EP0417047A2 - Microemulsions of aminopolysiloxans - Google Patents

Abstract

Aqueous microemulsions of protonated aminopolysiloxanes ( alpha ) which contain an amphoteric surfactant ( beta ) and preferably at least one nonionic emulsifier ( gamma ) and optionally hydrotropes ( delta ) and/or cationic emulsifiers ( eta ) and whose pH is </= 7 are highly suitable for use as stable, in particular shearing-stable, finishes for fibre materials, in particular textile materials.

Description

For the finishing of substrates, especially textile material, with aminopolysiloxanes, the finest possible distribution of the same in the treatment liquor is desired, and so aminopolysiloxanes have been emulsified in water using certain techniques and / or surfactants to form finely divided emulsions to microemulsions. From EP 138 192 A e.g. known to produce such microemulsions over an oil concentrate, using certain oil-soluble surfactants, and by rapidly stirring the oil concentrate into water, the fineness of the emulsion depending on the speed of the dispersion. As is known, such emulsions have the shortcomings in EP 358 652 A with regard to type conformity and thermal stability. It is known from EP 358 652 to formulate certain aminopolysiloxanes as microemulsions using certain water-soluble, in particular nitrogen-free emulsifiers and acid.

The microemulsions mentioned have a certain stability. In technology - especially in the field of textile treatment - there was still a need for aminopolysiloxane microemulsions that would be sufficiently stable under shear forces to remain stable even under very high dynamic loads on the textile treatment fleet, i.e. in order to ensure their fine distribution in the treatment fleet and consequently their effectiveness (e.g. to maintain their ability to draw onto the substrate) and to prevent silicone deposits caused by destabilization on the treated goods (which leads to the dreaded silicone stains) and on appart parts (which affects both the treated goods due to silicone lubrication and the proper operation of the equipment and time-consuming cleaning of the device Equipment required) to avoid.

It has now surprisingly been found that using amphoteric - in particular nitrogen-containing - surfactants (β), as defined below, and adjusting the pH as defined below, aqueous aminopolysiloxane microemulsions with high shear stability, in particular as described below, can be prepared.

The invention relates to aqueous emulsifier-containing microemulsions of aminopolysiloxanes as defined below, their preparation and their use.

The invention relates to aqueous microemulsions of an aminopolysiloxane (α) which are characterized by a content of an amphoteric surfactant (β) and a PH ≦ 7.

The term microemulsion is used here in the most general sense of the word and encompasses liquid systems in which the components in the continuous phase are distributed so finely that the clear two-phase systems represent colloidal solutions. Microemulsions are understood here in particular to be those which are translucent to transparent (translucent to optically clear), essentially those with an average particle diameter (number average) of the dispersed particles ≦ 0.2 μm, preferably ≦ 0.1 μm, primarily in which the particle diameter of the dispersed Particles are predominantly ≦ 0.2 µm, preferably ≦ 0.1 µm.

Suitable aminopolysiloxanes (α) are generally any aminopolysiloxanes with a polycationic character, essentially those which are composed of recurring dimethylsiloxy units and aminosiloxy units (in particular aliphatic aminosiloxy units in which the amino group is bonded to Si via carbon). They can have a linear structure or a branched and / or networked structure. The end groups can have a reactive substituent, especially e.g. -OH, be included or optionally blocked; a preferred blocked end group is the trimethylsiloxy group.

worin A einen zweiwertigen Kohlenwasserstoffrest mit 2-6 Kohlenstoffato­men,
B Wasserstoff, C₁₋₄-Alkyl oder -(CH₂)_m-NH₂,
m 2 oder 3,
Z -CH₃ oder -O-X
und X Wasserstoff, Methyl oder die Bindung zu Resten der untenstehen­den Formeln (c) oder (d) oder einen Polysiloxanrest aus Einhei­ten (a) und/oder (b)
bedeuten.The aminopolysiloxanes to be used according to the invention are preferred built up from recurring units of the following formulas

where A is a divalent hydrocarbon radical with 2-6 carbon atoms,
B is hydrogen, C₁₋₄-alkyl or - (CH₂) _m -NH₂,
m 2 or 3,
Z -CH₃ or -OX
and X is hydrogen, methyl or the bond to residues of the formulas (c) or (d) below or a polysiloxane residue composed of units (a) and / or (b)
mean.

worin Y Methyl, Methoxy oder Hydroxy bedeutet.The end groups of the aminopolysiloxane chains preferably correspond to the formulas (c) and / or (d)

where Y is methyl, methoxy or hydroxy.

In the formulas (b) and (d), A preferably represents an aliphatic monoethylenically unsaturated or preferably saturated hydrocarbon radical having 3-4 carbon atoms, in particular 1,3-propylene or 2-methyl-1,3-propylene.

B preferably represents hydrogen, aminoethyl or aminopropyl, in particular aminoethyl.

Z is preferably methyl.

The aminopolysiloxanes (α) advantageously have a viscosity in the range from 500-30,000, primarily 700-20,000, preferably 1000-15,000 cP (Brookfield rotational viscometer RV, spindle No. 5, 20 ° C.). The amine number of the aminopolysiloxanes (α) is advantageously in the range from 0.1-3.0, preferably 0.3-1.2.

worin W₁ und W₂ jeweils eine Gruppe der Formel (c) oder (d) bedeuten, das Molekül mindestens eine Gruppe der Formel (b) aufweist und die Indices x und y so gewählt werden, daß das Polymere die oben-angegebenen Werte für Aminzahl und Viskosität aufweist. Das Verhältnis der Anzahl Dimethylsi­loxyeinheiten zur Anzahl Aminosiloxyeinheiten, insbesondere der Formel

liegt vorteilhaft im Bereich von 3/1 bis 300/1, vorzugsweise 10/1 bis 100/1.The aminopolysiloxanes (α) to be used according to the invention can be represented schematically by the following general formula

wherein W₁ and W₂ each represent a group of formula (c) or (d), the molecule has at least one group of formula (b) and the indices x and y are chosen so that the polymer has the values for amine number and Has viscosity. The ratio of the number of dimethylsiloxy units to the number of aminosiloxy units, especially the formula

is advantageously in the range from 3/1 to 300/1, preferably 10/1 to 100/1.

