DE3929757A1 - Amino-polysiloxane micro-emulsions useful for textile finishing - Google Patents

Abstract

Aq. microemulsions (I) of aminopolysiloxanes contain an amphoteric surfactant (II) and have pH not above 7. (I) are -produced by mixing the aminopolysiloxane with the other components, with addn. of acid before, with and/or after addn. of (II). (I) contains 5-60 pts. wt. (II) per 100 pts. wt. polymer; (I) also contain non-ionic emulsifier(s) (III), pref. 10-60 pts. wt./100 pts. wt. (polymer), pref. with a hydrotropic cpd. (IV) and cationic surfactant(s) (V); (I) contain 15-70 wt.% (aminopolysiloxane + (II) m+ (III) + (IV) + (V)), of which the amt. of (IV) is 0-60 wt.% and the amt. of (V) is 0-30 wt.% (both w.r.t. aminopolysiloxane).

Description

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

The invention relates to aqueous microemulsions of an aminopoly siloxanes (α), which are characterized by a content of an amphoteric surfactant (β) and a pH 7 are characterized.

The term microemulsion is used here in the most general sense of the word used and includes liquid systems in which the components in the continuous phase are so finely distributed that they clear two phase systems up to colloidal solutions. As microemulsions In particular, those are understood here, the translucent to transpa rent (translucent to optically clear) are essentially those with a particle diameter of the dispersed particles 0.2 .mu.m, preferably way 0.1 microns.

Suitable aminopolysiloxanes (α) are in general any desired aminopo lysiloxanes of polycationic character essentially those which are repeating dimethylsiloxy units and aminosiloxy units (esp special aliphatic aminosiloxy units) are constructed. You can a linear structure or even a branched and / or networked  Have structure. The end groups may be blocked if necessary; a preferred blocked end group is the trimethylsiloxy group.

Preferably, the aminopolysiloxanes to be used according to the invention are composed of recurring units of the following formulas

and

wherein
A is a divalent hydrocarbon radical having 2-6 carbon atoms,
B is hydrogen, C _1-4 -alkyl or - (CH₂) _m -NH₂,
m 2 or 3,
Z is -CH₃ or -OX
and
X is hydrogen, methyl or the bond to radicals of the below formulas (c) or (d) or a polysiloxane radical of units (a) and / or (b)
mean.

The end groups of the Aminopolysiloxanketten preferably correspond to the Formulas (c) and / or (d)

wherein Y is methyl or hydroxy.

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

Advantageously, the aminopolysiloxanes (α) have a viscosity in the range from 500-30,000, preferably 1000-15,000 mPa · s (Brookfield Rotations viscometer RV, spindle no. 5, 20 ° C). The amine number of the aminopolysiloxanes (α) is advantageously in the range of 0.1-3.0, preferably 0.3-1.2.

Schematically, the aminopolysiloxanes to be used according to the invention can be used (α) are represented by the following general formula

wherein W₁ and W₂ each represent a group of the formula (c) or (d) which Molecule has at least one group of formula (b) and the indices x and y are chosen such that the polymer has the values given above for Amine number and viscosity. The ratio of the number of dimethylsilo  xyeinheiten to the number Aminosiloxyeinheiten, in particular the formula

is advantageously in the range of 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 having reactive Si-bonded hydrogen atoms, or primarily by copolymerization of amino-containing silanes with non-ionic mono- or polysiloxanes, preferably with α, ω-dihydro xypolydimethylsiloxanen, z. B. having an average weight Molekularge _n in the range from 500 to 10,000, preferably 1000 to 7000, or cyclic siloxanes such. For example, octamethylcyclotetrasiloxane. Suitable aminosilanes are, for example, amino-substituted trimethoxysilanes or dimethoxymethylsilanes, in which the amino group is bound via carbon to the silicon atom 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 Use of conventional aminoalkylating done.

