DE102005056864B4 - Preparations based on ammonium- and polyether-modified organopolysiloxanes and their use for the finishing of textile substrates - Google Patents

Abstract

Preparations characterized by a content, based on the total composition, of (1) 2 to 60% by weight of an ammonium- and polyether-modified organopolysiloxane of the general formulawherein one of the two radicals R 1 and R 2 has the meaning and the other of R 1 and R 2 is the meaning. ..

Description

The invention relates to preparations based on ammonium- and polyether-modified organopolysiloxanes and their use on textile substrates.

Organopolysiloxanes containing amino groups have been used as textile finishing agents for quite some time. In the treated textiles good soft-grip effects are achieved. Frequently, organopolysiloxanes are used which are laterally or terminally modified in the polymer chain with aminoethylaminopropyl or aminopropyl radicals. These amino-functional organopolysiloxanes are such as in WO 88/08436 formulated by protonation with weak acids and with the help of emulsifiers to aqueous microemulsions.

Disadvantages of these emulsions are the low stability under alkaline conditions of use, a poor resistance to shear stress, a pronounced yellowing tendency under temperature stress as well as a strong foaming during the application on modern finishing machines.

Many textile finishing processes require the application of high pH values in the aqueous treatment baths. Thus, the pretreatment, bleaching and dyeing of cellulosic substrates always requires the use of high amounts of alkalis. If not sufficiently neutralized and carefully washed out after such process steps, it may come in the subsequent treatment with soft-grip agents based on amino-functional organopolysiloxanes to destabilize the microemulsions and thus to significant depositions of the water-insoluble organopolysiloxane in the treatment unit. These deposits can then be reflected directly in the form of stains on the textile, which are difficult or impossible to remove.

Destabilization of the emulsions under alkaline conditions is due to deprotonation of the amino functional groups of the organopolysiloxane. Without the cationic charges on the organopolysiloxane, the coalescence of the microemulsion particles and thus the formation of undesired silicone oil droplets in the treatment liquor occur.

Aminofunctional organopolysiloxanes, when applied to finishing machines which exert high shear forces on the treatment liquor, often exhibit insufficient stability of the formulation. Particularly on the modern fully or partly flooded jet dyeing machines, high shear stresses occur during the pumping processes, which is why, for example, emulsion separation with the unwanted silicone spots on the textile substrate can again occur during use in the exhaust process.

Another disadvantage of the softener agents based on amino-functional organopolysiloxanes is the strong tendency to yellowing, which can occur in the treated, white and light-colored textile substrates at drying temperatures above 120 ° C.

Soft-grip agents based on amino-functional organopolysiloxanes usually contain relatively large amounts of nonionic emulsifiers, as a result of which the foam tendency of the application liquors increases greatly. As a result, the universal applicability is limited to the fast-running textile equipment machines, such as the Düsenfärbeapparaten because the foam produced in these devices by the strong mechanics significantly hindered the transport of the product to be treated in the machine, as well as the mass transfer between the treatment liquor and textile substrate.

In the DE-OS 19652524 describes a synthesis route for the preparation of organopolysiloxanes with laterally arranged quaternary ammonium groups. Organopolysiloxanes modified with lateral aminoethylaminopropyl groups are converted into microemulsions by alkylation with toluene-4-sulfonic acid methyl ester in the presence of emulsifiers and water, which are suitable as softening agents for finishing textiles.

DE 39 28 867 C1 describes the use of polyoxyalkylene block copolymers in the preparation of polyurethane foams. In the DE 10 2004 034 266 A1 phyllosilicate-containing polysiloxane compositions are described.

In WO 02/10256 are described mono- or polyquaternary modified polysiloxanes, in which two polysiloxane units via Alkylenamin- or Alkylenammoniumeinheiten are interconnected. The preparation is carried out by alkylation of monofunctional polysiloxanes containing tertiary amino groups with reactive, monofunctional polysiloxanes containing halogen or epoxy groups. The latter are obtained by hydrosilylation of monofunctional methylhydrogenpolysiloxanes with halogenated alkenes, unsaturated halocarboxylic acid esters and epoxy-functional alkenes. These polysiloxane compounds are used in cosmetic formulations, in surface treatment agents and as softening agents for textiles.

