EP0000494A1 - Esters of acylated amino carboxylic acids, process for their preparation, and their application for dyeing textile materials - Google Patents

Abstract

Surface-active esters of aliphatic polyols and acylaminocarboxylic acids containing at least 34 hydroxyl groups, of the formula <IMAGE> in which R is H, C1-C4-alkyl, C1-C22-alkoxy, C3-C22-alkenoxy, aryl, aralkyl, aroxy aralkoxy or the radical <IMAGE>, R1, R4 and R5 represent H, C1-C22-alkyl, C3-C22-alkenyl, cycloalkyl, aryl or aralkyl, or R5 represents a radical <IMAGE> divalent organic radical. R2 is H, COOH, COO C1-C4-alkyl or C1-C6-alkyl, R3 is C1-C10-alkylene and x is 0 or 1, where at least one of the radicals R1 to R5 contains at least 6 carbon atoms which contain alkyl , Alkenyl and cyclic radicals can carry substituents and the total carbon number is 20-60 if R5 is substituted by the said urea radical and is 12-30 in all other cases; Process for their preparation and their use as auxiliaries in the dyeing of textile materials.

Description

The invention relates to surface-active esters of aliphatic polyols containing at least 3 hydroxyl groups and aliphatic, cycloaliphatic or araliphatic acylaminocarboxylic acids, which contain a total of at least 8, preferably 12-60, carbon atoms and which are aliphatic or aromatic and araliphatic carboxylic acids, with 1-4 carbon atoms , aromatic or araliphatic sulfonic, carbonic or carbamic acids are acylated, a process for their preparation and their use as auxiliaries in the dyeing of textile materials.

ab, in der

• R für H, für C₁-C₄-Alkyl, C₁-C₂₂-Alkoxy, C₃-C₂₂-Alkenoxy, Aryl, Aralkyl, Aroxy Aralkoxy oder für den Rest
  
• R₁, R₄ und R₅ für H, C₁-C₂₂-Alkyl, C₃-C₂₂-Alkenyl, Cycloalkyl, Aryl oder Aralkyl stehen, oder R₅ für einen Rest
  
  mit R₆ = zweiwertiger organischer Rest . steht.
• R₂ für H, COOH, COO C₁-C₄-Alkyl oder C₁-C₆-Alkyl,
• R₃ für C₁-C₁₀-Alkylen und
• x für 0 oder 1 stehen, wobei mindestens einer der Reste R₁ bis R₅ mindestens 6 Kohlenstoffatome enthält, die Alkyl- , Alkenyl- und cyclischen Resten Substituenten tragen können und die Gesamtkohlenstoffzahl 20 - 60 beträgt, wenn R₅ durch den genannten Harnstoffrest substituiert ist, und für alle anderen Fälle 12 - 30 beträgt.

. Preferred esters according to the invention are derived from carboxylic acids of the formula

from where

• R for H, for C ₁ -C ₄ alkyl, C ₁ -C ₂₂ alkoxy, C ₃ -C ₂₂ alkenoxy, aryl, aralkyl, aroxy aralkoxy or for the rest
  
• R ₁ , R ₄ and R _{5 represent} H, C ₁ -C ₂₂ alkyl, C ₃ -C ₂₂ alkenyl, cycloalkyl, aryl or aralkyl, or R _{5 represents} a radical
  
  with R ₆ = divalent organic residue. stands.
• R _{2 is} H, COOH, COO C ₁ -C ₄ alkyl or C ₁ -C ₆ alkyl,
• R ₃ for C ₁ -C ₁₀ alkylene and
• x represents 0 or 1, where at least one of the radicals R ₁ to R _{5 contains} at least 6 carbon atoms, the alkyl, alkenyl and cyclic radicals can carry substituents and the total carbon number is 20-60 if R ₅ is substituted by the urea radical mentioned and is 12-30 for all other cases.

In particular is understood to mean cycloalkyl cyclohexyl, tetrahydronaphthyl, _D ekahydronaph- thyl and abietyl, and aralkyl is benzyl, phenylethyl and naphthylmethyl by aryl is phenyl and naphthyl.

These residues can carry further substituents. The rings mentioned can preferably have 1 or 2 substituents, such as halogen, in particular chlorine or bromine, cyano, carboxyl, C ₁ -C ₄ alkoxycarbonyl, carbamoyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl, benzyl or phenyl wear.

The alkyl and alkenyl radicals of the compounds (I) can be substituted by 1-3 further radicals such as halogen, for example fluorine, chlorine or bromine, cyano, carboxyl, C ₁ -C ₄ -alkoxycarbonyl, carbamoyl or C ₁ -C ₄ -Alkoxy.

O oder 1

_X, X₁ = Wasserstoff, C₁-C₄ -AlkylThe radical R ₆ is preferably C ₂ -C ₈ alkylene or a radical of the formulas

O or 1

_X , X ₁ = hydrogen, C ₁ -C ₄ alkyl

Examples of aliphatic polyols containing at least 2 hydroxyl groups are: glycerol, erythritol, erythrose, pentoses or hexoses such as arabinose, xylose, glucose, fructose, galactose or mannose, pentites or hexites, such as arabitol, xylitol, mannitol, sorbitol or dulcitol, di- or oligosaccharides, such as maltose, sucrose or hydrolyzates of polysaccharides, and polysaccharides, such as dextrin or starch. Other suitable polyols are, for example, synthetic sugar compounds of the formose type, polyvinyl alcohols, and derivatives of the abovementioned polyols, such as alkyl or hydroxyalkyl glycosides, hydroxyalkyl ethers or partial esters or ethers of polyhydroxyl compounds.

The surface-active esters can be prepared in a manner known per se by two different processes.

• Bei diesem Verfahren wird die acylierte Aminocarbonsäure oder ein Derivat einer solchen Säure, gegehenenfalls in Gegenwart von sauren oder basischen Katalysatoren, mit einem aliphatischen Polyol umgesetzt. Als Derivate der Carbonsäuren werden vorzugsweise Chloride oder niedrige Alkylester, insbesondere Methyl- und Äthylester eingesetzt. Bevorzugt werden die Methyl- oder Äthylester der Carbonsäuren (I) eingesetzt. Die Carbonsäuren (I) bzw. ihre Derivate lassen sich nach bekannten Verfahren, z.B. durch Acylierung von Aminosäuren oder Aminosäureestern mit üblichen Acylierungsmitteln, wie Isocyanaten, Carbonsäureanhydriden oder -halogeniden, oder Chlorameisensäureestern herstellen.

