GB2264500A - Low-foam surfactants and their use - Google Patents

Abstract

Mixture (G) of different oxyalkylated and optionally further reacted amines (E) and (F) as described in the specification are suitable as low-foaming assistants, in particular levelling agents, especially in combination with silicone-free low-foaming compounds or defoamers, especially for the dyeing of natural or synthetic polyamides. The said amines are especially long-chain fatty amines such as stearyl amino, tallow fatty amine, behenyl amino etc.

Description

Low-foam surfactants and their use In the treatment of fibrous material, in particular textile material, with conventional treatment agents, in particular dyes, from aqueous liquor, it is often necessary to add levelling agents. This is of particular importance in dyeing. Since conventional levelling agents have a more or less pronounced surface-active character and tend to foam-formation in the aqueous liquor and/or the presence of e.g. a wetting agent can favour foam -formation and e.g. higher speeds of the substrate and/or liquor (as in the case of high-speed conveyance of substrates or/and liquors in jet dyeing machines or in the case of the dyeing of cross-wound bobbins) particularly favour foam-formation, the addition of a defoamer is necessary in such cases, as a too high proportion of foam or an uncontrolled foam-formation during the process, in particular dyeing process, may considerably disturb this process. With procedures that are carried out in closed vessels an excess of foam may lead e.g. up to a stand-still of the machine and in procedures in open vessels or when opening a foam-containing closed vessel an excessive foam-formation may eventually cause a dangerous foam eruption.

Also with foam behaviours that are not so pronounced a too high amount of foam may also otherwise disturb the process, e.g. insofar as certain liqour components may float on a too stable foam blanket or the levelling activity of a levelling agent is disturbed or further the whole apparatus is soiled etc. Experience has, however, shown that the presence of surfactans of the above kind, in particular of levelling agents, may impair the defoaming or foam-inhibiting activity of defoamers. For an efficient depression or inhibiting of foam in aqueous systems, especially in those with a consi durable speed of goods or/and liquor and that as a consequencey strongly favour the formation of foam - temperature and pressure variations during the procedure may have an additonal influence - there are, thus, often employed the particularly efficient silicone-based defoamers.When using such strong defoamers it may happen that these are incompatible with certain components of the liquor and/or tend to destabilize under treatment-conditions so that the silicones may deposit on the substrate and there may e.g. be formed the particularly feared silicone specks on the treated goods.

It has now been found that the surfactant mixtures (G) described below are excellently suitable as low-foam assistants, in particular as low-foam levelling agents, for treatments in aqueous liquor and that the defoaming activity may be clearly increased by the addition of mild defoamers, i.e.

of such that are essentially free of defoaming silicones and preferably also free of paraffinic waxes and/or of difficultly soluble high polymers, specifically so that even at high speeds of liquor and/or substrate, in particular even in closed vessels, e.g. in dye-jet machines, the formation of a disturbing extent of foam may be substantially avoided.

The invention relates to the below defined mixtures (G), their production and their novel components, to the (G)-containing compositions (P) and to the use of (G) resp. (P) in the treatment of substrates in aqueous medium.

The invention thus provides a mixture (G) of (E) a compound of the general formula

wherein R is a radical of the formula

R1 O- or Ry-CO--NH (O (r) R1 signifies a hydrocarbon radical with 8 to 30 carbon atoms, R2 signifies a hydrocarbon radical with 7 to 29 carbon atoms, X signifies C2~6-alkylene, Y signifies a radical of the general formula

A signifies ethylene and optionally propylene with the proviso that at least 50 % of the Sm radicals A are ethylene, B signifies C4~6-alkylene or/and phenylethylene, W signifies hydrogen or an anionic radical W1 r is a number in the range of 0 to 3 if R = (o'), a number in the range of 1 to 4 if R = (ss), or a number in the range of 1 to 3 if R = (y), m is at least 1, Em is a number in the range of (r + p + 5) to 150, n is 0 or 1, En is a number in the range of 1 to (r + p + 2), x is a number in the range of 0 to m and p is 0 or 1 or a protonation and/or quaternization product thereof or a mixture of such compounds, with (F) a compound of the general formula

wherein R0 signifies a radical of the formula (ss) or (y) or of the for mula

and the symbols R1, R2, A, X, W, m, Zm, p and r have, indepen dently from (E), the significances indicated under (E), or a protonation and/or quaternization product thereof or a mix ture of such compounds.