The finishing of textiles with fluorocarbon polymers has been known for a long time. While the production of water repellency effects with paraffins and silicones only effects hydrophobization of the textile fibers, fluorocarbon polymers add to the dirt and oil repellency. Fluorocarbon equipment is suitable for a large number of articles. They are used in the clothing and home textiles sector, as well as in the technical textiles sector.

Typically, products for the fluorocarbon finish are based on polyurethanes or polyacrylates containing perfluoroalkyl groups of different chain lengths. The application of the preferably aqueous products is usually carried out by the exhaustion and padding process by spraying, foaming or padding, often in combination with other additives. This can z. Example, thermosetting resins based on methylol compounds that cause dimensional stability, wash fastness and stiffness. Furthermore, substances are used, which are referred to as extenders. These are usually fatty acid-modified melamine resins, mixtures of wax and zirconium salts or blocked polyisocyanates. The latter are often used to improve the water and oil repellency effects of the fluorocarbon finish and increase the wash permanence.

After the aqueous application of said fluorocarbon products, the drying or thermal treatment of the finished textile takes place in a further step at temperatures between 120 ° C. and 190 ° C. An orientation of the perfluoroalkyl side chains takes place, the fluorocarbon polymer unfolding its optimum level of effect. When using blocked polyisocyanates, elevated temperatures are required to effect deblocking of the reactive isocyanate groups. These can subsequently react with the fiber, with itself or with the fluorocarbon polymer. This results in crosslinked polyurethanes, which due to their polyvalent crosslinking lead to a better orientation of the perfluoroalkyl chains and thus to an improvement of the oil and water repellent properties. Furthermore, due to the crosslinking with the textile substrate, the washing resistance of the equipment is improved.

A disadvantage has been found that the crosslinked polyurethanes adversely affect the handle, the processing properties and the sewability of the finished textile. Particularly in the case of textiles based on native fibers, a pronounced hardening of the handle character can be observed.

In order to minimize these negative properties, it would be conceivable to use conventional silicone softeners based on amino-functional organopolysiloxanes. However, these products result in a severe deterioration of the water and oil repellency properties of the fluorocarbon finish. Another disadvantage of said aminofunctional organopolysiloxanes is a yellowing tendency, which can occur in the treated, white and light-colored textile substrates at drying temperatures above 120 ° C.

Compositions containing fluoropolymers, extenders and aminofunctional polysiloxanes and used for the treatment of fibrous materials are disclosed in U.S.P. DE 10139126 A1 described. The amino groups may optionally be present in quaternized form.

In the EP 314944 A2 formulations of fluorocarbon polymers with the concomitant use of polyethylene and modified polysiloxanes are recommended in which a soft feel is created on the textile. As the polysiloxane, hydrogen alkylpolysiloxanes are used in the form of aqueous dispersions. The disadvantage of these products is the much poorer softness compared to softeners based on amino-functional organopolysiloxanes.

In DE 3431075 A1 For example, epoxy-functional hydrogen-alkylpolysiloxanes and their use in combination with fluorocarbon polymers for oleo and hydrophobicization of fibers are described. The organopolysiloxanes used in this case also have a poorer softness in comparison to the softening agents based on amino-functional organopolysiloxanes.

It was now the object to provide a preparation for the treatment of textile substrates, which produces a good soft-touch effect and in which pH stability, shear resistance, low foaming and yellowing resistance are ensured. Furthermore, the preparation should be combinable with fluorocarbon finishing fleets without negatively affecting the good oil and water repellent effects of the fluorocarbon finish.

Unexpectedly, it has been found that this object can be achieved according to the invention by the claimed preparations of ammonium and polyether-modified organopolysiloxanes. The ammonium and polyther groups are positioned terminally on the organopolysiloxane in the α, ω position.

The preparations according to the invention are distinguished by high stability in the application liquor. They are stable against both high pH and high shear rates. When used on jet dyeing machines, the preparations according to the invention show only a slight tendency to foam. This is due to the fact that the ammonium- and polyether-modified organopolysiloxanes can be converted into stable emulsions without or with very small quantities of emulsifier. The negative influence of high amounts of surfactant on the foaming behavior of the application liquor is thus reduced.

The textiles finished with the preparations according to the invention have, in addition to a very good softness, a high yellowing resistance.

