GB2160522A - Sulphomethylated amino-esters - Google Patents

Abstract

Sulphomethylated amino-esters which are the reaction products of an alcanolamine of formula I HO-R4-NHR1 I where R1 is hydrogen, C1-4alkyl, -R5-OH or &lparstr& CH2 &rparstr& n NR2R3 R2 and R3 are, independently, hydrogen, -R5-OH or C1-4alkyl R4 and R5 are, independently, 1,2-ethylene or 1,2-propylene and n is 2 or 3 or a mixture thereof, with a fatty acid of formula II R-COOH II where R is optionally hydroxy substituted C11-21alkyl and/or alkenyl, the product amino-esters being sulphomethylated with, e.g., formaldehyde or a formaldehyde-yielding compound and a sulphite, SO2 or a compound of formula V HO-CH2-SO3M V where M is H or a cation, are useful as non permanent finishing agents for fibrous materials, particularly as softening agents for cellulosic materials.

Description

1

SPECIFICATION

Improvements in or relating to organic compounds GB 2 160 522 A 1 The present invention relates to sulphomethylated aminoesters useful as finishing agents for fibrous 5 substrates, particularly as softening agents, and their preparation.

The invention provides a sulphomethylated amino-ester which is a reaction product of an alcanolamine of formula I HO-R4-NHIR, where R, is hydrogen, Cl-4alkyl, -R5-OH or4- C1-12-)-,, NR2R3 R2 and R3 are, independently, hydrogen, -R5-OH or Cl-4alkyl R4 and R5 are, independently, 1,2-ethylene or 1,2-propylene and n is 2 or 3 or a mixture thereof, with a fatty acid of formula 11 R-COOH 1 10 11 where R is C11-21alkyl; C11-21alkenyl; hydroxy substituted C11-21alkyl or C11-21alkenyl; or a mixture of such alkyl and alkenyl or a functional derivative thereof.

Any alkyl as R,, R2 or R3 is preferably methyl or ethyl, especially methyl. A preferred significance for R4 or R5 is independently 1,2-ethylene, -R4-OH or -RF,-OH being preferably p- hydroxyethyi.

R, is preferably hydrogen or -R5-0H, more preferably hydrogen or phydroxyetheyl.

The alkyl or alkenyl moiety of R may be branched or linear. Preferably R is non substituted alkyl, alkenyl or a mixture of alkyl and alkenyl, more preferably C13-21alkyl, C13- 21alkenyl or r a mixture thereof, particularly 25 C15-21alkenyl or a mixture thereof, especially those derived from technical mixtures of fatty acids.

Suitable fatty acids R-COOH include lauric acid, myristic acid, palmitic acid, isopalmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic, acid arachidic acid, behenic acid or mixtures thereof, particularly those derived from technical mixtures of fatty acids, e.g. tallow fatty acid, coconut acid, isopalmitic acid, isostearic acid and mixtures of stearic and isostearic acids. By isopalmitic acid or isostearic acid is meant a 30 technical mixture of isomers such as disclosed for example in US Patent 2 812 342 or in Kirk-Othmer's "Encyclopedia of Chemical Technology", 3rd edition, vol. 4, page 862.

More preferably R-COOH is a saturated aliphatic fatty acid or a mixture of saturated aliphatic fatty acids, particularly stearic acid or steariclisostearic acid.

Preferred alcanolamines of formula 1 are mono- and di-ethanolamine, particularly diethanolamine. 35 A suitable functional derivative of the fatty acid of formula 11 may be for example the acid halogenide, e.g.

acid chloride or bromide, the anhydride and the methyl or ethyl ester.