As hydrocarbon radicals R1 come into consideration conventional alkylaromatic or purely aliphatic hydrocarbon radicals, as can occur in surface active compounds; they may be saturated or unsaturated. There may, in particular, be mentioned the following fatty radicals: capryl, caprinyl, lauryl, myristyl, cetyl, stearyl, arachidyl, behenyl, lignoceryl, cerotyl, oleyl, elaidoyl, linoleyl, linolenyl, gadoleyl, arachidonyl and docosenyl (brassidyl or the erucahydrocarbon fatty radical) and also technical hydrocarbon radical mixtures containing such fatty radicals, in particular coconut fat, tallow fat, tallow alkyl, technical oleyl, arachidyl/behenyl, arachidyl/behenyl/stearyl, stearyl/cetyl and oleyl/cetyl.As R2-C0- come in general into consideration conventional acyl radicals, in particular fatty acid radicals of conventional fatty acids with 8 to 30 carbon atoms, especially those corresponding to the above listed fatty radicals, particularly caproyl, caprinoyl, lauroyl, myristoyl, palmitoyl, stearoyl, arachidoyl, behenoyl, lignoceroyl, cerotoyl, oleoyl, elaidoyl, linoleoyl, linolenoyl, gadoleoyl, arachidoyl and the radical of erucic acid and technical mixtures, in particular the acyl radicals of technical, optionally hydrogenated fatty acids, especially of coconut fatty acid, tallow fatty acid, tallow alkyl fatty acid, technical oleic acid and technical palmitoleic acid. Among the mentioned radicals are preferred those with 12 to 24 carbon atoms, in particular with 16 to 24, especially 18 to 22 carbon atoms.Among the saturated and the non-saturated fatty radicals the saturated ones are preferred. Among the technical mixtures are preferred those that are predominantly saturated (advantageously 2 80 % by weight, preferably > 90 % by weight saturated). Among the radicals R2-C0- and R1 in the significance of R R1 is preferred.

X may be any bivalent C26-alkane radical as occurring in alkylene diamines and polyalkylenepolyamines, advantageously ethylene, propylene or hexamethylene, wherein, if r > 1, X preferably signifies ethylene and/or propylene and the r radicals X may have the same significance or different significances. Preferably X signifies ethylene, propylene-1,3 or hexamethylene, in particular propylene-1,3 if r = 1, ethylene and/or propylene-1,3 if r = 2, or ethylene if r = 3.

Advantageously r signifies 0 to 2, in particular 0 or 1.

The index p signifies preferably 0.

Of the total radicals -A-0- in formula (Ie), preferably at leat 80 % are ethyleneoxy groups. More preferably all radicals -A-0- in formula (Ie) signify ethylenoxy groups. Also in formula (If) advantageoulsly at least 80 % of the total radicals -A-0- are ethylenoxy groups, preferably all of the radicals -A-0- in formula (If) are ethylenoxy groups.

As C4~6-alkylene in the significance of B come in general into consideration conventional radicals as can be introduced into the molecule by addition of the respective cyclic oxides, especially oxiranes, preferably butylene, in particular butylene-1,2, -2,3 or -1,4. Preferably B signifies phenylethylene or/and in particular butylene, before all butylene-1,2.

The sum of the total of the groups -A-O- in (E), i.e. Em, is advantageously (r + p + 6) to 70 [resp. if p = 0, (r + 6) to 70], preferably 10 to 70, in particular 30 to 70, and in (F) preferably 30 to 70. The sum of the total of the groups -B-0- in (E), i.e. Sn, is advantageously in the range of 1 to (r + p + 1), and is advantageously < 3, in particular 1 to 2, before all 1 to 1.5.

Of the Sn groups -B- in (E) advantageously at least one half, preferably 0.5 to 2, in particular 1 to 2, on average are C46-alkylene, more preferably butylene, whereas preferably at most 0.5, i.e. 0 to 0.5, on average, are phenylethylene groups. With particular preference -B- signifies exclusively butylene.

Where in the concerned polyglycol chains (s) in (E) n = 1, the radical -B-0- may be in any position of the respective chain, i.e. if x = m, B is bound directly to N [or if in the radical (a) p = 1, it may also be directly linked to the CH-bound oxygen] or, if x = 0, B is bound directly to -0-W, or, if 0 < x < m -B-0- is inserted between two groups -A-0- e.g. as an intermediate element of a block-polymeric polyglycolether chain. With particular preference x = 0 and the group -B-0- is placed at the end of the added chain and is bound to W as -B-0-W.

