoxylation products with P40 1 o to form partial phosphoric esters and neutralization of the latter with alkanolamines. 10 DE-A-1 946 058 discloses mixtures of a) low-ethoxylated fatty diamines, b) an alkali metal salt of dinaphthylmethanedisulphonic acid and c) propoxylated mono- and diesters of orthophosphoric acid in a dyeing process to dye polyamide fabrics level and without stripes under low foam conditions. 15 DE-A 28 21 494 describes a process for dyeing polyester fibre wovens and knits with disperse dyes by adding an aqueous formulation of lecithin, an ethoxylated carboxylic acid and an ethoxylated alcohol to increase the dispersion stability and improve the levelling effect. 20 It is further known to use phosphoric esters as dispersants for inorganic and organic pigments not only in plastics but also in particular in coatings, printing inks and paints. EP-A-0 759 440 for example describes phosphoric esters prepared as follows: First an amine is reacted with an alkylene oxide or alkylene carbonate to form an 25 amino alcohol or amino ether alcohol. This amino alcohol or amino ether alcohol is esterified with a hydroxycarboxylic acid or a dicarboxylic acid and a diol or converted into a urethane using a diisocyanate and a diol. The resulting amino ester or amino ether ester or the amino urethane or amino ether urethane formed is finally converted (by phosphatization) into a phosphoric ester. These phosphoric esters have 30 a stabilizing effect on the pigment dispersions and inhibit pigment particle -3 agglomeration or flocculation. The use of these phosphoric esters as levelling agents in the dyeing of textile materials is not described. It is an object of the present invention to provide novel substances useful as levelling 5 agents in the dyeing of textile materials, especially wool. This object is achieved by novel phosphoric esters of the general formula 1 (OR')a

O=P-(OR

2 )b 1 3 (OR ) 10 where R I is an aliphatic radical of 1-30 carbon atoms, R2 is a radical of the general formula 2 15 X -CH2CH20-[CH2CH20];-N-[CH 2 CH20];-Y (2) where 20 n is from 0 to 30 m is from 1 to 29 X is an aliphatic radical of 4-24 carbon atoms and Y is H or PO(OM) 2 , where each M is independently hydrogen, alkali metal, ammonium, mono-, di-, tri- or tetra-(CI-C 6 -alkyl)-ammonium 25 ions or mono-, di-, tri- or tetra-(C 2

-C

6 -alkanol)-ammonium ions, R 3 is a radical of the general formula 3 -4 - [CH 2 CH-O]-Z 14 (3) R where p is from 4 to 35, 5 R4 is H, methyl, ethyl or phenyl or denotes mixtures of H and methyl and Z is H, methyl, ethyl or PO(OM) 2 , where each M is independently hydrogen, alkali metal, ammonium, mono-, di-, tri- or tetra-(CI-C 6 alkyl)-ammonium ions or mono-, di-, tri- or tetra-(C 2

-C

6 -alkanol) ammonium ions, and 10 a, b and c are each from 0 to 3 and a+b+c is = 3. The invention further provides a process for preparing the phosphoric esters of the formula 1 and for the use of these phosphoric esters as auxiliaries in the dyeing of 15 nitrogenous fibre materials, especially wool. In the phosphoric esters of the formula 1, R' is an aliphatic radical having 1 to 30 carbon atoms. This aliphatic radical is preferably a straight-chain or branched alkyl or alkenyl radical of 1-30 carbon atoms. Examples of straight-chain or branched Ci-C 8 20 alkyl groups are methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, I-ethylpropyl, n-hexyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 25 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1 -ethyl-2-methylpropyl, n-heptyl, 1 -methylhexyl, 1-ethylpentyl, 2-etylpentyl, 1-propylbutyl and n-octyl.