In general, the amino-esters produced from the reaction of the alcanolamine of formula 1 with the fatty acid of formula 11 or a functional derivative thereof, conform to the formula Ill R- CO-O-R4-NHRo Ill where R10 is hydrogen, -R5-0H, -Rs-O-CO-R or4-CH2--,NR20 45 R30 R20 is hydrogen, Cl-4alkyl, -CO-R, -R5-OH or -R5-0-CO-R R30 is hydgrogen, Cl4alkyl, -R5-OH or -R5-OH or -R5-0-CO-R and R, R4, R5 and n have a significance as given above. Depending on the compounds of formulae 1 and 11 used and their mole ratio, the resulting amino-esters may be obtained as a single compound or as a mixture. 50 The corresponding sulphomethylation products conform to the formula IV R-CO-O-R4-MR11)-CH2-SO3M IV where 55 R,, is hydrogen, Cl-4alkyl, -R5-0H, -R5-0-CO-R, -CH2-SO3M;--CH2+, -NR22R23 R21 is hydrogen, -R5-0H, Cl-4alkyl, -CO- R, -CH2-SO3M or -R5-0- CO-R R22 is Cl-4alkyl, -R5-0H, -R5-0-CO-R or -CH2-SO3M R23 is Cl-4alkyi, - R5-OH or -R5-0-CO-R M is hydrogen or a cation equivalent and 60 R, R4, R5 and n have a significance as given above. When M is a cation equivalent, it is preferably an alkali metal cation, e.g. sodium, potassium, or lithium, sodium being preferred.

2 GB 2 160 522 A 2 Preferred sulphomethylation products of the invention are those obtained by sulphomethylation of amino-esters which are the reaction products of a fatty acid of formula 11 or a functional derivative thereof, preferably stearic acid or a mixture of stearic acid and isostearic acid, with monoethanolamine or diethanolamine, particularly diathanolamine.

Particularly preferred sulphomethylation compounds of the invention are those of formula Ra R'-CO-O-CH2-CH2- N(R12)-CH2-SO3M where 10 M is as defined above 1Va R' is straight or branched primary C17-19alkyl or a mixture of such alkyl and R12 is hydrogen, -CH2CH2-0H, -CH2-CH2-0-CO-R' or -CH2-SO3M or a mixture thereof.

Most preferred sulphomethylation compounds of the invention are those obtained by sulphomethylation of the esterification product of diethanolamine with a mixture of steariclisostearic acid in a weight ratio of 65-35:35-65 in said mixture.

The sulphomethylated amino-esters of the invention are prepared by reacting an alcanolamine of formula 1 with a fatty acid of formula 11 or a functional derivative thereof, preferably a fatty acid in the free acid form, followed by sulphomethylation of non acylated primary andlor secondary amino groups present in the resulting amino-ester, with formaldehyde or a fornaldehyde yielding compound and a sulphite or S02.

The reaction between the alcanolamine of formula land the compound of formula 11 is an esterification and 20 accordingly the conditions of the reaction are selected so that the esterification of the compounds of formula 1 predominate. The reaction can be effected in the presence of an inert solvent; preferably it is carried out in the absence of a solvent, under such temperature conditions that the secondary condensation product, particularly the water produced by esterification can be evaporated or distilled off. The reaction is conveniently carried out at a temperature of from 100 to 250'C, preferably under reduced pressure.

To obtain an esterification degree as high as possible and lower the amidation to a minimum, it is preferred to use the compound of formula 11 in the free acid form and recommended to choose the mole ratio of compound of formula 11 to compound of formula 1 as low as possible. Preferably the acid of formula 11 is used in an amount of at least 0.5 mole per mole of alcanolamine of formula 1. When in the compound of formula 1 R, is primary amino group, this amino group may have a reactivity with the acid of formula 11 comparable to that of the hydroxy group. It is advantageous to use a primary N-(amino-alkyi)-aicanolamine of formula 1 in a molar ratio 1111 of 1.0.5-2, preferably 1: 1 -2. When the alcanolamine of formula 1 is diethanolam[ne, it is advantageously used in a molar ratio 1/11 of 1:0.5-2, preferably 11:0.6-2; when the alcanolamine of formula 1 is monoethanolamine, the molar ratio J111 is preferably 1:0.5A.