If W represents an anionic radical W1 this may be any anionic radical as conventionally employed for the anionic modification of polyglycol radicals, principally a sulphuric acid ester or phosphoric acid ester group or a dicarboxylic acid monoester group as may be formed by esterification of the respective terminal hydroxy groups, or a carboxy-(C1~3-alkyl) group (especially carboxymethyl) as may be formed by carboxyalkylation, in particular carboxymethylation, of the hydroxy group.These anionic groups W1 may be in the form of salts, for which conventional cations come into con sideration for salt-formation, principally alkali metal cations (lithium, sodium, potassium) or optionally substituted ammonium cations [unsubstituted ammonium or mono-, di- oder tri-(C1-3--alkyl)- or -(C23-hydroxyalkyl) -ammonium], or may form inner salts with basic amine groups of the molecule or further, especially at lower pH-values, may even be in the form of free acid, advantageously at least a part of the symbols W signifies hydrogen.

Advantageously the molecule contains on average not more than 1.5, preferably not more than one anionic substituent W1. With particular preference all symbols W signify hydrogen.

Preferred mixtures (G) are those in which A signifies ethylene, R signifies a radical of formaula (a), r signifies a number from 0 to 2, p signifies zero, Sm signifies (r + 6) to 70 and in (E) Sn signifies 1 to (r + 1), provided that at most one of the Sn radical -B- is phenylethylene, especially those in which R1 signifies an aliphatic hydrocarbon radical with 12 to 24 carbon atoms, X signifies propylene, x signifies zero and W signifies hydrogen and of the Sn radicals -B- in (E) 0 to 0.5 signify phenylethylene and the remaining, in particular 0.5 to (r + 1) signify butylene.

The compounds (F) are known or may be produced analogously to known method and serve as assistants for the treatment of substrates, in particular as levelling agents or the dyeing of fibrous material. The compounds (E) have also a levelling effect and their tendency to foaming is minimal. If (F) is blended with (E) the joined effect of the mixture is not worse than the one of (F) alone and the tendency to foaming is surprisingly clearly redu ced. The relative amounts of (E) and (F) may vary in a broad range and are suitably chosen so that both effects, i.e. the own (before all levelling) effect of (F) and the diminished tendency to foaming are efficiently displayed. The weight ratio (E)/(F) is advantageously in the range of 10/90 to 90/10, preferably 30/70 to-70/30, especially 1/2 to 2/1.

The invention further provides the new products (E1), i.e. products (E) which are as defined above and in which -B- signifies C4~6-alkylene and x = 0.

Compounds (E) and (F) may be produced in a manner known per se by oxyalkylation of the respective starting amines and optionally further reaction of the product by introduction of anionic radicals W1 and/or protonation and/or quaternization.

The process for the production of compounds of formula (E) is in particular characterized in that a compound of formula

in which Rx signifies a radical of the formula (B), (y) or

or a mixture of such compounds is reacted with the corresponding cyclic oxides (A) and (B), optionally at least one anionic radical W1 is introduced and the product is optionally protonated and/or quaternized.

The compounds (F) may be produced in an analogous way by oxyalkylating a compound of formula (IIa) or a mixture of such compounds with the corresponding A-oxide or oxides, optionally introducing at least one anionic radical W1 and optionally protonating and/or quaternizing the product.

According to a particularly advantageous procedure the mixtures (G) of (E) and (F) are produced directly by reacting at least one amine of formula (IIa) with A-oxide and B-oxide, where the quantity of B-oxide is chosen so that the corresponding mixtures can result. It is, however, also possible to produce the components (E) and (F) separately and then to mix them whith each other in the suitable quantitative ratio, or also to produce (F) in admixture with a part of (E) by mixed oxyalkylation and optional further reaction and then to add further component (E) up to the desired mixture ratio. Of course the production of (G) in admixture is indicated if in components (E) and (F) the symbols W, A and X and the indexes r and p as well as the sum Sm have the same significances and if R derives from the same radical Rx.By subsequent blending with further same of different component (F) the properties of the final mixture may be specifically adjusted. The separate production of (E) and (F) is especially suited, if in (E) Sn > 1 (especially if Sn on average is > 1.5) whereas the production in admixture is especially indicated if in compounds (E) Sn is predominantly = 1 (especially if Sn on average is 1 to 1.5).

The reaction of compounds of formula (IIa) with the respective cyclic oxides, principally oxiranes (A-oxide: ethylene oxide, propylene oxide; B-oxide: butylene oxide, pentylene oxide, hexylene oxide, styrene oxide), to introduce the respective radicals -A-0- and -B-0- may be carried out in any desired sequence. For the production of compounds (E) it is preferred to first react with A-oxide and then with B-oxide. The reaction may be carried out under reaction conditions conventional per se, principally at elevated temperature, in particular in the temperature range of 100 to 1800C, preferably 140 to 1700C, and in the presence of a suitable catalyst, in particular an alkali metal hydroxide (sodium hydroxide, potassium hydroxide, lithium hydroxide).The reaction may take place in an inert organic solvent or in the absence of any solvents, advantageously under displacement of air oxygen. The reaction with B-oxide is carried out advantageously as the last oxyalkylation.