Furthermore, the inventive preparations can be used together with aqueous fluorocarbon products and other additives such. As extenders or thermosetting resins, single-stage in the exhaust or padding process. The textiles treated with the preparations according to the invention in combination with fluorocarbon polymers have, in addition to good water and oil repellency, a very good softness. Likewise, the sewability compared to a pure Fluorcarbonausrüstung is significantly improved.

An advantage of the ammonium- and polyether-modified organopolysiloxanes is that they can be converted into stable emulsions without or with very small quantities of emulsifier. The negative influence of high amounts of emulsifier, which are necessary for the emulsification and stabilization of pure amino-functional organopolysiloxanes, can be reduced in the preparations according to the invention.

Furthermore, the ammonium- and polyether-modified organopolysiloxanes in combination with fluorocarbons show a high yellowing resistance at high drying temperatures. This is particularly advantageous when using blocked polyisocyanates (boosters). In order to initiate the deblocking of the isocyanate groups, high temperatures are required which lead to a strong yellowing in the case of organopolysiloxanes containing primary amino groups.

• (1) 2 bis 60 Gewichtsprozent eines ammonium- und polyethermodifizierten Organopolysiloxanes der allgemeinen Formel
  
  wobei einer der beiden Reste R¹ und R² die Bedeutung
  
  hat, und der andere der Reste R¹ und R² die Bedeutung R₄-(OC₂H₄)_n-(OC₃H₆)_o-O-R⁸ hat, wobei die genannten Einheiten (OC₂H₄) und (OC₃H₆) in Blöcken, statistisch verteilt oder teilweise in Blöcken und teilweise statistisch verteilt vorliegen,
  
  
  R⁵ = -(CH₂)_q-H, R⁶ = -(CH₂)_r-, R⁷ = -(CH₂)_s-, R⁸ = linearer oder verzweigter C₁₀-C₁₈-Alkylrest, vorzugsweise ein linearer C₁₆-C₁₈- oder ein verzweigter C₁₀-C₁₃-Alkylrest, A^– anorganische oder organische Anionen, m eine ganze Zahl von 10–1000, vorzugsweise 15–500, besonders bevorzugt 20–100, n eine ganze Zahl von 0–20, vorzugsweise 1–12, o eine ganze Zahl von 0–20, vorzugsweise 1–12, p eine ganze Zahl von 1–10, vorzugsweise 1, q eine ganze Zahl von 1–18, vorzugsweise 1, r eine ganze Zahl von 2–3, vorzugsweise 2 und s eine ganze Zahl von 2–5, vorzugsweise 2–4 bedeuten, mit der Maßgabe, dass die Summe von n und o mindestens 1 vorzugsweise 1–12 ist und der Gesamtstickstoffgehalt der Komponente (1) 0,04 bis 3,2 Gewichtsprozent, bevorzugt 0,1–1,5 Gewichtsprozent, insbesondere jedoch 0,1–1,0 Gewichtsprozent bezogen auf die Gesamtzusammensetzung von Komponente (1) beträgt, und
• (4) 20 bis 98 Gewichtsprozent Wasser.

The first subject of the invention are preparations characterized by a content based on the total composition

• (1) 2 to 60% by weight of an ammonium- and polyether-modified organopolysiloxane of the general formula
  
  wherein one of the two radicals R ¹ and R ^{2 is} the meaning
  
  has, and the other of the radicals R ¹ and R ^{2 is} the meaning R ₄ - (OC ₂ H ₄ ) _n - (OC ₃ H ₆ ) _o -OR ⁸ with said units (OC ₂ H ₄ ) and (OC ₃ H ₆ ) being present in blocks, randomly distributed or partially in blocks and partly statistically distributed,
  
  
  R ⁵ = - (CH ₂ ) _q -H, R ⁶ = - (CH ₂ ) _r -, R ⁷ = - (CH ₂ ) _s -, R ⁸ = linear or branched C ₁₀ -C ₁₈ -alkyl radical, preferably one linear C ₁₆ -C ₁₈ - or a branched C ₁₀ -C ₁₃ -alkyl radical, A ^- inorganic or organic anions, m is an integer of 10-1000, preferably 15-500, particularly preferably 20-100, n is an integer of 0-20, preferably 1-12, o is an integer of 0-20, preferably 1-12, p is an integer of 1-10, preferably 1, q is an integer of 1-18, preferably 1, r is a whole Number of 2-3, preferably 2 and s is an integer of 2-5, preferably 2-4, with the proviso that the sum of n and o is at least 1, preferably 1-12 and the total nitrogen content of component (1) 0.04 to 3.2 weight percent, preferably 0.1-1.5 weight percent, but especially 0.1-1.0 weight percent based on the total composition of component (1), and
• (4) 20 to 98% by weight of water.

