DE4303547A1 - New low foam surfactant mixt. and new modified alkylene oxide copolymer - for use in aq. formulation, esp. as levelling agent in dyeing and optical whitening with anionic cpd. - Google Patents

Abstract

A mixt. (I) of 3 different polyalkylene oxide alkoxyalkyl- or acylamidoalkyl-amines of the formula R-(X-N(Y))r-Y (II) and Ro-(X-N((A-O)m-W))r-(A-O)m-W (III) and/or their protonised and/or quaternised prods. is new. In the formulae R is (a) R1-(O-CH2-CH(O-Y)-CH2)p-N(Y)-, (b) R1-O- or (c) R2-CO-NH-; R1 is an 8-30C hydrocarbyl gp.; R2 is a 7-29 C hydrocarbyl gp.; X is 2-6C alkylene; Y is -(A-O)(m-x)-(B-O)n-(A-O)x-W; A is ethylene and opt. propylene, at least 50% of the total being ethylene; B is 4-6C alkylene and/or phenylethylene; W is H or an anionic gp. W1; r is 0-3 if R = (a), 1-4 if R = (b) and 1-3 if R = (c); m is at least 1; the sum of m = (r + p + 5) to 150; n is 0 or 1; the sum of n = 1 to (r + p + 2); x is O to m; p is 0 or 1; Ro = gp. (b) or (c) or R1-(O-CH2-CH(O-(S-O)m-W)-CH2)p-N(A-O)m-W)- (a1). Also claimed are: a) new modified alkylene oxide cpds. (IIA) of formula (II) with -B- = 4-6C alkylene and x = O; and b) aq. formulations (IV) contg. (I). USE/ADVANTAGE - For use as ancillary for the treatment of substrates from aq. medium, esp. as levelling agent for dyeing or optical whitening of fibres with anionic dyestuffs or anionic optical whiteners, esp. under HT conditions. It is esp. useful in dyeing textiles of synthetic, animal or vegetable fibres (natural polyamides, e.g. wool and silk, and/or synthetic polyamides and mixts. with e.g. cotton, polyesters, polyurethanes or polyacrylonitrile fibres), esp. with acid, metal complex, direct, vet, sulphur and mordant dyestuffs. (I) forms little foam and can be used with mild antifoams, rather than silicones, paraffin waxes and/or hardly soluble high polymers, making it esp. useful in closed equipment, e.g. jet dyeing appts.

Description

In the treatment of fiber material, in particular textile material, from aq riger fleet with conventional treatment agents, especially with dyes, it is often necessary to add leveling agents; this plays particularly a very important role in dyeing. Since the common leveling agents more or less pronounced surfactant character and in the aqueous Fleet tend to form foam and / or the presence z. B. one Wetting agent can promote the formation of foam and z. B. by strong dynamic stress on the substrate and / or liquor, as z. B. at high-speed substrates in nozzle dyeing machines or when dyeing Cheese is the case, foam formation is particularly favored, this requires the addition of a defoamer, because an excessive amount or an uncontrolled generation of foam during the process, ins special of the dyeing process, which can interfere significantly. At work exhibit in closed equipment, an excess of foam z. B. to bring the apparatus to a standstill and when using open apparatus doors or when opening closed equipment containing foam excessive foaming u. U. a dangerous foam burst ver causes. Even if the foam behavior is not so pronounced, a too large amounts of foam also interfere with the process, e.g. B. by be agreed to frame the fleet components on an excessively stable foam blanket can or the leveling effect of a leveling agent is disturbed or the entire apparatus is still contaminated etc. Now experience has it shown that the presence of surfactants of the above type, in particular special of leveling agents, the foam-suppressing and / or inhibiting We effect of defoamers. For effective damping or Inhibition of foam in aqueous systems, especially in those that be subjected to a strong dynamic load, and therefore be particularly strongly promote foam formation - with temperature and pressure Variations in the course of the process can have an additional influence - are consequently often the particularly effective defoamers based on silicone  used. When using such strong defoamers it can occur that these do not ver with certain components of a fleet are inert and / or under treatment conditions for destabilization tend so that the silicones can settle on the substrate and z. B. the particularly dreaded silicone stains appear on the treated goods can.

It has now been found that the surfactant mixtures (G) described below are excellent as a low-foaming aid, especially as a low-foaming agent Leveling agent, suitable for treatments in an aqueous liquor and that by Add mild mufflers, i.e. H. of those who are essentially free defoaming silicones, and preferably also free of paraffinic ones Wax and / or sparingly soluble high polymers are the defoaming Effect can be increased significantly, etc. so that even under strong dyna mixer loading of liquor and / or substrate, especially in closed apparatus, e.g. B. in nozzle dyeing apparatus, the formation of a disturbing amount of foam can be largely prevented.