The aminopolysiloxanes can be prepared in a manner known per se or analogously to known methods, for example by aminoalkylation of polysiloxanes which have reactive Si-bonded hydrogen atoms, or primarily by copolymerization of silanes containing amino groups with nonionic mono- or polysiloxanes, preferably with α, ω-Dihydroxypolydimethylsiloxanes, advantageously with an average molecular weight M _n in the range from 500 to 10,000, preferably 1000 to 7000, or cyclic siloxanes, for example octamethylcyclotetrasiloxane. Suitable aminosilanes are primarily amino-substituted trimethoxysilanes or dimethoxymethylsilanes, in which the amino group is bonded to the silicon atom via carbon and corresponds primarily to the formula -A-NH-B. Preferred radicals -A-NH-B are γ-aminopropyl and γ- (β-aminoethylamino) propyl.

The aminoalkylation can be carried out under conditions known per se using customary aminoalkylating agents.

The copolymerization can be carried out in a manner known per se, primarily by reacting the reactants at moderate or elevated temperature, in particular at temperatures in the range from 15-180 ° C, optionally in the presence of a catalyst and, if desired, using end-blocking groups, e.g. with hexamethyldisiloxane. Acids (in particular formic acid, acetic acid, sulfuric acid, acidic ion exchanger or trifluoroethanesulfonic acid) as well as alkali metal or ammonium compounds, in particular alkali metal or ammonium silanolates (for example potassium or tetramethylammonium silanolate), alkali metal hydroxides, carbonates, or sodium carbonates (eg or sodium bicarbonate) or benzyltrimethylammonium hydroxide. If desired, polymerization can be carried out in the presence of an inert solvent, which can then be removed, for example by distillation, under polymerization conditions or subsequently removed.

If an amino group-containing trimethoxysilane is used to introduce the units of the formula (b), depending on the reaction conditions, the methoxy group Z can be saponified to give the hydroxyl group or can also continue to participate in the copolymerization, so that the copolymer can be branched at this point.

Depending on the chosen copolymerization conditions, the amino group-containing units in the molecule can be randomly distributed or terminal, or can be grouped as in block polymers or can still accumulate against the extremities of the linear chains.

For the microemulsions according to the invention, those aminopolysiloxanes (α) are preferred which have an optionally branched, predominantly linear structure of the polysiloxane backbone, preferably those in which Z is methyl. Also preferred are those linear polymers which are not end-blocked, essentially those in which in groups (c) and (d) Y is hydroxy.

worin R-CO- den Rest einer Fettsäure mit 8-24 Kohlenstoffatomen,
n eine Zahl von 2 bis 6,
R₁ Wasserstoff, C₁₋₄-Alkyl, Benzyl oder β-Hydroxy-äthyl oder -propyl,
R₂ C₁₋₄-Alkyl,
R₃ C₁₋₄-Alkyl, Benzyl oder β-Hydroxyäthyl oder -propyl,
G C₁₋₃-Alkylen oder 2-Hydroxy-propylen-1,3,
L eine Carboxy- oder Sulfogruppe
und Q⁻ ein Gegenion zum Ammoniumkation
bedeuten, oder Gemische davon.Suitable amphoteric surfactants (β) are primarily those which in addition to a fat residue and an anionic group (or acid group) in the molecule contain at least one tertiary amino group or quaternary ammonium group (protonated in the dipolar form of the ampholyte), primarily those as described in "Amphotheric Surfactants", Surfactants Science Series, vol. 12 (Bernard R. Bluestein, Clifford L. Hilton, 1982) and particularly in Chapter 1, pages 2-7, 16-36 and 50-59, in Chapter 2, pages 75-97, 113-119 , 122-131, 133-143, 155, 159 and 160, and in Chapter 3, on pages 178-203, 209, 219 and 220, including those preferred here that are on pages 30, 31, 77, 78, 87, 197 and 220 are described. Advantageously used as (β) are those amphoteric surfactants in which (based on the non-dipolar form of the ampholyte) the acid group is a carbon or sulfonic acid group and the lipophilic residue is bonded to the rest of the molecule via a carbamoyl group or the 2-membered group Is a substituent of an amphoteric imidazoline or the imidazolinium ring of a betaine of the imidazolinium series. The amphoteric surfactants (β) used are preferably those of the following formulas [where formulas (II) and (IV) represent the non-dipolar form of the respective ampholyte, but also - depending on the pH - in the corresponding dipolar form, for example as inner salt, may be present]

where R-CO- is the residue of a fatty acid with 8-24 carbon atoms,
n is a number from 2 to 6,
R₁ is hydrogen, C₁₋₄-alkyl, benzyl or β-hydroxyethyl or propyl,
R₂ C₁₋₄ alkyl,
R₃ C₁₋₄ alkyl, benzyl or β-hydroxyethyl or propyl,
G C₁₋₃ alkylene or 2-hydroxypropylene-1,3,
L is a carboxy or sulfo group
and Q⁻ a counter ion to the ammonium cation
mean, or mixtures thereof.

R in formulas (IV) and (V) corresponds in meaning to the symbol R in formulas (II) and (III), i.e. it stands for a corresponding aliphatic hydrocarbon radical with 7-23 carbon atoms.

vorliegen. Der Einfachheit halber werden sie im folgenden nur mit der Formel (V) angegeben.The quaternary imidazolinium compounds which, in addition to the 2-radical R, carry the N-bonded radicals R₃ and -GL, can optionally also be in the isomeric form

are available. For the sake of simplicity, they are given below only with the formula (V).

R-CO- is preferably the residue of an aliphatic fatty acid with 12-18 carbon atoms and can be saturated or unsaturated. The following fatty acid residues can be mentioned: lauroyl, palmitoyl, myristoyl, Oleoyl, stearoyl, behenoyl and arachidoyl as well as the residues of technical fatty acids, in particular tallow fatty acid or coconut fatty acid.

R₁ is advantageously methyl, ethyl or preferably β-hydroxyethyl.

R₂ is preferably methyl.

R₃ is advantageously methyl, ethyl or β-hydroxyethyl, in the formula (III) preferably for methyl and in the formula (V) preferably for β-hydroxyethyl.

G advantageously represents methylene, ethylene or 1,3-propylene or 2-hydroxypropylene-1,3. If L is a carboxy group, then G is preferably C₁₋₃ alkylene, especially methylene; L stands for the sulfo group, then G preferably denotes C₁₋₃-alkylene or in particular 2-hydroxypropylene-1,3.