The course of the esterification can be followed according to known methods, e.g. by periodically determination of the distillate volume or of the acid value of the reaction mixture. Esterification is generally sufficient when for example the acid value of the reaction mixture is lower than 10 provided that the compound of formula 11 used as starting material is an acid in free form. As it will be appreciated, the resulting reaction mixture predominantly contains an amino-ester or a 40 mixture of amino-esters, particularly an amino-ester of formula Ill, optionally in admixture with a non significant amount of secondary products such as unreacted alcanolamine of formula 1 and/or a corresponding alcanolamide. If desired, the amino- ester or mixture of amino-esters may be separated from the resulting reaction mixture according to known methods. Preferably the reaction mixture is directly used for the subsequent sulphomethylation without any purification step. 45 The sulphomethylation of the resulting amino-esters is effected by reaction with formaldehyde, e.g. in the 45 form of an aqueous solution, or a formaldehyde yielding compound e.g. metaformaidehyde or paraformaidehyde, and a sulphite, e.g. an alkali metal sulphite, bisulphite or pyrosulphite or S02 in the presence of an alkali metal base. Preferred sulphites are the alkali metal pyrosulphites and bisulphites. Generally, in the course of the sulphonation, the cation of the sulphite used or of the alkali metal base 50 employed with S02 is introduced in the resulting molecule. A preferred cation is sodium. The reaction with formaldehyde is conveniently carried out in an aqueous medium at a temperature of from 50'C to the refluxing temperature, preferably from 80'C to 1 00'C. The subsequent sulphonation is preferably effected in the same reaction medium and at the same temperature as for the reaction with formaldehyde. 55 Alternatively the formaldehyde can be reacted firstwith a bisulphite or pyrosulphite to yield a compound 55 of formula V HO-CH2-SO3M V The reaction is suitably effected by mere admixture of the starting materials according to known methods, 60 e.g. by stirring in an aqueous medium and heating, e.g. at a temperature of from 30 to 70'C, preferably at 50'C. The compound of formula V is then reacted with the amino-ester under the same conditions as disclosed above forthe sulphomethylation.

3 GB 2 160 522 A 3 The amount of formaldehyde and sulphite, S02 or compound of formula V required tor the suiphomethylation mainly depends on the desired sulphomethylation degree. Before carrying out the sulphomethylation it is recommended to titrate the reactive hydrogen atoms bound to nitrogen atoms, present in the reaction mixture which results from esterification. This titration may be carried out according to known methods, e.g. with perchloric acid in glacial acetic acid; it gives the equivalent weight of amino-ester per gramm-equivalent of amino group capable of being sulphomethylated and is referred to in the following text as "amine val".

Advantageously the formaldehyde, form a ldhyde-yielding compound or compound of formula V is used in an amount of at least 0.2 mole per amine val, the upper limit being as high as required to ensure sulphomethylation of all the reactive amine groups present in the molecule. Preferably the formaldehyde, 10 formaldehyde-yielding compound or compound of formula V is employed in an amount of from 0.2 to 2.0, more preferably 0.8 to 1.6, moles per amine val.

The sulphite or S02 used for the sulphonation is advantageously used in a mole ratio equivalent to, preferably not lower than, that of the formaldehyde or formal dehyde-yiel ding compound. The ratio of moles sulphite or S02 to amine val lies within the same ranges as indicated above for the formaldehyde, the mole 15 ratio sulphite or S02 to formaldehyde (or formaldehyde-yielding compound) being conveniently 1-1.1: 1.

The resulting sulphomethylated compounds may be isolated and purified using conventional techniques. Preferablythe reaction mixture is used without a purification step. It may contain secondary products such as unreacted starting material, sulphomethylated amino-alcohols, non sulphomethylated esters, non sulphomethylated amides and/or sulphomethylated hydroxyalkylaminoalkylarnicles.