The invention relates to the mixtures (G) defined below, the manufacturers thereof tion and its new components, as well as the (G) -containing preparations (P) and the use of (G) or (P) in the treatment of substrates in aqueous Medium.

A first subject of the invention is therefore mixtures (G) of (E) compounds of the general formula

wherein
R is a radical of the formula

R₁ is a hydrocarbon radical with 8 to 30 carbon atoms,
R _{2 is} a hydrocarbon radical having 7 to 29 carbon atoms,
XC _2-6 alkylene,
Y is a radical of the general formula

A is ethylene and optionally propylene, where at least 50% of the Σm radicals A are ethylene,
BC _4-6 alkylene or / and phenylethylene,
W is hydrogen or an anionic radical W 1,
r 0 to 3 if R = (α), 1 to 4 if R = (β), or 1 to 3 if R = (γ),
m at least 1,
Σm (r + p + 5) to 150,
n 0 or 1,
Σn 1 to (r + p + 2),
x 0 to m and
p 0 or 1

mean, and / or their protonation and / or quaternization products, or mixtures of such compounds,
with (F) compounds of the general formula

wherein
R _{o is} a radical of the formula (β) or (γ) or of the formula

means and the symbols R₁, R₂, A, X, W, m, Σm, p and r independently of (E) have the meaning given under (E), and / or their protonation and / or quaternization products, or mixtures of such compounds.  

Suitable hydrocarbon radicals R ₁ are conventional alkylaromatic or purely aliphatic hydrocarbon radicals, such as can occur in surfactant compounds; they can be saturated or unsaturated: the following fatty residues should be mentioned in particular: capryl, caprinyl, lauryl, myristyl, cetyl, stearyl, arachidyl, behenyl, lignoceryl, cerotyl, oleyl, elaidyl, linoleyl, linolenyl, gadoleyl, arachidonyl and docosenyl (brassidyl or the erucohydrocarbon fat residue) as well as technical hydrocarbon residue mixtures containing such fat residues, in particular coconut fat, tallow fat, tallow alkyl, technical oleyl, arachidyl / behenyl, arachidyl / behenyl / stearyl, stearyl / cetyl and oleyl / cetyl. Suitable R ₂ -CO- are generally customary acyl residues, in particular fatty acid residues of common fatty acids with 8 to 30 carbon atoms, in particular as they correspond to the fat residues listed above, especially caproyl, caprinoyl, lauroyl, myristoyl, palmitoyl, stearoyl, arachidoyl, behenoyl , Lignoceroyl, Cerotoyl, Oleoyl, Elaidoyl, Linoleoyl, Linolenoyl, Gadoleoyl, Arachidoyl and the rest of the erucic acid as well as technical mixtures, in particular the acyl residues of technical, optionally hydrogenated fatty acids, especially the coconut fatty acid, the tallow fatty acid, the tallow alkyl fatty acid technical oleic acid. Among the radicals mentioned, those with 12 to 24 carbon atoms, in particular with 16 to 24, especially with 18 to 22 carbon atoms, are preferred. Among the saturated and unsaturated fat residues, the saturated are preferred; of the technical mixtures preferred are those which are predominantly saturated (advantageously 80% by weight, preferably 90% by weight saturated). Among the radicals R ₂ -CO- and R ₁ , R _{1 is} preferred in the meaning of R.

X stands for any divalent C _2-6 alkane radical, as occurs in alkylene diamines and polyalkylene polyamines, advantageously for ethylene, propylene or hexamethylene, where if r <1, X preferably means ethylene and / or propylene and the r radicals X can have the same meaning or different meanings. X is preferably 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 is.

R advantageously stands for 0 to 2, in particular 0 or 1.  

The index p is preferably 0.

Of the total residues -A-O- occurring in formula (Ie) are above preferably at least 80% for ethyleneoxy groups; particularly preferably meaning ten all -A-O- ethyleneoxy groups occurring in the formula (Ie). In formula (If) too, at least 80% of the total radicals are advantageous -A-O- ethyleneoxy groups, preferably all in the formula (If) before upcoming residues -A-O- ethyleneoxy groups.

Suitable C _4-6 alkylene in the meaning of B are generally customary radicals, such as can be introduced into the molecule by addition of the corresponding cyclic oxides, especially the oxiranes, preferably butylene, in particular 1,2-butylene , -2.3 or -1.4. B is preferably phenylethylene and / or in particular butylene, especially 1,2-butylene.

The sum of the total groups -A-O- in (E), i.e. H. Σm, is advantageous (r + p + 6) to 70 [or at 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 entire groups -B-O- in (E), d. H. Σn, is advantageously 1 to (r + p + 1) and is preferably 3, in particular 1 to 2, especially 1 to 1.5.