The copolymerization can be carried out in a manner known per se, primarily by reaction of the reactants in moderate or elevated temperature, for. B. at temperatures in the range of 15-180 ° C, gege if appropriate in the presence of a catalyst and, if desired, below Use of endblocking groups, eg. B. with hexamethyldisiloxane. When Catalysts may be, for example, alkali metal or ammonium silanolates be used, for. For example, potassium or tetramethylammonium silanolate, Alka limetal hydroxides, carbonates or bicarbonates, e.g. For example, potassium hydroxide, Sodium hydroxide or sodium bicarbonate or benzyltrimethylammonium hydroxide. If desired, in the presence of an inert solvent be polymerized, for. As an aliphatic alcohol, then, under Polymerization conditions or subsequently, for example abdestil can be liert.  

Is an amino group-containing trimethoxysilane for the introduction of Einhei Depending on the reaction conditions, the Methoxy group Z are hydrolyzed to the hydroxy group or even further at the Participate in copolymerization, so that at this point a branching of the copolymer can take place.

Depending on the chosen copolymerization conditions, the amino groups containing units in the molecule to be distributed statistically or terminally or be grouped in block polymers or even against the Piling limbs of linear chains.

For the microemulsions according to the invention are those Aminopolysilo xane (α) preferably having a substantially linear structure, preferably those in which Z is methyl. Next are those Preferably, linear polymers which are not endblocked are substantially those in which, in groups (c) and (d), Y is hydroxy.

As amphoteric surfactants (β) are primarily those which are In addition to a fat residue and an acid group in the molecule at least one tertiary amino group or quaternary ammonium group, distinguished such as in "Amphotheric Surfactants", Surfactants Science Series, vol. 12 (Bernard R. Bluestein, Clifford L. Hilton, 1982) and in particular Chapter 1, pages 2-7, 16-36 and 50-59, in Chapter 2, at pages 75-97, 113-119, 122-131, 133-143, 155, 159 and 160, and in chapter 3, pages 178-203, 209, 219 and 220, among which those are preferred here, on the Pages 31, 77, 78, 87, 197 and 220 are described. Be beneficial used as (β) such amphoteric surfactants, wherein the acid group is a Carbon or sulfonic acid group is and the lipophilic radical over a Carbamoyl group is attached to the rest of the molecule or the second Substituent of an amphoteric imidazoline or imidazolinium ring of a betaine of the imidazolinium series. Preferably, as ampho Tere surfactants (β) used those of the following formulas  

or

wherein R-CO- is the radical of a fatty acid having 8-24 carbon atoms,
n is a number from 2 to 6,
R₁ is hydrogen, C _1-4 -alkyl, benzyl or β-hydroxy-ethyl or -propyl,
R₂ is C _1-4 alkyl,
R₃ is C _1-4 -alkyl, benzyl or β-hydroxyethyl or -propyl,
GC _1-3 -alkylene or 2-hydroxy-propylene-1,3,
L is a carboxy or sulfo group
and Q⊖ is a counterion to the ammonium cation
mean, or mixtures thereof.
R in the formulas (IV) and (V) corresponds in meaning to the symbol R in the formulas (II) and (III), ie it represents a corresponding aliphatic hydrocarbon radical having 7-23 carbon atoms.

The quaternary imidazolinium compounds, in addition to the second radical
R bear the N-bonded radicals R₃ and -GL, may optionally also in the isomeric form

available. For the sake of simplicity, they will be described below only with the Formula (V) indicated.

Preferably, R-CO- is the residue of an aliphatic fatty acid having 12-18 carbon atoms and may be saturated or unsaturated. The following fatty acid residues may be mentioned: lauroyl, palmitoyl, myristoyl, oleoyl, stearoyl, behenyl and arachidoyl and the radicals of technical fatty acids, in particular tallow fatty acid or coconut fatty acid.
R₁ is preferably methyl, ethyl or β-hydroxyethyl; in the formulas (II) and (IV) R₁ is preferably β-hydroxyethyl and in the formula (III) is methyl. R₂ is preferably methyl.
G is advantageously methylene, ethylene or propylene-1,3 or 2-hydroxy-propylene-1,3. When L is a carboxy group, then G is preferably C _1-3 alkylene, especially methylene; L is the sulfo group, then G is preferably C _1-3 -alkylene or in particular 2-hydroxy-propylene-1,3.