The introduction of an anionic radical W1 may be carried out in a manner known per se and takes place advantageously by reaction with a suitable acid or a functional derivative thereof, e.g. with a C3~8-dicarboxylic acid or a functional derivative thereof, preferably the anhydride (with particular preference the cyclic anhydride, e.g. maleic, succinic or phthalic acid anhydride), with a C2-4-chloroalkane carboxylic acid, in particular chloroacetic acid, with phosphoric acid anhydride, with polyphosphoric acid or with sulphuric acid (optionally S03-containing) or a functional derivative thereof (e.g. chlorosulphonic acid or aminosulphonic acid) and, if required, with a base for salt formation.The reaction with a cyclic anhydride takes place e.g. at 0 to 800C, optionally in the presence of a catalyst, if desired with subsequent addition of a base for salt formation.

The reaction with chloroacetic acid takes place suitably under dehydrohalogenating conditions, e.g. at 45 to 800C, suitably with addition of an alkali metal hydroxide. The reaction with P205 takes place advantageously at 30 to 800C, if desired with subsequent addition of water and/or a base for salt formation. The reaction with aminosulphonic acid takes place advantageously in the presence of urea, suitably 10 to 200 % by weight of the used quantity of aminosulphonic acid, advantageously at temperatures between 75 and 1300C. The reaction with sulphuric acid takes place advantageously in a similar temperature range, if desired with subsequent addition of a base for salt formation.The reaction with chlorosulphonic acid takes place suitably under dehydrohalogenating conditions, e.g. at 45 to 800C, and with addition of alkali metal hydroxide.

For protonation there may be employed conventional acids, in particular mineral acids (sulphuric acid, phosphoric acid or preferably hydrochloric acid) or low molecular aliphatic carboxylic acids (e.g. with 1 to 4 carbon atoms, in particular formic, acetic, oxalic, lactic, tartaric or citric acid).

By quaternization there may be introduced conventional quaternizing radicals, in particular C1~4-alkyl, aryl-(013-alkyl) or -CH2-C0-NH2. For quaternization there may be employed conventional quaternizing agents, in particular aryl-(C1~3-alkyl)-halides (especially benzylchloride) C1~4-alkyl halides (preferably chlorides or bromides) or sulphates (e.g. dimethylsulphate or diethylsulphate) or chloroacetic acid amide. The quaternization may take place under conventional reaction conditions, e.g. in the temperature range of 40 to 120, preferably 60 to 1000C. Quaternization may be carried out exhaustively or partially, e.g. so that on average 0.5 to 1 basic nitrogen per molecule is quaternated. Preferably neither (E) nor (F) are quaternated.

The produced mixtures may be diluted directly with water to reach the desired solid substance content. The invention, thus, further provides compositions (P) comprising a mixture (G) which is as defined above.

The compositions (P) advantageously further contain (H) at least one non-ionic, cationic or weakly anionic antifoaming additive, which is essentially free of silicone-based defoamers and preferably also of defoaming paraffinic waxes and/or difficultly soluble high polymers.

As (H) come, in general, into consideration low foam compounds and foam inhibiting compounds, specifically low-foam surfactants as may conventionally be employed as dyeing assistants, e.g. low-foam wetting agents (e.g. fatty acid oligoethyleneglycol-monoesters or addition products of propylene oxide and ethylene oxide to fatty alcohols or to alkylphenols, e.g. with 12 to 24 carbon atoms in the lipophilic radical) or low-foam dyeing assistants that influence the affinity of the dye for the substrate (e.g. reaction products of fatty acids - e.g. such with 16 to 22 carbon atoms - with alkanolamines or aminoalkylalkanolamines, which are optionally oxyethylated and may be in protonated form), as well as typically defoaming additives, e.g. of the kind of the low alkyl esters of higher fatty acids, of the fatty acid alkylene bisamides, of the non-esterified fatty acids, of the higher molecular in particular also branched fatty alcohols, of the phosphoric acid trialkylesters, of the glycerine dialkyl ethers, or further of the emulsified oils, such as occur also as fat-liquors, especially if they are emulsified with weakly anionic emulsifiers (e.g. of the kind of the fatty acids and of the carboxymethylated derivatives of oxyalkylated high fatty alcohols). The choice and amount of the additives (H) is dictated essentially by the proposed field of use of the product.In general the relative quantities of (G) and (H) are chosen so that the reciprocal sustaining of the foam inhibiting effect is as pronounced as possible and at the same time the functional effect of the product (G) (in particular as levelling agent) may be efficiently displayed. The weight ratio (G)/(H) is advantageously 1/10 to 50/1, preferably 1.5/1 to 25/1.

