EP1921203A1 - Treatment of fiberfill fibers with aqueous dispersions of organopolysiloxanes - Google Patents

Abstract

Treatment of fiberfill fibers includes contacting fibers with aqueous dispersion of organopolysiloxane obtained by reacting organopolysiloxane comprising condensation-capable groups and specific siloxane units with silane or its hydrolysate in the presence of water and emulsifier. Treatment of fiberfill fibers includes contacting fibers with aqueous dispersion of organopolysiloxane obtained by reacting organopolysiloxane comprising condensation-capable groups and units of formula R a(OR 1>) bSiO (4-(a+b))/2(I) with silane of formula (R 3>O) 3SiCR 2>2-Y (II) or its hydrolysate in the presence of water, emulsifier, optionally further silane of formula (R 3>O) xR 3-xSi-R 6>-Z (III) or its hydrolysate, and optionally further materials which do not take part in the reaction of organopolysiloxane with silane (II). Provided that no metal-containing catalysts are used and the organopolysiloxane and silane (II) are used in such amounts that the organopolysiloxane forms toluene-insoluble elastomeric film after removal of water. R : H or 1-18C monovalent hydrocarbyl optionally substituted with heteroatoms N and/or O; R 1>H or 1-8C alkyl, preferably H, Me, or Et; a : 0-3; b : 0-2; R 2>1-4C monovalent alkyl or preferably H; R 3>1-8C alkyl; Y : -NHR 4>, -NR 4>2, or -NR 5>; R 4>1-18C monovalent hydrocarbyl optionally containing N and/or O; R 5>3-12C divalent hydrocarbyl optionally containing N and/or O; R 6>3-18C divalent hydrocarbyl; Z : amino, aminoalkylamino, epoxy, or (meth)acryloyloxy; and x : 1-3. Provided that a+b is = 3 and the organopolysiloxane contains an average OR 1>radical(s)/molecule.

Description

The invention relates to a process for the treatment of filler fibers with aqueous dispersions of organopolysiloxanes.

Emulsions of crosslinked silicones are known. For the crosslinking of silicones (heavy) metal-containing or metal-free catalysts and crosslinkers are needed. In part, inhibitors are also used to control reactivity and pot life to prevent undesired too early gelation.

1. (A) kondensationsfähige Gruppen aufweisende Organopolysiloxane,
2. (B) als Vernetzer fungierende (aminfreie) Organosiliciumverbindungen mit mindestens 3 vernetzungsreaktiven Gruppen,
3. (C) basischen Stickstoff aufweisende Organosiliciumverbindung, besonders bevorzugt deren Alkalisilikonate, die katalytisch wirksam sind.

Komponente(C) bewirkt einen sehr hohen pH-Wert der Produkte, was bei der Verarbeitung Schwierigkeiten bereitet.Metal-free aqueous RTV-1 dispersions are in EP 828 794 A and EP 655 475 A1 described. They can be produced using the three starting components:

1. (A) organopolysiloxanes having condensable groups,
2. (B) organosilicon compounds which function as crosslinkers (amine-free) and have at least 3 crosslinking-reactive groups,
3. (C) basic nitrogen-containing organosilicon compound, particularly preferably their alkali metal siliconates, which are catalytically active.

Component (C) causes a very high pH of the products, which causes difficulties in processing.

DE 102004038148 A1 (corresponding WO 2006/015740 A1 ) describes the preparation of highly viscous silicones (10,000 to 50,000,000 mPa · s) in emulsion by reacting silanol-terminated organopolysiloxanes with α-aminomethylalkoxysilanes. However, no elastomeric silicone films which are insoluble in toluene are obtained.

EP 510 631 A describes the preparation and equipment of a fiber finishing agent based on copolyesters grafted with polyorganosiloxanes for a soft feather-like Gripping on polyester filling fibers. The side grafting of polyorganosiloxanes to the polyester backbone gives a finishing agent that gives a smooth, low-friction feel to fibers, especially polyester filler fibers.

GB 1 458 319 A (= DE 24 20 151 A ) describes new synthetic fibers and a process for their preparation in which a reactive polysiloxane is used in combination with aminoalkoxysilane and a hardener, a metal salt of 2- to 4-valent metal ions, such as dibutyltin diacetate or zinc acetate, with heat treatment of 120 to 200 ° C. ,

DE 35 03 457 A discloses a process for impregnating organic fibers in which an organopolysiloxane having amino groups such as aminoethylaminopropyl groups is cross-linked with hydrogensiloxane in the presence of metal-containing catalysts such as dibutyltin dilaurate.

In EP 1 096 059 A For example, there is described an aqueous emulsion for treating polyester fibers containing a mixture of an emulsion of an amino functional organopolysiloxane with alkoxy groups and an emulsion of an amino functional organopolysiloxane with hydroxy groups. The two organopolysiloxanes must first be complex by reaction of α, ω-Dihydroxydimethylpolysiloxanen with N- (2-aminoethyl) (3-aminopropyl) methyldimethoxysilane or by reacting α, ω-Dihydroxydimethylpolysiloxanen or cyclic dimethylpolysiloxanes with the hydrolysis or condensation product of N - (2-aminoethyl) (3-aminopropyl) -methyldimethoxysilane.
It is from high molecular weight linear polysiloxanes, but no crosslinked films which are insoluble in toluene, prepared.

The object was to provide a process for the treatment of filler fibers with aqueous dispersions of organopolysiloxanes without the use of metal-containing catalysts.
Another object was to provide a process for treating filler fibers with aqueous dispersions of organopolysiloxanes in which the aqueous dispersions of organopolysiloxanes form elastomeric films which are insoluble in toluene after removal of the water, and this treatment gives the filler fibers a permanent soft feel and a permanent soft touch gives good buoyancy.
A further object was to provide a process for the treatment of filler fibers with aqueous dispersions of organopolysiloxanes, in which the dispersions are obtained by a simple process in which no complex chemical reactions have to take place, in which the treatment of the filling fibers can be carried out with short residence times and at in which the treatment of the filling fibers can be carried out even at low temperatures and the filler fibers thus treated have a lower yellowing.
Another object was to provide for the treatment of filler fibers aqueous dispersions of organopolysiloxanes which are finely divided, stable and preferably pH-neutral (range pH about 5-9) and which are free or nearly free of volatile organic compounds (VOC).
The object is achieved by the invention.

wobei
R ein Wasserstoffatom oder einen einwertigen, gegebenenfalls mit den Heteroatomen N und/oder O substituierten Kohlenwasserstoffrest mit 1 bis 18 Kohlenstoffatomen bedeutet, R¹ ein Wasserstoffatom oder einen Alkylrest mit 1 bis 8 Kohlenstoffatomen, bevorzugt ein Wasserstoffatom oder einen Methyl- oder Ethylrest bedeutet,

• a 0, 1, 2 oder 3 und
• b 0, 1 oder 2 ist,

mit der Maßgabe, dass die Summe a+b ≤ 3 ist und im Organopolysiloxan (1) durchschnittlich mindestens ein Rest OR¹ je Molekül, bevorzugt in der Bedeutung von R¹ gleich Wasserstoffatom, enthalten ist,
mit Silanen (2) der allgemeinen Formel

         (R³O)₃SiCR² ₂-Y     (II)

oder deren Hydrolysate,
wobei R² ein Wasserstoffatom oder einen einwertigen Alkylrest mit 1 bis 4 Kohlenstoffatomen, bevorzugt ein Wasserstoffatom bedeutet,
R³ einen Alkylrest mit 1 bis 8 Kohlenstoffatomen je Rest bedeutet,
Y einen Rest der Formel -NHR⁴, -NR⁴ ₂ oder

ist,
wobei R⁴ einen einwertigen, gegebenenfalls N- und/oder O-Atome enthaltenden Kohlenwasserstoffrest mit 1 bis 18 Kohlenstoffatomen und
R⁵ einen zweiwertigen gegebenenfalls N- und/oder O-Atome enthaltenden Kohlenwasserstoffrest mit 3 bis 12 Kohlenstoffatomen bedeutet,
in Gegenwart von Wasser (3),
Emulgator (4)
und gegebenenfalls weiteren Silanen (5) der allgemeinen Formel