All weights of the preparations according to the invention relate to the total composition of the preparation according to the invention. The preferred range for the component (1) is a range of 10-40% by weight.

• (2) bis 10 Gew.-% eines Emulgators und/oder
• (3) bis 15 Gew.-% eines Hydrotopikums.

Preferred is a preparation with a content of the components (1) and (4), characterized by a content, based on the total composition, of the additional components

• (2) to 10 wt .-% of an emulsifier and / or
• (3) to 15% by weight of a hydrotopic.

If component (3) is added, its concentration is preferably in the range of 1-10, in particular 3-7 weight percent. The preferred range of component (4) is 60-90, but especially between 70-90 weight percent.

The anions are derived from inorganic or organic acids. Examples of inorganic anions include chloride, bromide, iodide and sulfate; preferred are chloride and sulfate. Examples of organic anions are tosylate, formate and acetate; preferred is tosylate.

The preparation of the modified organopolysiloxanes is carried out by methods which are known to the person skilled in the art. The claimed component (1) is particularly accessible by the synthetic route described below.

mit einer Kettenlänge von m = 10–1000 wird, wie in DE-OS 1493384 (Beispiel 1) beschrieben, durch Hydrosilylierung mit ungesättigten Glycidylethern wie Allylglycidylether, (+)- bzw. (–)-Limonenoxid, oder 4-Vinyl-1-cyclohexen-1,2-epoxid ein epoxyfunktionelles Organopolysiloxan der Formel (II) erhalten

wobei

ist.Starting from methylhydrogensiloxanes having terminal Si-H units of the general formula (I)

with a chain length of m = 10-1000, as in DE-OS 1493384 (Example 1), obtained by hydrosilylation with unsaturated glycidyl ethers such as allyl glycidyl ether, (+) - or (-) - lime oxide, or 4-vinyl-1-cyclohexene-1,2-epoxide an epoxy-functional organopolysiloxane of the formula (II)

in which

is.

In the following synthesis steps, the epoxide groups are reacted with amines and alkyl alcohol alkoxylates with ring opening to give the inventive ammonium- and polyether-modified organopolysiloxanes.

wie auch tertiäre Amine der Formel (IV)

eingesetzt werden, wobei R³, R⁵, R⁶ und R⁷ die oben genannten Bedeutungen haben. Die Addition von tertiären Aminen der Formel (IV) an das epoxyfunktionelle Organopolysiloxan unter sauren Bedingungen erfolgt analog zu US 4,891,166 (Beispiel 1).As the amine component, both secondary amines of the formula (III _a ) and (III _b )

as well as tertiary amines of the formula (IV)

can be used, wherein R ³ , R ⁵ , R ⁶ and R ^{7 have} the meanings mentioned above. The addition of tertiary amines of the formula (IV) to the epoxy-functional organopolysiloxane under acidic conditions is analogous to US 4,891,166 (Example 1).

As the alkyl alcohol alkoxylate, ethoxylation and propoxylation products of linear or branched C ₁₀ -C ₁₈ -alcohols of the formula (V) H- (OC ₂ H ₄ ) _n - (OC ₃ H ₆ ) _o -OR ⁸ (V) used, wherein R ⁵ , n and o have the abovementioned meanings.

The order of addition of the amine and the alkyl alcohol alkoxylate is variable. The stoichiometry is chosen so that in each case after the first step, an epoxy group remains in the organopolysiloxane.

If the epoxy-functional organopolysiloxane is initially analogous to a secondary amine DE-OS 1493384 (Example 1) is reacted, the alkyl alcohol alkoxylate in the following step using basic catalysts as in US 6,495,727 (Example 1) to an amino- and polyether-modified organopolysiloxane reacted. This is then treated with alkylating agents such. As methyl iodide or methyl tosylate analogous to DE-OS 1493384 (Example 2) quaternized.