Since some foam hemming additives that may be employed as (H) may have an insufficient hydrosolubility and/or their solubility might, in some cases, be insufficient for the production of compositions of higher concentration, it is in such cases of advantage to add (L) at least one solubilizer and/or hydrotrope.

As solubilizers and/or hydrotropes there may be employed conventional hydrosoluble low molecular compounds, e.g. polyols, etheralcohols or amides, e.g. mono- oder diethyleneglycol and C14-monoalkylethers thereof, propyleneglycol and/or urea.

The quantity and choice of the respective solubilizer and/or hydrotrope depends essentially on the constitution of the other components and their quantities. The weight ratio (L)/[(G) + (H)]) is in particular in the range of 1/1 to 1/20.

The suitable amounts of (H) and also of (L) may be assessed by means of a few preliminary tests.

The mixtures (G) are advantageously formulated to aqueous compositions, preferably together with (H) and if required also together with (L), the dry substance content of which is in particular in the range of 5 to 80 % by weight, preferably 20 to 75 x by weight. The (G)-content of the aqueous compositions (P) is advantageously in the range of 5 to 60 % by weight, preferably 15 to 50 % by weight. They are distinguished by their storage stability.

The mixtures (G) according to the invention, preferably in the form of the above-defined aqueous compositions (P), serve as assistants, in particular as levelling agents, in the treatment, especially in the dyeing, of substrates from aqueous medium. As substrates come into consideration, principally fibrous materials, in particular textile material, which may be of synthetic, animal or vegetable origin, preferably of natural and/or synthetic polyamides (wool, silk, synthetic polyamides) and mixtures thereof with other materials, e.g. with cotton, polyesters, polyurethanes or polyacrylnitril fibres. The mixtures (G) serve in particular as levelling agents for the dyeing of the mentioned substrates with corresponding anionic dyes, as they are conventionally employed for the dyeing of wool, silk and/or synthetic polyamides, especially acid dyes, metal complex dyes, direct dyes, vat dyes, sulphur dyes and mordant dyes, and include as well the so -called milling dyes as the so-called neutral build-up dyes. The substrate may be in any processing form as conventionally employed for the respective dyeing processes, e.g. as loose fibres, filaments, yarns, strains, bobbins (also cross-wound bobbins), woven goods, knitted goods, carpets, tuftings, felts, non-wovens or velvet or also as half-ready-made or ready-made goods.

The dyeing may take place according to conventional impregnation or exhaust processes, e.g. by padding, dipping, spraying, foam application or preferably by exhaust process in short or long liquors, of which there are especially to be mentioned the processes involving considerable speed of the goods or/and the liquor (e.g. as the dyeing of cross-wound bobbins or in jet-dyeing machines) and those in which the substrate tends particularly to entrap air (e.g. the dyeing of skeins and looped substrates) since with these the effect of the compositions of the invention is displayed particularly clearly, as they not only inhibit the formation of foam, but favour also the deaeration of the substrate (e.g. in terry-cloth or where air -channels are formed in the skeins).The dyeing processes may be carried out under temperatures, pH-values and liquor-to-goods ratios, conventional per se and as suitable for the relative substrate [for natural polyamides advantageously at temperatures from room temperature (= 200C) to 1150C, e.g. 20 to 1000C, and pH-values in the range of 1.5 to 7.0, e.g. 3.5 to 6.5, and for synthetic polyamides, advantageously at temperatures in the range of 30 to 1500C and pH-values in the range of 2 to 9, e.g. 4.5 to 7.5; the liquor-to-goods ratios for exhaust process are advantageously in the range of 2:1 to 120:1, preferably 5:1 to 60:1].

The concentration of the products of the invention is chosen depending on the desired effect, especially levelling effect, in particular depending on the employed dye and liquor-to-goods ratio as well as on the substrate and special application method; it is, e.g. in the range of 0.1 to 5 g, preferably 0.2 to 2 g (G) per liter of aqueous liquor.

By the process of the invention and using the compositions of the invention there may be achieved excellent levelling effects, whilst the addition of strong defoamers may be avoided, especially of such that may tend to destabilization and/or may leave on the substrate disturbing deposits (e.g. of silicones, of paraffinic waxes or of high polymers), which lead then to specks that are very difficult to eliminate or may even not be eliminated without damaging the substrate. The further properties, in particular intensity and fastnesses of the dyeings, as well as the physical properties of the treated substrates are substantially not impaired.

In the following examples parts and percentages are by weight and the temperatures are indicated in degrees Celsius. In the Application Examples the percentages are referred to the weight of the substrate.