         (R³O)_xR_3-xSi-R⁶-Z     (III)

oder deren Hydrolysate,
wobei R⁶ einen zweiwertigen Kohlenwasserstoffrest mit 2 bis 18 Kohlenstoffatomen bedeutet und
Z einen Rest ausgewählt aus der Gruppe der Amino- oder Aminoalkylaminoreste, Epoxyreste und (Meth)acryloxyreste bedeutet, und
x 1, 2 oder 3, vorzugsweise 2 oder 3, bedeutet,
und gegebenenfalls weiteren Stoffen (6), die an der Umsetzung von Organopolysiloxan (1) mit Silan (2) nicht teilnehmen,
mit der Maßgabe, dass keine Metall-haltigen Katalysatoren mitverwendet werden und dass die Organopolysiloxane (1) und Silane (2) in solchen Mengen eingesetzt werden, dass die Organopolysiloxane nach dem Entfernen des Wassers (3) elastomere Filme bilden, die in Toluol unlöslich sind.The invention provides a process for the treatment of filler fibers with aqueous dispersions of organopolysiloxanes obtainable by
Reaction of condensable groups containing organopolysiloxanes (1) from units of the general formula

in which
R is a hydrogen atom or a monovalent hydrocarbon radical having 1 to 18 carbon atoms which is optionally substituted by the heteroatoms N and / or O, R ^{1 is} a hydrogen atom or an alkyl radical having 1 to 8 carbon atoms, preferably a hydrogen atom or a methyl or ethyl radical,

• a 0, 1, 2 or 3 and
• b is 0, 1 or 2,

with the proviso that the sum a + b ≦ 3 and in the organopolysiloxane (1) contains on average at least one radical OR ¹ per molecule, preferably in the meaning of R ¹ same as hydrogen atom,
with silanes (2) of the general formula

(R ³ O) ₃ SiCR ² ₂ -Y (II)

or their hydrolysates,
where R ² denotes a hydrogen atom or a monovalent alkyl radical having 1 to 4 carbon atoms, preferably a hydrogen atom,
R ^{3 is} an alkyl radical having 1 to 8 carbon atoms per radical,
Y is a radical of the formula -NHR ⁴ , -NR ⁴ ₂ or

is
wherein R ^{4 is} a monovalent, optionally N and / or O atoms containing hydrocarbon radical having 1 to 18 carbon atoms and
R ⁵ denotes a divalent hydrocarbon radical optionally containing N and / or O atoms and having 3 to 12 carbon atoms,
in the presence of water (3),
Emulsifier (4)
and optionally further silanes (5) of the general formula

(R ³ O) _x R _3-x Si-R ⁶ -Z (III)

or their hydrolysates,
wherein R ^{6 is} a divalent hydrocarbon radical having 2 to 18 carbon atoms, and
Z is a radical selected from the group of amino or aminoalkylamino radicals, epoxy radicals and (meth) acryloxy radicals, and
x is 1, 2 or 3, preferably 2 or 3,
and optionally other substances (6) which do not participate in the reaction of organopolysiloxane (1) with silane (2),
with the proviso that no metal-containing catalysts are used and that the organopolysiloxanes (1) and silanes (2) are used in amounts such that the organopolysiloxanes after removal of the water (3) form elastomeric films which are insoluble in toluene ,

It was surprising that through a simple implementation of only 2 components - in contrast to the two reactions in EP 1 096 059 A and also in contrast to the in DE 10 2004 038 148 A reaction - aqueous dispersions are obtained with high molecular weight partially crosslinked polymer particles, which after removal of the water, preferably by evaporation, yield an elastic film with formation of a high molecular elastic network and give the filler fibers thus treated a permanent soft feel.

In the process according to the invention, the reaction of organopolysiloxane (1) with silane (2) can be carried out both before the emulsion is prepared and by first emulsifying the organopolysiloxane (1), which is then mixed with the silane (2) in the emulsion droplet. responding.

The dispersions according to the invention already contain precrosslinked organopolysiloxanes, elastomeric films being formed after the removal of the water and containing crosslinked organopolysiloxanes which branched out into high molecular weight or dendrimer-like hyperbranched structures. On these elastomeric films, a viscosity measurement is not possible. The polymeric siloxane networks of the elastomeric films are typically insoluble in organic solvents such as toluene but may swell therein, but this is also to be understood as insoluble within the scope of this invention.
This is in contrast to uncrosslinked organopolysiloxanes, which may also be highly viscous, but where a viscosity measurement is possible and which are soluble in organic solvents such as toluene.

The fact that aqueous dispersions of crosslinked organopolysiloxanes can be obtained by this process was surprising since A. Adima et. al., Eur. J. Org. Chem. 2004, 2582-2588 described that α-aminomethyltrialkoxysilanes decompose in the presence of water to SiO ₂ and the corresponding methylated amine.

The dispersions according to the invention are preferably aqueous suspensions or aqueous emulsions of organopolysiloxanes.

The dispersions of the invention form on drying - without addition of catalyst or change in pH - an elastic silicone network. In the preparation of the crosslinked organopolysiloxanes according to the invention, only two (mutually reactive) components are preferably required: organopolysiloxanes (1) having condensable groups and crosslinking agents (2). These components preferably react with each other even at room temperature. To support this reaction no metal-containing additional catalysts are needed. The reaction also preferably proceeds in the neutral range, ie in the pH range of about 5 to 9, which results from the components themselves. Due to the high reactivity is also a targeted guided chemical reaction not necessary and preferably also no heating.

The dispersion of the invention is characterized by its high storage stability, even at elevated temperature, and by their high shear stability. The process according to the invention has the advantage that dispersions with a high solids content and filler content can be obtained. The content of non-volatile substances in the dispersion is preferably about 1 to 99% by weight, preferably 30 to 95% by weight, particularly preferably more than 50% by weight, based on the total weight of the dispersion.

In the process according to the invention, no metal-containing catalysts are used, i. It is preferable that no transition metals of VIII. Subgroup of the Periodic Table and their compounds and no metals of the III, IV and V main group of the Periodic Table and their compounds are used, wherein the elements C, Si, N, and P in this definition not as Metals apply.

Examples of hydrocarbon radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl; Hexyl radicals, such as the n-hexyl radical; Heptyl radicals, such as the n-heptyl radical; Octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical; Nonyl radicals, such as the n-nonyl radical; Decyl radicals, such as the n-decyl radical; Dodecyl radicals, such as the n-dodecyl radical; Octadecyl radicals, such as the n-octadecyl radical; Cycloalkyl radicals such as the cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; Alkenyl radicals such as the vinyl, 5-hexenyl, cyclohexenyl, 1-propenyl, allyl, 3-butenyl and 4-pentenyl radicals; Aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radicals; Alkaryl radicals, such as o-, m-, p-tolyl radicals; Xylyl residues and ethylphenyl; and aralkyl radicals, such as the benzyl radical, the α- and the β-phenylethyl radical.

The radicals R are preferably the methyl, ethyl, octyl and phenyl radicals, particularly preferably the methyl and ethyl radicals.

Examples of N or O-substituted hydrocarbon radicals R are hydrocarbon radicals which are substituted by amino groups, and
Polyethoxy or polypropoxy or polyethoxy-polypropoxy groups are substituted.
Examples of radicals R which are substituted by amino groups are radicals of the formula -R ⁶ -NR ⁷ ₂ ,
wherein R ^{6 has} the meaning given above and
R ^{7 is the} same or different and represents a hydrogen atom or an alkyl or aminoalkyl or iminoalkyl radical. A preferred example is the N- (2-aminoethyl) (3-aminopropyl) radical.

Preferably, R ^{1 is} a hydrogen atom. Examples of alkyl radicals R ¹ are the alkyl radicals listed above at R, wherein the methyl or ethyl radical is preferred.

Preferably, R ^{2 is} a hydrogen atom.

Examples of alkyl radicals R having 1 to 8 carbon atoms are also fully applicable to alkyl radicals R ³ . Preferred examples of alkyl radicals R ³ are the methyl and ethyl radicals.

Examples of hydrocarbon radicals R, such as alkyl, cycloalkyl, aryl, alkaryl and aralkyl radicals, apply in their entirety to hydrocarbon radicals R ⁴ . Preferred examples of alkyl radicals R ⁴ are methyl, ethyl, butyl, hexyl and octyl radicals, a preferred example of cycloalkyl radicals R ⁴ is the cyclohexyl radical.

A preferred example of R ⁵ is the radical of the formula -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

Preferred examples of radicals Y are the morpholino, piperazino, piperidino and cyclohexylamino radicals.

Preferably, the radical R ^{6 is} an alkylene radical, preferably a radical of the formula -CH ₂ CH ₂ CH ₂ -.