Procedure A:

• In this process, the acylated aminocarboxylic acid or a derivative of such an acid, if appropriate in the presence of acidic or basic catalysts, is reacted with an aliphatic polyol. Chlorides or lower alkyl esters, in particular methyl and ethyl esters, are preferably used as derivatives of the carboxylic acids. The methyl or ethyl esters of carboxylic acids (I) are preferably used. The carboxylic acids (I) or their derivatives can be prepared by known processes, for example by acylation of amino acids or amino acid esters with customary acylating agents, such as isocyanates, carboxylic acid anhydrides or halides, or chloroformic acid esters.

• Bei diesem Verfahren werden Ester aus Aminocarbonsäuren, die am Stickstoff noch mindestens ein Wasserstoffatom enthalten, und mindestens 3 Hydroxylgruppen enthaltenden aliphatischen Polyolen mit Acylierungsmitteln umgesetzt, wobei die Summe der Kohlenstoffatome im Aminocarbonsäurerest und im Acylrest des Acylierungsmittels mindestens 8, vorzugsweise 10 - 22, betragen soll. Bevorzugt werden Ester von Aminocarbonsäuren der Formel
  
  umgesetzt, wobei R₁, R₂, R₃ und x die in Formel (I) genannte Bedeutung besitzen.

Procedure B:

• In this process, esters of aminocarboxylic acids which still contain at least one hydrogen atom on the nitrogen and aliphatic polyols containing at least 3 hydroxyl groups are reacted with acylating agents, the sum of the carbon atoms in the aminocarboxylic acid residue and in the acyl residue of the acylating agent being at least 8, preferably 10-22 . Esters of aminocarboxylic acids of the formula are preferred
  
  implemented, wherein R ₁ , R ₂ , R ₃ and x have the meaning given in formula (I).

The acylation can be carried out using customary acylating agents, such as carboxylic acid esters, anhydrides or halides, chloroformic acid esters, sulfonic acid chlorides, or preferably using organic mono- or diisocyanates, if appropriate in the presence of catalysts or molar amounts of acid acceptors.

The process conditions of the two production processes A and B can vary within wide limits. The properties of the esters produced can be varied by selecting the molar ratio between aminocarboxylic acid or acylaminocarboxylic acid and aliphatic polyol.

In general, 0.5 to 2.0, preferably 0.8 to 1.2, moles of aliphatic polyol are used per equivalent of carboxyl group.

The reaction according to process A can be carried out with or without the addition of solvents at temperatures of 20-180 ° C., preferably at 70-140 ° C. In the case of the preferred lower alkyl esters of amino or acylaminocarboxylic acids, customary solvents such as xylene, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidine or dimethylacetamide can be used. It is recommended to use acidic or especially basic kata Add lysatoran to the reaction mixture in amounts of 0.5-20% (based on carboxylic acid). Suitable acidic catalysts are, for example, hydrogen chloride, sulfuric acid, toluenesulfonic acid or acidic ion exchangers. Alkaline or alkaline earth metal hydroxides, carbonates or alcoholates and organic bases can be used as basic catalysts. The acylation according to method B is carried out at 0 to 120 ^o C, preferably at 20 to 90 ° C, optionally in solvents such as lower alcohols, glycols, ketones, aromatic hydrocarbons, Carbonsäureestern or amides.

bevorzugt, in der

• _R' . für Wasserstoff, C₁-C₄-Alkyl, C₁-C₂₂-Alkoxy, C₃-C₂₂-Alkenyloxy, Phenyl, Naphthyl, Benzyl, Phenyläthyl, Naphthylmethyl, Phenyloxy, Benzyloxy, Phenyläthyloxy oder für einen Rest
  
  steht,
• R₁', R₄' und R₅' für Wasserstoff, C₁-C₂₂-Alkyl. C₃-C₂₂-Alkenyl, Cyclohexyl, Tetrahydronaphthyl, Dekahydronaphthyl, Abietyl, Phenyl, Naphthyl, Benzyl oder Phenyläthyl stehen oder
• R₅' für einen Rest der Formel.
  
  steht, in der
• R₂, R₃, R₆ und x die vorstehend genannte Bedeutung haben, mindestens einer der Reste R₁',R₂,R₃,R₄' und R₅' mindestens 6 Kohlenstoffatome enthält, und die Alkyl-, Alkenyl- und die cyclischen Reste durch Fluor, Chlor, Brom, Cyan, Carboxyl, C₁-C₄-Alkoxycarbonyl, Carbamoyl.oder C₁-C₄-Alkoxy substituiert sein können und die cyclischen Reste außerdem durch C₁-C₄-Alkyl.

Of the acids of formula (I) are the acids of formula

preferred in the

• _R '. for hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₂₂ alkoxy, C ₃ -C ₂₂ alkenyloxy, phenyl, naphthyl, benzyl, phenylethyl, naphthylmethyl, phenyloxy, benzyloxy, phenylethyloxy or for a radical
  
  stands,
• R ₁ ', R ₄ ' and R ₅ 'for hydrogen, C ₁ -C ₂₂ alkyl. C ₃ -C ₂₂ alkenyl, cyclohexyl, tetrahydronaphthyl, decahydronaphthyl, abietyl, phenyl, naphthyl, benzyl or phenylethyl or
• R ₅ 'for a radical of the formula.
  
  stands in the
• R ₂ , R ₃ , R ₆ and x have the meaning given above, at least one of the radicals R ₁ ', R ₂ , R ₃ , R ₄ ' and R ₅ 'contains at least 6 carbon atoms, and the alkyl, alkenyl and the cyclic radicals can be substituted by fluorine, chlorine, bromine, cyano, carboxyl, C ₁ -C ₄ alkoxycarbonyl, carbamoyl or C ₁ -C ₄ alkoxy and the cyclic radicals can also be substituted by C ₁ -C ₄ alkyl.