-5 Examples of straight-chain or branched Cs-C 3 o-alkyl groups are n-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl and n-docosyl. 5 The meaning of alkenyl group comprehends straight-chain and branched CI-C 30 alkenyl groups having 1, 2 or 3 double bonds. Preferably they are straight-chain or branched C 4

-C

30 -alkenyl, especially Cs-C 20 -alkenyl, groups. Examples of alkenyl groups are heptenyl, octenyl, nonenyl, decenyl, undecenyl, tridecenyl, tetradecenyl, 10 pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, hexadecadienyl, hexadecatrienyl, octadecadienyl and octadecatrienyl. The meaning of alkyl or alkenyl R1 also comprehends mixtures of various alkyl or alkenyl groups as occur for example in natural fats and oils, for example coconut oil, 15 palm kernel oil, soya oil, colza oil, olive oil, sunflower oil, cottonseed oil, groundnut oil, linseed oil, rapeseed oil or tallow fat. X in R 2 is an aliphatic radical having 4-24 carbon atoms. Useful aliphatic radicals are straight-chain and branched alkyl and alkenyl radicals having 4-24 carbon atoms, 20 preferably 12-24 and particularly preferably 16-22 carbon atoms. More particularly, X is a dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, octadecenyl or abietyl radical. The meaning of alkyl or alkenyl X likewise comprehends mixtures of various alkyl or 25 alkenyl groups as occur for example in natural fats and oils, for example coconut oil, palm kernel oil, soya oil, colza oil, olive oil, sunflower oil, cottonseed oil, groundnut oil, linseed oil, rapeseed oil or tallow fat. Y in R 2 is H or PO(OM) 2 . The cations M are independently hydrogen, alkali metal, 30 preferably sodium or potassium, ammonium, mono-, di-, tri- or tetra-(Ci-C 6 -alkyl)- -6 ammonium or mono-, di-, tri- or tetra-(C 2

-C

6 -alkanol)ammonium ions. The latter are derived in particular from mono-, di- or triethanolamine. The index n in R2 is from 0 to 30, preferably from 0 to 10, especially from 0 to 5. The 5 index n in R2 is from 0 to 29, preferably from 0 to 10, especially from 0 to 5. Z in R 3 is H, methyl, ethyl or PO(OM) 2 . Preferably Z is H or PO(OM) 2 . The cations M are independently hydrogen, alkali metal, preferably sodium or potassium, ammonium, mono-, di-, tri- or tetra-(Ci-C 6 -alkyl)ammonium or mono-, di-, tri- or 10 tetra-(C 2

-C

6 -alkanol)ammonium ions. The latter are derived in particular from mono-, di- or triethanolamine.

R

4 is hydrogen, methyl, ethyl, phenyl or else denotes mixtures of hydrogen and methyl. Preferably R 4 is hydrogen or methyl. In the case of mixtures of hydrogen and 15 methyl, not more than 80% of R 4 is methyl and not less than 20% of R 4 is hydrogen. The index p in R 3 is from 4 to 35, preferably from 9 to 22. The indices a, b and c in the formula I are each from 0 to 3, subject to the proviso that 20 a + b + c is = 3. Preferably a, b and c are each 1. Preference is given to phosphoric esters of the formula 1 where 25 R I is an aliphatic radical of 4-30 carbon atoms, R 2has n from 0 to 10, 30 m from 1 to 10, X an aliphatic radical of 12-24 carbon atoms and -7 Y H or PO(OM) 2 , where each M is independently hydrogen, alkali metal, ammonium, mono-, di-, tri- or tetra-(Ci-C 6 -alkyl)-ammonium ions or mono-, di-, tri- or tetra-(C 2

-C

6 -alkanol)-ammonium ions, and 5 R 3 has m from 3 to 35,

R

4 H or methyl and Z H, methyl, ethyl or PO(OM) 2 , where each M is independently hydrogen, alkali metal, ammonium, mono-, di-, tri- or tetra-(CI-C 6 10 alkyl)-ammonium ions or mono-, di-, tri- or tetra-(C 2

-C

6 -alkanol) ammonium ions, and a, b and c are each from 0 to 3 and a+b+c is = 3. 15 Particular preference is given to phosphoric esters of the formula 1 where Ri is an aliphatic radical of 8-20 carbon atoms,

R

2 has 20 n from 0 to 5, m from I to 5, X an aliphatic radical of 16-22 carbon atoms and Y H, 25 R3 has p from 9 to 22, R4 H and Z H and 30 a, b and c are each from 0 to 3 and a+b+c is = 3.