As counterions Q⊖ are generally customary counterions into consideration, as they arise in cyclization or quaternization reactions ago namely for the anion of a mineral acid (for example chloride or Sulfate) or in the formula (III) or (IV), for example, also for metho sulphate or ethosulphate, depending on the quaternizing agent used. Tensi de of formula (II) wherein n is 2, are by cyclization reaction into those of formula (IV) or (V) convertible and vice versa are surfactants  of the formula (IV) or (V) by hydrolysis to those of the formula (II) feasible, where n is 2.

In the microemulsions according to the invention are advantageously per 100 Parts by weight of aminopolysiloxane (α) 5-60, preferably 10-40, in particular 25-35 parts by weight of the amphoteric surfactant (β) used.

The microemulsions of the invention have a pH of 7 or less on what can be adjusted by acid addition, and the Aminopolysi loxanes (α) are at least in the microemulsions according to the invention partially in protonated form. The pH values of the invention Preparations are advantageously in the range of pH 2-5.

Advantageously, the microemulsions according to the invention contain at least a nonionic emulsifier (γ).

Suitable nonionic emulsifiers (γ) are, for example, those having an HLB value in the range of 5-16. The emulsifiers (γ) may have aliphatic and optionally also aromatic character, but are preferably purely aliphatic. Of particular note are sorbitol monoesters of C _8-16 (preferably C _11-14 ) fatty acids and oxyethylation products of fatty alcohols and of fatty acid amides wherein the fatty residue advantageously contains 8-22, preferably 10-18, carbon atoms; If appropriate, a number, in particular a smaller number, of propyleneoxy units may also be incorporated in the nonionic surfactant, in addition to the ethyleneoxy units. For example, oxethylation products of the following fatty alcohols and fatty acid amides may be mentioned: lauryl alcohol, myristyl alcohol, cetyl alcohol, oleyl alcohol, stearyl alcohol and technical alcohols, especially tallow fatty alcohol and coconut fatty alcohol, and the analog fatty acid amides, and branched, primary and secondary alcohols, predominantly synthetic alcohols , z. B. at least partially branched alcohols from the oxo process -. From propylene -, among which those having 10-15 carbon atoms are preferred, especially trimethylnonanol, tetramethylnonanol and tetramethyldecanol, especially the primary isotridecyl alcohol tetramethylnonanol-1; Among the sorbitol fatty acid esters, particular preference is sorbitan monolaurate. The degree of oxyethylation is appropriately selected so that the desired HLB value can be used. It is particularly advantageous to use two different emulsifiers (γ), u. zw. primarily non-ionic emulsifiers (γ₁) with a lower HLB value, advantageously an HLB value in the range of 5-12, preferably 6-12, and emulsifiers (γ₂) having a higher HLB value, which is advantageous in the range of 10-16, preferably 12-16, wherein the HLB value of (γ₂) is advantageously at least one unit, preferably at least two units higher than that of (γ₁).

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

Per 100 parts by weight of the aminopolysiloxane (α) are advantageously 10-60, preferably 15-50 parts by weight of the nonionic emulsifier (γ) or of the nonionic emulsifier mixture (γ₁) + (γ₂) used. The Weight ratio (γ₁): (γ₂) is advantageously in the range of 1: 9 to 9: 1, preferably 3: 7 to 7: 3.

If desired, especially when as (γ₁) emulsifiers having an HLB <10 decomposition-inert hydrotropes (δ) can be used become. The hydrotropes are decomposition inert, d. H. that they are together with the other components essentially no chemical decomposition cause or catalyze reactions or even decompose (ie, for example, that they do not undergo exchange reactions and no Abspal cause reactions, polymerizations or depolymerizations), although the formation of coordination bonds and / or attachments, Polarizations and, for anionic hydrotropes, the Bil formation of heteropolar bonds (eg protonation of amino groups) can take place.