oder

worin

• ^R ₇ für C₁-C₂₂-Alkyl, C₃-C₂₂-Alkenyl, Cyclohexyl, Tetrahydrohaphthyl, Dekahydronaphthyl, Abietyl, Phenyl, Naphthyl, Benzyl, Phenyläthyl oder einen Rest der Formel
  
  wobei
• R₆ die in Formel (I) angegebene Bedeutung hat,
• R₈ für Wasserstoff, C₁-C₂₂-Alkyl, C₃-C₂₂-Alkenyl, Cyclohexyl, Tetrahydronaphthyl, Dekahydronaphthyl, Abietyl, Benzyl oder Phenyläthyl,
• R₉ für Wasserstoff oder Carboxyl und
• R₁₀ und R₁₁ für Wasserstoff oder Methyl stehen, mindestens einer der Reste R₇ oder R₈ mindestens 8 Kohlenstoffatome besitzt, und die Alkyl-, Alkenyl-und cyclischen Reste die in Formel (III). genannten Substituenten tragen können,

mit mindestens 6 Kohlenstoffatome enthaltenden aliphatischen Polyolen umsetzt.Preferred esters according to the invention are prepared by using process A to lower alkyl esters, especially methyl esters, of acylaminocarboxylic acids of the formula

or

wherein

• ^R ₇ for C ₁ -C ₂₂ alkyl, C ₃ -C ₂₂ alkenyl, cyclohexyl, tetrahydrohaphthyl, decahydronaphthyl, abietyl, phenyl, naphthyl, benzyl, phenylethyl or a radical of the formula
  
  in which
• R _{6 has} the meaning given in formula (I),
• R _{8 represents} hydrogen, C ₁ -C ₂₂ alkyl, C ₃ -C ₂₂ alkenyl, cyclohexyl, tetrahydronaphthyl, decahydronaphthyl, abietyl, benzyl or phenylethyl,
• R ₉ for hydrogen or carboxyl and
• R ₁₀ and R _{11 are} hydrogen or methyl, at least one of the radicals R ₇ or R _{8 has} at least 8 carbon atoms, and the alkyl, alkenyl and cyclic radicals are those in formula (III). can carry the mentioned substituents,

with aliphatic polyols containing at least 6 carbon atoms.

Sorbitol, glucose, alkyl or hydroxyalkyl glycosides, trehalose, raffinose, sucrose cact, their mixtures and in particular sucrose are preferably used.

und mindestens 6 Kohlenstoffatome enthaltenden alipliatischen Polyolen mit Isocyanaten der Formel

wobei R₇ - R₁₀ die obengenannte Bedeutung haben,The preferred esters can also be prepared by Method B, by esters of amino carboxylic acids of the formula

and aliphatic polyols containing at least 6 carbon atoms with isocyanates of the formula

where R ₇ - R _{10 have} the meaning given above,

or be reacted with methyl formate, acetyl chloride or acetic anhydride. Examples of isocyanates are: methyl, ethyl, propyl, butyl, hexyl, 6-chlorohexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, phenyl, naphthyl, Allyl isocyanate, as well as butylene, hexamethylene, phenylene, toluene, hexahydrophenylene diisocyanate.

oder

wobei

• R₁₀ die obengenannte Bedeutung hat und
• ^R ₁₂ für C₁-C₂₂-Alkyl oder C₃-C₂₂-Alkenyl steht, und als aliphatische Polyole Sorbit, Glucose, Alkyl- oder ttydxoxyalkylglycoside, Trehalose, Raffinose oder insbesondere Saccharose zugrunde liegen.

As aminocarboxylic acid esters, those esters are preferably used, those of the formula as aminocarboxylic acids

or

in which

• R _{10 has} the meaning given above and
• ^R _{12 stands} for C ₁ -C ₂₂ alkyl or C ₃ -C ₂₂ alkenyl, and as aliphatic polyols are based on sorbitol, glucose, alkyl or tydxoxyalkyl glycosides, trehalose, raffinose or, in particular, sucrose.

und

und Saccharose, wobei R₇, R₈, R₁₀ und R₁₂ die obengenannte Bedeutung besitzen.Particularly preferred esters according to the invention are esters of acylaminocarboxylic acids of the formulas

and

and sucrose, where R ₇ , R ₈ , R ₁₀ and R _{12 have} the meaning given above.

Examples of suitable carboxylic acids of the formula (I) are:

The new compounds are fully biodegradable surface-active compounds, the properties of which can be varied within a wide range by changing the starting materials and the proportions. The compounds can therefore be used for a wide variety of applications, for example as detergents, cleaning agents or wetting agents, as emulsifiers, dispersants or thickeners, and as dyeing and printing aids.

The new compounds are preferably suitable for the continuous dyeing or printing of fiber materials with colorants customary for such fibers. The Ver- driving consists in impregnating or printing the fiber materials with an aqueous liquor which contains the dyes and the compounds according to the invention, and then a thermal aftertreatment. submits.

The required amounts of the products according to the invention can easily be determined by preliminary tests; in general the amounts of about 5-20 g per liter of padding liquor prove to be sufficient.

Suitable dyes for the process according to the invention are all dyes which are usually used for dyeing and printing textile materials, e.g. Acid staining agents, reactive dyes, post-chromating dyes, 1: 1 and 1: 2 metal complex dyes, cationic dyes, noun dyes and disperse dyes.

For example, the following dyes from the Color Index, 3rd Edition, Vol 5, are suitable:

• C.I. Acid Yellow 79
• C.I. Acid Red 80
• C.I. Acid Green 44
• C.I. Acid Red 111

As acidic dyes:

• CI Acid Yellow 79
• CI Acid Red 80
• CI Acid Green 44
• CI Acid Red 111

• C.I. Mordant Yellöw 5
• C.I. Mordant Black 65 C.I. Mordant Brown 21

As post-chromium dye

• CI Mordant Yellöw 5
• CI Mordant Black 65 CI Mordant Brown 21

• C.I. Acid Yellow 54
• C.I. Acid Red 214

As 1: 1 metal complex dyes:

• CI Acid Yellow 54
• CI Acid Red 214

• C.I. Acid Blue 199
• C.I. Acid Red 277
• C.I. Acid Brown 253
• C.I. Acid Blue 151
• C.I. Acid Green 86

As 1: 2 metal complex dyes:

• CI Acid Blue 199
• CI Acid Red 277
• CI Acid Brown 253
• CI Acid Blue 151
• CI Acid Green 86

• C.I. Reactive Blue 94
• C.I. Reactive Red 100
• C.I. Reaktive Yellow 69

As reactive dyes:

• CI Reactive Blue 94
• CI Reactive Red 100
• CI Reactive Yellow 69

• C.I. Basic Yellow 11
• C.I. Basic Blue 3
• C.I. Basic Red 18

As cationic dyes:

• CI Basic Yellow 11
• CI Basic Blue 3
• CI Basic Red 18

• C.I. Direct Orange 46
• C.I. Direct Blue 84

As noun dyes:

• CI Direct Orange 46
• CI Direct Blue 84

• C.I. Disperse Yellow 5
• C.I. Disperse Yellow 60
• C.I. Disperse Blue 56
• C.I. Disperse Blue 73

As disperse dyes:

• CI Disperse Yellow 5
• CI Disperse Yellow 60
• CI Disperse Blue 56
• CI Disperse Blue 73

• Die Farbstoffe werden unter kräftigem Rühren, gegebenenfalls unter Erwärmen auf etwa 70 - 80°C, im Wasser verteilt; dann werden die erfindungsgemäß zu verwendenden Verbindungen zugesetzt und die erhaltene Mischung gegebenenfalls mit niederen aliphatischen Cärbonsäuren, wie Essigsäure, Ameisensäure oder Oxalsäure, angesäuert oder mit in der Hitze Säure abspaltenden Verbindungen, wie Ammoniumsulfat oder Ammoniumacetat, versetzt. Mit dieser Flotte werden die Fasermaterialien z.B. auf einem Foulard imprägniert und anschließend einer thermischen Nachbehandlung unterworfen. Diese kann insbesondere bei Wolle und Polyacrylnitrilfasern in einer Behandlung bei etwa 100 - 110°C bestehen oder insbesondere bei synthetischen Polyamidfasern und Polyesterfasern in einer Trockenhitzebehandlung bei Temperaturen von 120 bis 220^oC. Nach der thermischen Behandlung wird das Faaermaterial gewaschen, gespült und getrocknet.

The dyeing and printing can be carried out, for example, in the following way:

• The dyes are distributed in the water with vigorous stirring, if appropriate with heating to about 70-80 ° C .; Then the compounds to be used according to the invention are added and the mixture obtained is optionally acidified with lower aliphatic carboxylic acids, such as acetic acid, formic acid or oxalic acid, or with compounds which split off in the heat, such as ammonium sulfate or ammonium acetate, are added. With this liquor, the fiber materials are impregnated, for example on a padder, and then subjected to a thermal aftertreatment. This may, in particular of wool and polyacrylonitrile fibers in a treatment at about 100 - made 110 ° C or, especially for synthetic polyamide fibers and polyester fibers in a dry heat treatment at temperatures from 120 to 220 ^o C. After the thermal treatment, the Faaermaterial is washed, rinsed and dried.

The colors and prints can be improved in many cases by using urea, thiourea or organic solvents, which have a good solubility for the dye used in each case; in this context, for example, buta may be mentioned nol, hexanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, diethylene glycol, triethylene glycol, thiodiethylene glycol, the monoethyl ether and monobutyl ether of ethylene glycol or diethylene glycol.

In many cases, an improvement in color or pressure can also be achieved by the use of alkyl sulfonamides and / or anion-active compounds, e.g. Alkyl sulfates, alkylarylsulfonates, fatty acid salts or preferably alkyl sulfonates, which can be used as sodium, potassium, ammonium or also as mono-, di- or triethanolamine salts.

It is also advisable to add an acid-resistant thickener to the padding liquors to improve the uniformity of the color, for example a locust bean flour derivative.

With the aid of the method according to the invention, it is possible to use textile materials, for example flakes, spun cables, slats, fabrics, knitted fabrics or nonwovens e.g. to dye or print from natural and synthetic polyamides, polyester, polyacrylonitrile and cellulose fibers, as well as their mixtures with each other.

A particular advantage of the method according to the invention is that its application is universal, i.e. all dyeable fiber materials can be dyed by the process.

The new compounds enable excellent fixation of the dyes. The dyeings obtained have good wet, sweat and rub fastness properties.

The appearance of a gray haze is prevented by the new connections.

The parts given in the following examples are parts by weight.

example 1

der durch Umsetzung von N-Octadecylasparaginsäure-dimethylester mit Methylisocyanat hergestellt wurde, zugesetzt. Aus der Reaktionsmischung werden dann unter Rühren innerhalb von 6 Stunden bei 90 - 100°C und ca. 110 Torr etwa-100 Teile einer Mischung aus Methanol und Dimethylformamid abdestilliert. Der Kolbenrückstand wird bei 100°C und einem Vakuum bis 2 Torr von Dimethylformamid befreit. Es werden 237 Teile eines braunen Harzes erhalten, das in der Kälte zu einem spöden, pulverisierbaren Harz erstarrt. Das Produkt ist klar wasserlöslich, schmilzt bei 150 - 160°C, besitzt eine OH-Zahl von 610, eine Verseifungszahl von 72 und erniedrigt die Oberflächenspannung des Wassers in O,1 %iger Lösung auf 46 dyn/cm.50 ml of dimethylformamide are distilled off from a solution of 136.8 parts of sucrose in 600 parts of nimethylformamide at 90-100 ° C. in vacuo over a column in the course of 1-2 hours. Then 4 parts of potassium carbonate and 94 parts of a dimethyl aspartate of the formula

which was prepared by reacting dimethyl N-octadecylaspartic acid with methyl isocyanate. About 100 parts of a mixture of methanol and dimethylformamide are then distilled off from the reaction mixture with stirring within 6 hours at 90-100 ° C. and about 110 Torr. The residue on the flask is freed of dimethylformamide at 100 ° C. and under a vacuum of up to 2 torr. 237 parts of a brown resin are obtained which solidify in the cold to form a brittle, pulverizable resin. The product is clearly water-soluble, melts at 150 - 160 ° C, has an OH number of 610, a saponification number of 72 and lowers the surface tension of the water in 0.1% solution to 46 dynes / cm.