Of the Σn groups -B- occurring in (E), at least half, preferably 0.5 to 2, in particular 1 to 2, C _4-6 alkylene, particularly preferably butylene, are advantageously advantageous on average, while preferably on average at most 0 , 5, ie 0 to 0.5, are phenylethylene groups. -B- is particularly preferably exclusively for butylene.

In the respective polyglycol chains (δ) occurring in (E), (at n = 1) the rest -B-O- in any position of the chain are, d. H. at x = m B is directly at N [or with p = 1 in the remainder (α) also directly bound to the CH-bound oxygen], or at x = 0 B is directly bound to -O-W, or at 0 <x <in -B-O-, e.g. B. as an intermediate link in a block polymer polyglycol ether chain, between two groups -A-O- switched on. X is particularly preferably 0 and the group -B-O- is located at the end of the attached chain, bound to W as -B-O-W.

If W stands for an anionic radical W ₁ , this can be any ionic radical, such as is usually used for the anionic modification of polyglycol radicals, primarily a sulfuric acid or phosphoric acid ester group or a dicarboxylic acid monoester group, as can be formed by esterification of the corresponding hydroxyl end groups, or a carboxy (C _1-3 alkyl) group (in particular carboxymethyl), as can be ent by carboxyalkylation, in particular carboxymethylation of the hydroxy group. These anionic groups W ₁ can be in salt form, with customary cations being considered for salt formation, primarily alkali metal cations (lithium, sodium, potassium) or optionally substituted ammonium cations (unsubstituted ammonium or mono-, di- or tri- (C _1-3 -alkyl) - or - (C _2-3 ) -hydroxyalkyl) -ammonium), or may form internal salts with basic amino groups of the molecule or, especially at lower pH values, may also be in the form of free acid. At least some of the symbols W advantageously represent hydrogen. The molecule advantageously contains on average not more than 1.5, preferably not more than one anionic substituent W ₁ . All W particularly preferably denote hydrogen.

Preferred mixtures (G) are those in which
A ethylene,
R is a radical of the formula (α),
r is a number from 0 to 2,
p zero,
Σm (r + 6) to 70
and Σn, in (E), 1 to (r + 1), where at most one of the Σn radicals is -B-phenylethylene, in particular those in which
R _{1 is} an aliphatic hydrocarbon radical with 12 to 24 carbon atoms,
X propylene,
x zero
and W is hydrogen, where the Zn radicals are -B-, in (E), 0 to 0.5 phenylethylene and 0.5 to (r + p + 2) butylene.

The compounds (F) are known or can be analogous to known methods are produced and serve as aids for the treatment of sub straten, especially as a leveling agent for dyeing fiber material. The compounds (E) also have an equalizing effect and their nei foaming is low; if (F) is blended with (E), it is overall effect of the mixture not worse than that of (F) allei ne, the tendency to foam surprisingly significantly sets is. The relative amounts of (E) and (F) can vary widely fluctuate richly and are appropriately chosen so that both effects, d. H. the own (especially leveling) effect of (F) and the reduced Tendency to foam to develop. The ge is advantageous weight ratio (E) / (F) in the range of 10/90 to 90/10, preferably 30/70 to 70/30, especially 1/2 to 2/1.

A special subject of the invention are the new products (E ₁ ), ie products (E) which are as defined above and in which -B- C _4-6 alkylene means and x = 0.

The compounds (E) and (F) can be prepared in a manner known per se by oxalylation of the respective starting amines and, if appropriate, further reaction of the product by introducing anionic radicals W ₁ and / or protonation and / or quaternization.

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

wherein R _{x is} a radical of the formula (β), (γ) or

means, or a mixture of such compounds, with the corresponding cyclic oxides

implements, if necessary introduces an anionic radical W 1 and the product if necessary protonated and / or quaternized.  

The compounds (F) can be prepared in an analogous manner by oxalkylating a compound of the formula (IIa) or a mixture of such compounds with the corresponding A-oxide (or the corresponding A-oxides), optionally introducing at least one anionic radical W ₁ and the product may protonate and / or quaternize.

According to a particularly advantageous process, mixtures (G) of (E) and (F) are prepared directly by reacting at least one amine of the formula (IIa) with A-oxide and B-oxide, the amount of B-oxide being chosen in this way will result in the corresponding mixtures. However, it is also possible to prepare the components (E) and (F) separately and then to mix them in a suitable quantitative ratio or to produce (F) in a mixture with part of (E) by mixed oxyalkylation and, if appropriate, further reaction, and then add further component (E) up to the desired mixing ratio. The preparation of (G) in a mixture is of course suitable if the symbols W, A, X and the indices r and p, and the sum Σm have the same meaning in components (E) and (F), and if R in each case derived from the same residue R _x . The properties of the final mixture can then be particularly adjusted by subsequent blending with further identical or different (F). The separate preparation of (E) and (F) is particularly suitable if in (E) Σn <1 (especially if Σn <1.5), while production in a mixture is particularly suitable if in the compounds (E) Σn predominantly = 1 [especially if in (E) Σn is on average 1 to 1.5].