Preferred organopolysiloxanes (1) are siloxanes of the general formula

(R ¹ O) R ₂ SiO (SiR ₂ O) _e SiR ₂ (OR ¹ ) (IV)

wherein R and R ^{1 have} the meaning given above, and
e is an integer from 1 to 1000,
with the proviso that 25 to 100%, preferably 50 to 100% of all radicals R ^{1 are} hydrogen atoms used.

Further examples of organopolysiloxanes (1) are resins of the general formula

[(R ₃ SiO _1/2 ) _f (R ₂ SiO _2/2 ) _g (R ₁ SiO _3/2 ) _h (SiO _4/2 ) _k ] (V)

where R has the meaning given above and additionally R in formula (V) can also be (OR ¹ ) with the meaning given above, with the proviso that at least one radical -OR ¹ , where R ^{1 is} a hydrogen atom, contained per molecule,
f, g, h and k are an integer from 0 to 1000 and h / (f + g + h + k) is preferably> 0.2.

Examples of siloxanes (1) are commercially available silanol-terminated polydimethylsiloxanes and alkoxy-terminated polydimethylsiloxanes.

Further examples of siloxanes (1) are commercially available functionalized siloxanes, such as amine oils, e.g. Amine oils having 3- (2-aminoethyl) aminopropyl functions, glycol oils, phenyl or phenylmethyl oils containing silanol or alkoxy groups.

Further examples of organopolysiloxanes (1) are resinous siloxanes, for example methylsilicone resins, with 80 mol% CH ₃ SiO _3/2 and 20 mol% (CH ₃ ) ₂ SiO _2/2 and a molecular weight of about 5000 g / mol or 98 mol% CH ₃ SiO _3/2 and 2 mol% (CH ₃ ) ₂ SiO _2/2 and a molecular weight of about 5000 g / mol, or eg methylphenylsilicone resins with 65 mol% C ₆ H ₅ SiO _3/2 and 35 mol% (CH ₃ ) ₂ SiO _2/2 , whose remaining free valencies R ¹ O groups of the above meaning carry.

These compounds are commercially produced in large quantities and are very inexpensive to access, whereby the dispersions used in the process according to the invention can be produced inexpensively.

For preparing these dispersions, one kind of organopolysiloxane (1) or various kinds of organopolysiloxane (1) can be used.

The organopolysiloxanes (1) used preferably have viscosities of 1 mPa.s to 5,000,000 mPa.s at 25 ° C, preferably 50 mPa.s to 100,000 mPa.s at 25 ° C and particularly preferably 100 mPa.s to 10,000 mPa at 25 ° C.

In the method of producing the dispersion of the present invention, one kind of silane (2) or various kinds of silane (2) may be used.

The radical -CR ² ₂ -Y in silane (2) of the formula (II) is preferably a radical of the formula -CH ₂ -Y.
Examples of radicals -CR ² ₂ -Y in silane (2) of the formula (II) are the aminomethyl, methylaminomethyl, dimethylaminomethyl, diethylaminomethyl, dibutylaminomethyl, cyclohexylaminomethyl, morpholinomethyl, piperidinomethyl, piperazinomethyl, (( diethoxymethylsilyl) methyl) cyclohexylaminomethyl,
((Triethoxysilyl) methyl) cyclohexylaminomethyl, anilinomethyl, 3-dimethylaminopropylaminomethyl and
Bis (3-dimethylaminopropyl) aminomethyl.

Examples of silanes (II) are Dibutylaminomethyltriethoxysilan, Dibutylaminomethyltributoxysilan, cyclohexylaminomethyltrimethoxysilane, cyclohexylaminomethyltriethoxysilane, Anilinomethyltriethoxysilan, morpholinomethyltriethoxysilane, Morpholinomethyltrimethoxysilan, Morpholinomethyltriisopropoxysilan, 3-dimethylaminopropyl-aminomethyltrimethoxysilane, Ethylcarbamoylmethyltrimethoxysilan, Morpholinomethyltributoxysilan, Morpholinomethyltrialkoxysilan wherein the alkoxy group is a C ₁ -C ₄ -alkoxy radical, in particular a Is a mixture of methoxy and ethoxy radical,
Bis (dimethylaminopropyl) aminomethyltriethoxysilane, diisopropylaminomethyltriethoxysilane, piperazinomethyltriethoxysilane, piperidinomethyltriethoxysilane bis (diethoxymethylsilylmethyl) cyclohexylamine, bis (triethoxysilylmethyl) cyclohexylamine, morpholinomethyltri (2-hydroxyethoxy) silane
Preference is given to silanes (2) of the formula (II) in which the radical (R ³ O) - is an ethoxy group.

The silanes (2) of the formula (II) may contain up to 30% by weight of difunctional silanes of the formula

(R ³ O) ₂ RSiCR ² ₂ -Y (II ')

or their hydrolysates
contain.
The silane of formula (II ') is chain extending for organopolysiloxanes (1) but does not interfere with the crosslinking reaction of silane of formula (II) with the chain extended organopolysiloxane (1). Crosslinked organopolysiloxanes according to the invention are obtained.

The degree of crosslinking depends on the ratio of the equivalents used -OR ³ in silane (2) of the formula (II) to -OR ¹ in organopolysiloxane (1) of the formula (I).

To prepare the novel dispersions of organopolysiloxane (1) and silane (2), silane (2) or its partial hydrolysates is preferably present in amounts of at least 0.6 equivalents of -OR ³ , preferably at least 0.7 equivalents of -OR ³ , particularly preferably 0 , 6 to 2 equivalents of -OR ³ , especially 0.65 to 1 equivalent of -OR ³ , more preferably of 0.7 to 0.99 equivalents of -OR ³ , per equivalent of -OR ¹ in organopolysiloxane (1) used, wherein R ¹ in (1) is preferably a hydrogen atom.

The crosslinking frequency depends both on the chain lengths of the organopolysiloxanes (1) and on the stoichiometry of the SiOR ¹ groups of the organopolysiloxane (1) and the SiOR ³ groups of the silane (2) which react with one another. High levels of crosslinking are achieved when the same number of SiOR ¹ groups of the organopolysiloxane (1) and SiOR ³ groups of the silane (2) react with each other. Losses due to volatility or side reactions may require a stoichiometric ratio other than 1.0: 1.0. If desired, a stoichiometric excess of SiOR ³ - of silane (2) to SiOR ¹ - groups of organopolysiloxane (1) can be used. Surprisingly, it was found that even with a stoichiometric deficit of SiOR ³ - from silane (2) to SiOR ¹ groups of organopolysiloxane (1), for example 0.7: 1.0, elastic films can be achieved.

The dispersions according to the invention are prepared by intensive mixing of organopolysiloxanes (1) with silanes (2),
Water (3),
Emulsifiers (4),
optionally further silanes (5),
and optionally other substances (6) with each other. The preparation can be discontinuous or continuous, such as in DE 102004023911 A or in WO 2005100453 is described.

Technologies for the preparation of dispersions or emulsions of organopolysiloxanes are known. Thus, intensive mixing and dispersion can be carried out in rotor-stator agitators, colloid mills, high-pressure homogenizers, microchannels, membranes, jet nozzles and the like, or by means of ultrasound. Homogenizers and methods are eg in Ullmann's Encyclopaedia of Industrial Chemistry, CD-ROM Edition 2003, Wiley-VCH Verlag , described under the keyword "emulsions".

Although the silanes (2) are known to contain hydrolysis-sensitive groups, especially when R ^{3 is} a hydrogen atom or a methyl or ethyl radical, even in the presence of Water surprisingly crosslinked organopolysiloxanes obtained by reaction with a plurality of organopolysiloxanes (1).

The nature of the mixture of the components for preparing the dispersions of the invention is not very critical and can be practiced in various orders. Depending on the components (1), (2), (3), (4), optionally (5) and optionally (6), however, preferred procedures may result, which should be checked in individual cases.

It can e.g. the components (1) and (2) are premixed with each other, then the (or) the emulsifier (s) (4) is added and then the water (3) and optionally further substances (5) and (6) are incorporated. It is also possible to meter the components (1) and (2) and (3) to (6) in sequence into the emulsifying apparatus. In special cases it may e.g. due to the siloxane viscosity or reactivity, it is advantageous to mix silane (2) with an organopolysiloxane (1) and then incorporate another organopolysiloxane (1), or vice versa, depending on how more favorable rheological properties result for the processing of the components.