The surfactants (β) can be used in the form of the free acids (or internal salts) or preferably as salts, in which L is -COOM or -SO₃M and M is a cation. M is preferably an alkali metal cation (in particular lithium, sodium or potassium).

Suitable counterions Q⁻ are generally conventional counterions, such as those formed in cyclization or quaternization reactions, primarily for the anion of a mineral acid (for example chloride or sulfate) or, particularly in the formula (III), advantageously also for methosulfate or ethosulfate, depending on the quaternizing agent used. Surfactants of the formula (II) in which n is 2 can be converted into those of the formula (IV) by cyclization reaction and conversely, surfactants of the formula (IV) can be converted into those of the formula (II) by hydrolysis in which n is 2.

In the microemulsions according to the invention, 5-60, preferably 10-40, in particular 15-35 parts by weight of the amphoteric surfactant (β) are advantageously used per 100 parts by weight of aminopolysiloxane (α).

The microemulsions according to the invention have a pH of 7 or less, which can be adjusted by adding acid, and the aminopolysi Loxanes (α) are present in the microemulsions according to the invention at least partially in protonated form. The pH values of the preparations according to the invention are advantageously in the range from pH 2-5, preferably pH 3-5.

Suitable acids (ε) which can be used for pH adjustment are any sufficiently strong acids, preferably
(ε₁) aliphatic carboxylic acids with 1-8 carbon atoms, in particular simple carboxylic acids with 1-6, preferably 1-4 carbon atoms (mainly formic acid, acetic acid, propionic acid and butter-re), dicarboxylic acids with 2-6 carbon atoms (mainly oxalic acid, succinic acid, glutaric acid and adipic acid) and hydroxycarboxylic acids with 3-8, preferably 3-4 carbon atoms (primarily lactic acid, tartaric acid, citric acid, gluconic acid and glucoheptonic acid),
and stronger acids
(ε₂) preferably mineral acids (especially hydrochloric acid, sulfuric acid or phosphoric acid) and stronger organic acids (especially trichloroacetic acid and trifluoromethanesulfonic acid)
Among the acids (ε₁) formic acid and acetic acid are preferred. Among the acids (ε₂), sulfuric acid and hydrochloric acid are preferred.

The microemulsions according to the invention advantageously contain at least one nonionic emulsifier (γ).

Suitable, non-ionic emulsifiers (γ) are especially those with an HLB value in the range of 5-16. The emulsifiers (γ) can have an aliphatic and optionally also aromatic character, but are preferably purely aliphatic. Sorbitol monoesters of C₈₋₁₆- (preferably C₁₁₋₁₄ -) fatty acids and oxyethylation products of fatty alcohols or of fatty acid amides, in which the fat residue advantageously contains 8-22, preferably 10-18, carbon atoms; optionally, in addition to the ethyleneoxy units, a number, in particular a smaller number, of propyleneoxy units can also be incorporated in the nonionic surfactant. Oxethylation products of the following fatty alcohols and fatty acid amides can be mentioned in particular: Lauryl alcohol, Myris tyl alcohol, cetyl alcohol, oleyl alcohol, stearyl alcohol and technical alcohols, especially tallow fatty alcohol and coconut fatty alcohol, as well as the analog fatty acid amides, and weakly or strongly branched, primary or secondary synthetic alcohols from oxo synthesis - e.g. from propylene - among which those with 10-15 carbon atoms are preferred, primarily trimethyl nonanol, tetramethyl nonanol and tetramethyl decanol, especially the primary isotridecyl alcohol tetramethyl nonanol-1; sorbitan monolaurate is particularly preferred among the sorbitol fatty acid esters. The degree of ethylation is expediently chosen so that the desired HLB value can be set. It is particularly advantageous to use two different emulsifiers (γ), etc. primarily non-ionic emulsifiers (γ₁) with a lower HLB value, advantageously an HLB value in the range 5-12, preferably 6-12, and emulsifiers (γ₂) with a higher HLB value, advantageously in the range 10 -16, preferably 12-16, the HLB value of (γ₂) advantageously being at least one unit, preferably at least two units, higher than that of (γ₁).

The HLB values of the oxyethylation products can be calculated using the known formula HLB = E / 5 (E =% by weight ethyleneoxy in the molecule).

Per 100 parts by weight of the aminopolysiloxane (α) advantageously 10-60, preferably 15-50 parts by weight of the nonionic emulsifier (γ) or the nonionic emulsifier mixture (γ₁) + (γ₂) are used. The weight ratio (γ₁) :( γ₂) is advantageously in the range from 1: 9 to 9: 1, primarily 1.5: 8.5 to 8.5: 1.5, preferably 4: 6 to 6: 4.

If desired, especially if (γ₁) emulsifiers with an HLB <10 are used, hydrotropes (δ) can be used.

Suitable as (δ) generally known, advantageously aliphatic, low-molecular compounds, preferably non-ionic C / H / O compounds, in particular with 4 to 24 carbon atoms, primarily aliphatic alcohols and / or ethers with 4 to 18, especially 4-12 carbon atoms. Preferred hydrotropes are polyols [in particular 1,3-butanediol, neopentyl glycol, pentaerythritol, 1,1,1-tris (hydroxymethyl) ethane or propane, 2,5-hexanediol and 2-methyl-pentane-2,4-diol] , Oligoalkylene glycols and their alkyl ethers [primarily di-, tri-, tetra-, penta- and Hexaethylene glycol and their mono- or di- (C₁₋₆-alkyl) ether, especially di-, tri- or tetraethylene glycol monobutyl ether and bis- (2-hydroxypropyl) ether, and dipropylene glycol] and on the anomeric hydroxy group by C₁₋₆- Alkyl etherified glucosides (preferably butyl glucoside).

Up to 60 parts by weight, preferably up to 50 parts by weight, in particular 5 to 50 parts by weight (δ), are advantageously used per 100 parts by weight (α).