Example 1 To 1 mole of N-(y-aminopropyl)-fatty amine are added, in conventional way, after addition of 1 % of sodium hydroxide, referred to the amine, 35 moles of ethylene oxide during 4 to 5 hours at 150-1650C; subsequently there are further added 0.5 moles of butylene oxide (98 Z) and the addition reaction is carried out at the same temperature. There is obtained a brown pasty substance.

The employed N-(y-aminopropyl)-fatty amine (DINORAM 42, of the firm PROCHI NOR) is a technical mixture of molecular weight 420, the fatty radical of which consists mainly of the following components: stearyl about 25 ; arachidyl about 25-35 t; behenyl about 30-40 %; Czo-22-unsaturated about 2-5 %.

Example 2 The procedure is carried out as in Example 1 using, however, in place of the there employed N-(r-aminopropyl)-fatty amine, the equimolar amount of N-(y-aminopropyl)-tallow fatty amine.

Example 3 The procedure is carried out as described in Example 1, with the difference that in place of the there employed N-(v-aminopropyl)-fatty amine there is employed the equimolar amount of tallow fatty amine.

Example 4 The procedure is carried out as described in Example 3, with the difference that in place of the tallow fatty amine, there is employed equimolar amount of a technical fatty amine mixture, consisting essentially of behenylamine and arachidylamine.

Example 5 The procedure is carried out as in Example 1, with the difference that in place of 0.5 moles of butylene oxide, there is added 1 mole of butylene oxide.

Example 6 The procedure is carried out as described in Example 1, with the difference that in place of 0,5 moles of butylene oxide, there is added 1 mole of styrene oxide.

Example 7 The procedure is carried out as in Example 6, with the difference, that in place of 1 mole of styrene oxide, there are added 1.5 moles of styrene oxide.

Example 8 The procedure is carried out as in Example 6, with the difference that in place of 1 mole of styrene oxide there are added 2 moles of styrene oxide.

Example 9 The procedure is carried out as described in Example 1, with the difference that subsequently there are further added 0.5 moles of styrene oxide under otherwise identical reaction conditions.

Example 10 The procedure is carried out as in Example 1, with the difference that in place of 0.5 moles of butylene oxide, there are added 0.7 moles of butylene oxide.

Example 11 The procedure is carried out as in Example 1, with the difference that in place of 0.5 moles of butylene oxide, there are added 0.8 moles of butylene oxide.

Example 12 The procedure is carried out as in Example 4, with the difference that in place of 35 moles of ethylene oxide, there are added 50 moles of ethylene oxide and in place of 0.5 moles of butylene oxide, there are added 0.8 moles of butylene oxide.

Example 13 The procedure is carried out as in Example 4, with the difference that in place of 35 moles of ethylene oxide, there are added 55 moles of ethylene oxide.

Example 14 The procedure is carried out as described in Example 13, with the difference that subsequently there are further added 0.5 moles of styrene oxide under otherwise identical reaction conditions.

Examples 15, 16 and 17 The products of Examples 5, 6 and 9 are each blended with the equimolar quantity of the non-butoxylated ethylene oxide addition product of Example 1.

Examples 18 and 19 The products of Examples 7 and 8 are each blended with the equimolar amount of the product of Example 1 and with the sesquimolar amount of the non-butoxylated ethylene oxide addition product of Example 1.

Composition 1 The product of Example 1 is diluted with demineralized water to a solids content of 30 % and adjusted with formic acid to pH 5.

Composition 2 400 parts of the product of Example 1 are melted in a stirrer flask at 600C and then the following components are sequentially separately added and stirred: 180 parts of propylene glycol, 20 parts of tetramethylnonanol, 280 parts of demineralized water and 120 parts of urea then cooling is allowed with stirring; when reaching 250C the pH is adjusted to 7 by addition of formic acid.

Composition 3 The procedure is carried out as in Composition 2, with the difference that to the 400 parts of the pre-melted product of Example 1 there are added sequentially and with stirring the following components: 20 parts of the addition product of 6.5 moles of ethylene oxide to 1 mole of oleic acid 20 parts of tetramethylnonanol 140 parts of propylene glycol 320 parts of demineralized water and 100 parts of urea and at 250C the pH is adjusted with formic acid to 7.

Composition 4 The procedure is carried out as described for Composition 2, with the difference that to the 400 parts of the pre-melted product of Example 1 there are added sequentially the following products: 60 parts of propylene glycol 100 parts of butylglycol 50 parts of glycerindiisobutylether-1,3 270 parts of demineralized water and 120 parts of urea and at 250C the pH is adjusted to 7 with formic acid.

Composition 5 The procedure is carried out as described for Composition 2, with the difference that in place of 400 parts of the product of Example 1, 400 parts of the product of Example 6 are pre-melted at 600C and the following products are added sequentially.