There are suitable as (δ) generally known, advantageously aliphatic, low molecular weight compounds, preferably non-ionic or anioni cal C / H / O compounds, in particular having 2 to 24 carbon atoms, mainly aliphatic alcohols and / or ethers with 4 to 18, in particular 6-12 carbon atoms and carboxylic acids and hydroxycarboxylic acids having 2 to 12, especially 3 to 8 carbon atoms. Preferred hydrotropes are glycols (eg 2,5-hexanediol and 2-methyl-pentane-2,4-diol), oligoal kylenglykole and their alkyl ethers [z. As di-, tri-, tetra-, penta- and hexaethylene glycol and their mono- or di- (C _1-6 alkyl) ether, in particular bis (2-hydroxypropyl) ether and Diäthylenglykolmonobutyläther)], to the anomeric hydroxy group glucosides etherified by C _1-6 -alkyl (eg butylglucoside), dicarboxylic acids (eg oxalic acid, succinic acid, glutaric acid and adipic acid) and hydroxycarboxylic acids (eg lactic acid, tartaric acid, gluconic acid, glucoheptonic acid and citric acid).

Advantageously, up to 50 percent by weight (δ) per 100 parts by weight (α) used.

The aqueous microemulsions according to the invention advantageously contain 10-70 wt .-%, preferably 20-50 wt .-% of the total components [(α) + (β) + (γ) + (δ)], wherein the content of (δ) 0-50 wt .-% based on (α) is.

The microemulsions according to the invention can be prepared by mixing the respec be prepared components (β) of the non-protonated or the protonated form of (α) can be added and required if, after addition of (β), the pH is adjusted to the desired value is presented. The setting of required or desired acidic pH values are expediently carried out by acid addition. In general, you can Usual acids (ε) are used, namely inorganic or organic acids, e.g. B. mineral acids (mainly hydrochloric acid, sulfur acid or phosphoric acid) or aliphatic carboxylic acids (eg, simple Monocarboxylic acids having 1-6 carbon atoms - especially formic acid, Acetic, propionic or butyric acid dicarboxylic acids of 2 to 6 Carbon atoms - especially those mentioned above - and hydroxycarbon acids having 3 to 8, preferably 3-4 carbon atoms - in particular the mentioned above). For the adjustment of acidic pH values in copoly merization are the mineral acids and the simple monocarboxylic acids, especially formic acid and acetic acid, preferred.  

The adjustment of the pH values can take place in one or more stages, d. H. by one or more acid additions. For the setting the pH values of the preparations according to the invention, in particular after success ter addition of (β) and optionally other components [(γ) and / or (δ)] are primarily acids (ε₂), d. H. the mineral acids and optionally stronger carboxylic acids, in particular the stronger and less volatile polycarboxylic acids (eg, citric acid tartaric acid, Succinic acid); Preferably as acids (ε₂) mineral acids puts. As far as (δ) an acid as mentioned above, the pH may be additional also be included with it. For the acid addition in a preliminary stage, z. B. before the addition of (β) and / or (δ) or at the same time, are suitable preferably organic carboxylic acids (ε₁), in particular those such mentioned above, preferably simple monocarboxylic acids or di- and Tricarboxylic acids (eg those mentioned above) although (ε₂) is used therefor can be. In the above-mentioned precursor is advantageously a pH of 3-6.5 set.