Alternatively, in the first stage, the epoxy-functional organopolysiloxane can be prepared in the presence of acidic catalysts as in EP 002519 (Example 1) described are reacted with alkyl alcohol alkoxylates. The remaining epoxide group is then subsequently reacted with the corresponding amines. In the addition of one mole of the tertiary amine of the formula (IV) to the epoxy group, under acidic conditions analogously to US 4,891,166 (Example 1), initially only a quaternary ammonium group is obtained. The remaining tertiary amino group is analogous to DE-OS 1493384 (Example 2) with z. As methyl iodide or methyl tosylate quaternized. It is also possible to add secondary amines of the formula (III _a ) or (III _b ) to the epoxy group and in a final step analogously to DE-OS 1493384 (Example 2) by quaternization with z. As methyl iodide or methyl tosylate to obtain the inventive ammonium- and polyether-modified organopolysiloxanes. The above-mentioned documents and their specified passages are part of the present description.

As emulsifiers optionally present in the preparations according to the invention (component (2)), those based on cationic, nonionic or amphoteric base or mixtures of these compounds can be used. Preferably, cationic emulsifiers or ethoxylation products of aliphatic alcohols containing from 6 to 22 carbon atoms are used which contain up to 50 moles of ethylene oxide. The Alcohols preferably contain from 8 to 16 carbon atoms. They may be saturated, linear or branched, preferably branched, and may be used alone or in a mixture. Of particular advantage in terms of low foaming in the application liquors are alcohols of the type mentioned, when the alkylene oxide is composed of ethylene oxide and 1,2-propylene oxide in random distribution and preferably in a block-like distribution. Nonionic emulsifiers from the group of ethoxylated, branched aliphatic alcohols have proven particularly useful due to their favorable overall properties. Therefore z. For example, ethoxylates of 2,6,8-trimethyl-4-nonanol, of isodecyl alcohol or of isotridecyl alcohol having in each case 2 to 50 mol, in particular 3 to 15 mol, of attached ethylene oxide are preferred for the preparation of the preparations according to the invention. Particularly preferred is isotridecyl alcohol with 6 moles of attached ethylene oxide.

Preferred cationic emulsifiers are, for example, quaternary ammonium salts, such as di (C ₁₀ -C ₂₄ ) -alkyldimethylammonium chloride, (C ₁₀ -C ₂₄ ) -alkyldimethylethylammonium chloride or bromide, (C ₁₀ -C ₂₄ ) -alkyltrimethylammonium chloride or bromide, (C ₁₀ -C ₂₄ ) -alkyldimethylbenzylammonium chloride, N- (C ₁₀ -C ₁₈ ) -alkylpyridinium chloride or bromide, N- (C ₁₂ -C ₁₈ ) isoquinolinium chloride, bromide or monoalkylsulfate, N- (C ₁₂ -C ₁₈ ) - Alkyl-N-methyl-ammonium morpholinium chloride, bromide or monoalkyl sulfate, N- (C ₁₂ -C ₁₈ ) alkyl-N-ethylammonium morpholinium chloride, bromide or monoalkyl sulfate; N- (C ₁₂ -C ₁₈ ) -Alkylmethylpolyoxyethylenammoniumchlorid, bromide or monoalkylsulfat and salts of primary, secondary and tertiary fatty amines having 8 to 24 carbon atoms with organic or inorganic acids called.

The component (3) optionally present in the preparations according to the invention, a hydrotrope, can be selected from the group of polyfunctional alcohols. Thus, dialcohols having 2-10, preferably 2-6, but especially 2-4 carbon atoms per molecule can be used. Also suitable are their mono- and diethers and the mono- and diesters of these dialcohols. Particularly preferred examples of component (3) to be used are butyldiglycol, 1,2-propylene glycol and dipropylene glycol.

The preparations according to the invention are generally prepared by stirring the ammonium- and polyether-modified organopolysiloxanes (component (1)), the emulsifier (component (2)), the hydrotopic agent (component (3)) and the water (component (4)) 70 ° C. The claimed ammonium- and polyether-modified organopolysiloxanes (component 1) generally already have a good emulsifiability because of their structure. If this should be insufficient in individual cases, it may be appropriate to prepare the preparations of components (1) to (4) with stirring at 70 ° C in the presence of small amounts of organic acids (for example acetic acid or lactic acid) to the polymer to bring into the form of an emulsion applicable from aqueous medium.