In the case of very reactive silanes (2), it may be advantageous first to convert the component (1) with emulsifier (4) and the water (3) into a stiff phase, and then to pass the silane (2) neat or diluted in an inert substance ( 6) before further dilution with water if necessary.

Furthermore, it is also possible to add silane (2) in the finished emulsion of organopolysiloxanes (1) so as to achieve the desired reaction and crosslinking of the organopolysiloxane (1) in the emulsion. Further, the silane (2) may be previously partially or completely hydrolyzed by adding water. To obtain VOC-free hydrolyzate of silane (2), For example, the by-product alcohol R ³ OH can be partially or completely removed by suitable known measures, such as distillation, membrane processes or other separation processes.

In the process according to the invention, water (3) is used in amounts of preferably from 1 to 99% by weight, particularly preferably from 5 to 95% by weight, based in each case on the total weight of all the ingredients of the dispersion.

Preferably, the process for the preparation of dispersions can be carried out continuously. The organopolysiloxanes (1) required for the preparation of the dispersion are preferably prepared continuously and passed on continuously to the emulsifying apparatus, and mixed continuously with silanes (2), emulsifiers (4) and at least part of the water as dispersant (3) before emulsification, and This mixture is continuously fed to a first high shear mixer and it is formed in this mixer, a viscous phase, wherein the pressure and the temperature are measured after this mixer and adjusted so that a high quality and finely divided as possible dispersion. Next silanes (5) and other substances (6) can be added before or after the first high-shear mixer. Optionally, after the first high shear mixer, the emulsion may be further diluted by mixing in water.

In the inventive method can be used as emulsifiers (4) all previously known, ionic and nonionic emulsifiers both individually and as mixtures of different emulsifiers with which previously aqueous dispersions, especially aqueous emulsions of organopolysiloxanes could be produced.

1. 1. Alkylsulfate, besonders solche mit einer Kettenlänge von 8 bis 18 C-Atomen, Alkyl- und Alkarylethersulfate mit 8 bis 18 C-Atomen im hydrophoben Rest und 1 bis 40 Ethylenoxid (EO)- bzw. Propylenoxid(PO)einheiten.
2. 2. Sulfonate, besonders Alkylsulfonate mit 8 bis 18 C-Atomen, Alkylarylsulfonate mit 8 bis 18 C-Atomen, Tauride, Ester und Halbester der Sulfobernsteinsäure mit einwertigen Alkoholen oder Alkylphenolen mit 4 bis 15 C-Atomen; gegebenenfalls können diese Alkohole oder Alkylphenole auch mit 1 bis 40 EO-Einheiten ethoxyliert sein.
3. 3. Alkali- und Ammoniumsalze von Carbonsäuren mit 8 bis 20 C-Atomen im Alkyl-, Aryl-, Alkaryl- oder Aralkylrest.
4. 4. Phosphorsäureteilester und deren Alkali- und Ammoniumsalze, besonders Alkyl- und Alkarylphosphate mit 8 bis 20 C-Atomen im organischen Rest, Alkylether- bzw. Alkaryletherphosphate mit 8 bis 20 C-Atomen im Alkyl- bzw. Alkarylrest und 1 bis 40 EO-Einheiten.

Examples of anionic emulsifiers are:

1. 1. Alkyl sulfates, especially those having a chain length of 8 to 18 carbon atoms, alkyl and alkaryl ether sulfates having 8 to 18 carbon atoms in the hydrophobic radical and 1 to 40 ethylene oxide (EO) - or propylene oxide (PO) units.
2. 2. sulfonates, especially alkyl sulfonates having 8 to 18 carbon atoms, alkylaryl sulfonates having 8 to 18 carbon atoms, taurides, esters and half esters of sulfosuccinic acid with monohydric alcohols or alkylphenols having 4 to 15 carbon atoms; optionally, these alcohols or alkylphenols may also be ethoxylated with 1 to 40 EO units.
3. 3. alkali metal and ammonium salts of carboxylic acids having 8 to 20 carbon atoms in the alkyl, aryl, alkaryl or aralkyl radical.
4. 4. Phosphoric acid partial esters and their alkali metal and ammonium salts, especially alkyl and alkaryl phosphates having 8 to 20 C atoms in the organic radical, alkyl ether or alkaryl ether phosphates having 8 to 20 C atoms in the alkyl or alkaryl radical and 1 to 40 EO- Units.

• 5. Polyvinylalkohol, der noch 5 bis 50 %, vorzugsweise 8 bis 20 % Vinylacetateinheiten aufweist, mit einem Polymerisationsgrad von 500 bis 3000.
• 6. Alkylpolyglycolether, vorzugsweise solche mit 3 bis 40 EO-Einheiten und Alkylresten von 8 bis 20 C-Atomen.
• 7. Alkylarylpolyglycolether, vorzugsweise solche mit 5 bis 40 EO-Einheiten und 8 bis 20 C-Atomen in den Alkyl- und Arylresten.
• 8. Ethylenoxid/Propylenoxid(EO/PO)-Blockcopolymere, vorzugsweise solche mit 8 bis 40 EO- bzw. PO-Einheiten.
• 9. Additionsprodukte von Alkylaminen mit Alkylresten von 8 bis 22 C-Atomen mit Ethylenoxid oder Propylenoxid.
• 10. Fettsäuren mit 6 bis 24 C-Atomen.
• 11. Alkylpolyglykoside der allgemeinen Formel R*-O-Z_o, worin R* einen linearen oder verzweigten, gesättigten oder ungesättigten Alkylrest mit im Mittel 8 - 24 C-Atomen und Z_o einen Oligoglykosidrest mit im Mittel o = 1 - 10 Hexose- oder Pentoseeinheiten oder Gemischen davon bedeuten.
• 12. Naturstoffe und deren Derivate, wie Lecithin, Lanolin, Saponine, Cellulose; Cellulosealkylether und Carboxyalkylcellulosen, deren Alkylgruppen jeweils bis zu 4 Kohlenstoffatome besitzen.
• 13. Polare Gruppen, enthaltend insbesondere die Elemente O, N, C, S, P, Si, enthaltende lineare Organo(poly)siloxane, insbesondere solche mit Alkoxygruppen mit bis zu 24 C-Atomen und/oder bis zu 40 EO- und/oder PO-Gruppen.

Examples of nonionic emulsifiers are:

• 5. polyvinyl alcohol, which still has 5 to 50%, preferably 8 to 20% Vinylacetateinheiten, with a degree of polymerization of 500 to 3000.
• 6. Alkylpolyglycolether, preferably those having 3 to 40 EO units and alkyl radicals of 8 to 20 carbon atoms.
• 7. Alkylarylpolyglycolether, preferably those having 5 to 40 EO units and 8 to 20 carbon atoms in the alkyl and aryl radicals.
• 8. Ethylene oxide / propylene oxide (EO / PO) block copolymers, preferably those having 8 to 40 EO or PO units.
• 9. Addition products of alkylamines having alkyl radicals of 8 to 22 carbon atoms with ethylene oxide or propylene oxide.
• 10. Fatty acids with 6 to 24 carbon atoms.
• 11. Alkylpolyglycosides of the general formula R * -OZ _o , where R * is a linear or branched, saturated or unsaturated alkyl radical having an average of 8-24 carbon atoms and Z _{o is} an oligoglycoside radical having on average o = 1-10 hexose or pentose units or mixtures thereof.
• 12. Natural products and their derivatives, such as lecithin, lanolin, saponins, cellulose; Cellulosealkyl ethers and carboxyalkylcelluloses whose alkyl groups each have up to 4 carbon atoms.
• 13. Polar groups, containing in particular the elements O, N, C, S, P, Si, containing linear organo (poly) siloxanes, especially those with alkoxy groups having up to 24 carbon atoms and / or up to 40 EO and / or or PO groups.

• 14. Salze von primären, sekundären und tertiären Fettaminen mit 8 bis 24 C-Atomen mit Essigsäure, Schwefelsäure, Salzsäure und Phosphorsäuren.
• 15. Quarternäre Alkyl- und Alkylbenzolammoniumsalze, insbesondere solche, deren Alkylgruppen 6 bis 24 C-Atome besitzen, insbesondere die Halogenide, Sulfate, Phosphate und Acetate.
• 16. Alkylpyridinium-, Alkylimidazolinium- und Alkyloxazoliniumsalze, insbesondere solche, deren Alkylkette bis zu 18 C-Atome besitzt, speziell die Halogenide, Sulfate, Phosphate und Acetate.