Example 2

umgesetzt, der durch Umsetzung von N-Dodecylasparaginsäuredimethylester mit Methylisocyanat hergestellt wurde. Nach dem Abdestillieren des Dimethylformamids werden 200 Teile eines bei Raumtemperatur spröden, pulverisierbaren Harzes erhalten. Das klar wasserlösliche Produkt besitzt eine OH-Zahl von 650, eine Verseifungszahl von 78 und erniedrigt die Oberflächenspannung des Wassers in 0,1 %iger Lösung auf 35 dyn/cm.Under the conditions given in Example 1, a solution of 136.8 parts of sucrose in 600 parts of dimethylformamide in the presence of 2 parts of potassium carbonate with 77.2 parts of an aspartic acid ester of the formula

implemented, which was prepared by reacting dimethyl N-dodecylaspartate with methyl isocyanate. After the dimethylformamide has been distilled off, 200 parts of a resin which is brittle and pulverizable at room temperature are obtained. The clearly water-soluble product has an OH number of 650, a saponification number of 78 and lowers the surface tension of the water in 0.1% solution to 35 dynes / cm.

Example 3

umgesetzt, der durch Umsetzung von N-Kokosfettalkylasparaginsäure-dimethylester mit n-Butylisocyanat hergestellt wurde. Nach Abdestillieren des Düaethylformamids werden 278 Teile eines klar wasserlöslichen, harzartigen Produktes erhalten.Under the conditions given in Example 1, a solution of 171 parts of sucrose in 650 parts of dimethylformamide in the presence of 4 parts of potassium carbonate with 108.8 parts of an aspartic acid of the formula

implemented, which was prepared by reacting dimethyl N-coconut fatty alkyl aspartate with n-butyl isocyanate. After the diethyl formamide has been distilled off, 278 parts of a clearly water-soluble, resinous product are obtained.

The product has an OH number of 540, a saponification number of 60 and lowers the surface tension of the water in 0.1% solution to 33 dynes / cm.

Example 4

umgesetzt, der durch Umsetzung von 207 Teilen N-Octadecylasparaginsäure-dimethylester mit 30 Teilen Toluylendiisocyanat erhalten wurde. Nach dem Entfernen des Dimethylformamids im Vakuum werden 220 Teile eines wasserlöslichen, spröden, pulverisierbaren Harzes erhalten.In the manner described in Example 1, 136.8 parts of sucrose and 2 parts of potassium carbonate in 600 parts of dimethylformamide with 100 parts of an aspartic acid ester of the formula

implemented, which was obtained by reacting 207 parts of dimethyl N-octadecylaspartate with 30 parts of tolylene diisocyanate. After removing the dimethylformamide in vacuo, 220 parts of a water-soluble, brittle, pulverizable resin are obtained.

The product has an OH number of 684 and a saponification number of 98.5, and lowers the surface tension of the water in 0.1% solution to 52 dynes / cm.

Example 5

umgesetzt, der durch Umsetzung von 168 Teilen N-Kokosalkyl-asparaginsäuredimethylester mit 66 Teilen Essigsäureanhydrid hergestellt wurde. Nach dem Entfernen des Dimethylformamids im Vakuum werden 350 Teile eines harzartig erstarrenden,klar wasserlöslichen Produktes erhalten.In the manner described in Example 1, 232 parts of sucrose and 2 parts of potassium carbonate in 630 parts of dimethylformamide with 152 parts of an aspartic acid ester of the formula

implemented, which was prepared by reacting 168 parts of dimethyl N-coconut alkyl aspartate with 66 parts of acetic anhydride. After removing the dimethylformamide in vacuo, 350 parts of a resin-like solidifying, clearly water-soluble product are obtained.

It melts at 80 - 84 ° C, has an OH number of 675, a saponification number of 151 and reduces the surface tension of the water in 0.1% solution to 30.5 dynes / cm.

Example 6

aus 255 Teilen N-Dodecyl-asparaginsäuredimethylester und 152 Teilen n-Dodecyl-isocyanat umgesetzt. Nach dem Entfernen des Lösungsmittels im Vakuum werden 229 Teile eines in Wasser leicht löslichen, harzartigen, pulverisierbaren Produktes erhalten. Es schmilzt bei 140 - 145°C und besitzt eine Verseifungszahl von 65 und eine Hydroxylzahl von 660.In the manner described in Example 1, 137 parts of sucrose and 2 parts of potassium carbonate in 450 parts of dimethylformamide with 110 parts of a reaction product of the formula

reacted from 255 parts of dimethyl N-dodecyl aspartate and 152 parts of n-dodecyl isocyanate. After removing the solvent in vacuo, 229 parts of a readily soluble, resinous, pulverizable product are obtained. It melts at 140 - 145 ° C and has a saponification number of 65 and a hydroxyl number of 660.

Example 7

In the manner given in Example 1, 146 parts of sorbitol and 4 g of potassium carbonate in 550 parts of dimethylformamide with 150 parts of a reaction product from 1 mol N-coconut alkyl aspartic acid dimethyl ester and 1 mol of methyl isocyanate. After the dimethylformamide has been distilled off, 286 parts of a clearly water-soluble resin are obtained which solidifies into a sticky mass. The product has a saponification number of 85 and a hydroxyl number of 826.

Example 8

die durch Umsetzung von 3-Isocyanatopropionsäure-isobutylester mit Octadecylalkohol hergestellt wurde, umgesetzt.In the manner given in Example 1, 103 parts of sucrose and 2 parts of sodium methylate in 500 parts of dimethylformamide with 110 parts of the compound of the formula

which was prepared by reacting isobutyl 3-isocyanatopropionate with octadecyl alcohol.

Instead of the methanol-dimethylformamide mixture, a mixture of isobutanol and dimethylformamide is distilled in vacuo. After removing the solvent, 195 parts of a light brown, powderable resin are obtained. The product is soluble in warm water and reduces the surface tension of the water in 0.1% solution to 55 dynes / cm. The saponification number is 54 and the hydroxyl number is 630.

Example 9

die durch Umsetzung von 3-Octadecylamino-isobutteraäure mit Essigsäureanhydrid erhalten wurde, umgesetzt. Nach dem Entfernen des Lösungsmittels im Vakuum werden 198 Teile eines wasserlöslichen, braunen Harzes erhalten. Das Produkt setzt die Oberflächenspannung des Wassers in 0,1%iger Lösung auf 39,3 dyn/cm herab. Es besitzt eine Hydroxylzahl von 552 und eine Verseifungszahl von 55.In the manner given in Example 1, 103 parts of sucrose and 4 parts of calfum arbonate in 500 parts of dimethylformamide with 103 parts of the compound of the formula

which was obtained by reacting 3-octadecylamino-isobutyric acid with acetic anhydride. After removing the solvent in vacuo, 198 parts of a water-soluble, brown resin are obtained. The product reduces the surface tension of the water in 0.1% solution to 39.3 dynes / cm. It has a hydroxyl number of 552 and a saponification number of 55.