The sulphomethylated amino-esters of the invention are useful as finishing agents forfibrous textile and non-textile substrates, particularly as softening agents. They impart softness properties to the substrate and are particularly suitable forfinishing optically brightened substrates, the degree of optical whiteness and the hydrophily of the optically brightened substrates being not significantly impaired. Depending on the conditions or agents used, the degree of optical whiteness is maintained or even improved. The compounds 25 of the invention may be used in purified form or in the form of the final reaction mixture; the latter is preferred on the economical point of view as the secondary products which may be present do not deleteriously affect the properties of the sulphomethylated amino-esters. Compounds obtained by a high and selective esterification rate of the starting alcanolamines and in which a maximum of the amino groups capable of being sulphomethylated are sulphomethylated, are preferred; they have good softening 30 properties without impairing the hydrophily of the substrate and when they are applied to an optical brightened substrate, they do not deleteriously affect the optical brightening.

Suitable substrates include hydrophilic textile materials comprising natural, synthetic or semi-synthetic fibres, and paper. Preferred substrates are paper and textile materials containing natural or regenerated cellulose, e.g. cotton, linen, jute or hemp, optionally blended with synthetic fibres such as polyester or polyamide. The material may be in any conventional form, for example as fibres, yarn, woven or knitted goods, non-wovens, paper, felts, velvet, carpets or tufted goods.

The finishing of the substrate with the softening agents of the invention may be carried out according to known methods. The sulphomethylated amino-esters may be applied by any conventional textile finishing technique, for instance by exhaustion from an aqueous solution with a long or short liquor to goods ratio 40 conveninently at a temperature from 15 to 40'C. They are applicable within a wide pH region from alkaline to acidic, e.g. from about 3.5 to 9, the neutral to slightly acidic pH conditions being preferred, particularly a pH from 7 to 4.5.

The softening agents of the invention are preferably applied to a cellulosic substrate optically brightened with an optical brightener such as commonly used for cellulosic materials. Such optical brighteners are known and disclosed e.g. in US Patents 3 970 647 and 3 018 287, G13 Patents 1313 469,896 553,11243 276 and 967 110, Canadian Patent 921658, German Patents 731 558,1793 982 and 1795 047, German published patent applications 1811715,1963 065, 2 065 195, 2 233 429,2 403 455,2 430 624,2 601749 and 2 715 864 and in Swiss Patents 318 190 and 321 109. Optical brighteners of the bis- (triazinylamino)-stilbene disulphonic acid series are particularly preferred.

Alternatively, the finishing treatmentwith the sulphomethylated compounds according to the invention can be effected simultaneously with the optical brightening of the substrate. The softening agents may also be applied on a substrate which has successively been optically brightened and then dyed or printed according to known methods, in such a case the softening is preferably carried out simultaneously with the last rinsing step.

On completion of the softening treatment, the substrate can by hydroextracted or expressed and then dried conveniently, e.g. at room temperature or preferably at a temperature from 80 to 140'C.

The concentration of sulphomethylated amino-esters on the substrate can vary within wide limits depending on the desired effect and the application technique. Preferably the concentration lies between 0.3 to 10%, more preferably 0.5 to 5% based on the dry weight of the substrate.

The sulphomethylated amino-esters of the invention are obtained in the final reaction mixture as an aqueous compositions which may be further diluted with water before use. Preferred concentrated aqueous compositions contain from 3 to 50%, particularly 8 to 30% by weight of sulphomethylated compound.

4 GB 2 160 522 A Conveniently the sulphomethylated amino-esters of the invention are used in admixture with a non-ionic surfactant, preferably a non-ionic surfactant suitable for the preparation of oil-in-water emulsions. A finishing composition containing a sulphomethylated product according to the invention together with a non-ionic surfactant or a mixture of non- ionic surfactant forms also part of the invention. The non-ionic surfactant is conveniently added directly to the final reaction mixture, in an amount preferably kept as low as possible so as to obtain a stable preparation. Advantageously the amount of non-ionic surfactant is of from 3 to 50%, preferably 10 to 25% by weight of the sulphomethylated product. Further auxiliaries may be added to the finishing preparation of the invention, e.g. a fungicide.

Preferred non-ionic surfactants are those having an HLB value of from 6 to 19, more preferably 8-19, particularly those which are hydrosoluble.