The microemulsions according to the invention are preferably by addition of (β) and preferably (γ) [in particular (γ₁) and (γ₂)] and given if (δ) and the required amount of water and acid (ε) to (α) manufactured. The order of additions is generally arbitrary as long as the respective mixtures are easy to stir. So, for example (α) first with (γ₁) or with (δ) or with a mixture of (γ₁) and (δ) be mixed and then with the remaining components in succession or as mixtures [e.g. B. (γ₂) + (β) or (γ₁) + (γ₂) + (β)] further mixed or (γ₁) + (γ₂) + (β) and optionally (δ) and / or (ε₁) are added together to (α). Water and acid (ε₁) can be separated or mixed with the respective components. benefit Accidental sequences of additions of components (β), (γ₁), (γ₂), (δ), (ε₁) and (ε₂) to (α) can be represented by the following scheme  

where (ε₁) is arbitrary in one or more of the stages 1 to 5 and / or the intermediates between 1 and 2, 2 and 3, optionally 3 and 4 and optionally 4 and 5 can be added, (δ), as far as it is added is, optionally in one or more of the stages 1 to 5 and / or the Intermediates between 1 and 2, 2 and 3, optionally 3 and 4 and optionally 4 and 5 and / or after the addition of (ε₂) are added can, and if desired, one or more components (ζ) arbitrarily in one or more of the stages 1 to 5 and / or the intermediates zwi 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; (ζ) means one or more remaining or further components (γ₁), (γ₂), (β) and / or another additive (eg fungicide, perfume, antifreeze medium).

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

Option A):
Addition to (α) of (γ₁), then [(γ₂) + water], then (β) and then (ε₂)

with the following sub-variants for the addition of (ε₁):
a₁), adding (ε₁) before (γ₁)
a₂): addition of (ε₁) between (γ₁) and (γ₂) or together with (γ₁) or (γ₂)
a₃), adding (ε₁) between (γ₂) and (β) or together with (β)

and the following further subvariants for the addition of (δ):
a _w1 : (δ) before or together with (γ₁)
a _w2 : (δ) before or together with (γ₂)
a _w3 : (δ) before or together with (β)
a _w4 : (δ) after (β) and before (ε₂)
a _w5 : (δ) after (ε₂)
where w = 1, 2 or 3, another variant is (a _w41 ) for the additional addition of residual (γ₁) with or after (β) and before (ε₂).

Variant b):
Addition to (α) of (γ₁), then [(γ₂) + (β) + water] and then of (ε₂)

with the following sub-variants for the addition of (ε₁):
b₁): (ε₁) before (γ₁)
b₂): (ε₁) 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) or in admixture with (ε₂)

with the following further subvariants for the additional addition of (δ):
b _w1 : (δ) before (γ₁)
b _w2 : (δ) between (γ₁) and [(γ₂) + β + water] or together with (γ₁) or [(γ₂) + (β) + water]
b _w3 : (δ) to [(γ₂) + (β) + water]
(w = 1, 2 or 3)

Variant c):
Addition of (α) a mixture of (γ₁) + (γ₂) + (β) and then adding (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) or in admixture with (ε₂)

and the following further sub-variants for the additional addition of (δ):
c _w1 : (δ) before [(γ₁) + (γ₂) + (β)]
c _w2 : (δ) together with [(γ₁) + (γ₂) + (β)]
c _w3 : (δ) after [(γ₁) + (γ₂) + (β)] and before (ε₂)
c _w4 : (δ) to (ε₂)
(w = 1, 2 or 3)

The required water or optionally additionally required Water may be added in one or more stages, for example example with the 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 (ε₂).

By mixing the components (α), (β), (γ₁) and (γ₂) and water can, especially under neutral to basic conditions, cloudy emulsions (macroemulsions) arise, but which by acid addition - also only by adding (ε₁) - and optionally adding (δ₁) in light permeable to clear microemulsions can be converted. Becomes used from the beginning the protonated form of (α), then by Stirring in (γ₁), (γ₂) and water already produce a microemulsion.  

The addition of the respective components can be carried out with any suitable speed, ie. H. it can, for. B. the water given a optionally aqueous component or an optionally aqueous components mixture rapidly added with rapid stirring in a few minutes or easiest by slow stirring in the course of one to several quarters of an hour (for example, within half an hour to two hours).