Example 10

20 parts of the dye C.I. No. 61590 (3rd edition, volume 4) are dissolved in 600 parts of soft water at approx. 80 ° C; 8 parts of the compound of Example 5 and 2 parts of sodium lauryl sulfonate are then added with stirring. The solution is added to 200 parts of a 4% strength aqueous preparation of a commercially available carob seed flour derivative with constant stirring. Then the homogeneous solution is mixed with 20 parts of acetic acid (60%). Finally, the dye preparation is made up to 1000 parts with cold, soft water.

A wool comb is impregnated with this dye liquor on a foulard; the fleet intake is about 100%. It is then continuously steamed in a steamer with saturated steam at 1 ₀ 2 - 103 ° C for 15 minutes. The comb is then washed on a lisseuse with warm water at around 50 ° C and acidified with acetic or formic acid.

An excellent green color is obtained, which means that it has very good perspiration, washing and water fastness and has no gray haze.

Example 11

15 parts of C.I. 18170 (3rd edition, volume 4) are poured with 600 parts of hot, soft water at 80 ° C; then 10 parts of the compound of Example 3 are added. The solution is added to 200 parts of a 4% strength aqueous preparation of a commercially available locust bean gum derivative with vigorous stirring. The solution is then cooled to about 50 ° C and mixed with a mixture of 20 parts of chromium fluoride, 30 parts of formic acid (85%) and 100 parts of hot water. Finally, the dye preparation is made up to 1000 parts with cold, soft water.

A wool comb is soaked with the dye liquor obtained in this way and squeezed between two paddle rollers, the weight gain being approximately 100%, and then continuously steamed for 40 minutes in a steamer with saturated steam at 102-103 ° C. Then the dyeing is rinsed again with warm water at 50 ° C. An excellent gray coloration is obtained with very good fastness to perspiration, walking, washing and hot water.

Example 12

The procedure is as given in Example 11, but with the difference that 10 parts of the compound of Example 7 are used instead of the compound listed there.

This also gives a gray color that has no gray haze.

Example 13

und 2 Teilen Diäthylenglykolmonobutyläther hinzugegeben. Die Lösung wird unter ständigem Rühren zu 200 Teilen einer 4 %igen wäßrigen Zubereitung eines handelsüblichen Johannisbrotkernmehlderivates hinzugefügt. Darauf wird. die homogene Lösung mit 20 Teilen Essigsäure (60 %) versetzt. Anschließend wird die Farbstoffzubereitung mit kaltem, weichem Wasser auf 1000 Teile aufgefüllt.10 parts of the 1: 2 chromium complex of the dye 2-aminophenol-4-ethylsulfone → 1-methylsulfonylamino-7-oxynaphthalene are dissolved in 600 parts of hot, soft water at 84 ° C .; then a mixture of 8 parts of the compound of Example 2 and 2 parts of the compound of the following formula

and 2 parts of diethylene glycol monobutyl ether were added. The solution is added to 200 parts of a 4% aqueous preparation of a commercially available locust bean gum derivative with constant stirring. On it. 20 parts of acetic acid (60%) are added to the homogeneous solution. The dye preparation is then made up to 1000 parts with cold, soft water.

A combed of polyamide 6 fibers is padded with this dye liquor, the liquor absorption being about 80%, and then continuously steamed in a steamer at 102-103 ° C. for 15 minutes. The comb is then washed on a lisseuse with warm water at 50 ° C and rinsed. A very uniform gray coloration is obtained with very good fastness to light, washing and perspiration.

Example 14

A mixture of 20 parts of the dye according to CI 15710 (3rd edition, volume 4) and 500 parts of soft water at about 90 ° C. is stirred with 10 parts of the compound of Example 2
and 3 parts of sodium lauryl sulfonate and 2 parts of benzyl alcohol were added and then added to 100 parts of a 4% strength aqueous preparation of a commercially available locust bean gum derivative. The solution is then cooled to about 50 ° C. and a mixture of 12 parts of chromium fluoride, 20 parts of formic acid (85%) and 100 parts of hot water is added. Finally, the dye preparation is made up to 1000 parts with cold, soft water.

This color paste is used to print a woolen comb on a Vigoureux printing machine (roller 50:50) and then steaming it for 20 minutes in a pressure damper with saturated steam at around 108 ° C. The comb is then washed on a lisseuse with warm water at 50 ° C , rinsed and acidified with formic acid.

In this way you get a black print with very good light and wet fastness properties.

Example 15

hinzugefügt. Die Mischung wird auf 80 - 90°C erhitzt und unter kräftigem Rühren zu 100 Teilen einer 4 %igen wäßrigen Zubereitung eines handelsüblichen Johannisbrotkernmehlderivates hinzugegeben. Darauf wird die Lösung unter Rühren mit 5 Teilen Essigsäure (60 %) versetzt. Die nunmehr entstandene Farbflotte wird dann mit weichem Wasser auf 1000 Teile aufgefüllt. Diese Farbflotte wird mittels eines Auftragswerkes auf einen Polyamid 6.6-Tufted-Teppich gleichmäßig aufgetragen, wobei die Gewichtszunahme ca. 300 % beträgt, und anschließend wird der Teppich 15 Minuten in einem Dämpfer mit Sattdampf bei 102 - 103°C kontinuierlich gedämpft. Danach wird er auf einer Kontinue-Breitwaschmaschine mit warmem Wasser von 50°C gewaschen und gespült.5 parts of the 1: 2 chromium complex of the monoazo dye anthranilic acid → 1.-phenyl-3-methyl-pyrazolone are poured over with 500 parts of soft water at 70 ° C .; then a mixture of 4 parts of the compound of Example 5 and 2 parts of sodium lauryl sulfonate and 2 parts of the compound of the following formula

added. The mixture is heated to 80-90 ° C. and added to 100 parts of a 4% strength aqueous preparation of a commercially available locust bean gum derivative with vigorous stirring. 5 parts of acetic acid (60%) are then added to the solution while stirring. The resulting liquor is then made up to 1000 parts with soft water. This dye liquor is applied evenly to a polyamide 6.6 tufted carpet using a coating unit, the weight gain being approximately 300%, and then the carpet is continuously steamed for 15 minutes in a steamer with saturated steam at 102-103 ° C. It is then washed and rinsed on a continuous wide-angle washing machine with warm water at 50 ° C.