The aqueous microemulsions according to the invention advantageously contain up to 70% by weight, primarily 15-70% by weight, preferably 20-60% by weight, in particular 30-50% by weight, of the total components [(α) + (β) + (γ ) + (δ)], the content of (δ) being 0-60% by weight based on (α).

in Betracht, worin
T einen Rest der Formel R′-CH₂-, R′-CO-NH-T′- oder R′-CH₂-O-T˝-,
R′ einen aliphatischen Kohlenwasserstoffrest mit 7-23 Kohlenstoff­atomen,
T₁ C₂₋₆-Alkylen,
T′ C₂₋₆-Alkylen,
T˝ C₂₋₆-Alkylen oder -CH₂-CHOH-CH₂-,
R₄ jeweils C₁₋₄-Alkyl oder einen Rest der Formel -(CH₂-CH₂-O)_q-H,
R₅ jeweils Wasserstoff oder C₁₋₄-Alkyl,
R₆ C₁₋₄-Alkyl, einen Rest der Formel -(CH₂-CH₂-O)_q-H oder T,
p eine Zahl von 1 bis 2,
q jeweils mindestens 1, wobei Σq ≦ 70,
und Q₁⁻ ein Gegenion zum Ammoniumkation
bedeuten.According to a preferred embodiment of the invention, the microemulsions according to the invention contain at least one cationic surfactant (η). Suitable cationic surfactants (η) are primarily ammonium compounds which contain at least one lipophilic residue, which is advantageously an aliphatic fat residue with 8-24 carbon atoms, preferably no more than one such lipophilic residue per ammonium group in the molecule. Cationic surfactants (η) are preferably those of the following formula

considering where
T is a radical of the formula R'-CH₂-, R'-CO-NH-T'- or R'-CH₂-OT˝-,
R ′ is an aliphatic hydrocarbon radical with 7-23 carbon atoms,
T₁ C₂₋₆ alkylene,
T ′ C₂₋₆ alkylene,
T˝ C₂₋₆ alkylene or -CH₂-CHOH-CH₂-,
R₄ in each case C₁₋₄-alkyl or a radical of the formula - (CH₂-CH₂-O) _q -H,
R₅ are each hydrogen or C₁₋₄ alkyl,
R₆ C₁₋₄ alkyl, a radical of the formula - (CH₂-CH₂-O) _q -H or T,
p is a number from 1 to 2,
q at least 1, where Σq ≦ 70,
and Q₁⁻ a counter ion to the ammonium cation
mean.

eingesetzt werden, welche dann, spätestens bei der Einstellung des pH-­Wertes auf pH ≦ 7, protoniert werden.If R₅ in the formula (VI) is hydrogen, the corresponding protonatable, free bases of the formula can advantageously

are used, which are then protonated, at the latest when the pH is adjusted to pH ≦ 7.

The radical R 'advantageously contains 11 to 21 carbon atoms. The radicals R'-CH₂- are primarily the following: lauryl, palmityl, cetyl, oleyl, stearyl, behenyl, arachidyl, tallow alkyl and cocoalkyl, among which those with 12-18 carbon atoms are preferred. Suitable residues R'-CO- are in particular the acyl residues of the corresponding fatty acids, e.g. as mentioned above for R-CO-.

T₁ and T 'are preferably T₂, i.e. for ethylene or propylene, of which 1,3-propylene is particularly preferred.

T˝ is preferably ethylene, propylene or 2-hydroxypropylene-1,3.

T is preferably T₀, i.e. for R'-CH₂- or R'-CO-NH-T'-.

In a preferred subgroup (η₁) of the cationic surfactants (η) mean
R₄ R₄ ′, ie methyl or ethyl,
R₅ R₅ ′, ie C₁₋₄ alkyl, preferably methyl or ethyl,
R₆ R₆ ′, ie C₁₋₄ alkyl, preferably methyl or ethyl,
and the index pp ′, ie 0 or 1, preferably 0; Q₁⁻ stands for conventional anions, in particular as they arise through quaternization, for example as mentioned above for Q⁻.

In a further preferred subgroup (η) of the cationic surfactants (η) mean
R₄ R₄˝, ie a radical of the formula - (CH₂-CH₂-O) _q ₁-H,
R₅ hydrogen,
R₆ R₆˝, ie a radical of the formula - (CH₂-CH₂-O) _q ₁-H,
pp˝, ie 0 or 1,
and q q1, ie at least 2, where Σq1 = 5 to 40, preferably 8 to 20; Q₁⁻ stands for a counter ion, such as that formed by protonation, in particular how it is formed by adding the acids (ε).

Die quaternären Tenside (η₁) entsprechen vorteilhaft der Formel

vorzugsweise der Formel

Preferred amines of the formula (VII) correspond to the formula

The quaternary surfactants (η₁) advantageously correspond to the formula

preferably of the formula

Preferably used as cationic surfactants (η) quaternary compounds (η₁), advantageously of formula (IX), preferably of formula (X), which advantageously with (η₂) or with the protonatable amines of formula (VII), preferably the Formula (VIII) can be blended. If (η₁) is blended with (η₂) or in particular with protonatable amines of the formula (VII) or (VIII), the weight ratio of (η₁) to (η₂) [the latter is calculated as a protonatable, free base of the formula (VII) ], preferably from surfactant of formula (IX) or (X) to surfactant of formula (VIII), advantageously in the range from 1 to 2 to 5 to 1, preferably 1/1 to 3/1.

The surfactants (η) are used particularly advantageously when surfactants (γ₁), in particular those of HLB ≦ 9, preferably HLB = 5 to 9, and / or oil-soluble surfactants (γ₁) are used, the surfactants here being referred to as oil-soluble , if at least 1g of it in 20g of a clear aminopolysiloxane (α) [in the form of the free amine and / or in (ε) protonated form] at 20 ° C give a clear solution.

Up to 30, preferably 8 to 20 parts by weight (η) are advantageously used per 100 parts by weight (α). The total content of [(α) + (β) + (γ) + (δ) + (η)] in the microemulsions according to the invention is advantageously in the range from 15 to 70% by weight, primarily 20 to 60% by weight, preferably 30 to 50% by weight, the content of (δ) being 0-60% by weight based on (α) and the content of (η) being 0-30% by weight based on (α).

The microemulsions according to the invention can be prepared by mixing the respective components, it being possible to add (β) to the non-protonated or protonated form of (α) and, if necessary, to adjust the pH to the desired value after adding (β) . The required or desired acidic pH values are expediently adjusted by adding acid, preferably by adding (ε), in particular (ε₁) and / or (ε₂).