-8 The invention also provides a process for preparing phosphoric esters according to the formula 1, by reacting the alcohols R'OH, R 2 OH and R 3 OH with phosphorus oxychloride, R1, R 2 and R 3 each being as defined for the formula 1, but Y exclusively representing hydrogen and z representing either hydrogen or methyl or ethyl. 5 In a suitable embodiment of the process according to the invention, 3 mol of a mixture of the alcohols R'OH, R 2 OH and R 3 OH are reacted with 1-2 mol, preferably 1.0 to 1.2 mol, of phosphorus oxychloride. 10 The three alcohols R'OH, R 2 OH and R 3 OH are used in the following mixing ratios: R'OH 10 - 40, preferably 30 - 40, mol % R2OH 20 - 80, preferably 30 - 40, mol % and R'OH 10 - 40, preferably 30 - 40, mol %, 15 the amounts of the three alcohols always adding up to 100 mol%. It is customary to initially charge the alcohols R'OH, R 2 OH and R 3 OH, to heat this mixture to melt the alcohols and to add the phosphorus oxychloride at 40 to 60'C. 20 This addition is accompanied by an increase in the temperature, generally to not less than 80'C. Subsequently the reaction mixture is stirred at elevated temperature, preferably about 100'C. By reducing the pressure it is possible to remove the HCl of reaction from the reaction product. It is further advantageous to subsequently add a base such as aqueous sodium hydroxide solution or diethanolamine to set a pH of 5 25 to 7. The R OH alcohols are generally available. The R 2OH alcohols can be prepared according to methods known to one skilled in the art, for example as described in DE-A-1 940 178. Initially 2 to 60 mol of ethylene oxide are added to an aliphatic 30 amine X-NH 2 , where X is as defined above. Useful aliphatic amines are in particular -9 dodecyl-, tetradecyl-, hexadecyl-, octadecyl-, eicosyl-, docosyl, octadecenyl- or abietyl-amine. Preferred examples further include reaction products of 1 mol of tallow fatty amine 5 with 2 mol, 5 mol or 10 mol of ethylene oxide. The esterification of the terminal OH group in the R 2 radical, so that Y is PO(OM) 2 , is possible in the course of the reaction of the alcohols with phosphorus oxychloride, provided an excess of phosphorus oxychloride is used. 10 The R 3 0H alcohols are generally available. Preferred examples of R 3 0H are tri ethylene glycol and polyethylene glycols having average molecular weights of 200 to 1500 g/mol or monomethyl or monoethyl ethers of these compounds. 15 It will be appreciated that any other methods known to one skilled in the art for preparing phosphoric esters are suitable for preparing the compounds of the invention, for example the transesterification of triethyl phosphate with the alcohols R IOH, R 2 OH and R 3 0H. 20 The compounds of the formula I according to the invention are generally in solid, waxy form at room temperature. They start to melt in the range from 30 to 60'C. To convert the phosphoric esters into a liquid form because it is more convenient to meter in that form, it is advisable to prepare organic or aqueous-organic formulations. 