_M an receives a very even yellow coloration that does not contain a gray haze and has very good light, water and shampoo fastness.

Example 16

werden in 600 Teilen heißem, weichem Wasser von 80°C gelöst; anschließend werden 8 Teile der Verbindung des Beispiels 2 und 2 Teile.Natriumlaurylsulfonat und 2 Teile der Verbindung folgender Formel

hinzugefügt. Die Lösung wird unter ständigem Rühren zu 200 Teilen einer 4 %igen wäßrigen Zubereitung eines handelsüblichen Johannisbrotkernmehlderivates hinzugegeben. Hierauf wird die homogene Lösung mit 5 Teilen Essigsäure (60 %) versetzt. Abschließend wird die Farbstoffzubereitung mit kaltem, weichem Wasser auf 1000 Teile aufgefüllt. Eine Wollgabardine wird mit dieser Farbflotte auf einem Foulard imprägniert; die Gewichtszunahme beträgt etwa 80 %. Anschließend wird sie in einem Dämpfer mit Sattdampf während 15 Min. bei 102 - 103°C kontinuierlich gedämpft. Danach wird die Färbung mit warmem Whsser von 50°C, das einen pH-Wert von etwa 8,5 aufweist, gewaschen,gespült und mit Essig- bzw. Ameisensäure abgesäbert.10 parts of the dye of the following formula

are dissolved in 600 parts of hot, soft water at 80 ° C; then 8 parts of the compound of Example 2 and 2 parts. Sodium lauryl sulfonate and 2 parts of the compound of the following formula

added. The solution is added to 200 parts of a 4% strength aqueous preparation of a commercially available locust bean gum derivative with constant stirring. Then the homogeneous solution is mixed with 5 parts of acetic acid (60%). Finally, the dye preparation is made up to 1000 parts with cold, soft water. A wool gabardine is impregnated with this dye liquor on a foulard; the weight gain is about 80%. It is then continuously steamed in a steamer with saturated steam for 15 minutes at 102 - 103 ° C. The dyeing is then washed with warm water at 50 ° C., which has a pH of about 8.5, rinsed and washed off with acetic or formic acid.

Mrn gets a brilliant red color that does not contain a gray haze. 1

Example 17

20 parts of the dye according to CI 58005 (3rd edition, volume 4) are dissolved in 600 parts of hot, soft water at 80 ° C; then a mixture of 10 parts of the compound of Example 1
and 4 parts of sodium lauryl sulfonate and 2 parts of ethylene glycol monobutyl ether were added. The solution is added to 200 parts of a 4% strength aqueous preparation of a commercially available locust bean gum derivative with vigorous stirring. The solution is then cooled to about 50 ° C and mixed with a mixture of 20 parts of chromium fluoride, 30 parts of formic acid (85%) and 100 parts of hot water. Finally, the dye preparation is made up to 1000 parts with cold, soft water.

Loose wool is impregnated with the dyes obtained in this way and squeezed between two paddle rollers, the weight gain being approximately 120%, and then continuously steamed in a steamer with saturated steam at 102-103 ° C. for 45 minutes. Then the dyeing is rinsed again with warm water at 50 ° C.

An excellent bluish red color is obtained with very good sweat, water and wash fastness.

Example 18

werden unter kräftigem Rühren in 500 Teile_warmem Wasser von 50°C, das 12 Teile der Verbindung des Beispiels 7 enthält, eingestreut. Die Dispersion wird unter ständigen Rühren zu 200 Teilen einer 4 %igen wäßrigen Zubereitung eines handelsüblichen Johannisbrotkernmehlderivates hinzugegeben. Darauf wird die Farbstoffzubereitung unter Rühren mit 5 Teilen Essigsäure (60 %) versetzt. Abschließend wird sie mit kaltem Wasser auf 1000 Teile aufgefüllt. \15 parts of the disperse dye of the following formula

are sprinkled with vigorous stirring in 500 parts of warm water at 50 ° C., which contains 12 parts of the compound of Example 7. The dispersion is added to 200 parts of a 4% strength aqueous preparation of a commercially available locust bean gum derivative with constant stirring. 5 parts of acetic acid (60%) are then added to the dye preparation while stirring. Finally, it is made up to 1000 parts with cold water. \

This dye liquor is used to impregnate a fabric made of polyethylene terephthalate on a foulard, the liquor absorption being approx. 60%, and steamed in a pressure damper at 135 ° C. for 5 minutes. Then the dyeing is rinsed again with warm water at approx. 50 ° C.

A very even scarlet color is obtained in this way.

Example 19

10 parts of C.I. 48040 (3rd edition, volume 4) are dissolved in 350 parts of hot, soft water at 90 ° C., which contains 1 part of acetic acid (60%).

And 6 parts of the dye C.I. 40215 (3rd edition, volume 4) are dissolved in 350 parts of hot, soft water at 90 ° C. First, the latter dye solution and then the solution of the cationic dye are added with stirring to 75 parts of a 4% aqueous preparation of a commercially available locust bean gum derivative, which contains 10 parts of the compound of Example 2. Finally, the dye preparation is made up to 1000 parts with cold, soft water.

A furniture upholstery fabric consisting of polyacrylonitrile fibers (pile) and cotton (back) is impregnated on a foulard with the dye liquor described above, the liquor absorption being approx. 100%. It is then steamed continuously in a steamer for 15 minutes at 102 - 103 ° C. The dyeing is then rinsed again on a continuous wide-washing machine with warm water at 50 ° C.

An excellent yellow coloration is obtained which has no gray haze.