The adjustment of the pH values can be done in one or more stages, i.e. by one or more acid additions. It is advantageous only with (ε₁) to a pH e.g. in the range of 3-7, favorably adjusted to a weakly acidic to neutral pH, preferably pH 6-7; the final pH, preferably in the range of 2-5, in particular 3-5, is preferably set with (ε₂). However, it is also possible to proceed only with (ε₁) or only with (ε₂).

The microemulsions according to the invention are preferably added to (α) by adding (β) and preferably (γ) [in particular (γ₁) and (γ₂)] and optionally (δ) and / or (η) and the required amount of water and acid (ε) ) produced. The order of additions is generally as long as the respective mixtures are easy to stir. For example, (α) can be mixed first with (γ₁) or with (δ) or with a mixture of (γ₁) and (δ) and then with the remaining components one after the other or as mixtures [eg (γ₂) + (β), or (γ₁) + (γ₂) + (β)], or (γ₁) + (γ₂) + (β) and optionally (δ) and / or (ε₁) can be added together to (α). Water and acid (ε₁) can be added separately or together with the respective components. (η) can be used in any stage, advantageously according to the other surfactants and preferably according to (ε). Advantageous sequences of additions of components (β), (γ₁), (γ₂), (ε₁) and (ε₂) to (α) can be represented by the following scheme 1 SCHEME 1 1. 2nd 3rd 4th 5. α γ₁ γ₂ β ε₂ α γ₁ γ₂ + β ε₂ α γ₁ + γ₂ β ε₂ α γ₁ + γ₂ + β ε₂ where (ε₁) can be added as desired in one or more of stages 1 to 5 and / or the intermediate stages between 1 and 2, 2 and 3, optionally 3 and 4 and optionally 4 and 5, (δ) if added is, optionally in one or more of stages 1 to 5 and / or the intermediate stages between 1 and 2, 2 and 3, optionally 3 and 4 and optionally 4 and 5 and / or after the addition of (ε₂) can be added.

The water required can be added separately or together with one or more of the components, advantageously with (β), (γ₂) and / or (δ). (β) is advantageously used as an aqueous preparation. Advantageous variants in the order of additions are in particular the following:

Variant a): Add to (α) first of (γ₁), then of [(γ₂) + water], then of [(β) + water] and then of (ε₂)
with the following sub-variants for the addition of (ε₁):
a₁): addition of (ε₁) before (γ₁),
a₂): addition of (ε₁) between (γ₁) and (γ₂) or together with (γ₁) or (γ₂),
a₃): addition of (ε₁) between (γ₂) and (β) or together with (β),
a₄): addition of (ε₁) after (γ₁), (γ₂) and (β),
and the following further sub-variants for the addition of (δ):
a _w ₁): (δ) before or together with (γ₁),
a _w ₂): (δ) before or together with (γ₂),
a _w ₃): (δ) before or together with (β),
a _w ₄): (δ) after (β) and before (ε₂),
where w = 1, 2, 3 or 4;
a further sub-variant is (a _w ₄₁) for the additional addition of residual (γ₁) with or after (β) and before (ε₂).

Variant b): Add to (α) first of (γ₁) then of [(γ₂) + (β) + water] and then of (ε₂)
with the following sub-variants for the addition of (ε₁):
b₁): (ε₁) before (γ₁),
b₂): (ε₂) between (γ₁) and [(γ₂) + (β) + water] or together with (γ₁) or [(γ₂) + (β) + water],
b₃): (ε₁) after [(γ₂) + (β) + water] and before the addition of (ε₂);
with the following further sub-variants for the additional addition of (δ):
b _w ₁): (δ) before (γ₁),
b _w ₂): (δ) between (γ₁) and [(γ₂) + (β) + water] or together with (γ₁) or [(γ₂) + (β) + water],
b _w ₃): (δ) according to [(γ₂) + (β) + water],
(w = 1, 2 or 3).

Variant c): addition to (α) a mixture of (γ₁) + (γ₂) + (β) and then addition of (ε₂)
with the following sub-variants for the addition of (ε₁):
c₁): (ε₁) before [γ₁) + (γ₂) + (β)],
c₂): (ε₁) together with [γ₁) + (γ₂) + (β)],
c₃): (ε₁) after [γ₁) + (γ₂) + (β)] and before (ε₂);
and the following further sub-variants for the additional addition of (δ):
c _w ₁): (δ) before [(γ₁) + (γ₂) + (β)],
c _w ₂): (δ) together with [(γ₁) + (γ₂) + (β)],
c _w ₃)): (δ) after [(γ₁) + (γ₂) + (β)] and before (ε₂), (w = 1, 2 or 3).

(η) can be added to any stage, advantageously after the addition of (β), advantageously after the addition of (ε₂). The water required and any water additionally required can be added in one or more stages, for example with variant c) together with (γ₁), (γ₂) and (β) and / or after the addition of (γ₁), (γ₂) and (β) before and / or simultaneously with the addition of (ε₁).

Particularly favorable sequences of additions of (β), (γ₁), (γ₂), (ε) [optionally divided into (ε₁) and (ε₂)] and optionally (δ) and / or (η) [optionally divided into (η₁ ) and (η₂)] can be represented by the following scheme 2 SCHEME 2 1. 2nd 3rd 4th 5. 6. 7. α γ₁ (β + γ₂) ¹ δ ε₁ ε₂ (η₁ + η₂) ² α γ₁ (β + γ₂ + δ) ¹ ε₁ ε₂ (η₁ + η₂) ² α γ₁ (β + γ₂ + δ + ε₁) ¹ ε₂ (η₁ + η₂) ² α γ₁ + γ₂ β¹ δ ε₁ ε₂ (η₁ + η₂) ² α γ₁ + γ₂ (β + δ) 1 ε₁ ε₂ (η₁ + η₂) ² α γ₁ + ε₁ (β + γ₂) ¹ δ ε₂ (η₁ + η₂) ² α γ₁ + ε₁ (β + γ₂ + δ) ¹ ε₂ (η₁ + η₂) ² α γ₁ + δ (β + γ₂) ¹ ε₁ ε₂ (η₁ + η₂) ² α δ (β + γ₁ + γ₂) ¹ ε₁ ε₂ (η₁ + η₂) ² α γ₁ + γ₂ + β δ¹ ε₁ ε₂ (η₁ + η₂) ² α (β + γ₁ + γ₂ + δ) ¹ ε₁ ε₂ (η₁ + η₂) ² ¹ Together with the main amount of water ² As an aqueous solution

By mixing the components (α), (β), (γ₁) and (γ₂) and water, and optionally (δ), cloudy emulsions (macroemulsions) can be formed, especially under neutral to basic conditions, even at elevated temperature, which but by adding acid - even only by adding (ε₁) - can be converted into translucent to clear microemulsions. If the (ε) protonated form won (α) is used from the beginning, then a microemulsion can already be formed by stirring in (γ₁), (γ₂) and water.