Another object of the invention is the use of the preparation according to the invention in aqueous baths and application liquors for finishing textile substrates.

The textile substrates are woven, knitted fabrics, braids and textile composites of native fibers, such as cotton or wool, but also of synthetic fibers, such as viscose, polyester, polyamide or polyacrylonitrile. When used on textile substrates, the preparations according to the invention can also be combined with the textile auxiliaries customary in the textile industry. Worth mentioning are agents which improve the Entknitterungseigenschaften, for example, methylol compounds of Dihydroxyethylenharnstoffes or Methylolmelaminether different degrees of methylolation.

Another object of the invention is the use of the preparations according to the invention in combination with fluorocarbon polymer formulations. The formulations are aqueous preparations of fluorocarbon polymers based on perfluorinated polyacrylates or perfluorinated polyurethanes, optionally with other auxiliaries such. As blocked polyisocyanates (booster) or extender are mixed. All components of these formulations can also be used separately in the application liquor.

The application to the textile substrates is generally carried out with runs of 1-5 wt .-%, but preferably 1-3 wt .-% of the dry matter of the inventive preparation (ie components 1, 2 and 3) based on the weight of the treated sheet. Usually, a liquor is made in the desired concentration by means of a forced application of aqueous medium by padding, spraying, padding, foam application. The fleet takes between 40 and 100%. Subsequently Pre-drying at 80-110 ° C and then a heat treatment at 130-170 ° C for 1-5 minutes. The duration of the heat treatment depends on the temperatures used.

Another possibility for application to textile fabrics is given by the exhaust process known to those skilled in the art.

The invention is explained in more detail in the following examples.

Example 1 (not according to the invention):

hergestellt und mit 80 Gramm Wasser verrührt.Analogous to DE 3928867 C1 (Example 1) are 20 grams of an organopolysiloxane having the formula

prepared and stirred with 80 grams of water.

Example 2 (not according to the invention):

hergestellt und anschließend mit 15 Gewichtsprozent eines Isodecylalkoholes mit 7 Ethylenoxidgruppen, 3 Gewichtsprozent Butyldiglykol, 0,4 Gewichtsprozent Essigsäure 60% und 61,6 Gewichtsprozent Wasser verrührt.Analogous to US 4,891,166 (Example 1) are 20 grams of an organopolysiloxane having the formula

and then stirred with 15 weight percent of an isodecyl alcohol with 7 ethylene oxide groups, 3 weight percent butyl diglycol, 0.4 weight percent acetic acid 60% and 61.6 weight percent water.

Example 3 (not according to the invention):

hergestellt und mit 12 Gramm eines Isodecylalkoholes mit 7 Ethylenoxidgruppen, 3 Gewichtsprozent Butyldiglykol, 0,4 Gramm Essigsäure 60% und 64,6 Gramm Wasser verrührt.Analogous to EP 1000959 A2 (Example 5) are 20 grams of an organopolysiloxane having the formula

and stirred with 12 grams of an isodecyl alcohol with 7 ethylene oxide groups, 3 weight percent butyl diglycol, 0.4 grams of 60% acetic acid, and 64.6 grams of water.

Example 4 (according to the invention)

mit 10,0 Gramm (0,1 mol) N-Methylpiperazin analog zu DE-OS 1493384 (Beispiel 1). Anschließend addiert man analog zu US 6,495,727 (Beispiel 1) 71,0 Gramm (0,1 mol) eines Stearylalkohols mit 10 EO Einheiten.The production of the ammonium- and polyether-modified organopolysiloxane is carried out by reacting 759.8 grams (0.1 mol) of α, ω-diepoxypolydimethylsiloxane having the formula

with 10.0 grams (0.1 mol) of N-methylpiperazine analogous to DE-OS 1493384 (Example 1). Then you add analogously to US 6,495,727 (Example 1) 71.0 grams (0.1 mol) of a stearyl alcohol with 10 EO units.

mit einem Gesamtstickstoffgehalt von 0,32% bezogen auf die Gesamtzusammensetzung von Komponente (1).The tertiary amino groups are completely mixed with 28.2 grams (0.2 mol) of methyl iodide analogously DE-OS 1493384 (Example 2) quaternized. An ammonium- and polyether-modified organopolysiloxane of the following structure is obtained

with a total nitrogen content of 0.32% based on the total composition of component (1).