Example 20

8 parts of C.I. 51004 (3rd edition, volume 4) are dissolved in 350 parts of hot, soft water at 90 ° C, which contains i part of acetic acid (60%).

werden in 350 Teilen heißem, weichem Wasser von 90°C gelöst. Zunächst die letztgenannte Farbstofflösung und dann die Lösung des kationischen Farbstoffes werden unter Rühren zu 75 Teilen einer 4 'igen wäßrigen Zubereitung eines handelsüblichen Johannisbrotkernmehiderivates, die 7 Teile der Verbindung des Beispiels 1 und 3 Teile Natriumlaurylsulfonat und 2 Teile Triacetin enthält, hinzugegeben. Abschließend wird die Farbstoffzubereitung mit kaltem, weichem Wasser auf 1000 Teile aufgefüllt.And 6 parts of the dye of the following formula

are dissolved in 350 parts of hot, soft water at 90 ° C. First the latter dye solution and then the solution of the cationic dye are under Stirring is added to 75 parts of a 4% aqueous preparation of a commercial locust bean gum derivative which contains 7 parts of the compound of Example 1 and 3 parts of sodium lauryl sulfonate and 2 parts of triacetin. Finally, the dye preparation is made up to 1000 parts with cold, soft water.

A furniture plush, consisting of polyacrylonitrile fibers (pile) and cotton (back), is impregnated on a foulard with the dye liquor mentioned above, the liquor absorption being approximately 100%. It is then steamed continuously in a steamer for 15 minutes at 102 - 103 ° C. The dyeing is then rinsed again on a continuous wide-washing machine with warm water at 50 ° C. An excellent blue color is obtained which has no gray haze.

Claims (10)

1. Surface-active esters of at least 3 hydroxyl-containing aliphatic polyols and aliphatic, cycloaliphatic or araliphatic acylaminocarboxylic acids which contain a total of at least 8, preferably 12-60, carbon atoms and which are aromatic or araliphatic carboxylic acids, aliphatic, aromatic, by aliphatic carboxylic acids having 1-4 carbon atoms or araliphatic sulfonic, carbonic or carbamic acids are acylated. 2. Surface-active esters according to claim 1, characterized in that they are derived from acylamine carboxylic acids of the formula

in the R for H, for C ₁ -C ₄ alkyl, C ₁ -C ₂₂ alkox ^y, C ₃ -C ₂₂ alkenoxy, aryl, aralkyl, aroxy aralkoxy or for the rest

R ₁ , R ₄ and R _{5 represent} H, C ₁ -C ₂₂ alkyl, C ₃ -C ₂₂ alkenyl, cycloalkyl, aryl or aralkyl, or R _{5 represents} a radical

with R ₆ = divalent organic radical, R _{2 is} H, COOH, COO C ₁ -C ₄ alkyl or C ₁ -C ₆ alkyl, _R3 for C ₁ -C ₁₀ alkylene and x represents 0 or, where at least one of the radicals R ₁ to R _{5 contains} at least 6 carbon atoms, the alkyl, alkenyl and cyclic radicals can carry substituent clay and the total carbon number is 20-60 if R ₅ is substituted by the urea radical mentioned , and for all other cases is 12-30. 3. Surface-active esters according to claim 1, characterized in that they are derived from acylaminocarboxylic acids of the formula

in the R 'is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₂₂ alkoxy. C ₃ -C ₂₂ alkenyloxy, phenyl, naphthyl, benzyl, phenylethyl, naphthylmethyl, phenyloxy, benzyloxy, phenyltlthyloxy or for a radical

stands, R ₁ ', R _4' and R ₅ 'is hydrogen, C ₁ -C ₂₂ alkyl, ^C ₃ - ^C ₂₂ alkenyl, cyclohexyl, tetrahydronaphthyl, Dekahydronaphthyl, abietyl, phenyl, naphthyl; Benzyl or Phenyläthyl stand or R ₅ 'for a radical of the formula

stands, R ₆ for C ₂ -C ₈ alkylene or a radical of the formulas

X, X ₁ = hydrogen, C ₁ -C ₄ alkyl. and in which R ₂ , R ₃ and x have the meaning given in Claim 2 and at least one of the radicals R ₁ ', R ₂ , R ₃ , R ₄ ' and R ₅ 'contains at least 6 carbon atoms, and the alkyl , Alkenyl and the cyclic radicals can be substituted by fluorine, chlorine, bromine, cyano, carboxyl, C ₁ -C ₄ alkoxycarbonyl, carbamoyl or C ₁ -C ₄ alkoxy and the cyclic radicals can also be substituted by C ₁ -C ₄ - Alkyl, derivative 4. Surface-active esters according to claim 1, characterized in that they are derived from acylaminocarboxylic acids of the formula

or.

wherein R ₇ for C ₁ -C ₂₂ alkyl, C ₃ -C ₂₂ alkenyl, cyclohexyl, tetrahydronaphthyl, decahydronaphthyl, abietyl, phenyl, naphthyl, benzyl, phenylethyl or a radical of the formula

in which R _{6 has} the meaning given in claim 3, R _{8 represents} hydrogen, C ₁ -C ₂₂ alkyl, C ₃ -C ₂₂ alkenyl, cyclohexyl, tetrahydronaphthyl, decahydronaphthyl, abietyl, benzyl or phenylethyl, R ₉ for hydrogen or carboxyl and R ₁₀ and R ₁₁ stand for hydrogen or methyl, at least one of the radicals R ₇ or R _{8 has} at least 8 carbon atoms, and the alkyl, alkenyl and cyclic radicals can carry the substituents mentioned in claim 3. 5. Surface-active esters according to claim 1, characterized in that they are derived from sorbitol, glucose, alkyl or hydroxyalkyl glycosides, tetralose, raffinose, sucrose or mixtures thereof. 6. A process for the production of surface-active esters of Claim 1, characterized in that aminocarboxylic acids containing at least one hydrogen atom on the nitrogen, or their derivatives, in particular alkyl esters, anhydrides or halides containing at least 3 hydroxyl groups aliphatic polyols and _A cylierungsmitteln in any Order implemented. 7. The method according to claim 6, characterized in that carboxylic acids of the formula

wherein R ₁ , R ₂ , R ₃ and x have the meaning given in claim 2, with at least 3 hydroxyl-containing aliphatic polyols and acylating agents of the formulas

wherein R, R ₄ and R _{6 have} the meaning given in claim 2, and Y represents a C ₁ -C ₄ alkoxy group, halogen or the group -O-COR. 8. The method according to claim 6, characterized in that 0.8 to 1.2 mol of aliphatic polyol are used per equivalent of carboxyl group. 9. Use of the compounds according to claim 1 as an aid in dyeing and printing materials made of natural and / or synthetic fibers. 10. Use of the compounds according to claim 1 as auxiliary agents for the continuous dyeing or printing of textile materials made of natural and / or synthetic fibers.