FR2566399A1 - NEW ESTERS, THEIR PREPARATION AND THEIR APPLICATION AS FINISHING AGENTS - Google Patents

Abstract

THE INVENTION AIMS AT THE SULFOMETHYLATION PRODUCTS OF AMINO-ESTERS OBTAINED BY REACTION OF AN ALKANOLAMINE OF FORMULA: HO-R -NHR IN WHICH R MEANS A 1,2-ETHYLENE OR 1,2-PROPYLENE GROUP AND R MEANS L 'HYDROGEN OR AN ALKYL REMAINING SUBSTITUTE, WITH FATTY ACID. THESE PRODUCTS MAY BE USED FOR THE FINISHING OF FIBROUS MATERIALS, PARTICULARLY AS SOFTENING AGENTS FOR CELLULOSIC MATERIALS.

Description

The subject of the present invention is new esters, their preparation and

  their application as finishing agents for fibrous substrates,

  in particular as softening agents.

  More particularly: the invention relates to the sulfomethylation product of an amino ester,

  the amino ester being the reaction product of an alkanol-

amine of formul I

HO-R NHR 1 (I)

  in which R1 represents hydrogen, a C1-C4 alkyl group or a group -RH or H2 --- NR2R3 R2 and R3 represent, independently of one another, hydrogen, a group -R5-OH or a C1-C49 alkyl group R4 and R5 represent, independently of one another, a 1,2-ethylene group or 1,2-propylene, and n signifies 2 or 3, or of a mixture of alkanolamines of formula I, with a fatty acid of formula II

R-COOH (II)

  in which R represents a C1-C21 alkyl group, a C1-C21 alkenyl group, a C1-C21 alkyl group or C1-C21 alkenyl substituted by a hydroxy group, or a mixture of these alkyl and alkenyl groups,

  or a functional derivative of this acid.

  When R1, R2 or R3 signifies an alkyl group, it is preferably a methyl or ethyl group, especially a methyl group. R4 and R5, independently of each other, preferably mean

  a more special 1,2-ethylene group, -R4-OH or -R5-OH-

a 5-hydroxyethyl group.

  R1 preferably signifies hydrogen or a group -R5oOH, more especially hydrogen or

a 5-hydroxyethyl group.

  R can be a linear or branched alkyl or alkenyl group. Preferably, R denotes an unsubstituted alkyl or alkenyl group or a mixture of these groups, in particular a C 3 -C 21 alkyl or C 13 -C 21 alkenyl group or a mixture of these groups, more particularly a C 15 alkyl group. C2 or C -C2 alkenyl or a mixture of these groups, especially those derived from technical mixtures of fatty acids. Suitable fatty acids R-COOH include

  lauric acid, myristic acid, palmitic acid

  that, isopalmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleVic acid, arachidic acid, behenic acid and their mixtures, in particular those derived from technical mixtures of fatty acids, for example fatty acid

  tallow, coconut oil acid, isopalmi-

  tick, isostearic acid and acid mixtures

  stearic and isostearic acid. By isopalmi acid-

  tick or isostearic means a technical mixture of isomers as described for example in the patent

  No. 2,812,342 or in Kirk-Othmer, "Encyclo-

  pedia of Chemical Technology ", 3rd edition, volume 4,

page 862.

  R-COOH acid is more particularly a saturated aliphatic fatty acid or a mixture of acids

  saturated aliphatic fat, especially stearic acid

  that or a mixture of stearic acid and isostearic acid The preferred alkanolamines of formula I are mono- and di-ethanolamine, in particular

diethanolamine.

  As an appropriate functional derivative of the fatty acid of formula II, there may be mentioned, for example, the acid halide, for example the chloride or the

  acid bromide, acid anhydride and methyl ester

lique or ethyl.

  In general, the amino ester resulting from the reaction of the alkanolamine of formula I with the acid

  fat of formula II or its corresponding functional derivative

  pond to the formula III R-CO-0-R4-NHRio (III) in which Rlo represents hydrogen or a group -R5-OH, -R-0-CO-R or CH2. NR20R30, R20 represents hydrogen or a C -C4 alkyl group, -CO-R, -R5-OH or -R5- 0-CO-R, R30 represents hydrogen or a C 1 -C 4 alkyl group, -R5- OH or -R5-0-CO-R, and

  R, R4, R5 and n have the meanings given above.

  is lying. Depending on the compounds of formulas I and II used and their molar ratio, the resulting amino-ester can

  be a well-defined compound or a mixture of compounds.