Examples of cationic emulsifiers are:

• 14. Salts of primary, secondary and tertiary fatty amines having 8 to 24 carbon atoms with acetic acid, sulfuric acid, hydrochloric acid and phosphoric acids.
• 15. Quaternary alkyl and alkylbenzene ammonium salts, in particular those whose alkyl groups have 6 to 24 carbon atoms, in particular the halides, sulfates, phosphates and acetates.
• 16. Alkylpyridinium, alkylimidazolinium and Alkyloxazoliniumsalze, especially those whose alkyl chain has up to 18 carbon atoms, especially the halides, sulfates, phosphates and acetates.

• 17. Langkettig substituierte Aminosäuren, wie N-Alkyl-di-(aminoethyl-)glycin oder N-Alkyl-2-aminopropionsäuresalze.
• 18. Betaine, wie N-(3-Acylamidopropyl)-N,N-dimethylammoniumsalze mit einem C₈-C₁₈-Acylrest und Alkyl-imidazolium-Betaine.

Particularly suitable as ampholytic emulsifiers:

• 17. Long-chain substituted amino acids, such as N-alkyl-di- (aminoethyl) glycine or N-alkyl-2-aminopropionsäuresalze.
• 18. Betaines, such as N- (3-acylamidopropyl) -N, N-dimethylammonium salts having a C ₈ -C ₁₈ acyl radical and alkyl imidazolium betaines.

Preferred emulsifiers are nonionic emulsifiers, in particular the alkyl polyglycol ethers listed under 6. above
The constituent (4) may consist of one of the abovementioned emulsifiers or of a mixture of two or more of the abovementioned emulsifiers; it may be used in pure form or as solutions of one or more emulsifiers in water or organic solvents.

In the inventive method, the emulsifiers (4) in amounts of preferably 0.1 to 60 wt .-%, particularly preferably 0.5 to 30 wt .-%, each based on the total weight of organopolysiloxanes (1) and silanes (2 ).

If the organopolysiloxane (1) or the silane (2) or the resulting crosslinked organopolysiloxane itself acts as an emulsifier, the addition of separate emulsifier (4) can be dispensed with.

In the preparation of the dispersions of the invention further silanes (5) of the formula (III) can be used.

Silanes (5) act as adhesion-promoting silanes. Furthermore, they can be used in addition to silane (2) and can act as additional crosslinkers in the case of x = 3.

Z in formula (III) is preferably a radical of the formula -NR ⁷ ₂ ,
wherein R ^{7 is the} same or different and represents a hydrogen atom or an alkyl or aminoalkyl or Iminoalkylrest.
A preferred example of the radical Z is the radical of the formula -NH (CH ₂ ) ₂ NH ₂ .
Preferably, x is 2.
Preferably, R ⁶ in formula (III) is a radical of the formula -CH ₂ CH ₂ CH ₂ -.

Examples of silane (5) are
(3-methacryloxypropyl) trimethoxysilane,
3-aminopropyltrimethoxysilane,
3- (cyclohexylamino) propyltrimethoxysilane
N- (2-aminoethyl) (3-aminopropyl) methyldimethoxysilane,
N- (2-aminoethyl) (3-aminopropyl) methyl diethoxysilane,
N- (2-aminoethyl) (3-aminopropyl) trimethoxysilane,
N- (2-aminoethyl) (3-aminopropyl) triethoxysilane and
(3-glycidoxypropyl) triethoxysilane.

Examples of water-miscible liquids that can be used as further substances (6) are acids, such as formic acid, acetic acid, propionic acid, oxalic acid and citric acid and silicone or non-silicone emulsions.

Further, as further substances (6) commercial preservatives for dispersions, such as isothiazolinones or parabens, or their aqueous formulations may be added.

The dispersions can be prepared as dispersions of undiluted crosslinked organopolysiloxanes, but sometimes for reasons of handling, dilution with organic solvents or low-viscosity oligomers / polymers is recommended.

Examples of water-immiscible liquids which can be used as further substances (6) are therefore organic solvents, such as toluene, n-hexane, n-heptane and technical gasoline fractions and low-viscosity oligomers / polymers, such as silicone oils, preferably siloxanes, such as dimethylpolysiloxanes ,

Examples of water-soluble solids that can be used as further substances (6) are ammonium phosphates and polyphosphates, ammonium formates and lithium formate, which may act as antistatic agents and / or flame retardants.
Examples of water-insoluble solids which can be used as further substances (6) are reinforcing and non-reinforcing and flame-retardant fillers. Examples of reinforcing fillers, ie fillers with a BET surface area of at least 50 m ² / g, are fumed silica, precipitated silica or silicon-aluminum mixed oxides having a BET surface area of more than 50 m ² / g and silicone particles, such as MQ resins. The fillers mentioned may be hydrophobic. Examples of non-reinforcing and also flame-retardant fillers, ie fillers having a BET surface area of less than 50 m ² / g, are powders of quartz, chalk, cristobalite, diatomaceous earth, calcium silicate, zirconium silicate, montmorillonites, such as bentonites, zeolites, metal oxides, such as Aluminum or zinc oxide or their mixed oxides or titanium dioxide, metal hydroxides, such as aluminum hydroxide, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide and boron nitride.

The emulsification process for preparing the dispersion is preferably carried out at temperatures below 120.degree. C., preferably at 5.degree. C. to 100.degree. C., more preferably at 10.degree. C. to 80.degree. The temperature increase is preferably due to the entry of mechanical shear energy needed for the emulsification process. The temperature increase is not needed to accelerate a chemical process. Furthermore, the dispersion is preferably carried out at the pressure of the surrounding atmosphere, but may also be carried out at higher or lower pressures.

The dispersion which is used for the process according to the invention has the advantage that it can be prepared without the addition of catalysts, in particular without the addition of metal catalysts. The reaction of (1) with (2) preferably proceeds completely in a few minutes to several hours, where methoxysilanes also react faster than ethoxysilanes. The condensation can be accelerated by acids and bases.

The alcohols which are obtained as condensation by-products in the preparation of the dispersion can remain in the dispersion or can also be removed, for example by distillation under reduced pressure, membrane processes or by extraction.

The measured by light scattering in the dispersions average particle size is in the range 0.001 to 100 microns, preferably 0.002 to 10 microns. The pH values can vary from 1 to 14, preferably 3 to 9, particularly preferably 5 to 9.

Examples of filler fibers which are treated with the dispersions according to the invention are those of polyester, polyamide, polylactate (PLA), polybutyric acid, polyolefins, viscose, modal and lyocell.

Filling fibers of polyester are preferred.
The filling fibers are preferably staple fibers or crimped staple fibers, from which a bulky cotton wool is produced by opening and laying on cards.
These can be used as wadding, filling material or cushioning material in pillows, upholstery, blankets, comforters, mattresses, sleeping bags, insulating clothing (eg coats, sports anoraks).

The filling fibers can be treated by contacting the filler fibers with the dispersions of the invention by dipping, spraying, rolling, printing, padding or curtain casting, preferably by spraying the aqueous dispersions onto the filler fibers by spraying, dipping, padding or curtain-coating be applied. Thereafter, the water (3) is removed.

The water is preferably removed by drying the filler fibers at a temperature of from 1 to 230 ° C., preferably from 30 to 180 ° C., more preferably in the temperature range from 70 to 120 ° C.
The drying time depends on parameters such as temperature, air circulation, substrate thickness and application quantity.
In the case of the filling fibers, the dispersions according to the invention remain after drying as a film on the surface of the filling fibers.

The process according to the invention has the advantage that the filler fibers treated with the dispersions according to the invention have a permanent soft feel, increased elasticity, gloss and smoothness, reduction of frictional resistance and improved hydrophobicity and dirt repellency. The film obtained by the evaporation of the water from the dispersion adheres well to the filler fibers and gives the surface of the Filling fibers a particularly soft smoothness and elasticity with a return force.
Due to the good permanent adhesion on the fiber, the filling fiber can be well carded and there is hardly any abrasion / deposition of silicone polymers on the card fittings, which would cause a parking of the cards and increased cleaning.