25 The invention accordingly further provides organic or aqueous-organic formulations containing 25-70% by weight of the phosphoric esters according to the formula 1. These formulations can be prepared using the reaction mixture of the process according to the invention without further work-up. Useful organic solvents are inert with regard to the phosphoric esters and water-miscible. Preference is given to the 30 use of mono-, di- or oligoethylene glycols, oligopropylene glycols or -10 oligoethylene/propylene glycols, their mono- or diethers or mixtures thereof, especially butyldiglycol or methyldiglycol. The invention further provides for the use of the phosporic esters of the formula I or 5 of the corresponding organic or aqueous-organic formulations as dyeing auxiliaries in the dyeing of nitrogenous fibre materials, preferably wool. The phosphoric esters of the formula 1 or the organic or aqueous-organic formulations, are added to the dyeing liquors. The dyeing of nitrogenous textile 10 materials, especially wool, in the presence of compounds of the formula 1 according to the invention can be carried out by initially introducing the material to be dyed into a hot dyeing liquor at 40 to 50*C which contains the dye, the phosphoric esters of the formula 1 and acids, for example acetic acid. The dyebath is then gradually heated to 100-130'C and maintained at that temperature until it is exhausted. It is likewise 15 possible to pretreat the textile material at 40 to 50 0 C for a short time with an aqueous liquor containing only phosphoric esters of the formula 1 and acid and only then to add the dyes to this liquor at temperatures between 40 and 98'C, subsequently to gradually increase the temperature of the dyebath to 100-130'C and to maintain it at that temperature until it is exhausted. 20 Useful dyes include the anionic dyes suitable for the dyeing of nitrogenous fibre materials, especially wool, for example acid dyes, 1:1 metal complex dyes, 1:2 metal complex dyes or chromium dyes and also mixtures thereof. 25 The amounts in which the compounds of the invention is added to the dyebaths can vary within wide limits. The amounts are readily ascertainable by preliminary experimentation. Useful amounts generally range from 0.25 to 3.0%, preferably from 0.5 to 1.0%, of the weight of the material to be dyed. 30 The dyeing process is useful for all nitrogenous fibre materials which are dyeable with the dyes mentioned, especially for natural polyamides, such as wool and silk, for - 11 synthetic polyamides, such as hexamethylene diadipate, poly-e-caprolactam and poly 01-aminoundecanoic acid, for cationically modified polyacrylonitriles and also their mixtures with each other or with other fibre materials, such as fibre materials composed of natural and regenerated cellulose, polyacrylonitrile, polyurethanes or 5 polyesters. The dyeable fibre materials mentioned can be present in a wide variety of processing forms, for example as staple, top, textured threads, tow, yam, wovens, knits or nonwovens. The phosphoric esters of the formula 1 provide very uniform dyeing of these 10 nitrogenous textile materials. In addition to their outstanding quality as dyeing auxiliaries, the phosphoric esters of the formula 1 are surprisingly also readily biodegradable.