The respective components can be added at any suitable rate, i.e. e.g. an aqueous component or mixture of components can be added quickly and with rapid stirring in a few minutes or, most simply, by slowly stirring in over a period of one to several quarters of an hour (e.g. in the course of half an hour to two hours). The components can be mixed at any suitable temperature, e.g. in the range from 15 ° C. to the reflux temperature, advantageously from room temperature (= 20 ° C.) to 80 ° C., temperatures <50 ° C. also being particularly suitable.

The microemulsions according to the invention, in particular those prepared as described above, are suitable as finishing agents for fiber material and, as they are formulated, can be used directly to formulate the application liquor or, if necessary, can be diluted with water from aqueous medium to give more dilute stock dispersions, e.g. up to a dry matter content of 2 to 4% by weight. If desired, the aqueous preparations according to the invention can also contain other customary additives, such as fragrances or fungicides. They are suitable for the finishing of fiber material, in particular textile material from an aqueous medium, in particular for improving the grip and sliding properties.

It is suitable for any textile material as it occurs in the textile industry, etc. Both natural and synthetic and semi-synthetic materials and their mixtures, in particular natural or regenerated cellulose, natural or synthetic polyamide, polyester, polyurethane or polyacrylonitrile-containing material, as well as mixtures thereof (e.g. PES / CO and PAN / CO). The material can be in any form of processing, e.g. as loose fibers, filaments, threads, yarn strands and spools, fabrics, knitted fabrics, nonwovens, nonwovens, felts, carpets, velvet, tufted goods or also semi-finished or finished goods. Cross-wound bobbins, textile webs, textile tubular goods (in particular knitted tubular goods) or piece goods are preferably equipped.

The equipment is expediently carried out from an aqueous, clearly acidic to almost neutral medium, in particular in the pH range from 3.0 to 7.5. The concentration of the preparations according to the invention, based on the substrate, can vary within wide limits depending on the type and nature of the substrate and the desired effect and, calculated on component (α), is advantageously in the range from 0.1-1, preferably 0.2-0.6%, aminopolysiloxane (α), based on the dry weight of the substrate.

The finishing process according to the invention is advantageously carried out as the last finishing stage of the material, preferably following a bleaching, an optical brightening process and / or a dyeing process, optionally together with an additional treatment, e.g. a permanent finish (synthetic resin finish) of the fiber material. The equipment can be carried out by any conventional method, e.g. after impregnation process or after pull-out process. With pull-out processes, processes from both long and short fleets can be considered, e.g. with liquor ratios in the range from 100: 1 to 0.5: 1, in particular between 60: 1 and 2: 1; the application temperature can also be at customary values, for example in the range between room temperature and 60 ° C., preferably in the range from 25 ° C. to 40 ° C., the pH is preferably in the range from 4 to 6. The impregnation can also be carried out according to usual procedures are carried out, for example by dipping, padding, foam application or spraying, preferably at temperatures of 15-40 ° C and at pH values in the range of 3.5-7. After the impregnation process or after the pull-out process, the treated goods can be dried in the usual way, e.g. at 30 to 180 ° C, preferably 60 to 140 ° C.

The microemulsions according to the invention are notable for excellent resistance (particularly shear stability) and the application liquors are stable and remain effective, in particular even when the liquor and / or textile material is subjected to high dynamic loads; They are therefore suitable, for example, for finishing in reel runners, in jiggers, in yarn dyeing machines, in piece dyeing machines (so-called "garment dyeing machines") and in particular also in nozzle dyeing machines, etc. even in those in which extremely high shear forces (including impact and rebound forces) are effective. The preparations according to the invention are also very suitable for the wet finishing of packages. In this case too, the strong dynamic loading of the liquor, which is forced outwards from the inside of the bobbin by the threads of the cheese, has practically no negative effect on the preparation according to the invention and the equipment obtained with it. The preparations according to the invention - in particular those containing (η) - are, in the treatment liquors, also resistant to impurities, which may originate, for example, as residues from a previous treatment of the substrate, in particular to anionic impurities, for example dyes, optical brighteners or surfactants.

In the following examples, the parts are parts by weight and the percentages are percentages by weight, the temperatures are given in degrees Celsius; Parts by weight relate to parts by volume like g to ml.

worin R˝-CO- Oleoyl bedeutet und R˝ in (β₁) die gleiche Bedeutung (C₁₇H₃₃) wie in (β₂), (β₃) und (β₄) aufweist.
*technisches Isomerengemisch aus der OxosyntheseThe surfactants (β) used are the following:

wherein R˝-CO- oleoyl and R˝ in (β₁) has the same meaning (C₁₇H₃₃) as in (β₂), (β₃) and (β₄).
* Technical mixture of isomers from oxosynthesis

The emulsifiers (γ₁) and (γ₂) used are the following:
(γ₁₁) adduct of 4 moles of ethylene oxide with 1 mole of technical isotridecyl alcohol *
(γ₁₂) adduct of 5 moles of ethylene oxide and 1 mole of technical isotridecyl alcohol *
(γ₁₃) adduct of 6 moles of ethylene oxide with 1 mole of 2,6,8-trimethylnonanol-4 (Tergitol TMN-6, UNION CARBIDE)
(γ₁₄) adduct of 3 moles of ethylene oxide with 1 mole of C₁₁₋₁₅ alkanol (Tergitol 15-S-3)
(γ₁₅) sorbitan monolaurate
(γ₂₁) adduct of 9.5 mol of ethylene oxide with 1 mol of technical isotridecyl alcohol *.

worin C₁₇H₃₅-CO- den Stearoylrest bedeutet,
C₁₈H₃₅- den Oleylrest bedeutet
und v + z = 15.The surfactants (η₁) and (η₂) used are the following:

in which C₁₇H₃₅-CO- means the stearoyl radical,
C₁₈H₃₅- means the oleyl radical
and v + z = 15.