The microemulsions according to the invention, in particular those as above described microemulsions according to the invention are suitable as fiber fiber finishing materials and can be formulated as they are are used directly for the formulation of the application liquor or, if necessary, prior to application from an aqueous medium diluted with water to more dilute stock dispersions, eg. Up to a dry matter content of 2 to 4 wt .-%. If desired, the According to the invention aqueous preparations still further conventional additives ent such as antifreeze or fungicides. They are for the equipment of fiber material, in particular textile material from aqueous medium, into special suitable for improving grip and sliding properties.

It is suitable for any textile material, as in the textile industry occurs, u. between both natural and synthetic and semisynthetic materials and their mixtures, in particular natural or active regenerated cellulose, natural or synthetic polyamide, polyester, polyurethane or polyacrylonitrile-containing material, as well as mixtures thereof (eg PES / CO and PAN / CO). The material can be in any Bearbei form, for. B. as loose fibers, filaments, threads, yarn strands and bobbins, fabrics, knitted fabrics, nonwovens, nonwovens, felts, carpets, velvet, Tuftingware or semi-finished or finished goods. Preferably be Cheeses, textile webs, textile tubular goods (in particular knitted fabrics hose) or piece goods.

The equipment is expediently from aqueous, significantly acidic to almost neutral medium, especially in the pH range of 3.0-7.5. The Kon concentration of the preparations according to the invention, based on the substrate,  may vary depending on the nature and nature of the substrate and the desired effect vary within wide limits and is advantageously values in the range of 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 advantageously takes place as the last Equipment level of the material, preferably following a lead che, an optical brightening process and / or a dyeing process if necessary together with an additional treatment, eg. B. a permanent th equipment (synthetic resin equipment) of the fiber material. Equipment can be done by any conventional method, for. B. after Impregnation method or by exhaustion. In exhaust process Both long and short fleet procedures can be considered come, for. At liquor ratios ranging from 100: 1 to 0.5: 1, in particular between 60: 1 and 2: 1; the application temperature can also at usual values, for example in the range between room temp temperature and 60 ° C, preferably in the range of 25 ° C to 50 ° C, the pH is preferably in the range of 3.5 to 5.5. The impregnation can also be done by conventional methods, for. B. by diving, Padding, foam application or spraying, preferably at tempera tures z. From 15-40 ° C and at pH's in the range of 3.5-7. After this Impregnation or after the exhaust process, the treated Goods are dried in the usual way, for. B. at 30 to 180 ° C, preferably wise 60 to 140 ° C.

The microemulsions according to the invention are distinguished by a outstanding resistance (especially shear stability) and the Applika fleets are especially under strong dynamic Beanspru Fleece and / or textile material stable and unchanged and are therefore suitable for. B. for the equipment in the winch, in Jigger, in Garnfärbeapparaten, in piece-dyeing apparatus (so-called "Garment dyeing machines") and in particular in Düsenfärbeappara th, u. even in those where extremely high shear forces (also impact and rebound forces) become effective. The preparations according to the invention are also very suitable for the wet finish of cheeses; also  in this case, the strong dynamic load of the fleet, the forced from the inside of the coil to the outside by the threads of the cheese is no negative impact on the preparation of the invention and the equipment achieved with it. They are, in the treatment fleets, too against contamination, the z. B. as residues from a previous one Treatment of the substrate can stem, resistant, especially against anionic impurities, e.g. As dyes, optical brighteners or Surfactants.

In the following examples, parts are parts by weight and the Pro percentages by weight, the temperatures are given in degrees Celsius; Parts by weight stand for parts by volume such as g to ml; the Tensi used de (β) are the following

wherein R is -CO- oleoyl and R in (β₁) has the same meaning (C₁₇H₃₃) as in (β₂), (β₃) and (β₄);
the emulsifiers (γ₁) and (γ₂) used are the following:

(γ₁₁) addition product of 4 moles of ethylene oxide to 1 mole of technical isotridecyl alcohol *
(γ₁₂) addition product of 5 moles of ethylene oxide with 1 mol of technical isotridecyl alcohol *
(γ₁₃) addition product of 6 moles of ethylene oxide to 1 mole of 2,6,8-trimethyl nonanol-4 (Tergitol TMN-6, UNION CARBIDE)
(γ₂₁) addition product of 9.5 moles of ethylene oxide to 1 mol of technical Isotridecylalkohol *.