60 parts of a 30 % aqueous solution of the condensation product of 1 mole of oleic acid with 1 mole of N-(ss-aminoethyl)-ethanolamine, oxyethylated with 2 moles of ethylene oxide and protonated with formic acid 20 parts of metiloil (commercially available mixture of fatty acid methylesters) and 520 parts of demineralized water and then at 250C the pH is adjusted with formic acid to 7.

Composition 6 The procedure is carried out as described for Composition 5, with the difference, that to the pre-melted product of Example 6 there are added sequentially the following components: 80 parts of the 30 % condensation product indicated in Composition 5 240 parts of an aqueous 25 % addition product of 2 moles of ethylene oxide and 1 mole of propylene oxide to 1 mole of oleic alcohol and 280 parts of demineralized water and at 250C the pH is adjusted with formic acid to 7.

Composition 7 The procedure is carried out as described for Composition 2, with the difference that 380 parts of pre-melted product of Example 1 are prepared and the following components are sequentially added with stirring: 100 parts of the 25 X aqueous addition product of 2 moles of ethylene oxide and 1 mole of propylene oxide to 1 mole of oleyl alcohol 60 parts of propylene glycol and 460 parts of demineralized water, and at 250C the pH is adjusted to 7 with formic acid.

Composition 8 The procedure is carried out as described for Composition 7, with the difference that to the 380 parts of the pre-melted product of Example 1 there are added sequentially the following products with stirring: 100 parts of a fat-liquor of the following composition 26 % of palmkernel oil 8 X of paraffin oil 3 % of oleic acid 12 % of the carboxymethylated addition product of 12 moles of ethylene oxide to 1 mole of oleyl alcohol as sodium salt rest water, 60 parts of propylene glycol and 460 parts of demineralized water and at 250C the pH is adjusted to 7 with formic acid.

Composition 9 The procedure is carried out as described for Composition 2, with the difference that instead of the 400 parts of the product of Example 1 there are employed 400 parts of the product of Example 4.

Composition 10 The procedure is carried out as described for Composition 4, with the difference that instead of the 400 parts of the product of Example 1 there are employed 400 parts of the product of Example 4.

Analogously as described in Compositions 1 to 10, the other products of Examples 1 to 19 may be employed.

Application Example A In a laboratory-jet of the firm MATHYS with a nozzle of 55 mm of diameter a polyamide 6 (perlon)-tricot is dyed under maintenance of the following parameters: liquor volume = 6 1, flow = 60 l/min., speed of the goods = 20 m/min., and with the following additions: dyestuff = 0.5 % of the dye Colour Index Acid Blue 72, levelling agent: Composition 2, 1 g/l, acetic acid to pH 6, as follows: the liquor is heated during 40 minutes from 300C to 980C, then dyeing is continued for 30 minutes at 980C and then it is cooled.

During the heating stage foam formation is very small and does not reach a disturbing proportion; in the subsequent course of the dyeing at 90-980C the little foam disappears nearly completely; in the cooling stage the foam formation is also only minimal.

Application Example B Machine: THEN HT Jet Material: 7 kg of warp knit fabric of texturized polyamide 66, prewashed, rinsed, soured and dried Liquor: 40:1 (soft water) Additions: 1.0 g/l ammoniumsulphate 2.0 % of Composition 2 0.1 X Lanasyn Rubine S-5BL = C.I. Acid Violet 128.

The goods are fed into the jet with water, then the ammoniumsulphate and Composition 2 are added and the jet is operated for 5 minutes at 300C.

Only little foam is formed. Speed 150 m/min.

Subsequently the dye is added and the bath is heated by 1OC/min. to 800C and then by 20C/min. to 1000C; dyeing is continued at this temperature for 15 minutes and then the jet is heated by 20C/min. to 1150C, maintained 5 minutes at this temperature and then cooled and the goods are rinsed.

The little foam present at 300C diminishes clearly at 600C, does, however, never disappear completely, i.e. during the whole dyeing process there is always present a little foam, but no foam blow occurs even if during the cooling of the machine, e.g. at 950C, the pressure is reduced on purpose very quickly. The dyeing is level and speckless.

Application Example C Machine: OBERMAIER HT dyeing machine Material: 3 kg of texturized polyamide 66 yarn dtex 22f7 on spring tubes, bobbin-weight about 1 kg Liquor: 10:1 soft water Additions: 0.2 g/l sodium carbonate 1.0 g/l of the acid-yielding agent of USP 4 568 351, Example 1, 0.8 g/l of Composition 4 1.4 % of C.I. Acid Violet 48 1.08 % of C.I. Acid Blue 278 Liquor circulation: 1 cycle/min. in 4 out, no reversal.