Example 1 (Products A, B, C and D)

185.4 parts of α, ω-dihydroxypolydimethylsiloxane with a hydroxyl number of 26 (determined by the phenyl isocyanate method) and an average molecular weight M _n of 5000 (determined by vapor pressure osmometry) are briefly stirred with 12.2 parts of N- (β-aminoethyl) -γ- (methyldimethoxysilyl) propylamine. Then 2.4 parts of glacial acetic acid are added and the mixture is heated to 75 ° C. under nitrogen. After 5 hours at this temperature it is reduced to 50 ° C cools, the nitrogen supply is turned off and 30 parts (γ₁₂) are added. Then 480.5 parts of a solution of 30 parts (γ₂₁) in 450.5 parts of water are added dropwise within 1 hour. As soon as about 140.0 parts of the aqueous solution have been added dropwise, the emulsion becomes transparent. Now add 3.5 parts of glacial acetic acid at 30 ° C as well
(for product A) 120 parts of a 50% aqueous solution of (β₁) or
(for product B) 120 parts of a 50% aqueous solution of (β₂) or
(for product C) 120 parts of a 50% aqueous solution of (β₃) or
(for product D) 120 parts of a 50% aqueous solution of (β₄).

The pH is then adjusted to 4.0 with 36.5% hydrochloric acid. Transparent aminopolysiloxane microemulsions which are stable under shear forces are obtained.

Example 2 (Product E)

188.70 parts of α, ω-dihydroxypolydimethylsiloxane (as in Example 1) are stirred with 12.50 parts of N- (β-aminoethyl) -γ- (methyldimethoxysilyl) propylamine and mixed with 0.07 part of 50% sodium hydroxide solution. The mixture is then heated to 112 ° C. under nitrogen, 1 volume part of distillate being collected. After 3½ hours it is cooled to 40 ° C. As soon as this temperature has been reached, 0.02 part of sodium bicarbonate is added and the mixture is heated to 110 ° C. under vacuum (at 70 mbar). It is then cooled to 50 ° C and relieved of nitrogen, and 30 parts (γ₁₂) are added. Then 480 parts of a solution of 30 parts (γ₂₁) in 450 parts of water are added dropwise within 1 hour. Then 3 parts of glacial acetic acid, 100 parts of a 50% aqueous solution of (β₄), 147 parts of water and 20 parts of (γ₁₃) are added and the pH is adjusted to 4 with about 20 parts of 36.5% hydrochloric acid , 0 a. First, a shear force stable aminopolysiloxane microemulsion (product E).

Example 3 (Product F)

200.0 parts of a by condensation of 600.0 parts of α, ω-dihydroxypolydimethylsiloxane (as in Example 1) and 39.6 parts of N- (β-aminoethyl) -γ- (Methyldimethoxysilyl) propylamine, with the addition of 7.7 parts of glacial acetic acid as a catalyst, prepared aminopolysiloxane are mixed at 50 ° C with 30 parts (γ₁₁) and 20 parts of butyl monoglucoside. Then 480.5 parts of a solution of 30 parts (γ₂₁) in 450.5 parts of water are added dropwise within 1 hour. Then 120 parts of a 50% aqueous solution of (β₄), 138.5 parts of water and 11.0 parts of formic acid are added. A shear force stable aminopolysiloxane microemulsion (product F) is obtained.

Example 4 (Product G)

200.0 parts of a by condensation of 600.0 parts of α, ω-dihydroxypolydimethylsiloxane (as in Example 1) and 39.6 parts of N- (β-aminoethyl) -γ- (methyldimethoxysilyl) propylamine with the addition of 7.7 parts Glacial acetic acid aminopolysiloxane are mixed at 50 ° C with 30 parts (γ₁₁). Then 480.5 parts of a solution of 30 parts (γ₂₁) in 450.5 parts of water are added dropwise within 1 hour. Then 3.7 parts of glacial acetic acid, 120.0 parts of a 50% aqueous solution of (β₄), 87.8 parts of water, 18.0 parts of 36.5% hydrochloric acid are used to adjust the pH to 4.0 and 60.0 parts of dipropylene glycol were added in succession. A shear-stable aminopolysiloxane microemulsion (product G) is obtained.

Example 5 (Product H)

300.00 parts of α, ω-dihydroxypolydimethylsiloxane with a hydroxyl number of 26 (determined by the phenyl isocyanate method) and an average molecular weight M _n of 5000 (determined by vapor pressure osmometry) are heated to 75 ° C. with 19.80 parts of N-aminoethyl-aminopropyl-methyldimethoxysilane and 3.84 parts of glacial acetic acid until a Brookfield rotational viscosity in the range of 30,000-40 '000 cP is reached. Then 3.58 parts of potassium hydroxide dissolved in 5.38 parts of water are added and the reaction is continued under nitrogen at 75 ° C. until a Brookfield rotational viscosity in the range from 7000 to 9000 cP is reached. Now the heating and nitrogen addition are turned off and 49.00 parts (γ₁₄) are added. Now let an aqueous solution consisting of
762.15 parts water
49.00 share (γ₂₁)
195.96 parts of a 50% aqueous solution of (β₄)
and 130.64 parts of an 80% aqueous butyl monoglucoside solution
flow to. Then about 13.00 parts of glacial acetic acid and 25.00 parts of 36.5% hydrochloric acid are added in order to adjust the pH to 4.0. A transparent product is obtained which also contains 16.33 parts (η₂₁) and 26.65 parts (η₁₁) dissolved in 11.76 parts of water and 26.91 parts of dipropylene glycol are added. 1633.00 parts of product H with good shear stability are obtained.

Example 6 (Product J)

The procedure is as in Example 5 until the heating and the nitrogen supply are switched off. Now 16.33 parts (γ₁₄) and 32.67 parts (γ₁₅) are added. Then an aqueous solution consisting of
745.81 parts water
49.00 share (γ₂₁)
195.96 parts of a 50% aqueous solution of (β₄)
and 130.64 parts of an 80% aqueous butyl monoglucoside solution
flow to. Then about 13.00 parts of glacial acetic acid and 25.00 parts of 36.5% hydrochloric acid are added to adjust the pH to 4.0. A transparent product is obtained, which is mixed with 39.98 parts (η₁₁) dissolved in 17.64 parts of water and 40.37 parts of dipropylene glycol. 1633.00 parts of product J with good shear stability are obtained.