Methods of execution in the laboratory:

Film formation test:
The amount of emulsion is weighed, from which about 1 g of residue is formed; eg at 66% emulsion about 1.5 g, at 50% approx. 2 g. This amount is diluted 1: 1 with water and placed in a tinplate lid (diameter 10 cm). The product is spread over the entire surface by pivoting the lid and the sample is placed open (at room temperature in the hood for 24 h, or in the oven at 120 ° C or 170 ° C for 20 min).
The judgment is made when the water or solvent is completely evaporated. Grades from 1 to 5 are given (marks: 1 = oily, uncrosslinked, 2 = oily, viscous, 3 = viscous, cross-linked, 4 = cross-linked, sticky, 5 = solid with tack-free dry surface).

Fiberfill:

For equipment, 117 g of the dispersions described in the Examples and Comparative Experiments were diluted to 1000 g with demineralized water and 400 ml of it were placed in a 1 beaker. Curled polyester staple fibers with a denier of 61 dtex and 50 mm staple length are opened on a card or a shredder to bulky cotton wool. 20 g of this fiber are immersed in the beaker for 1 minute and completely wetted.

Then the wet fiber is removed and separated from it in a sling (salad spinner) so much liquid that a weight gain of 70% is maintained. To remove the residual water and to complete condensation, place the wet fibers in a drying oven for 10 minutes (optionally at 120 or 170 ° C) or, optionally, the treated fibers are spread at 23 ° C for 24 hours and dried.

Extraction with Soxhlet apparatus:

To investigate permanence, 10 g of filler fiber material (with or without silicone equipment) was extracted for 3 hours in a 500 ml round-bottomed flask under reflux with 220 g of hexane and the residue was determined after evaporating the hexane.

Preparation of the film-forming silicone dispersions:

Example 1:

In an Ultra-Turrax T 50 emulsifier (Janke & Kunkel / IKA) is from 5 g Isotridecyldecaethoxylat, 85% in water, commercially available under the trade name Lutensol TO 109 (BASF), and 8 g of deionized water an emulsifier to which 100 g of a freshly prepared homogeneous siloxane polymer / silane mixture consisting of 99.65 g of polydimethylsiloxane diol containing 1100 ppm by weight of terminal OH groups as siloxane (1) and 0.39 g of N-morpholinomethyl triethoxysilane (molecular weight 263.4) as silane (2), is metered. It is then diluted in portions with a total of 90.1 g of deionized water to give a milky white emulsion having an average particle size of 309 nm. The solids content of the emulsion is 50.7%, the pH is 6.0. The emulsion is homogeneous and stable even after 6 months storage at room temperature.

If 0.5 g of this emulsion are poured into 8 g of tetrahydrofuran, a precipitate of the crosslinked and THF-insoluble organopolysiloxane elastomer is formed immediately. The precipitation does not dissolve even within 24 h.

Evaporation of the emulsion gives, after a drying time of 24 h / 25 ° C., a gel-like elastic film which adheres well to glass or aluminum.

Examples 2 to 6:

Further emulsions are prepared analogously to Example 1, using the amounts indicated in Table 1. Table 1: example Siloxane (1) in g Silane (2) in g Fixed content (%) pH Particle size (nm) Film evaluation after drying 24 h / 25 ° C B2 99.56 (1a) 0.44 50.5 7 478 very elastic, transparent B3 99.40 (1a) 0.60 49.9 7 481 elastic, transparent B4 99,22 (1a) 0.79 50.5 6.5 --- elastic, opaque B5 94.0 (1a) 6.0 49.8 8th --- not very elastic, opaque B6 20.0 (1b)
80.0 (1a) 0.37 52.0 7 2810 very elastic, transparent

The solid content is determined at 150 ° C to constant weight with device: Mettler Toledo HR 73.

The particle sizes are determined with Coulter N4 plus.

Example B6 uses two siloxanes (1a, 1b);
as siloxane (1b) a copolymer of 3- (2-aminoethylamino) propylmethylsiloxy and dimethylsiloxy units having an amine number of 0.145, a viscosity of 4700 mm ² / s (at 25 ° C) and an end group ratio of OH / OMe = 54/46 ;
as siloxane (1a) is used:
Polydimethylsiloxanediol containing 1100 ppm by weight of terminal OH groups.

As silane (2) is used: N-morpholinomethyl-triethoxysilane

The elasticity of the films produced from the emulsion decreases from B1 to B5 as the amount of silane (2) increases.

The elastomeric film prepared from Dispersion B3 is cut apart and placed in toluene for 24 hours. The cut edges are still sharp afterwards. The film is swollen but insoluble in toluene.
Comparative Experiment 1a-1e to EP 828 794 A and EP 655 475 A1:

• 0,60g Vinyltrimethoxysilan (VTMO) gemäß Beispiel 1 von EP 828 794 A

Vergleich 1b:

• 0,34 g Vinyltrimethoxysilan (Molmasse 148,2)
• (0,34 g = 1,1 Äquivalente Si-OCH₃ des Vinyltrimethoxysilans bezogen auf 1 Äquivalent SiOH des Siloxans (1) analog Beispiel B3)

Vergleich 1c:

• 0, 60 g α,ω-Dimethoxypoly(N-(2-aminoethyl)-3-aminopropylmethylsiloxan) gemäß Beispiel 1 von EP 828 794 A

Vergleich 1d:

• 0,60 g eines Harzgemisches gemäß Beispiel 1 von EP 655 475 A1 bestehend aus 16 Teilen Organopolysiloxanharz der Formel [(CH₃)₃SiO_1/2] [SiO₂] mit einem durchschnittlichen Molekulargewicht von 2000 und einem durchschnittlichen Ethoxygehalt von 2,1 Gewichtsprozent, bezogen auf das Harzmolekül, und 17 Teilen Organopolysiloxanharz der Formel [(CH₃)₂SiO]_0,2[(CH₃)SiO_3/2]_0,8 mit einem durchschnittlichen Molekulargewicht von 3000 und einem durchschnittlichen Ethoxygehalt von 2,6 Gewichtsprozent, bezogen auf das Harzmolekül.

Vergleich 1e:

• Analog Vergleich V 1d mit der Abänderung, dass zu dem Harzgemisch KOH zugegeben wird und der pH-Wert 11 beträgt.

Vergleich 1f:

• 0,60 g eines 1:1 Gemisches von Vinyltrimethoxysilan (VTMO) und α,ω-Dimethoxypoly(N-(2-aminoethyl)-3-aminopropylmethylsiloxan) gemäß Beispiel 1 von EP 828 794 A
• Die Ergebnisse sind in der Tabelle 2 zusammengefasst:

Tabelle 2: Vergleich Siloxan (1) in g Ersatz von Silan (2) pH Aussehen der getrockneten Emulsion nach in g durch 24 h/23°C 7 Tage/23°C V1a 99,40 0,60 VTMO¹⁾ 5 ölig, ölig, dünn, dünn, klar klar V1b 99,40 0,34 VTMO¹⁾ 5 ölig, ölig, dünn, dünn, klar klar V1c 99,40 0,60 GF95-H²⁾ 10 ölig, ölig, dünn, dünn, trüb trüb V1d 99,40 0,60 Harz ³⁾ 5 ölig, ölig, dünn, dünn, trüb trüb V1e 99,40 0,60 Harz³⁾ + 11 ölig, ölig, KOH bis dünn, dicker, pH 11 trüb trüb V1f 99,40 0,60 VTMO¹⁾ + 9⁴⁾ ölig, ölig, GF95-H²⁾ dünn, dicker, trüb trüb ¹⁾ Vinyltrimethoxysilan
²⁾ GF95-H = α,ω-Dimethoxypoly(N-(2-aminoethyl)-3-aminopropylmethylsiloxan)
³⁾ Harzgemisch aus Beispiel 1 von EP 655 475 A1 (siehe Beschreibung oben unter Vergleich 1d)) The procedure of Example B3 is repeated with the modification that 0.60 g of morpholinomethyltriethoxysilane, the inventive silane (2), by the component indicated in Table 2 is replaced:
Comparison 1a:

• 0.60 g of vinyltrimethoxysilane (VTMO) according to Example 1 of EP 828 794 A

Comparison 1b:

• 0.34 g of vinyltrimethoxysilane (molecular weight 148.2)
• (0.34 g = 1.1 equivalents of Si-OCH ₃ of vinyltrimethoxysilane based on 1 equivalent of SiOH of the siloxane (1) analogously to Example B3)

Comparison 1c:

• 0.60 g of α, ω-dimethoxypoly (N- (2-aminoethyl) -3-aminopropylmethylsiloxane) according to Example 1 of EP 828 794 A

Comparison 1d:

• 0.60 g of a resin mixture according to Example 1 of EP 655 475 A1 consisting of 16 parts of organopolysiloxane resin of the formula [(CH ₃ ) ₃ SiO _1/2 ] [SiO ₂ ] having an average molecular weight of 2000 and an average ethoxy content of 2.1% by weight, based on the resin molecule, and 17 parts of organopolysiloxane resin of the formula [ (CH ₃ ) ₂ SiO] _0.2 [(CH ₃ ) SiO _3/2 ] _0.8 having an average molecular weight of 3000 and an average ethoxy content of 2.6% by weight based on the resin molecule.