  The corresponding sulfomethylation product is a product corresponding to the formula IV R-CO-0-R4-N (R1l) -CH2-SO3M (IV) in which

  R, R4, R5 and n have the meanings given above.

  ment, R11 represents hydrogen or a C1-C49-alkyl group -R5-OH, R5-O-CO-R, -CH2-SO3M, --CH2-n NHR21, 5 23 - (- H2- nHR21 '- --CH2 -nJ-N (R22) -CH2- SO3M or - CH2 + -n R22R23, R21 represents hydrogen or a C1-C4 alkyl group, -R5-OH, -CG-R, -CH2S03M or - R5-0-CO = R, R22 represents a C1-C4 alkyl group -R5-OH, -R5-0-CO-R or -CH2: S03M, R23 represents a C1-C alkyl group,: 5 $ 0H or -R5- OCO-R, and

  M represents hydrogen or the equivalent of a cation.

  When M represents the equivalent of a cation, it is preferably an alkali metal cation such as sodium, potassium or lithium, of

preferably sodium.

  The preferred sulfomethylation products are those obtained by sulfomethylation of amino esters resulting from the reaction of a fatty acid of formula-II or of a functional derivative of this acid, preferably stearic acid or a mixture of acid stearic and isostearic acid, with monoethanolamine or

  diethanolamine, in particular diethanolamine.

  Particular sulfomethylation products

  Rely preferred are those corresponding to the formula IVa R'-CO-OoCH2-CH2N (R12) -CH2-SO3M (IVa) in which M has the meaning given above, R 'represents a linear or branched C17Cl9 primary alkyl group or a mixture of such alkyl groups, and R12 represents hydrogen or a group -CH2-CH2-OH, -CH2-CH2-0-CO-R 'or -CH2-SO3M,

and their mixtures.

  The more particularly preferred sulfomethylation products are those obtained by sulfomethylation of the esterification product of diethanolamine with a mixture of stearic acid and isosteraric acid, the weight ratio of these

  last in said mixture being 65-35: 35-65.

  The sulfomethylated amino esters of the invention

  tion are obtained by reaction of an alkanolamine of formula I with a fatty acid of formula II or its functional derivative, preferably a fatty acid in the form of free acid and subsequent sulfomethylation of the primary and / or secondary non-acylated amino groups

  present in the resulting amino ester, with the formal-

  dehyde or a formaldehyde-releasing compound and a

sulfite or SO2.

  The reaction between the alkanolamine of formula I and the compound of formula II being an esterification, the conditions of the reaction will therefore be chosen in such a way that the esterification of the compound of formula I is favored. The reaction can be carried out in the presence of an inert solvent; preferably, it is carried out in the absence of solvent, under temperature conditions such

  that the secondary condensation product, in particular

  bind the water produced by esterification can be evaporated or removed by distillation. The reaction is advantageously carried out at a temperature comprised

  between 100 and 250 C, preferably under reduced pressure.

  In order to obtain as high a degree of esterification as possible and to minimize amidation, the compound of formula II should preferably be used in the form of free acid and a molar ratio of the compound of formula II to the compound should be chosen. of formula I, as low as possible. Preferably, the acid of formula II is used in an amount of at least 0.5 mole per mole of alkanolamine of formula I. When -NR2R3 signifies a primary amino group in the compound of formula I, the reactivity of this amino group with the acid of formula II can be compared to that of the hydroxy group. When the compound of formula I used is a primary N- (aminoalkyl) alkanolamine, the molar ratio of the compound of formula I to the compound of formula II

  is advantageously 1: 0.5-2D, preferably l: 112.

  When the alkanolamine of formula I used is diethanolamine, the molar ratio of the latter to the compound of formula II is advantageously 1: 0.5o2 preferably O0 1: O06-2oet when the alkanolamine of formula I used is monoethanolamine, the molar ratio thereof

  the compound of formula II is preferably: 105-1.

  The process of esterification can be

  follow-up according to known methods, for example by determining periodi-

  only the distilled volume or the acid number of the reaction mixture.