The reaction of the compounds of formula (IIa) with the respective cycli oxides, primarily oxiranes (A-oxide: ethylene oxide, propylene oxide; B-oxide: butylene oxide, pentylene oxide, hexylene oxide, styrene oxide), for introduction The respective residues -A-O- or -B-O- can be used in any order be performed; preferably for the preparation of the compounds (E) first reacted with A-oxide and then with B-oxide. The implementation can be found at usual reaction conditions are carried out, mainly at elevated temperature, especially in the temperature range from 100 to 180 ° C, preferably 140 to 170 ° C, and in the presence of a suitable catalyst, especially an alkali metal hydroxide (sodium hydroxide, potassium hydroxide, Lithium hydroxide); the reaction can be carried out in an inert organic medium or in the absence of solvents, favorably with displacement  of atmospheric oxygen. The reaction with B-oxide is advantageous as the last oxalkylation.

The introduction of an anionic radical W ₁ can be carried out in a manner known per se and is advantageously carried out by reaction with a suitable acid or a functional derivative thereof, e.g. B. with a C _3-8 dicarboxylic acid or a functional derivative thereof, preferably the anhydride (particularly preferably the cyclic anhydride, for example maleic, Bernstein- or phthalic anhydride), with a C _2-4 chloroalkane carboxylic acid, in particular Chloroacetic acid, with phosphoric anhydride, with polyphosphoric acid or with sulfuric acid (possibly containing oleum) or a functional derivative thereof (e.g. chlorosulfonic acid or aminosulfonic acid), and if necessary with a base for salt formation. The reaction with a cyclic anhydride takes place, for. B. at 0 to 80 ° C, optionally in the presence of a catalyst, if desired with subsequent addition of a base for salt formation. The reaction with chloroacetic acid is advantageously carried out under dehydrohalogenating conditions, e.g. B. at 45 to 80 ° C, advantageously with the addition of an alkali metal hydroxide. The reaction with P ₂ O ₅ is advantageously carried out at 30 to 80 ° C., if desired with the addition of water and / or a base for salt formation. The reaction with aminosulfonic acid is advantageously carried out in the presence of urea, before 10 to 200% by weight of the amount of aminosulfonic acid used, before geous at temperatures between 75 and 130 ° C; the reaction with sulfuric acid is advantageously carried out in a similar temperature range, if desired with subsequent addition of a base for salt formation; the reaction with chlorosulfonic acid is advantageously carried out under dehydrohalogenating conditions, for. B. at 45 to 80 ° C and with the addition of alkali metal hydroxide.

Conventional acids, in particular mine, can be used for protonation ralic acids (sulfuric acid, phosphoric acid or preferably hydrochloric acid) or low-molecular aliphatic carboxylic acids (e.g. with 1 to 4 carbon atoms, especially formic acid, acetic acid, oxalic acid, lactic acid, wine acid or citric acid).

The quaternization can be used to introduce customary quaternizing radicals, in particular C _1-4 -alkyl, aryl- (C _1-3 -alkyl) or -CH ₂ -CO-NH ₂ ; conventional quaternizing agents can be used for the quaternization, in particular aryl (C _1-3 alkyl) halides (especially benzyl chloride), C _1-4 alkyl halides (preferably chlorides or bromides) or sulfates (e.g. dimethyl sulfate or diethyl sulfate) or chloroacetamide. The quaternization can take place under customary reaction conditions, for example in the temperature range from 40 to 120, preferably 60 to 100 ° C. The Qua ternierung can be exhaustive or partial, for. B. so that an average of 0.5 to 1 basic nitrogen is quaternized per molecule; preferably (E) and (F) are both non-quaternized.

The mixtures produced can directly to the desired solid content to be diluted with water and another object of the invention are the preparations (P) by a mixture (G), as above defined, marked.

The preparations (P) advantageously also contain (H) at least one non-ionic, cationic or weakly anioni foam-inhibiting additive that is essentially free of Ent foaming on silicone basis and preferably also of defoaming paraffin waxes and / or poorly soluble high polymers.