The non-ionic surfactant generally is one or more compounds having at least one lipophilic hydorcarbon residue of at least 9, preferably 9-24 carbon atoms and at least one non-ionic hydrophilic residue, which is preferably a mono- or polyethylene glycol group, optionally containing propylene glycol units, orthe residue of a polyol e.g. glycerol, mannitol, pentaerythritol and sorbitol. Other suitable types include hydrophobic Pluronics and Tetronics in which the high propylene oxide content can be regarded as the lipophilic residue.

Specifictypes of non-ionic surfactants include: Products obtainable by addition of ethylene oxide (EO) and/or propylene oxide (PO) (preferably EO alone) to saturated and/or unsaturated, linear and/or branched aliphatic alcohols, alkyl phenols, fatty acids, fatty acid alkanolamides, partial fatty acid esters of polyols, and vegetable or animal fats or oils; partial fatty acid esters of polyols; EO/PO copolymers with high EO content (Pluronic type); EO/PO addition products to ethylene diamine, having a high EO content (Tetronic type).

In the addition products of EO to fatty alchols, alkyl phenols orfatty acids, the number of EO units is an average value and need not be integral.

Fatty acid residues may be saturated or unsaturated (if unsaturated, preferably monoethylenically unsaturated) and are preferably acyl groups having 9-24, preferably 12-20, carbon atoms, particularly residues of lauric, myristic, stearic and oleic acid. If an alkyl group is the sole lipophilic group, it has preferably 9-24, more preferably 9-18, carbon atoms and may be straight chain or branched. In alkylaryl groups the alkyl group preferably has 4- 12 carbon atoms and may also be straight or branched.

Preferred partial fatty acid esters of polyols are mono-, di- or triesters more preferably mono- or di-esters, especially mono-esters of aliphatic polyols having 3 or more hydroxy groups, preferably glycerol, mannitol, 30 pentaerythritol or sorbitol.

Particularly preferred surfactants are those of formula VI and VII 4 Rs--OCH2CH2±OH v] 35 (R7-CO)q-X VIl where R6 is C9-24alkyl, C9-24alkenyl or a radical of formula (a) (Rs)r 40 ( R 8) r (a) each 45 R7, independently, is Cl,_lgalkyl or Cl,_19 or Cl,_lgalkenyl or a mixture thereof R8 is C4-12alkyl X is a mono- or divalent residue of sorbitol, glycerol, pentaerythritol or of a polethylene glycol of formula so H04-CH2CH2 -0 -)-j H p is 5 to 100 q is 1 or2 r is 1 or 2 and s is 3 to 60 and the polethoxylation products of compounds of formula VII the number and length of the lipophilic residue and the number of ethyleneoxy units being so that the compound or mixture of compounds has an average HLB value of from 6 to 19, preferably 8 to 19.

The HLB values of the non-ionic surfactant may be calculated by use of a standard formula.

The finishing with the sulphomethylated amino-esters of the invention is a non-permanent treatment. It 60 has a softening effect and improves the handle of the goods. It is particularly intended for the finishing of textiles used for the manufacture of clothes.

The following Examples, in which all percentages are by weight and the temperature in degrees Centigrade, illustrate the invention.

GB 2 160 522 A 5 Example 1

285 9 (1 M) stearic acid and 105 g (1 M) diethanolamine are reacted at 160-170' under reduced pressure until no water distills off, at which point the condensation product reaches an acid number of 2.5. Titration of this produce with perchloric acid in the presence of glacial acetic acid gives an equivalent weight of 762 g 5 condensation product per gram m-equivalent of amino group capable of being sulphomethylated.

g (1.5 M) 36% aqueous formaldehyde are then added to the reaction mixture per amino group capable of being sulphomethylated (= 7 g product) and the mixture is heated to 85-100'. 390 9 (1.5 M) or 40% aqueous sodium bisulphite are then added dropwise at 85-100' and the reaction mixture is subsequently held for 6 hours atthis temperature while stirring.