*) Technical mixture of isomers from the oxo synthesis

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

185.4 parts of α, ω-dihydroxypolydimethylsiloxane having a hydroxyl number of 26 (determined by the phenyl isocyanate method) and a mean molecular weight _n of 5000 (determined by vapor pressure osmometry) are reacted with 12.2 parts of N- (β-aminoethyl) -γ - (methyldimethoxysilyl) -propylamine stirred briefly. Then you are 2.4 parts of glacial acetic acid and heated under nitrogen to 75 ° C. After 5 hours at this temperature is cooled to 50 ° C abge, the nitrogen supply turned off and there are 30 parts (γ₁₂) give added. Subsequently, 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 water have been added dropwise, the emulsion becomes transparent. Now 3.5 parts of glacial acetic acid are added at 30 ° C and

(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)

Subsequently, the pH is adjusted to 4.0 with 36.5% strength hydrochloric acid. Transparent shear stable aminopolysiloxane microemulsions are obtained.  

Example 2 (product E)

188.70 parts of α, ω-dihydroxypolydimethylsiloxane (as in Example 1) with 12.50 parts of N- (β-aminoethyl) -γ- (methyldimethoxysilyl) -propylamine stirred and treated with 0.07 parts of 50% sodium hydroxide solution. It is then heated to 112 ° C under nitrogen, with 1 part by volume Distillate is collected. After 3½ hours, it is cooled to 40.degree. Once this temperature is reached, 0.02 parts of sodium bicarbonate is added and it is heated to 110 ° C under vacuum (at 70 mbar). Then it is cooled to 50 ° C, relieved with nitrogen, and it will be 30 parts (γ₁₂) was added. Subsequently, 480 parts within 1 hour a solution of 30 parts (γ₂₁) added dropwise in 450 parts of water. thereupon 3 parts of glacial acetic acid, 100 parts of a 50% aqueous solution of (β₄), 147 parts of water and 20 parts (γ₁₃) and to adjust the pH with about 20 parts of 36.5% hydrochloric acid to 4.0. You get 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-Dihydroxypoly dimethylsiloxane (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 catalyst, produced Aminopolysiloxans are at 50 ° C with 30 parts (γ₁₁) and 20 parts butyl monoglucoside added. Subsequently are within 1 hour 480.5 parts of a solution of 30 parts (γ₂₁) in 450.5 parts of water added dropwise. Then 120 parts of a 50% igen aqueous solution of (β₄), 138.5 parts of water and 11.0 parts of amei Sensory acid added. A shearing-stable aminopolysiloxane is obtained microemulsion (product F).

Example 4 (product G)

200.0 parts of a by condensation of 600.0 parts of α, ω-Dihydroxypoly dimethylsiloxane (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 prepared Aminopolysiloxans are at 50 ° C with 30 parts (γ₁₁) ver puts. Subsequently, within 1 hour 480.5 parts of a solution of 30 parts (γ₂₁) added dropwise in 450.5 parts of water. Then there are 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 hydrochloric acid 36.5% to adjust the pH to 4.0 and 60.0 parts of dipropylene glycol are added sequentially. you obtains a shear stable aminopolysiloxane microemulsion (product G).

Application Examples A to C

A. 1 kg of the substrate to be finished (textile, cotton single jer sey, blue) are at 40 ° C and a liquor ratio of 1: 8 on a Laborjet from MATHIS (Switzerland) with 40 g finishing agent (Pro treated A to G). The liquor circulation is 60 l / min. and the treatment time is 20 min. The water has a hardness of 10 ° dH (according to DIN 53905) and a pH of 4. After the treatment will that Spun substrate for 90 sec. At 140 ° C without tensioning dried and the softness determined. It occurs during the treatment No deposits or greasy deposits on. On the Textile goods are no stains noted. After draining the Fleet no residues can be observed in the apparatus. Sämtli che products (A to G) are shear stable and give a clear Improvement of the handle of the treated textile (compared to the treated accordingly without silicone microemulsion).