Comparison 1e:

• Analogous to V 1d with the modification that KOH is added to the resin mixture and the pH is 11.

Comparison 1f:

• 0.60 g of a 1: 1 mixture of vinyltrimethoxysilane (VTMO) and α, ω-dimethoxypoly (N- (2-aminoethyl) -3-aminopropylmethylsiloxane) according to Example 1 of EP 828 794 A
• The results are summarized in Table 2:

Table 2: comparison Siloxane (1) in g Replacement of silane (2) pH Appearance of the dried emulsion after in g by 24 h / 23 ° C 7 days / 23 ° C V1a 99.40 0.60 VTMO ¹⁾ 5 oily, oily, thin, thin, clear clear V1b 99.40 0.34 VTMO ¹⁾ 5 oily, oily, thin, thin, clear clear V 1c 99.40 0.60 GF95-H ²⁾ 10 oily, oily, thin, thin, cloudy cloudy V 1d 99.40 0.60 Resin ³⁾ 5 oily, oily, thin, thin, cloudy cloudy V1E 99.40 0.60 Resin ³⁾ + 11 oily, oily, KOH up thin, thick pH 11 cloudy cloudy v1f 99.40 0.60 VTMO ¹⁾ + 9 ⁴⁾ oily, oily, GF95-H ²⁾ thin, thick cloudy cloudy ¹⁾ vinyltrimethoxysilane
²⁾ GF95-H = α, ω-dimethoxypoly (N- (2-aminoethyl) -3-aminopropylmethylsiloxane)
³⁾ resin mixture from Example 1 of EP 655 475 A1 (see description above under comparison 1d))

All emulsions do not form a film when dried. The residual oily silicones are soluble in toluene (tested as a 20% solution in toluene), ie they are not cross-linked.

Comparative experiment 2

The viscosity increase was measured after mixing the components siloxane (1) and silane (2) according to Example B3, ie, α, ω-dihydroxypolydimethylsiloxane with morpholinomethyltriethoxysilane.
In comparison, morpholinomethyltriethoxysilane was replaced by the component indicated in Table 3 in V2a - V2f (analogously to Comparative Experiments V1a - V1f) and the viscosity increase was likewise measured.
The results are summarized in Table 3.

While the viscosity rapidly increases when using the components (1) and (2) according to the invention, as in Example 3, has doubled after 2 hours and after 5 hours is no longer measurable, since an elastomer has formed, the viscosity increases Comparative tests V2a - V2e only very slowly and it formed even after 7 days no cross-linked elastomer particles. Table 3: Measurement of Viscosity Increase comparison Siloxane (1) in g Replacement of silane (2) Viscosity at 23 ° C measured with Brookfiled [mPa · s] in g immediately after mixing after 2 h after 24 h after 2 days after 6 days v2a 99.40 0.60 VTMO ¹⁾ 5410 5740 5680 5720 5810 v2c 99.40 0.60 GF95-H ²⁾ 6100 6240 6200 6200 6390 v2d 99.40 0.60 Resin ³⁾ 5860 5980 5960 5950 6020 V2e 99.40 0.60 Resin ³⁾ + KOH to pH 11 5950 6530 7480 7960 9280 V2f 99.40 0.60 VTMO ¹⁾ + GF95-H ²⁾ 5810 6580 8710 12650 36700 analogously to Example 3 99.40 0.60 According to the invention: morpholinomethyltriethoxysilane 350000 736000 not measurable, networked, elastic not measurable, networked, elastic not measurable, networked, elastic Siloxane (1) = polydimethylsiloxane diol containing 1100 ppm by weight of terminal OH groups Comparative experiment 3 according to DE 102004038148 A1

In an Ultra-Turrax emulsifier T 50 (Janke & Kunkel / IKA) is from 9.38 g Isotridecyldecaethoxylat (Lutensol TO 109, Fa., BASF AG), 3.90 g castor oil G 1300 (Atlas) and 4, 55 g of water, a stiff emulsifier prepared to the 125.28 g of a freshly prepared homogeneous polymer / silane mixture of 124.63 g of polydimethylsiloxane with a content of terminal OH groups of 765 ppm by weight as organopolysiloxane (1) and 0.86 g N-Morpholylmethylmethyldiethoxysilane is metered. It is then diluted in portions with a total of 106.65 g of water, whereupon a stable emulsion having an average particle size of 275 nm is obtained. The silicone content of the emulsion is 50%.

Evaporation of the emulsion after a service life of 24h / 25 ° C and reextraction of the siloxane polymer with n-heptane is obtained after evaporation of the solvent, a highly viscous polysiloxane having a viscosity of 3400 Pa.s (25 ° C), which is soluble in toluene and so that is uncrosslinked. The dispersion containing this highly viscous polysiloxane is not in accordance with the invention.

Example 7

In an Ultra-Turrax T 50 emulsifier (Janke & Kunkel / IKA) is from 6 g of isotridecyldecaethoxylate, 85% in water, commercially available under the trade name Lutensol TO 109 (BASF), and 6 g of deionized water an emulsifier made to the 60 g of a freshly prepared homogeneous siloxane polymer / silane mixture consisting of
33.2% of a polydimethylsiloxane diol (1a) containing 1100 ppm by weight of terminal OH groups,
66.41% of a copolymer of 3- (2-aminoethylamino) propylmethylsiloxy and dimethylsiloxy units (1b) with a Amine number of 0.145, a viscosity of 4700 mm ² / s (at 25 ° C) and an end group ratio of OH / OMe = 54/46 and
0.39% N-morpholinomethyltriethoxysilane as silane (2),
is dosed. It is then diluted in portions with a total of 23 g of deionized water, whereupon a michig-white emulsion having an average particle size of 210 nm is obtained. To the emulsion is added 1 g of N- (2-aminoethyl) (3-aminopropyl) methyldimethoxysilane as component (5) and 0.4 g of 80% acetic acid as component (6) with stirring. The solids content of the emulsion is 66%, the pH 7.5. The emulsion is homogeneous and stable even after 6 months storage at room temperature.

Example 8

3 g of N- (2-aminoethyl) (3-aminopropyl) -methyldimethoxysilane are added slowly as a further component (5) to 97 g of the emulsion from Example 7 with vigorous stirring. The solids content of the emulsion is about 66%, the pH 10.5.

Comparative experiment 4

In an Ultra-Turrax T 50 emulsifier (Janke & Kunkel / IKA) is from 6 g Isotridecyldecaethoxylat, 85% in water, commercially available under the trade name Lutensol TO 109 (BASF), and 6 g of deionized water an emulsifier made to the 60 g of a freshly prepared homogeneous siloxane polymer / silane mixture consisting of
33.2% of a polydimethylsiloxane diol (1a) containing 1100 ppm by weight of terminal OH groups,
66.41% of a copolymer of 3- (2-aminoethylamino) propylmethylsiloxy and dimethylsiloxy units (1b) having an amine number of 0.145, a viscosity of 4700 mm ² / s (at 25 ° C) and an end group ratio of OH / OMe = 54 / 46 is dosed. It is then mixed with a total of 23 g of deionized water diluted in portions to give a michig-white emulsion having an average particle size of 210 nm. To the emulsion is added 1 g of N- (2-aminoethyl) (3-aminopropyl) -methyldimethoxysilane as component (5) and 0.4 g of 80% strength acetic acid as further component (6) with stirring. The solids content of the emulsion is 66%, the pH 7.5. The emulsion is homogeneous and stable even after 6 months storage at room temperature.

Comparative experiment 5

3 g of N- (2-aminoethyl) (3-aminopropyl) -methyldimethoxysilane are added slowly as a further component (5) to 97 g of the emulsion from Comparative Experiment 4 with vigorous stirring. The solids content of the emulsion is about 66%, the pH 10.5.