20% based on the dry weight content of the above reaction mixture, of the addition product of 1 M oleyl 10 alcohol with 25 M ethylene oxide are added to the mixture followed by the addition of water at 80-900 so that the resulting preparation has a dry weight content of 13%.

Example 2

92.70 g isostea ric acid with an equivalent weig ht of 309, 81.00 g stearic acid and 63.00 g diethanolami ne 15 are reacted u nder reduced pressu re at 150-160' until no water distil Is off, at which point the condensation product reaches an acid number of 4. 5. Titration gives an equivalent weight of 1236.6 g condensation product per gramm-equivalent of amino group cable of being sulphomethylated.

22.84 9 36% aqueous formaldehyde, 50 g water and 28.03 g sodium pyrosulphite (Na2S205) are reacted at 50'for 30 minutes to give the addition product of formula V.

This addition product is added to the above mixture and the reaction mixture is subsequently held for 5.5 hours at 85-95'while stirring.

14.1 % based on the anhydrous weight of the sulphomethylated product, of the addition product of 1 M nonylphenol with 50 M ethylene oxide are added to the mixture which is then emulsified with water at 80-900 to the extent that the resulting preparation has a dry weight content of 20%.

By following the procedure of Example 1 or 2 but using the starting materials indicated in the Table below, further finishing preparations as disclosed may be obtained.

a) TABLE

Ex. Alcanolamine Acid of Mole ratio Mole formaldehyde non-ionic surfactant Dry weight No. of formula 1 formula 11 acid/alcanol- and mole bisurfactant based on the content amine sulphite per amino sulphomethy group lated product 3 Diethanolamine coconut acid 2:1 3720 1.5/1.5 as in Ex. 2 25% 25% 4 do. stearic acid 0.6:1 439 1.5/1.5 oleyl-poly 20% 18% (25)-ethylene glycol ether do. do. 0.61 443 1.75/1.75 do. 20% 18% 6 do. do. 0.6:1 445 0.85/0.85 do. 20% 18% 7 do. do, 0.6:1 435 0.21/0.21 do. 20% 18% 8 do. oleic acid 2:1 5058 1.5/1.5 do, 22% 15% 9 do. 12-hydroxy- 1.5:1 1503 1.5/1.5 as in Ex. 2 22% 20% stearic acid 17% 18% diisopropanolbehenic acid 1:1 1077 1.5/1.5 as in Ex. 4 amine 16% 13% 11 Monoethanol lauric acid 1:1 4807 1.5/1.5 oleic acid amine polyglyethy leneglycol 300 monester 16% 13% 12 N-(2-hydroxy- coconut acid 2:1 1703 1.5/1.5 do.

ethyl)ethylene diamine g condensation product per amino group per gramm-equivalent of amino group capable of being sulphomethylated G) m rl.) 0) C UI N N) 1 1 1 i i a) 7 GB 2 160 522 A 7 Application Example A Caustic soda treated cotton tricot is padded to a pick-up of 85% based on its dry weight, with an aqueous liquor containing 0.6 g/[ of the optical brightener of formula S03Na 5 N 0 - NH-b"-NI CH so 3 Na 03Na H3C-CH01-1-CH2-N-CH2CH2CN.2 10 and 30 g/I of the finishing preparation of Example 1. The impregnated substrate is then dried at 140'for 90 seconds.

A sample of the resulting cotton is further treated at 150' for 10 minutes.

Application Example B The procedure of Example A is repeated but carried out in two steps. In the first step the tricot is impregnated to a pick up of 85% based on its dry weight, with an aqueous liquor containing 0.6 g/I of the optical brightener and then dried at 140' for 90 sec. In the second step the resulting substrate is padded to a 20 pick-up of 85% based on its dry weight, with an aqueous liquor containing 30 g/I of the finishing preparation of Example 1. The substrate is then dried at 140'for 90 seconds.