  It is considered that the alkanolamine of formula I is generally esterified

  at a satisfactory rate when for example the acid number of the

  reaction mixture is less than 10, provided that the compound of formula II used as starting material is acid in the form

free.

  Note that the reaction mixture results

  both essentially contain an amino ester or a mixture of amino esters, in particular an amino ester of formula III, optionally in admixture with minor quantities of secondary products such as the alkanolamine of formula I 'which has no not reacted and / or the corresponding alkanolamide. If desired, the amino ester or mixture of amino esters can be isolated from the resulting reaction mixture, according to known methods. The reaction mixture is preferably used directly for the

  subsequent sulfomethylation, without prior purification.

  The sulfomethylation of the resulting amino ester is carried out by reacting the latter with the

  formaldehyde, for example in the form of a solution -

  aqueous, or with a formaldehyde releasing compound such as metaformaldehyde or paraformaldehyde, and an alkali metal sulfite, for example a sulfite, bisulfite or pyrosulfite, or SO2 in the presence of an alkali metal base. The preferred sulfites are the alkali metal pyrosulfites and bisulfites. During the sulfonation, the cation of the sulfite used or the cation of the alkali metal base used with SO 2,

  is generally introduced into the resulting molecule

  aunt. The preferred cation is that of sodium.

  The reaction with formaldehyde advantageously carried out in an aqueous medium and at a temperature between 500 ° C. and the reflux temperature,

  preferably between 80 and 100 Co The sulfonation

  quente is preferably carried out under the same conditions of reaction medium and temperature as

  those used for the reaction with formaldehyde.

  Alternatively, formaldehyde can

  be reacted first with a bisulfite or pyro-

  sulfite to give a compound of formula V

HO-CH2-S03M (V)

  in which M has the meaning already given.

  The reaction is carried out in an appropriate manner by simple mixing of the starting materials according to known methods, for example with stirring in an aqueous medium and with heating, for example at a temperature

  between 30 and 70 C, preferably 50 C.

  The compound of formula V is then reacted with the amino ester under the same conditions as those

  described above for sulfomethylation.

  The amount of formaldehyde and the amount of sulfite, SO2 or compound of formula V necessary for sulfomethylation depend essentially on the degree of sulfomethylation desired. Before carrying out the sulfomethylation, it is recommended to measure the reactive hydrogen atoms which are linked to the nitrogen atoms present in the reaction mixture resulting from the esterification. This assay can be carried out according to known methods, for example with perchloric acid in glacial acetic acid; this dosage

  gives the corresponding amino-ester weight & an equi-

  equivalent to a gram of amino group capable of being sulfomethylated, and will be designated in the remainder of the

present description "amine val" o

  The formaldehyde, the formaldehyde-releasing compound or the compound of formula V is advantageously used in an amount of at least 0.2 mole per amine val, the greater amount being as high as necessary to ensure the sulfomethylation of all the reactive amino groups present in the molecule. The formaldehyde, the formaldehyde-releasing compound or the compound of formula V is preferably used in an amount between 0.2 and 2.0 moles, more particularly in an amount

  between 0.8 and 1.6 mole per amine val.

  The sulfite or SO used for sulfona-

  tion is advantageously used in an identical molar ratio, preferably slightly higher, than that

  formaldehyde or formaldehyde releasing compound.

  The amount of moles of tulfite or SO2 relative to the amine val, is of the same order as that indicated above for formaldehyde, the molar ratio of sulfite or SO2 to formaldehyde, or to the compound released from formaldehyde, being advantageously of 1-l911: o The resulting sulfomethylated compound can

  be isolated and purified according to the usual methods.

  The reaction mixture is preferably used as it is without prior purification. It may contain side products such as unreacted starting materials, sulfomethylated amino alcohols, non-sulfomethylated esters, non-sulfomethylated amides and / or sulfomethylated hydroxyalkylaminoalkylamides. The sulfomethylated amino esters of the invention can be used as textile finishing agents and other materials made of fibers, in particular as softening agents. They confer a softening effect on the treated substrate and are particularly suitable for the finishing of optically azure substrates, the degree of optical whiteness and the hydrophilicity of optical azure substrates =

  being very little influenced.