-12 Examples Example 1 (Preparation of a compound according to the invention) 5 A mixture of 27.0 g (0.1 mol) of stearyl alcohol, 40.0 g (0.1 mol) of polyethylene glycol having an average molecular weight of 400 g/mol and 48.8 g (0.1 mol) of a reaction product of 1 mol of tallow fatty amine with 5 mol of ethylene oxide is initially charged at 55'C and admixed with 15.3 g (0.1 mol) of phosphorus oxychloride over 10 min, during which the temperature rises to 90'C. The batch is 10 subsequently stirred at 100'C for 5 hours under a slow stream of nitrogen. This is followed by a further hour of stirring under a reduced pressure of 20 mbar. The batch is cooled down to 50 0 C and neutralized by careful addition of 45% strength aqueous sodium hydroxide solution to a pH of 6 to 7. After cooling down to room temperature, the reaction product solidifies into a waxy mass. The yield is 138 g. On 15 reheating, the reaction product starts to melt at about 44'C. Example 2 (Preparation of a compound according to the invention) Example 1 is repeated, except that the end of the reaction is followed by 20 neutralization to a pH of 6 to 7 with diethanolamine instead of with aqueous sodium hydroxide solution. The yield is 143 g. On reheating the reaction product starts to melt at about 42'C. Example 3 (Preparation of a compound according to the invention) 25 Example 1 is repeated to react 24.2 g (0.1 mol) of hexadecyl alcohol, 40.0 g (0.1 mol) of polyethylene glycol having an average molecular weight of 400 g/mol and 48.8 g (0.1 mol) of a reaction product of I mol of tallow fatty amine and 5 mol of ethylene oxide. The reaction mixture is neutralized with 45% strength aqueous 30 sodium hydroxide solution. The yield is 135 g of a waxy product having a melting point of about 44'C - 13 Example 4 (Preparation of a compound according to the invention) Example 3 is repeated, except that the end of the reaction is followed by neutralization with diethanolamine instead of with aqueous sodium hydroxide 5 solution. The yield is 140 g of a waxy product having a melting point of about 43*C. Example 5 (Production of a liquid preparation of the phosphoric ester of Example 2) 10 100 g of the phosphoric ester of Example 2 are stirred with 100 g of butyldiglycol at 50'C until a clear solution is obtained. This is followed by cooling. Example 6 (Production of a liquid preparation of the phosphoric ester of Example 2) 15 30 g of the phosphoric ester of Example 4 are stirred with 40 g of butyldiglycol and 30 g of demineralized water at 50'C until a clear solution is obtained. This is followed by cooling. 20 Example 7 (Use) 30 g of worsted wool yarn are dyed as follows (percentages are on weight of fibre; ISOLAN* are dyes from DyStar Textilfarben GmbH & Co. Deutschland KG) in a circulation dyeing machine (Color Star from Mathis): - 14 1. Dyeing Liquor circulation: Alternately 4 min in to out and 2 min out to in Liquor: ISOLAN Yellow K-GLN 250 % 0.3 % 5 ISOLAN Bordeaux R 220 % 0.15% ISOLAN Grey K-BRLS 200 % 0.3 % Sodium sulphate 5 % Acetic acid 60 % strength 3 % Auxiliary as per Example 1 0.5 % 10 pH of liquor: 4.5 Liquor ratio: 20:1 Starting temperature: 50'C Dyeing procedure: 15 - 10 min prerun at 50'C - heating to 98'C (heating rate 2 0 C/min) - maintain at 98'C for 30 min - cool to 70'C (cooling rate 2 0 C/min) - maintain at 70'C for 5 min 20 - drop the liquor - 15 2. Rinsing Liquor circulation: Alternately 4 min in to out and 2 min out to in Temperature: 40 0 C Rinse time: 12 min 5 - drop rinse liquor - add new rinse liquor Temperature: 60 0 C 10 Rinse time: 12 min - drop rinse liquor 3. Hydroextraction and drying of worsted yarn package 15 12 hours at 50 0 C The dyed worsted wool yarn is knitted up inside-middle-outside. The knitted piece is assessed for the hue profile, ie. the differences in hue between the inside, middle and outside regions of the yarn package. 20 The knitted piece is observed to have a satisfactory hue profile. Example 8 Repeating Example 5 with the following liquor: 25 ISOLAN Yellow S-GL 0.3 % ISOLAN Red S-RL 0.3% ISOLAN Grey S-GL 0.3 % Sodium sulphate 5 % Acetic acid 60% 3 % 30 Auxiliary as per Example 3 1.0 % likewise affords a knitted piece having a satisfactory hue profile.