In general, low-foam compounds and foam-suppressing compounds come as (H) Connections into consideration, etc. both low-foam surfactants, such as those used as dyestuffs Tools can be used, e.g. B. low-foaming wetting agents (e.g. Fatty acid oligoethylene glycol monoesters or addition products of propylene oxide and ethylene oxide on fatty alcohols or on alkylphenols, e.g. B. with 12 to 24 carbon atoms in the lipophilic residue) or low-foaming coloring aids, which affect the affinity of the dye for the substrate (e.g. implementation products of fatty acids - e.g. B. those with 16 to 22 carbon atoms - With alkanolamines or aminoalkylalkanolamines, which may be oxa are thylated and may be in protonated form), as well as typically defoaming additives, e.g. B. of the lower alkyl ester type of higher Fatty acids, the fatty acid alkylene bisamides, the non-esterified fatty acids, the higher molecular weight, in particular also branched fatty alcohols, the phos trialkyl phosphate, the glycerol dialkyl ether or the emulsified Oils as they can also appear as fat lickers, especially if they are are emulsified with weakly anionic emulsifiers (e.g. of the fat type acids and the carboxymethylated derivatives of oxethylated higher fat  alcohols). The choice and amount of additives (H) is essentially determined by the intended area of application of the product. In general the relative amounts of (G) and (H) are appropriately chosen so that the mutual support of the foam-inhibiting effect as pronounced as possible and at the same time the functional effect of the product (G) (in particular which can effectively develop as a leveling agent). Is advantageous the weight ratio (G) / (H) 1/10 to 50/1, preferably 1.5 / 1 to 25/1.

Since some foam inhibiting additives, such as those that can be added as (H), may have insufficient water solubility and / or their solubility ability to produce more concentrated preparations u. Maybe not in such cases, it is an advantage (L) at least one solubilizer and / or a hydrotropic agent to admit.

Conventional water-soluble low-molecular compounds can be used as solubilizers and / or hydrotroping agents, e.g. B. polyols, ether alcohols or amides, e.g. B. mono- or diethylene glycol and C _1-4 mono alkyl ether thereof, propylene glycol and / or urea.

The amount and selection of the respective solubilizers and / or hydrotro Piermittel depends essentially on the nature of the other additives and their amount. The weight ratio (L) / ((G) + (H)) is in particular others in the range of 1/1 to 1/20.

The suitable amounts of (H) and also of (L) can be determined by some preliminary tests search can be determined.

The mixtures (G), preferably together with (H) and if necessary, together with (L), in the form of aqueous preparations formulated, the dry matter content for example in the range of 5 to 80 % By weight, preferably 20 to 75% by weight; the (G) content of the aqueous Preparations (P) are advantageously in the range from 5 to 60% by weight, preferably as 15 to 50 wt .-%. They are characterized by their shelf life out.  

The mixtures (G) according to the invention, preferably in the form of the above-defined th aqueous preparations (P) serve as aids, especially as Egali siermittel, in the treatment, especially in the coloring, of substrates from aqueous medium. Primarily fibrous materials come as substrates into consideration, in particular textile material, which is synthetic, animal or can be of vegetable origin, preferably from natural and / or synthetic polyamides (wool, silk, synthetic polyamides) and their Mixtures with other materials, e.g. B. with cotton, polyester, polyure thanen or polyacrylonitrile fibers. The above mixtures (G) serve in particular special as leveling agent for dyeing the substrates mentioned corresponding anionic dyes, such as those used for dyeing wool, Silk and / or synthetic polyamides are usually used, especially acid dyes, metal complex dyes, direct dyes, Vat dyes, sulfur dyes and mordant dyes, and include both the so-called whale dyes and the so-called neutralzie dyes. The substrates can be processed in any way form, as is usually the case for the respective dyeing process are used, e.g. B. as loose fibers, filaments, threads, strands, spools (also packages), fabrics, knitted fabrics, carpets, tufted goods, felts, nonwovens or velvet or as semi-finished or finished goods. The dyeing can after usual impregnation processes or pull-out processes take place, for. B. by Padding, dipping, spraying, foam application or preferably by pull-out drive in short or long fleet, especially the procedures below heavy dynamic stress on substrate and / or liquor (e.g. the Dyeing cross-wound bobbins or in jet dyeing apparatus) and those in which the substrates have a particular tendency to trap air (e.g. the coloring of Strands and of loop goods) are to be emphasized, because with these the Effect of the preparations according to the invention is particularly evident comes by not only inhibiting the formation of foam, but also that Deaeration of the substrate (e.g. in terry goods or in the formation of Favor air ducts in strands). The dyeing process can be done at usual temperatures, pH values and liquor lengths as they are suitable for the respective substrate (for natural poly amides advantageous at temperatures from room temperature (= 20 ° C) to 115 ° C, e.g. B. 20 to 100 ° C, and pH values in the range of 1.5 to 7.0, z. B. 3.5 to 6.5, and advantageous for synthetic polyamides at temperatures in the range from 30 to 150 ° C and pH values in the range from 2 to 9, e.g. B. 4.5 to 7.5; the liquor length for exhaust processes is advantageously in the range of 1: 2  to 1: 120, preferably 1: 5 to 1:60).

The concentration of the products according to the invention depends on the desired one Effect, especially leveling effect, chosen, etc. depending on the set dye and liquor length, as well as by substrate and special Application method, and is for example in the range from 0.1 to 5 g, preferably 0.2 to 2 g (G) per liter of aqueous liquor.