  the agent used, the degree of optical whiteness

  is maintained or even improved. The compounds of the invention

  tion can be used in a purified form or in the form of the final reaction mixture; from an economic point of view, the compounds of the invention are preferably used in the form of the final reaction mixture, since the secondary products possibly

  present do not affect the properties of amino-

  sulfomethylated esters. The preferred compounds are those obtained with a high and selective esterification rate of the starting alkanolamines and in which a maximum of amino groups capable of reacting have been sulfomethylated; these compounds provide a good softening effect on the substrate without modifying the hydrophilicity and the optical whitening is not influenced

  when applied to an optically azure substrate

  only. Suitable substrates include hydrophilic textile materials comprising natural, synthetic or semi-synthetic fibers, and paper. The preferred substrates are paper and textile materials containing natural or regenerated cellulose, such as cotton, linen, jute or hemp, optionally in admixture with synthetic fibers such as polyesters or polyamides. The material can be in any form, for example in the form of fibers, threads, woven or knitted articles, nonwovens, paper, felt, velvet, carpets or tufted articles. The finishing of the substrates with the adducting agents of the invention can be carried out according to known methods. The sulfomethylated amino esters of the invention can be applied according to any conventional technique for finishing textiles,

  for example by impregnation, such as foular-

  spraying, spraying or application. with foam, or by exhaustion in an aqueous bath, in a long or short bath advantageously at a temperature between and 40 C. They can be used in a wide pH range ranging from an alkaline to acid pH, for example to a pH around 3.5 to 9, preferably under neutral to slightly acidic pH conditions,

  especially at a pH of 7 to 495.

  The softening agents of the invention are preferably applied to a cellulosic substrate treated with an optical brightener usually used for the brightening of cellulosic materials. Such optical brighteners are known and are described, for example, in US Pat. Nos. 3,970,647 and 3 018,287, in British Patents Nos. 1,313,469, 896,533, 1,243,276 and 967,110, in Canadian Patent Nos. 921,658, in German Patents Nos. 731,558, 1,793,982 and

  1. 795 047, in the German patent applications.

  published in 1,811,715, 1,963,065, 2,056,195, 2,233,429, 2,403,455, 2,430,624, 2,601,749 and 2,715,864 and in Swiss Patents Nos. 318,190 and 321,109. Particularly preferred optical brighteners are those belonging

  to the bis- (triazinylamino) -stilbene- acid series

disulfonic.

  According to another variant, the finishing with the sulfomethylated compounds of the invention can be carried out simultaneously with the optical brightening of the substrate. The compounds can also be applied to a substrate which has first been optically brightened and then dyed or printed according to known methods, the softening treatment in this case preferably being carried out at the same time

  than the last rinse step.

  When the softening treatment has ended, the substrate can be drained or expressed and then: dried, for example at room temperature or preferably

  at a temperature between 80 and 140 C.

  The concentration of sulfomethylated amino ester on the substrate can vary within wide limits

  depending on the desired effect and the application technique.

  Preferably, the concentration is between-

  0.3 and 10%, more particularly between 0.5 and 5%

  relative to the weight of the substrate in the dry state.

  The sulfomethylated amino esters of the invention are obtained in the final reaction mixture in the form of an aqueous composition which can be

  further diluted with water before use.

  The concentrated aqueous compositions which are preferred are those containing from 3 to 50%, in particular of

  8 to 30% by weight of sulfomethylated compound.

  The sulfomethylated amino esters of the invention

  tion are advantageously used in admixture with a nonionic surfactant, preferably a

  nonionic surfactant suitable for the preparation

  ration of oil in water emulsions. The invention

  also includes a finishing composition containing

  In addition, in addition to the sulfomethylated product according to the invention, 9 a nonionic surfactant or a mixture of nonionic surfactants. The nonionic surfactant is advantageously added directly to the final reaction mixture, in an amount also preferably

  as low as possible to obtain a stable preparation.

  The amount of nonionic surfactant added is advantageously from 3 to 50%, preferably from

  25% by weight relative to the weight of the sulfomethylated product.

  The finishing compositions of the invention may contain other auxiliary products9 for example

a fungicide.

  Preferred nonionic surfactants

  are those with an HLB value of 6 to 19.9 more

  especially from 8 to 19, and in particular those which are water-soluble.