B. Apparatus: THIES-Jet R95, 3 chambers substrate: 360 kg polyester / cotton (50:50) single jersey, green color (dispersion and reactive dye) Product: 2.0% (based on weight of goods) Product C Fleet: 2000 liters of permutate water Liquor ratio: 1: 5.5 PH value: 4.5 Temperature: 30 ° C Treatment time: 20 min Web speed: 2000 m / min. Workflow: The product is dosed in 150 l of prediluted water in 5 min. There are no residues, deposits or stains. The appearance of the goods and the softness of the dry goods are impeccable.

As described in Application Example B, instead of the Pro the product A, B, D, E, F or G is used.

C. apparatus: 3-reel jet by AVESTA (Sweden) substrate: 150 kg polyester / cotton (50:50) Intimate jersey dyed with reactive and disperse dyestuffs (one-bath two-stage) and post-treated with cation. Product: 2.0% (based on weight of goods) Product C Fleet: 2200 liters of permutate water Liquor ratio: 1:15 PH value: 4.5 Temperature: 30 ° C Treatment time: 20 min. Web speed: 90 m / min. Workflow: The product is dosed in 150 l of prediluted water in 5 min. The temperature remains constant. When unloading the goods no stains or deposits on the goods or in the apparatus. After drying, the treated product shows an excellent softness.

Analogously as described in Application Example C instead of Product C uses the product A, B, D, E, F or G.

As in the case of the AVESTA-Jet, application example C uses a GASTON-COUNTY-Jet proceed.

Claims (16)

1. Aqueous microemulsions of an aminopolysiloxane (α), characterized by an amphoteric surfactant (β) content and a pH of 7. 2. Aqueous microemulsions according to claim 1, characterized the aminopolysiloxane has an amine number in the range from 0.1 to 3.0 and having a viscosity in the range of 500-30,000 mPa · s. 3. Aqueous microemulsion according to claim 1 or 2, characterized gekennzeich net, that the amphoteric surfactant (β) an amino acid with tertiary Amino group or a betaine. 4. Aqueous microemulsion according to claim 3, characterized the acid group in (β) is a carboxylic or sulfonic acid group and the lipophilic group via a carbamoyl group to the rest of the Molecule bound or the second substituent of an amphoteric imidazoline or imidazolinium ring of a betaine Imidazoliniumreihe is. 5. Aqueous microemulsion according to any one of claims 1-4, comprising at least one nonionic emulsifier (γ). 6. Aqueous microemulsions according to claim 5, wherein the non-ionic Emulsifiers (γ) have an HLB in the range of 5 to 16. 7. Aqueous microemulsions according to any one of claims 1-6, containing per 100 parts by weight of aminopolysiloxane (α) 5-60 parts by weight amphoteric surfactant (β). 8. Aqueous microemulsions according to claim 5, 6 or 7, comprising 10-60 parts by weight of nonionic surfactant (γ) per 100 parts by weight Aminopolysiloxane (α).   9. Aqueous microemulsions according to any one of claims 5-8, containing an inert hydrotrope (δ). 10. Aqueous microemulsions according to any one of claims 1-9, containing 10-70 parts by weight (α + β + γ + δ). 11. A process for the preparation of the microemulsions according to one of Claims 1-10 by mixing (α) with the remaining microemulsions components, characterized in that before, with and / or after adding (β) acid. 12. Use of the microemulsions according to one of claims 1-10 for Equipping fiber material. 13. Use according to claim 12 for finishing textile material aqueous liquor. 14. Use according to claim 13 for finishing textile material in Jet dyeing machines. 15. The method of claim 12, 13 or 14 to the final equipment. 16. The according to claim 12, 13, 14 or 15 equipped material.