By the method according to the invention and using the Excellent preparations can be achieved with equalizing effects, with the addition of strong defoamers, especially those for May have a tendency to destabilize and / or residues disturbing on the substrate de (e.g. of silicones, of paraffinic waxes or of high polymers) can deposit, which then lead to stains that are very difficult to remove are or u. U. can not be removed at all without the goods damage, can be dispensed with. The other properties, esp special intensity and fastness of the dyeings as well as the physical Properties of the treated substrate are practically not affected is pregnant.

In the following examples, the parts mean parts by weight and the pro percent weight percentages, the temperatures are given in degrees Celsius; in the application examples, the percentages are based on the weight of the goods based.

example 1

1 mol of N- (γ-aminopropyl) fatty amine in the usual way, after addition of 1% sodium hydroxide based on the amine, at 150-165 ° C 35 moles of ethylene oxide deposited in the course of 4 to 5 hours; then still 0.5 mol of butylene oxide (98%) added and at a constant temperature attached. A brown pasty substance is obtained.

The N- (γ-aminopropyl) fatty amine used (DINORAM 42, from PROCHINOR) is a technical mixture with a molecular weight of 420, the fat residue mainly consisting of the following components: stearyl approx. 25%; Arachidyl about 25-35%; Behenyl approx. 30-40%; C _20-22 unsaturated approx. 2-5%.

Example 2

The procedure is as in Example 1, but is used instead of the one used there ten N- (γ-aminopropyl) fatty amines the equimolar amount of N- (γ-aminopropyl) - tallow fatty amine.

Example 3

The procedure is as described in Example 1, with the difference that place the equimolar of the N- (γ-aminopropyl) fatty amine used there Amount of tallow fatty amine is used.

Example 4

The procedure is as described in Example 3, with the difference that replace the tallow fatty amine with the equimolar amount of a technical fatty amine Mixture is used, which consists essentially of behenylamine and Arachidylamine exists.

Example 5

The procedure is as described in Example 1, with the difference that place of 0.5 mol of butylene oxide 1 mol of butylene oxide is added.

Example 6

The procedure is as described in Example 1, with the difference that place of 0.5 mol of butylene oxide 1 mol of styrene oxide is added.

Example 7

The procedure is as described in Example 6, with the difference that place of 1 mole of styrene oxide 1.5 moles of styrene oxide.

Example 8

The procedure is as described in Example 6, with the difference that place of 1 mole of styrene oxide 2 moles of styrene oxide.  

Example 9

The procedure is as described in Example 1, with the difference that finally 0.5 mol of styrene oxide with otherwise constant reaction conditions are attached.

Example 10

The procedure is as described in Example 1, with the difference that place of 0.5 mol of butylene oxide, 0.7 mol of butylene oxide.

Example 11

The procedure is as described in Example 1, with the difference that place of 0.5 mol of butylene oxide, 0.8 mol of butylene oxide.

Example 12

The procedure is as described in Example 4, with the difference that instead of 35 moles of ethylene oxide, 50 moles of ethylene oxide are added and instead of 0.5 mol of butylene oxide, 0.8 mol of butylene oxide can be added.

Example 13

The procedure is as described in Example 4, with the difference that place of 35 moles of ethylene oxide 55 moles of ethylene oxide can be added.

Example 14

The procedure is as described in Example 13, with the difference that finally 0.5 mol of styrene oxide with otherwise constant reaction conditions are attached.

Examples 15, 16 and 17

The products of Examples 5, 6 and 9 are each equimolar Amount of the non-butoxylated ethylene oxide adduct of Example  1 blended.

Examples 18 and 19

The products of Examples 7 and 8 are each with the equimolar amount of the product of Example 1 and with the sesquimolar amount of not butoxylated ethylene oxide addition product of Example 1 blended.

Preparation 1

The product of Example 1 is mixed with demineralized water Solids content of 30% diluted and brought to pH 5 with formic acid poses.

Preparation 2

400 parts of the product from Example 1 are premelted in a stirred flask at 60 ° C. and the following components are then added individually in succession and stirred:
180 parts of propylene glycol,
20 parts of tetramethylnonanol,
280 parts of demineralized water
and 120 parts of urea and then allowed to cool with stirring; when 25 ° C. is reached, the pH is adjusted to 7 by adding formic acid.

Preparation 3

The procedure is as in preparation 2, the following components being added in succession to the 400 parts of premelted product from example 1:
20 parts of the adduct of 6.5 mol of ethylene oxide and 1 mol of oleic acid,
20 parts of tetramethylnonanol,
140 parts of propylene glycol,
320 parts of demineralized water
and 100 parts of urea and the pH at 25 ° C is adjusted to 7 with formic acid.