-16 Examples 9 and 10 (for comparison) Conducting the dyeing described in Examples 7 and 8 without the auxiliary of the 5 invention results in the dyed worsted wool yam giving rise to a knitted piece which exhibits a very distinct inside-middle-outside effect, ie. a pronounced hue difference within the knitted piece. Examples 11 and 12 (for comparison) 10 Again a very distinct inside-middle-outside effect is observed on carrying out the dyeing of Example 7 by replacing the compounds of the invention with the following comparative compounds: 15 reaction product of 27.0 g (0.1 mol) of stearyl alcohol, 40.0 g (0.1 mol) of poly ethylene glycol having an average molecular weight of 400 g/mol and 46.4 g (0.1 mol) of a reaction product of 1 mol of oleyl alcohol with 5 mol of ethylene oxide. The subsequent neutralization is effected with aqueous sodium hydroxide solution. 20 Reaction product of of 3.2 g (0.1 mol) of methanol, 10.6 g (0.1 mol) of diethylene glycol and 48.8 g (0.1 mol) of a reaction product of 1 mol of tallow fatty amine with 5 mol of ethylene oxide. The subsequent neutralization is effected with aqueous sodium hydroxide solution.

Claims

1. Phosphoric esters of the general formula 1 (OR)a O=P-(OR 2 )b (ORs)C where R' is an aliphatic radical of 1-30 carbon atoms, 10 R2 is a radical of the general formula 2 x -- CH2CH20-[CH2CH20]-N-[CH2CH20]-Y (2) where 15 n is from 0 to 30 m is from I to 29 X is an aliphatic radical of 4-24 carbon atoms and Y is H or PO(OM) 2 , where each M is independently H, alkali 20 metal, ammonium, mono-, di-, tri- or tetra-(Ci-C 6 -alkyl) ammonium ions or mono-, di-, tri- or tetra-(C 2 -C 6 -alkanol) ammonium ions, R 3 is a radical of the general formula 3 25 -[CH 2 CH-O]P-Z 14 (3) R -18 where p is from 4 to 35, R 4 is H, methyl, ethyl or phenyl or denotes mixtures of H and 5 methyl and Z is H, methyl, ethyl or PO(OM) 2 , where each M is independently H, alkali metal, ammonium, mono-, di-, tri- or tetra-(Ci-C 6 -alkyl)-ammonium ions or mono-, di-, tri- or tetra (C2-C 6 -alkanol)-ammonium ions, and 10 a, b and c are each from 0 to 3 and a+b+c is = 3.

2. Phosphoric esters according to Claim 1, wherein 15 R 1 is an aliphatic radical of 4-30 carbon atoms, R2 has n from 0 to 10, m from 1 to 10, X an aliphatic radical of 12-24 carbon atoms and 20 Y H or PO(OM) 2 , where each M is independently H, alkali metal, ammonium, mono-, di-, tri- or tetra-(C;-C 6 -alkyl)-ammonium ions or mono-, di-, iri- or tetra-(C2-C 6 -alkanol)-ammonium ions, and R 3has 25 m from 3 to 35, R 4 H or methyl and Z H, methyl, ethyl or PO(OM) 2 , where each M is independently H, alkali metal, ammonium, mono-, di-, tri- or tetra-(Ci-C 6 alkyl)-ammonium ions or mono-, di-, tri- or tetra-(C 2 -C 6 30 alkanol)-ammonium ions. -19 a, b and c are each from 0 to 3 and a+b+c is = 3.

3. Phosphoric esters according to Claim 1, wherein 5 Ri is an aliphatic radical of 8-20 carbon atoms, R2 has n from 0 to 5, 10 m from 1 to 5, X an aliphatic radical of 16-22 carbon atoms and Y H, R 3 has 15 p from 9 to 22, R4 H and Z H and a, b and c are each from 0 to 3 and a+b+c is = 3. 20

4. Process for preparing phosphoric esters according to one or more of Claims I to 3, characterized in that a mixture of the alcohols R OH, R 2OH and R'OH is reacted with phosphorus oxychloride, R , R2 and R3 each being as defined for the formula 1, but Y exclusively representing hydrogen and z representing 25 either hydrogen or methyl or ethyl.

5. Process according to Claim 4, characterized in that 3 mol of the mixture of the alcohols R OH, R 2OH and R OH is reacted with 1-2 mol, preferably 1.0 to 1.2 mol, of phosphorus oxychloride. 30 - 20

6. Process according to Claim 4 or 5, characterized in that the alcohols R'OH, R 2OH and R3 OH are used in the following mixing ratios: R'OH 10 - 40, preferably 30 - 40, mol % R2OH 20 - 80, preferably 30 - 40, mol % and 5 R'OH 10 - 40, preferably 30 - 40, mol %, the amounts of the three alcohols always adding up to 100 mol%.

7. Organic or aqueous-organic formulations containing 25 to 70% by weight of the phosphoric esters of the formula 1. 10

8. Organic or aqueous-organic formulations according to Claim 7, characterized in that the organic solvents used are mono-, di- or oligoethylene glycols, oligopropylene glycols or oligoethylene/propylene glycols, their mono- or diethers or mixtures thereof, especially butyldiglycol or methyldiglycol. 15

9. Use of the phosporic esters according to one or more of Claims 1-3 or of the formulations according to Claim 7 or 8 as dyeing auxiliaries in the dyeing of nitrogenous fibre materials, preferably wool. 20

10. Use according to Claim 9, wherein the dyeing is carried out with acid dyes, 1:1 metal complex dyes, 1:2 metal complex dyes, chromium dyes or mixtures thereof.