  The nonionic surfactant is generally

  LEMENT consisting of one or more compounds having at least one lipophilic hydrocarbon residue containing at least 9 carbon atoms9 preferably from 9 to 24 carbon atoms, and at least one non-ionic hydrophilic residue, the latter preferably being a group

  mono- or polyethylene glycolic containing any-

  propyleneoxy9 units or the rest of a

  polyol, such as glycerol, mannitol, penta-

  erythritol and sorbitol. Other types of suitable nonionic surfactants include hydrophobic copolymers such as those sold under the brands Pluronic and Tétronic in which the high number of units

  propyleneoxy can be considered as lipophilic residue.

  Specific types of nonionic surfactants include: Products obtained by the addition of ethylene oxide and / or propylene oxide, preferably

  ethylene oxide alone, on alipha-

  saturated and / or unsaturated, linear and / or branched ticks, alkylphenols, fatty acids, alkanolamides of fatty acids, partial polyol esters with fatty acids and fats or vegetable or animal oils, partial polyol esters with fatty acids, ethylene oxide copolymers and

  propylene oxide with a high content of ethylene units-

  oxy (of the Pluronic type), and the adducts of ethylene oxide and propylene oxide on ethylenediamine having a high content of units

ethyleneoxy (Tetronic type).

  In the adducts of ethylene oxide on fatty alcohols, alkylphenols or fatty acids, the number of ethyleneoxy units

  is an average number which can be fractional.

  The fatty acid residues can be saturated or unsaturated, these residues preferably containing a single ethylenic bond when they are unsaturated; the fatty acid residues are preferably acyl groups having from 9 to 24 carbon atoms, preferably from 12 to 20 carbon atoms, in particular the residues of lauric, myristic, stearic and oleic acid. When an alkyl group represents the only lipophilic group, it preferably contains from 9 to 24 carbon atoms, more particularly from 9 to 18

  carbon atoms, and can be linear or branched.

  In alkylaryl groups, the alkyl residue preferably contains from 4 to 12 carbon atoms and can be

linear or branched.

  Partial polyol esters with

  fatty acids are preferably mono-, di: or tri-

  esters, more particularly mono- or diesters, especially monoesters of aliphatic polyols containing 3 or more hydroxy groups, preferably those of glycerol, mannitol, pentaerythritol or sorbitolo

  Particular nonionic surfactants

  particularly preferred are those corresponding to formulas VI and VII R6 t == OCH2CH2 p O (VI) 2o (R7'- CO) q: x -. (R7 === GO) q = X (VII) in which R6 represents a C9-C24 alkyl group, C9-C24 alkenyl or a radical of formula (a) (R8) r (a) o R8 represents a C4-C12 alkyl group and r signifies 1 or 2, each R7, independently, represents a C1-C19 alkyl or C1-C19 alkenyl group or a mixture of such groups,

  X represents a monovalent or bivalent residue of the sor-

  bitol, glycerol, pentaerythritol or a poly-

ethylene glycol of formula

HO- ± CH2CH2-0 ± H

  o s means a number from 3 to 60, p means a number from 5 to 100, and q means 1 or 2, and the polyethoxylation products of the compounds of

  formula VII, the number and the length of the lipo-

  phile and the number of ethyleneoxy units being such that the compound or mixture of compounds has a value

  HLB average from 6 to 19, preferably from 8 'to 19.

  The HLB values of the nonionic surfactants can be calculated according to the methods

known.

  Finishing with sulfo amino esters

  methylated of the invention is a non-permanent treatment.

  It gives a softening effect and improves the feel of articles. It is particularly intended for the finishing of textiles used for manufacturing

clothing.

  The following examples illustrate the present invention without in any way limiting its scope. In these examples, the percentages are by weight and the

  temperatures are given in degrees Celsius.

Example 1

  285 g (1 mole) of stearic acid and 105 g (1 mole) of diethanolamine are reacted at 160-170 and under reduced pressure until it no longer separates out of water by distillation; the acid number of the condensation product is then 2.5. The dosage of this product with perchloric acid in

  presence of glacial acetic acid gives an -equal weight

  worth 762 g of condensation product per equivalent

  slow gram of amino group likely to be sulfo-

  methyl. Then added to the reaction mixture

  g (1.5 mole) of a 36% aqueous solution of formal-

  dehyde per amino group capable of being sulfomethylated (= 762 g of condensation product) and the mixture is heated to 85100 390 g (1.5 mol) of a 40% aqueous solution are added dropwise to 851100D sodium bisulfite and the reaction mixture is kept for 6

  hours at this temperature with stirring.