Preparation 4

The procedure is as described for preparation 2, with the difference that the following products are added in sequence to the 400 parts of the premelted product from example 1:
60 parts of propylene glycol,
100 parts of butyl glycol,
50 parts glycerol diisobutyl ether 1,3,
270 parts of demineralized water
and 120 parts of urea and the pH at 25 ° C is adjusted to 7 with formic acid.

Preparation 5

The procedure is as described for preparation 2, with the difference that instead of 400 parts of the product from example 1, 400 parts of the product from example 6 are premelted at 60 ° C. and the following products are added in succession:
60 parts of a 30% aqueous solution of the condensation product oxyethylated with 2 mol of ethylene oxide and protonated with formic acid from 1 mol of oleic acid with 1 mol of N- (β-aminoethyl) ethanolamine 20 parts of metiloil (commercially available mixture of fatty acid methyl esters)
and 520 parts of demineralized water and then adjusting the pH to 7 at 25 ° C with formic acid.

Preparation 6

The procedure is as described for preparation 5, with the difference that the following components are added to the premelted product from example 6:
80 parts of the 30% condensation product specified in preparation 5,
240 parts of an aqueous 25% adduct of 2 moles of ethylene oxide and 1 mole of propylene oxide with 1 mole of oleyl alcohol
and 280 parts of demineralized water and the pH is adjusted to 7 with formic acid at 25 ° C.

Preparation 7

The procedure is as described for preparation 2, with the difference that 380 parts of the premelted product from example 1 are introduced and the following components are added in sequence, with stirring:
100 parts of the 25% aqueous adduct of 2 moles of ethylene oxide and 1 mole of propylene oxide with 1 mole of oleyl alcohol
60 parts of propylene glycol
and 460 parts of demineralized water,
and the pH is adjusted to 7 with formic acid at 25 ° C.

Preparation 8

The procedure is as described for preparation 7, with the difference that the following components are added in sequence to the 380 parts of premelted product from example 1, with stirring:
100 parts of fat liquor containing 26 X palm oil,
8% paraffin oil,
3% oleic acid,
12% carboxymethylated adduct of 12 moles of ethylene oxide and 1 mole of oleyl alcohol as sodium salt,
Rest of water,
60 parts of propylene glycol
and 460 parts of demineralized water and the pH is adjusted to 7 with formic acid at 25 ° C.

Preparation 9

The procedure is as described for preparation 2, with the difference that instead of the 400 parts product of Example 1, 400 parts of the product of Example 4 can be used.

Preparation 10

The procedure is as described for preparation 4, with the difference that instead of the 400 parts product of Example 1, 400 parts of the product of Example 4 can be used.

In an analogous manner, as described in preparations 1 to 10, the remaining of the products of Examples 1 to 19 used.

Application example A

In a laboratory jet from MATHYS with a nozzle of 55 mm diameter, polyamide 6 (Perlon) jersey is made in compliance with the following parameters:
Fleet = 6 l,
Flow = 60 1 / min.,
Goods run = 20 m / min.,
and with the following additions:
Dye = 0.5% of the Color Index Acid Blue 72 dye,
Leveling agent: product according to preparation 2, 1 g / l,
Acetic acid up to pH 6,
dyed as follows: the liquor is heated from 30 ° C. to 98 ° C. in the course of 40 minutes, then dyeing is continued at 98 ° C. for 30 minutes, after which it is cooled.

In the course of the heating phase, the foaming is very small and achieved no disturbing extent; in the further course of the dyeing process at 90-98 ° C the little foam disappears almost completely; is in the cooling phase Foaming only slight.

Application example B

Machine:
THEN HT Jet

Material:
7 kg warp chair fabric made of textured polyamide 66, pre-washed, rinsed, acidified and dried

Fleet:
1:40 (soft water)

Additions:
1.0 g / l ammonium sulfate
2.0% preparation 2
0.1% Lanasyn Ruby S-5BL = CI Acid Violet 128

The goods are drawn into the jet with water, then ammonium sulfate and Preparation 2 is added and the jet is run for 5 minutes at 30 ° C. Little foam develops. Running speed 150 m / min.

Then the dye is added and at 1 ° C / min to 80 ° C and then heated to 100 ° C at 2 ° C / min; it will be 15 minutes at this temperature further colored and then at 2 ° C / min. heated to 115 ° C, 5 minutes at treated at this temperature, cooled and rinsed.

The little foam present at 30 ° C becomes significantly lower from 60 ° C, ver but never disappears completely, d. H. throughout the dyeing process is always there is a little foam but there is no burst of foam, either when cooling the machine, e.g. B. at 95 ° C, the pressure on purpose very is drained quickly. The coloring is irrelevant and stain-free.