Example 7 (Product K)

The procedure is as in Example 5 until the addition of (γ₁₄). Now let an aqueous solution consisting of
729.48 parts water
49.00 share (γ₂₁)
195.96 parts of a 50% aqueous solution of (β₄)
and 130.64 parts dipropylene glycol
flow to. Then about 13.00 parts of glacial acetic acid and 25.00 parts of 36.5% hydrochloric acid are added to adjust the pH to 4.0. A transparent product is obtained, which is mixed with 16.33 parts (η₂₁) and 39.98 parts (η₁₁) dissolved in 17.64 parts of water and 40.37 parts of dipropype glycol. 1633.00 parts of product K with good shear stability are obtained.

Example 8 (Product L)

The procedure is as in Example 7, with the difference that 1,3-butanediol is used instead of dipropylene glycol.

Examples 6bis, 7bis and 8bis (products J ′, K ′ and L ′)

The procedure is as described in Examples 6, 7 and 8, with the difference that instead of the solution of 39.98 parts (η₁₁) in 17.64 parts of water and 40.39 parts of dipropylene glycol or 1,3-butanediol Solution of 39.98 parts (η₁₁) in 58.01 parts of water is used. 1633.00 parts of product J ′, K ′ and L ′ with good shear stability are obtained.

Example 9 (Product M)

337.46 parts of octamethylcyclotetrasiloxane, 10.50 parts of N-aminoethylaminopropylmethyldimethoxysilane and 0.75 part of a 35% solution of benzyltrimethylammonium hydroxide in methanol are stirred together and heated to 80.degree. After 4 hours at 80 ° C., the mixture is warmed to 150 ° C. within 30 minutes and after 1 hour at 150 ° C. the unreacted octamethylcyclotetrasiloxane is distilled off under vacuum. This gives 26.62 parts of distillate and 322.09 parts of an amino-modified polydimethylsiloxane, which is cooled to room temperature. Now 32.21 parts (γ₁₄) and then an aqueous solution consisting of
644.18 parts water
64.42 parts (γ₂₁)
322.09 parts of a 50% aqueous solution of (β₄)
and 128.84 parts of an 80% aqueous butyl monoglucoside solution admitted. A cloudy emulsion is obtained, which is adjusted to pH 4.0 using 14.82 parts of glacial acetic acid and 23.83 parts of 36.5% hydrochloric acid. The cloudy emulsion is now heated to 50 ° C, creating a clear product. Now it is cooled to room temperature and, before unloading, 80.52 parts of a 50% solution of (η₁₂) in isopropanol are added. 1633.00 parts of the shear-stable product M are obtained.

Application examples A to C

• A. 1 kg of the substrate to be finished (textile, cotton single jersey, blue) are treated at 40 ° C and a liquor ratio 1: 8 on a laboratory jet from MATHIS (Switzerland) with 40g finishing agent (products A to M). The liquor circulation is 60 l / min. and the treatment time 20 minutes. The water has a hardness of 10 ° dH (according to DIN 53905) and a pH of 4. After the treatment, the substrate is spun, dried for 90 seconds at 140 ° C. without stretching and the soft feel is determined. There are no deposits or greasy deposits during treatment. There are no stains on the textile goods. No residues can be observed in the apparatus after the fleet has been drained. All products (A to M) are shear stable and result in a significant improvement in the feel of the treated textile goods (compared to those treated without silicone microemulsion). Analogous to that described in application example A, product A, B, D, E, F, G, H, J, J ', K, K', L, L 'or M is used instead of product C.
• B. Apparatus: THIES-Jet R95, 3 chambers;
  Substrate: 360kg polyester / cotton (50/50) single jersey, green color (disperse and reactive dye);
  Product: 2.0% (based on product weight) Product C;
  Fleet: 2000 l permutite water;
  Liquor ratio: 1: 5.5;
  pH: 4.5;
  Temperature: 30 ° C;
  Treatment time: 20 minutes;
  Goods speed: 200 m / min .;
  Workflow: The product is pre-diluted in 150 l of water in 5 minutes. No residues, deposits or stains are formed. The product appearance and the soft feel of the dry goods are flawless.
• C. Apparatus: 3-reel jet from AVESTA (Sweden); Substrate: 150kg polyester / cotton (50/50) intimate blend jersey, dyed with reactive and disperse dyes (one-bath, two-stage) and cationically treated;
  Product: 2.0% (based on product weight) Product C;
  Fleet of 2200 l permutite water;
  Liquor ratio: 1:15;
  pH: 4.5;
  Temperature: 30 ° C;
  Treatment time: 20 minutes;
  Goods speed: 90 m / min .; Workflow: The product is pre-diluted in 150 l of water in 5 minutes. The temperature remains constant. When unloading the goods, there are no stains or deposits on the goods or in the apparatus. After drying, the treated goods have an excellent soft feel.

Analogously as described in application examples B and C, products H, J and K are used instead of product C.

In application example C, a GASTON-COUNTY jet is used in the same way as on the AVESTA jet.

Claims (10)

1. Aqueous microemulsions of an aminopolysiloxane (α), characterized by a content of an amphoteric surfactant (β) and a pH ≦ 7. 2. Aqueous microemulsions according to claim 1 containing per 100 parts by weight of aminopolysiloxane (α) 5-60 parts by weight of amphoteric surfactant (β). 3. Aqueous microemulsion according to claim 1 or 2, containing at least one non-ionic emulsifier (γ). 4. Aqueous microemulsions according to claim 3, containing 10-60 parts by weight of non-ionic surfactant (γ) per 100 parts by weight of aminopolysiloxane (α). 5. Aqueous microemulsions according to claims 3 or 4, containing a hydrotropic compound (δ). 6. Aqueous microemulsions according to any one of claims 1-5 containing at least one cationic surfactant (η). 7. Aqueous microemulsions according to any one of claims 1-6, containing 15-70 percent by weight [(α) + (β) + (γ) + (δ) + (η)], the content of (δ) 0-60 wt % based on (α) and the content of (η) 0-30% by weight based on (α). 8. A process for the preparation of the microemulsions according to any one of claims 1-7 by mixing (α) with the other microemulsion components, characterized in that before, with and / or after the addition of (β) acid (ε) is added. 9. Use of the microemulsions according to any one of claims 1-8 for finishing textile or non-textile fiber material. 10. Use according to claim 9 for finishing textile material in nozzle dyeing apparatus.