  The product obtained by adding 25 moles of ethylene oxide to one mole of olepic alcohol is added to the mixture in an amount representing% of the dry product content of the above reaction mixture, and water is added. at 80O90 so that the resulting preparation has a product content

13% dry.

Example 2

  92.7 g of isostearic acid are reacted under reduced pressure at 150-160 with a molar weight equivalent to 306.81 g of stearic acid and 63 g of diethanolamine, until it does not separates more water by distillation; the acid number of the condensation product is then 4D50. The assay gives an equivalent weight of 1236.6 g of condensation product per gram equivalent of amino group capable of being sulfomethylated. 22.84 g of 36% formaldehyde aqueous solution, 50 g of water and 28.03 g of sodium pyrosulfite (Na2S205) are reacted at 50 for 30 minutes to obtain the adduct of formula V. This product addition is added to the above mixture and heated to 85-95 for 5 hours and

half with stirring.

  The product obtained by adding 50 moles of ethylene oxide to one mole of nonylphenol in an amount representing 14.1% of the dry weight of the sulfomethylated product is added to the mixture, and the mixture is emulsified with water at 80-90 so that the resulting preparation has a dry product content

20%.

  The finishing preparations indicated in the table below were obtained by proceeding as described in example 1 or 2 and using the

  starting materials which are indicated in this table.

(Table see next page)

BOARD

BOARD

  h s * | o Moles of formal-% of agent Ex. AlcanolamiineAcd e Rportm- Ex. A1 canol ami ne Acid of Ratio mo-> C O dehyde et molea Surfactant Content of formula I formula II of surfactant bisulfite relative to dry weight alkanolamine 4. by tif group not to product (in%)

At, 4 4D0

amino ionic sulfo-

  o _ 0 0 methylation Acid as in

  3 Diethanolamine coconut oil 2: 1 3720 I, 5/15 'ex. 2 - 25 25.

  coconut oil 4 do. Stearic acid 0.6: 1,439 1.5 / 1.5 stretch poly (25) .. ethylene glyco-20 18

lique de lVal-

  cool allqu O do. do. 0.6: 1,443 1.75 / 1.75 do. 20 '18 6 do. do. 0.6: 1,445,085 / 0.85 do. 20 18 7 do. do. 0.6: 1,435 0.21 / 0.21 do. 20 18 8 do. Acidolated! That 2: 1 5058 1 5/195 do. o 22 15 9 do. Acid 12-hy- 5: 1 1503 175/195 as in 22 20 stearic droxy. lVexo 2 Diisopropanol-.1: 1 1077.5 / 1.5 as in 17. 18 amine Behenic acid ex. 4 1 Monoethanol Lauric acid 1: 1 4807 1.5 / 1.5 mono-coleate 1 13 '

polyethylene amine

  leneglycol. 12 N- (2-hydroxy-acid 2: 1 1703 15 / 1q5 300 16 13

ethyl) ethyl oil from o.

  diamine coco oc prquvln-amedgrueaios '* per gram-equivalent of amino group capable of being sulfomethylated' o Example of application A A cotton knitted fabric treated with caustic soda has a padding at a bath absorption rate of 85% relative to the weight of the substrate in the dry state, with an aqueous bath containing 0.6 g / 1 of the optical brightener of formula SO3Ne 1S03Na T

NH N CH =

H3C-CHOH-CH2-N-CCH2CN 2

  and 30 g / l of the finishing preparation of Example 1.

  The impregnated substrate is then dried at 1400 for

90 seconds.

  A cotton sample thus obtained is

  then treated at 150 for 10 minutes.

  Example of application B The process of example A is repeated, but we proceed in two stages. In the first step, the knitted fabric is impregnated at a bath absorption rate of 85% relative to the weight of the substrate in the dry state, with an aqueous bath containing 0.6 g / l of the optical brightener and dries it at 140 for 90 seconds. In the second step, the substrate thus obtained is padded at a bath absorption rate of 85% relative to the weight of the substrate in the dry state, with an aqueous bath containing

  g / 1 of the finishing preparation of Example 1.

  The substrate is then dried at 140 for 90 seconds.