Application example C

Machine:
OBERMAIER HT dyeing machine

Material:
3 kg textured polyamide 66 yarn dtex 22f7 on spring sleeves, spool weight approx. 1 kg

Fleet:
1:10 soft water

Additions:
0.2 g / l sodium carbonate
1.0 g / l of the acid donor according to USP 4 568 351, Example 1,
0.8 g / l preparation 4
1.4% CI Acid Violet 48
0.08% CI Acid Blue 278

Fleet circulation:
1 cycl / min, inside → outside, no reversal.

The coloring is started at 40 ° C and it is raised to 105 ° C at 2 ° C / min heats, it is dyed at this temperature for 15 minutes, then indirectly Cooled 70 ° C and once after draining the well-exhausted dyebath cold water rinsed. The knitting test after drying shows one completely uniform coloring.

The foaming behavior of the products can also be done in a PRETEMA dyeing machine can be simulated and the foam behavior shows a similar picture there in the MATHYS laboratory jet.

Like preparation 2 or 4, the other of the above can also be used Use preparations in the above staining procedures and in the PRETEMA test.

Claims (17)

1. Mixtures (G) of
(E) compounds of the general formula wherein
R is a radical of the formula R₁ is a hydrocarbon radical with 8 to 30 carbon atoms,
R _{2 is} a hydrocarbon radical having 7 to 29 carbon atoms,
XC _2-6 alkylene,
Y is a radical of the general formula A is ethylene and optionally propylene, where at least 50% of the Σm radicals A are ethylene,
BC _4-6 alkylene or / and phenylethylene,
W is hydrogen or an anionic radical W 1,
r 0 to 3 if R = (α), 1 to 4 if R = (β), or 1 to 3 if R = (γ),
m at least 1,
Σm (r + p + 5) to 150,
n 0 or 1,
Σn 1 to (r + p + 2),
x 0 to m and
p 0 or 1
mean, and / or their protonation and / or quaternization products,
with (F) compounds of the general formula wherein
R _{o is} a radical of the formula (β) or (γ) or of the formula means and the symbols R₁, R₂, A, X, W, m, Σm, p and r independently of (E) have the meaning given under (E), and / or their protonation and / or quaternization products. 2. Mixtures (G) according to claim 1, wherein
A ethylene,
R is a radical of the formula (α),
r is a number from 0 to 2,
p zero,
Σm (r + 6) to 70,
and Σn, in (E), mean 1 to (r + 1), where at most one of the Σn radicals is -B-phenylethylene. 3. Mixtures (G) according to claim 1 or 2, wherein
R _{1 is} an aliphatic hydrocarbon radical with 12 to 24 carbon atoms,
X propylene,
x zero
and W is hydrogen, of the Σn radicals -B-, in (E), 0 to 0.5 phenylethylene and 0.5 to (r + p + 2) butylene. 4. Mixtures (G) according to one of claims 1 to 3, characterized in that that in (E) Σm = (r + p + 6) to 70 and in (F) Σm = 30 to 70.   5. Mixtures (G) according to any one of claims 1 to 4, wherein the weight ratio (E) / (F) is in the range of 10/90 to 90/10. 6. Mixtures (G) according to claim 5, wherein the weight ratio (E) / (F) in Range is 1/2 to 2/1. 7. The new products (E), as defined in claim 1, wherein -B- is C _4-6 alkylene and x = 0. 8. A process for the preparation of the compounds (E) as defined in claim 1, characterized in that a compound of the formula wherein R _{x is} a radical of the formula (β), (γ) or means, or a mixture of such compounds, with the corresponding cyclic oxides implemented, optionally introducing at least one anionic radical W 1 and optionally protonating and / or quaternizing the product. 9. Aqueous preparation (P) characterized by a content of a Ge mix (G) defined as in one of claims 1 to 6. 10. Aqueous preparation (P) according to claim 9, which is free from defoamers It is based on silicone and contains a mixture (G) and (H) at least one non-ionic, cationic or weakly anionic anti-foaming additive that is essentially free silicone defoamers, is marked. 11. Aqueous preparation (P), according to claim 10, characterized in that the weight ratio (G) / (H) is in the range from 1/1 to 50/1.   12. Aqueous preparation (P) according to claim 10 or 11, additionally containing (L) at least one solubilizer and / or a hydrotrope medium. 13. An aqueous preparation (P) according to claim 12, wherein the weight ratio (L) / ((G) + (H)) is in the range of 1/1 to 1/20. 14. Aqueous preparation (P) according to one of claims 9 to 13 with a Dry matter content in the range of 5 to 80 wt .-%. 15. Use of the mixtures (G) according to one of claims 1 to 6, given if necessary in the form of preparations (P) according to one of Claims 9 to 14, as an aid in the treatment of substrates from an aqueous medium. 16. Use according to claim 15 as a leveling agent in dyeing or opti brightening of fiber material with anionic dyes or ionic optical brighteners. 17. Use according to claim 16 for dyeing under HT conditions.