Examination of the film formation of the emulsions from Examples 7 and 8 and Comparative Experiments 4 and 5:

According to the film test method described above, the emulsions from Examples 7 and 8 and Comparative Experiments 4 and 5 were diluted, weighed in the lid and dried at 23 ° C / 24 h, or at 120 and 170 ° C for 20 min. dried. The results are summarized in Table 4.

While the emulsions of Comparative Experiments 4 and 5 (even with an increase in the amount of N- (2-aminoethyl) (3-aminopropyl) methyldimethoxysilane) dry to an oily residue, formed in the emulsions of the invention from Examples 7 and 8 a solid film both at 23 ° C, at 120 ° C and also at 170 ° C off. Shortly after drying, the film with an increased proportion of N- (2-aminoethyl) (3-aminopropyl) -methyldimethoxysilane (Example 8) is still very slightly tacky, but becomes dry on storage.

When dried at 120 ° C, the films remain free of yellow, while at 170 ° C, a slight yellowing or significant yellowing with increased amount of N- (2-aminoethyl) (3-aminopropyl) methyldimethoxysilane is visible.
The emulsions of Examples 7 and 8 thus reach crosslinking without yellowing even at low temperature and achieve a higher molecular weight network with film character than the emulsions from Comparative Experiments 4 and 5. Table 4: Comparison of film formation Movie character notes * Appearance 23 ° C 120 ° C 170 ° C 23 ° C, 120 ° C 170 ° C Example 7 4-5 5 5 transparent yellowish Example 8 4 4-5 4-5 transparent yellow Comparison 4 1 1 1 transparent yellowish Comparison 5 1 1 1 transparent yellow * Notes: 1 = oily, uncrosslinked, 2 = oily, viscous, 3 = viscous, cross-linked, 4 = elastic, cross-linked, sticky, 5 = elastic, cross-linked with tack-free dry surface. Grade 4 or 5 films are insoluble in toluene.

Finishing fiber equipment with the emulsions of Examples 7 and 8 and Comparative Experiments 4 and 5:

The emulsions of Examples 7 and 8 and Comparative Experiments 4 and 5 were respectively crimped polyester staple fibers with a titer of 61 dtex and 50 mm staple length after laboratory description and dried at 3 different temperatures of 23 °, 120 ° and 170 °. After this drying, the finished fibers were conditioned in a climatic room at 23 ° C 50% humidity for 24 hours and judged manually by 5 people by the handle (dryness, softness, slipperiness, bulkiness and recoil behavior). For this purpose, the samples were strung together according to the handle judgment and set a grading scale of 1 -5 with 5 as the softest, most sliding spring-like grip with the best resilience and 1 as a dry grip with noticeable permanent deformation and low restoring force.
The results are summarized in Table 5.

The handle of the fibers treated with Examples 7 and 8 is judged to be softer, more slippery, less abrasive, and bulkier. In particular, the good feel is significantly improved even at room temperature, but especially at 120 ° C drying compared to the non-inventive Comparative Experiments 4 and 5. Table 5: Comparison of the handle of crimped polyester staple fibers equipped with the following emulsions finishes Handle after drying at 23 ° C 120 ° C 170 ° C Example 7 2.5 3.5 4.5 Example 8 3.5 4 5 Comparison 4 1.5 2 3 Comparison 5 1.5 2 3

Further, the finished fibers were split and half of the samples were placed in a rinse net and washed with mild detergent at 40 ° C (color wash setting). After the wash cycle, the nets were emptied and the fibers dried and conditioned in a climate chamber at 23 ° C 50% Hüftheuchte.

The washed samples were then hand-rated by hand (grade 1 to 5, 5 as the most slippery, bulky handle).
The results are summarized in Table 6. Table 6: Comparison of the handle of finished crimped polyester staple fibers after a fine wash Handle for a wash: drying at finishes 120 ° C 170 ° C Example 7 3 3.5 Example 8 3.5 4 Comparison 4 1.5 2 Comparison 5 1.5 2.5

After washing, the grip in the treated with Examples 7 and 8 fibers is significantly better than in the treated with Comparative Experiments 4 and 5 fibers.

Further, the durability of the finishing agent on the fiber was tested against hexane as an organic detergent by extracting the fiber in a Soxhlet apparatus for 3 hours and determining the extraction amount.
The results are summarized in Table 7. Table 7: Comparison of Hexane Extractable Content of Equipped Fibers. finishes Extracted amount 3 h with boiling hexane drying at 170 ° C Example 7 1.78% Example 8 1.61% Comparison 4 2.26% Comparison 5 2.01%

The extractable portion is considerably lower in Examples 7 and 8 at 1.78% and 1.61% than in noninventive Comparative Experiments 4 and 5 and thus an indication of a higher permanence of the formed silicone film according to the invention on the fiber, also towards organic solvent ,

Claims (9)

Process for the treatment of filler fibers with aqueous dispersions of organopolysiloxanes obtainable by reacting condensable groups containing organopolysiloxanes (1) from units of the general formula

in which
R is a hydrogen atom or a monovalent hydrocarbon radical having 1 to 18 carbon atoms which is optionally substituted by the heteroatoms N and / or O,
R ^{1 represents} a hydrogen atom or an alkyl radical having 1 to 8 carbon atoms, preferably a hydrogen atom or a methyl or ethyl radical,
a 0, 1, 2 or 3 and
b is 0, 1 or 2,
with the proviso that the sum a + b ≦ 3 and in the organopolysiloxane (1) contains on average at least one residue OR ¹ per molecule,
with silanes (2) of the general formula

(R ³ O) ₃ SiCR ² ₂ -Y (II)

or their hydrolysates,
wherein R ^{2 represents} a hydrogen atom or a monovalent alkyl radical having 1 to 4 carbon atoms,
R ^{3 is} an alkyl radical having 1 to 8 carbon atoms per radical,
Y is a radical of the formula -NHR ⁴ , -NR ⁴ ₂ or

wherein R ^{4 is} a monovalent, optionally N and / or O atoms containing hydrocarbon radical having 1 to 18 carbon atoms and
R ⁵ denotes a divalent hydrocarbon radical optionally containing N and / or O atoms and having 3 to 12 carbon atoms,
in the presence of water (3),
Emulsifier (4)
and optionally further silanes (5) of the general formula

(R ₃ O) _x R _3-x Si-R ⁶ -Z (III)

or their hydrolysates,
wherein R ^{6 is} a divalent hydrocarbon radical having 3 to 18 carbon atoms and
Z is a radical selected from the group of amino or aminoalkylamino radicals, epoxy radicals and (meth) acryloxy radicals, and x is 1, 2 or 3,
and optionally other substances (6) which do not participate in the reaction of organopolysiloxane (1) with silane (2),
with the proviso that no metal-containing catalysts are used and that the organopolysiloxanes (1) and silanes (2) are used in amounts such that the organopolysiloxanes after removal of the water (3) form elastomeric films which are insoluble in toluene , A method according to claim 1, characterized in that silane (2) is used in amounts such that 0.6 to 2 equivalents of -OR ³ per equivalent -OR ¹ in organopolysiloxane (1) are present. A method according to claim 1 or 2, characterized in that are used as filler fibers of polyester, polyamide, polylactate (PLA), polybutyric acid, polyolefins, viscose, modal and lyocell. A method according to claim 1, 2 or 3, characterized in that as organopolysiloxanes (1) those of the general formula

(R ¹ O) R ₂ SiO (SiR ₂ O) _e SiR ₂ (OR ¹ ) (IV)

wherein R and R ^{1 have} the meaning given in claim 1 meaning and
e is an integer from 1 to 1000,
with the proviso that 50 to 100% of all radicals R ^{1 are} hydrogen atoms,
be used. Method according to one of claims 1 to 4, characterized in that R ^{2 is} a hydrogen atom. Method according to one of claims 1 to 5, characterized in that the aqueous dispersions are applied to the filler fibers by spraying, dipping, padding or curtain-casting. Method according to one of claims 1 to 6, characterized in that the aqueous dispersions are applied to the filling fibers and the water (3) is subsequently removed from the dispersions, whereupon elastomeric films are formed, which are insoluble in toluene. A method according to claim 7, characterized in that the water (3) is removed by mixing with the aqueous Dispersions treated filler fibers at a temperature of 1 to 230 ° C, preferably 30 to 180 ° C, more preferably 70 to 120 ° C to be dried. Filler fibers which are treated by the process according to claims 1 to 8.