Application example C

  A cotton yarn that has been treated by the azu-

  the optical rant of Example A, is introduced into an aqueous bath containing 1 g / l of sodium acetate, 0.75 ml / l of acetic acid and 0.5% (relative to the weight of the substrate) of the finishing preparation of Example 1 (calculated as dry weight content). The bath ratio is 1:10. The bath is then heated to 300 with constant stirring for 30 minutes and is kept at 30 for a further 30 minutes. We then remove

spun it and dried it.

  The procedure of Examples A9 B and C is repeated using the preparations described

in examples 2 to 12.

  In the examples above, the treated substrates have a soft and pleasant feel without significant influence on the degree of whiteness

  optics and hydrophilicity of the substrate, even for fishing

  cotton tillon of example A which has undergone a treatment

subsequent hot.

Claims (20)

  1.- The sulfomethylation product of an amino ester, Il'amino ester being the reaction product of an alkanolamine of formula I HO-R4 -NHR1 (I)   in which R1 represents hydrogen, a C1-C4 alkyl group or a group -R5-OH or CH2 --- NR2R3, R2 and R3 represent, independently of one another, hydrogen, a group - R5-OH or a C1-C4 alkyl group, R4 and R5 represent, independently of one another, a 1,2ethylene or 1,2opropylene group, and n signifies 2 or 3, or of a mixture of alkanolamines of formula 1, with a fatty acid of formula II R-COOH (II)   in which R represents a C1-C2 alkyl group, a C1-C21 alkenyl group, a C1-C221 alkenyl group or a C1-C21 alkenyl group substituted by a hydroxy group, or a mixture of these alkyl groups and alkenyl,   or a functional derivative of this acid.   2. A sulfomethylated amino ester according to claim 1, characterized in that R4 or R5 in   formula I represents a 1,2-ethylene group.   3.- A sulfomethylated amino ester according to claim 1 or 2, characterized in that R in formula II signifies a C13-C21 alkyl group or 3 0 32   C13-C21 alkenyl or a mixture of these groups.   4.- A sulfomethylated amino ester according to one   any of claims 1 to 3, characterized in   what the amino-ester corresponds to the formula III R-CO-O-R4-NHR1o (III) in which Rlo0 represents hydrogen or a group -R5-OH3 R -O-CO-R or - CH2 -) --NR20R30 R20 represents hydrogen or a C1-C4 alkyl group, -CO-R, -R5-OH or -R5-O-CO-R, R30 represents hydrogen or a C1-C4 alkyl group, - R50H or -R5-O-CO-R and   R, R49 R5 and n have the meanings given in re-   vendication 1, 5.- A sulfomethylated amino ester according to one   any one of claims 1 to 4, characterized in   what it responds to formula IV (IV) RR4 (R11) X2 3M   in which R11 represents hydrogen or a C -C4 alkyl group, R5-OH, -R5-O-CO-R, -CH2-SO3M, --CH2-n NHR21 'CH2 -_ N (R22) -CH2 -SO03. or x CH2 ± HNR22R23, R21 represents hydrogen or a C1-C4 alkyl group, -R5-OH, -CO-R, -CH2SO3M or -R5-O-CO-R, R22 represents a G1- alkyl group C4, -Rs5-OH, -R5-O-GO-R or -CH2-SO3M, R23 represents a C1-C4 alkyl group, -R5-OH or -R5 O-CO-R,   M represents hydrogen or the equivalent of a cation, and R, R4, R5 and n have the meanings given in claim 1.   6.- A sulfomethylated amino ester according to claim 5, characterized in that it is a compound corresponding to the formula IVa R'-CO- O- CH2 = C2 N (R12) -CH2- -S03M (IVa) in which M represents hydrogen or the equivalent of a cation, R 'represents a primary C7 -C alkyl group 17 19   linear or branched or a mixture of such alkyl groups, and R12 represents hydrogen or a group -CH2-CH2-OH, -CH2-CH2-O-CO-R 'or -CH2SO3M, or a mixture of these compounds.   7.7 A sulfomethylated amino ester according to   any one of claims 1 to 6, characterized   in that the amino ester is the reaction product of diethanolamine with a mixture of stearic acid and iso-stearic acid, the molar ratio of stearic acid to iso-stearic acid in said mixture being 65-35: 35-65.   8.