The dyeing is started at 400C and the bath is heated by 20C/min. to 1050C, dyeing is continued during 15 minutes at this temperature, then the bath is indirectly cooled to 700C and, after draining off of the well exhausted dye-bath, the goods are rinsed once with cold water. After drying a knit ting test sample shows a completely even dyeing.

The foam behaviour of the products can also be simulated in a PRETEMA dyeing machine and the foam behaviour displays similarly as in the MATHYS laboratory-jet.

Like Composition 2 or 4 also the other ones of the above Compositions may be used in the above dyeing processes and in the PRETEMA-test.

Claims (17)

CLAIMS:

1. A mixture (G) of (E) a compound of the general formula

wherein R is a radical of the formaula

R-O- , or R2-CO-NH-, (ss) (#) R1 signifies a hydrocarbon radical with 8 to 30 carbon atoms, R2 signifies a hydrocarbon radical with 7 to 29 carbon atoms, X signifies C2~6-alkylene, Y signifies a radical of the general formula

A signifies ethylene and optionally propylene with the proviso that at least 50 % of the #m radicals A are ethylene, B signifies C46-alkylene or/and phenylethylene, W signifies hydrogen or an anionic radical W1, r is a number in the range of O to 3 if R = (a), a numeral in the range of 1-4 if R = (ss), or a numeral in the range of 1 to 3, if R = m is at least 1, Sm is a number in the range of (r + p + 5) to 150, n is O or 1, Sn is a number in the range of 1 to (r + p + 2), x is a number in the range of O to m and p is O or 1, or a protonation and/or quaternization product thereof or a mixture of such compounds, with (F) a compound of the general formula

wherein R0 signifies a radical of the formula (ss) or (y) or of the formula

and the symbols R1, R2, A, X, W, m, Sm, p and r have, independently from (E), the significances indicated under (E) or a protonation and/or quaternization product thereof or a mixture of such compounds.

2. A mixture (G) according to Claim 1, wherein A signifies ethylene, R signifies a radical of the formula (a), r signifies a number from 0 to 2, p signifies zero, Sm signifies (r + 6) to 70 and Sn signifies 1 to (r + 1) and at most one of the Sn radicals -B- is phenylethylene.

3. A mixture (G) according to Claim 1 or 2, wherein R1 signifies an aliphatic hydrocarbon radical with 12 to 24 carbon atoms, X signifies propylene, x signifies zero and W signifies hydrogen and of the Sn radicals -B- O to 0.5 signify phenylethylene and the remaining ones signify butylene.

4. A mixture (G) according to anyone of Claims 1 to 3, wherein Sm = 30 to 70.

5. A mixture (G) according to anyone of Claims 1 to 4, wherein the weight ratio (E)/(F) is in the range of 10/90 to 90/10.

6. A mixture (G) according to Claim 5, wherein the weight ratio (E)/(F) is in the range of 1/2 to 2/1.

7. The novel products (E), which are defined as in Claim 1, wherein -B signifies C4~6-alkylene and x = 0.

8. A process for the production of a compound (E) defined as in Claim 1, wherein a compound of the formula

in which Rx signifies a radical of the formula (B), (r) or

or a mixture of such compounds is reacted with the corresponding cyclic oxides (A) and (B), at least one anionic radical W1 is optionally introduced and the product is op tionally protonated and/or quaternized.

9. An aqueous composition (P) comprising a mixture (G) defined as in any one of Claims 1 to 6.

10. An aqueous composition (P) according to Claim 9, which is essentially free of silicone-based defoamers and comprises a mixture (G) and (H) at least one non-ionic, cationic or weakly anionic foam in hibiting additive, which is essentially free of silicone-based defoamers.

11. An aqueous composition (P) according to Claim 10, wherein the weight ratio (G)/(H) is in the range of 1/1 to 50/1.

12. An aqueous composition (P) according to Claim 10 or 11, further con taining (L) at least one solubilizer and/or hydrotrope.

13. An aqueous composition (P) according to Claim 12, wherein the weight ratio (L)/[(G) + (H)] is in the range of 1/1 to 1/20.

14. An aqueous composition (P) according to anyone of Claims 9 to 13 with a dry substance content in the range of 5 to 80 % by weight.

15. A process for the treatment of substrates from aqueous medium, wherein a mixture (G) according to anyone of Claims 1 to 6, optionally in the form of a composition (P) according to anyone of Claims 9 to 14, is employed as an assistant.

16. A process according to Claim 15 wherein (G) is used as a levelling agent in the dyeing or optical brightening of fibrous material with anionic dyestuffs or anionic optical brighteners.

17. A process according to Claim 16, in the dyeing under HT-conditions.