Application Example C Cotton yarn which has been optically brightened with the optical brightener of Example A is introduced in an aqueous bath containing 1 g/l sodium acetate, 0.75 ml/l acetic acid and 0.5% (based on the weight of the substrate) of the finishing preparation of Example 1 (calculated as dry weight content). The liquor to goods ratio is 10: 1. The bath is heated to 30'with constant agitation over 30 minutes and maintained at 30'for a further 30 minute period. The yarn is then removed and dried.

The procedure of Examples A, B or C can be repeated but a preparation according to Exampes 2 to 12 is 30 used.

In the above Examples, the finished substrate exhibits a soft pleasing handle with the degree of optical whiteness and the hydrophily being significantly impaired, even for the further heat treated cotton tricot of ExampleA.

Claims (27)

1. A sulphomethylated amino-ester which is a reaction product of an alcanolamine of formula] HO-R4-NHI'll where R, is hydrogen, Cl-4alkyl, -R5-OH or--CH2--nNR2R+CH2-)-g3 R2 and R3 are, independently, hydrogen, -R5-OH Or Cl-4alkyl 45 R4 and R5 are, independently, 1,2-ethylene or 1,2-propylene and n is 2 or 3 or a mixture thereof, with a fatty acid of formula 11 R-COOH 11 where R is C11-21alkyl; C11-21alkenyl; hydroxy substituted C11-21alkyl or C11-21alkenyl; or a mixture of such alkyl and alkenyl or a functional derivative thereof.

2. Asulphomethylated amino-ester according to Claim 1, in which R4or R5 is 1,2-ethylene.

3. A sulphomethylated amino-ester according to Claim 1 or 2, in which R is C14-22alky], C14-22alkenyl or a mixture thereof.

1 40 8 GB 2 160 522 A 8

4. A sulphomethylated amino-ester according to anyone of the preceding claims, in which the amino-ester is of formula Ill R-CO-O-R4-NHIR1o where Rjo is hydrogen, -RE-OH, -R5-0-CO-R or--CH2.nNR2OR30 R20 is hydrogen, Cl-4alkyl, -CO-R, -R5-OH or -R5-0-CO-R 10 R30 is hydrogen, Cl- 4alkyl, -R5-OH or -R5-0-CO-R and R, R4, R5 and n are as defined in Claim 1.

5. Asulphomethylated amino-ester according to anyone of the preceding claims, of formula W R-CO-O-R4-N(R11)-CH2SO3M IV 15 where IR,, is hydrogen, Cl-4alkyl, -R5-0H, -R5-0-CO-R, -CH2-SO3M,+CH2+ nNHR21,+CH2+,,N(R22)-CH2-- S03M or +CH2 +,ffi22R23 20 R21 is hydrogen, -Rr,-OH, Cl-4alkyl, -CO-R, - CH2-SO3M or -R5-0-CO-R R22 is Cl-4alkyl, -R5-0H, -R5-0-CO-R or -CH2-SO3M R23 is Cl-4alkyl, -R5-OH or -R5-0-CO-R M is hydrogen or a cation equivalent and R, R4, RE; and n are as defined in Claim 1. 25

6. A sulphomethylated amino-ester according to Claim 5, of formula 1Va R'-CO-O-CH2-CH2-N(R12)-CH2-SO3M 1Va where M is hydrogen or a cation equivalent R' is straight or branched primary C17-19alkyl or a mixture of such alkyl and R12 is hydrogen, -CH2CH2-0H, - CH2-CH2-0-CO-R'or -CH2-SO3M or a mixture thereof.

7. A sulphomethylated amino-ester according to anyone of the preceding claims, which amino- ester is the reaction product of diethanoiamine with a mixture of stearic/isostearic acid.

8. A sulphomethylated amino-ester according to Claim 7 in which the weight ratio of the stearicl isostearic acid mixture is 65-35:35-65.

9. A process for the production of a sulphomethylated amino-ester according to anyone of Claims 1 to 8, which process comprises reacting an alcanolamine of formula 1 HO-R4NHI31 where R, and R4 are as defined in Claim 1 or a mixture thereof with a fatty acid of formula 11 R-COOH Ill 5 1 11 45 where R is as defined in Claim 1 or a functional derivative thereof and sulphomethylating non acylated primary andlor secondary amino groups of the resulting amino-ester, with formaldehyde or a formaldehydeyielding compound and a sulphite, S02 or a compound of formula V HO-CH2-SO3M where M is hydrogen or a cation equivalent.