- A process for the preparation of an amino-   sulfomethylated ester according to any one of the claims   tions 1 to 7, characterized in that it comprises the reaction of an alkanolamine of formula I HO-R NHR (I)   in which R1 and R4 have the meanings given in claim 1, or of a mixture of alkanolamines of formula I, with a fatty acid of formula II R-COOH (II)   in which R has the meaning given to the res-   dication 1, or a functional derivative of this acid,   and sulfomethylation of primary amino groups and / or-   non-acylated secondary side of the resulting amino ester,   with formaldehyde or a formal-releasing compound   dehyde and a sulfite, SO or a compound of formula V H-CH2-S3M (V HO-CH2-SO3M (V)   in which M represents hydrogen or the equivalent of a cation.   9. A process according to claim 8, characterized in that at least 0.5 mole of fatty acid of formula II is reacted per mole of alkanolamine of formula I. O10.- A process according to claim 9, characterized in that the α-lcanolamine of formula I   is diethanolamine, the molar ratio of diethanol-   amine to fatty acid of formula II being 1: 05-2.   11.- A process according to any one of   claims 8 to 10, characterized in that the   formaldehyde, the formaldehyde releasing compound or the compound of formula V is used in an amount at least 0.2 mole per amine val.   12.- A process according to any one of   claims 8 to 11, characterized in that the ratio   sulfite or SO2 molar with formaldehyde or   formaldehyde-releasing compound is 1-1.1: 1.   13.- The use of amino esters sulfo-   methylated as specified in any one   of claims 1 to 7 or obtained by the process   described in any one of claims 8 to 12,   as finishing agents for fibrous substrates.   14.- A process for finishing a fibrous substrate. ,, characterized in that a sulfomethylated amino ester is applied to the substrate as specified   to any of claims 1 to 7 or such   that obtained by the process specified in any one from claims 8 to 12.   15.- A method according to claim 14, characterized in that the substrate is paper or a textile substrate comprising natural cellulose or regenerated.   16.- A method according to claim 14 or 15, characterized in that the finishing is carried out   simultaneously or after the optical brightening of the substrate.   17.- A process according to any one   claims 14 to 16, characterized in that the   concentration of sulfomethylated amino ester on the substrate is between 0.3 and 10% relative to   the weight of the substrate in the dry state.   18.- An aqueous composition, characterized in that it contains from 3 to 50% by weight of a sulfomethylated amino ester as specified in one   any of claims 1 to 7, or obtained according to   the process specified in any of the claims 8 to 12.   19.- An aqueous composition according to the resale   dication 18, characterized in that it also contains a nonionic surfactant having a average HLB value from 6 to 19.   20. An aqueous composition according to claim 18 or 19, characterized in that the non-ionic surfactant is chosen from the products obtained by addition of ethylene oxide and / or propylene on saturated and / or unsaturated, linear and / or branched aliphatic alcohols, alkylphenols, fatty acids, alkanolamides of fatty acids, partial polyol esters with fatty acids, or vegetable or animal oils or fats ; partial esters of polyols with fatty acids, ethylene oxide copolymers and   of propylene oxide with a high content of ethylene units-   oxy, the adducts of ethylene oxide and propylene oxide on ethylenediamine and having a high content of ethyleneoxy units, or mixtures thereof.   21.- An aqueous composition according to the resale   dication 20, characterized in that the surfactant   non-ionic active is a compound of formula VI or VII R6 --- OCH2CH2 OH (V I)   (R7 CO) q: X in which R6 represents a C9C24 alkyl group, C9 C24 alkenyl or a radical of formula (a) (R8) r (a) o R8 represents a CC2 alkyl group and r signifies 1 or 2 each R7, independently, represents a C 1 -C 19 alkyl or C 1 -C 19 alkenyl group or a mixture of such groups,   X represents a monovalent or bivalent residue of the sor-   bitol, glycerol, pentaerythritol or a poly-   ethylene glycol of formula H0 - = CH2CH2 0 s = H o s means a number from 3 to 60, p means a number from 5 to 100, and q means 1 or 2, and the polyethoxylation products of the compounds of formula VII, or a mixture of these compounds.   22.- A process according to any one of   Claims 14 to 17, characterized in that the amino-   sulfomethyl ester is used in the form of a compound   tion as specified in any of the resales dications 18 to 21.