10. A process according to Claim 9, in which the fatty acid of formula 11 is reacted in an amount of at least 55 0.5 mole per mole of alcanolamine of formula 1.

11. A process according to Claim 10, in which when the alcanolamine of formula 1 is diethanolamine the mole ratio of diethanolamine to the fatty acid of formula 11 is 1:0.5-2.

12. A process according to anyone of Claims 9 to 11, in which the formaldehyde, formaldehyde-yielding compound or compound of formula V is used in an amount of at least 0.2 mole per amine val.

13. A process according to Claim 12, in which the formaldehyde, formaldehyde-yielding compound or 60 compound of formula V is used in an amount from 0.2 to 2.0 per amine val.

14. A process according to anyone of Claims 9to 13, in which the mole ratio sulphite or S02tO formaldehyde or formaldehyde yielding compound is 1 -AA.

15. A suiphomethylated amino-ester substantially as hereinbefore described with reference to Examples 1 to 12.

9 GB 2 160 522 A 9

16. A process for finishing a fibrous substrate comprising applying to the substrate a sulphomethylated amino-ester as defined in any one of Claims 1 to 8 and 15.

17. A process according to Claim 16 in which the substrate is paper or a textile substrate comprising natural or regenerated cellulose.

18. A process according to Claim 16 or 17 in which the finishing is carried out simultaneously with or 5 after the optical brightening of the substrate.

19. A process according to anyone of Claims 16to 18, in which the sulphomethylated amino-ester concentration on the substrate is from 0.3 to 10% based on the dry weight of the substrate.

20. A process substantially as hereinbefore described with reference to anyone of Examples Ato C.

21. An aqueous composition containing from 3 to 50% by weight of a sulphomethylated amino-ester as 10 defined in any one of Claims 1 to 15.

22. An aqueous composition according to Claim 21 containing additionally a non-ionic surfactant.

23. An aqueous composition according to Claim 22 in which the non-ionic surfactant has an average HLB valuefrom6to'19.

24. An aqueous composition according to Claim 22 or 23 in which the nonionic surfactant is selected from products obtainable by addition of ethylene oxide (EO) and/or propylene oxide (PO) to saturated and/or unsaturated, linear and/or branched aliphatic alcohols, alkyl, phenols, fatty acids, fatty acid alkanolamides, partial fatty acid esters of polyols, and vegetable or animal fats or oils; partial fatty acid esters of polyols; EO/PO copolymers with high EO content (Pluronic type); EO/PO addition products to ethylene diamine, having a high EO content (Tetronic type) or a mixture thereof.

25. An aqueous composition according to Claim 24 in which the non-ionic surfactant is a compound of formula VI or VII R6-(-OCH2CH2-POH (R7-CO)q-X where R6 is C9-24alkyl, C9-24alkenyl or a radical of formula (a) (R8), each V1 W] ( R 8) r,.

(a) R7, independently, is C11_119alkyl or C11-19alkenyl or a mixture thereof RB is C4-12alkyl X is a mono- or divalent residue of sorbitol, glycerol, pentaerythritol or of a polyethylene glycol of formula HO+CH2CH2-0+.H p is 5 to 100, q is 1 or 2 r is 1 or 2 and s is 3 to 60 and the polethoxylation products of compounds of formula V11 and a mixture thereof.

26. An aqueous composition according to anyone of Claims 22to 25, containing from 3 to 50% by weight of the non-ionic surfactant based on the weight of the sulphomethylated amino-ester.

27. An aqueous composition substantially as hereinbefore described with reference to Examples 1 to 12.

Printed in the UK for HMSO, D8818935, 1V85, 7102.

Published by The Patent Office, 25 Southampton Buildings, London, WC2A lAY, from which copies may be obtained.