A preparation is prepared from 15 grams of the thus prepared ammonium- and polyether-modified organopolysiloxane (component (1)) by stirring with 5 grams of isotridecyl alcohol with 6 ethylene oxide groups (component (2)) and 5 grams of butyldiglycol (component (3)) in 73 grams of water ( Component (4)), which is mixed with 2 grams of acetic acid (60%) prepared.

Example 5 (according to the invention)

mit 18,7 Gramm (0,1 mol) Bis-[3-(dimethylamino)-propyl]-amin analog zu DE-OS 1493384 (Beispiel 1).The preparation of the ammonium- and polyether-modified organopolysiloxane is carried out by reacting 330.6 g (0.1 mol) of α, ω-diepoxypolydimethylsiloxane having the formula

with 18.7 grams (0.1 mole) of bis [3- (dimethylamino) -propyl] -amine analogous to DE-OS 1493384 (Example 1).

mit einem Gesamtstickstoffgehalt von 1,0% bezogen auf die Gesamtzusammensetzung von Komponente (1).Then you add analogously to US 6,495,727 (Example 1) 33.2 grams (0.1 mole) of an isotridecyl alcohol with 3 EO units. The tertiary amino groups are completely analogous to 42.3 grams (0.3 moles) of methyl iodide DE-OS 1493384 (Example 2) quaternized. An ammonium- and polyether-modified organopolysiloxane of the following structure is obtained

with a total nitrogen content of 1.0% based on the total composition of component (1).

A preparation is prepared from 15 grams of the thus prepared ammonium- and polyether-modified organopolysiloxane (component (1)) by stirring with 3 grams of isotridecyl alcohol with 6 ethylene oxide groups (component (2)) and 5 grams of butyl diglycol (component (3)) in 75 grams of water ( Component (4)), which is mixed with 2 grams of acetic acid (60)%.

Example 6 (according to the invention)

mit 10,0 Gramm (0,1 mol) N-Methylpiperazin analog zu DE-OS 1493384 (Beispiel 1).The preparation of the ammonium- and polyether-modified organopolysiloxane is carried out by reacting 199.0 grams (0.1 mol) of α, ω-diepoxypolydimethylsiloxane having the formula

with 10.0 grams (0.1 mol) of N-methylpiperazine analogous to DE-OS 1493384 (Example 1).

Then you add analogously to US 6,495,727 (Example 1) 56.6 grams (0.1 mole) of an isodecyl alcohol with 4 EO units and 4 PO units.

mit einem Gesamtstickstoffgehalt von 0,95% bezogen auf die Gesamtzusammensetzung von Komponente (1).The tertiary amino groups are completely mixed with 28.2 grams (0.2 mol) of methyl iodide analogously DE-OS 1493384 (Example 2) quaternized. An ammonium- and polyether-modified organopolysiloxane of the following structure is obtained

with a total nitrogen content of 0.95% based on the total composition of component (1).

A preparation is prepared from 15 grams of the thus prepared ammonium- and polyether-modified organopolysiloxane (component (1)) by stirring with 6 grams of isotridecyl alcohol with 6 ethylene oxide groups (component (2)) and 4 grams of butyldiglycol (component (3)) in 73 grams of water ( Component (4)), which is mixed with 2 grams of acetic acid (60%) prepared.

equipment

The application of the finishes to textile fabrics was carried out on a laboratory tampon type LFV 350/2 "RFA" (Benz, Switzerland) with subsequent drying and heat treatment on a laboratory clamping frame type TKF 15 / M 350 (Benz, Switzerland). The liquor pickup was determined by weighing the finished test samples before and after the application.

Carrying out the handle assessment

To evaluate the handle, sections of a bleached, non-visually brightened cotton woven fabric with an aqueous liquor containing 20 g / l of the formulations prepared according to the examples and 0.5 g / l acetic acid (60%) were placed on a laboratory tampon with a wet pickup of 80%. impregnated and then dried for 2 minutes at 120 ° C and condensed at 170 ° C for 2 minutes. (Table 1: Grip assessment I.)

Likewise, the formulations prepared according to the examples were tested in combination with a fluorocarbon polymer and a booster. For this purpose, sections of a bleached, non-visually brightened cotton woven fabric with an aqueous liquor containing 20 g / l of the preparations prepared according to the examples, 20 g / l hydrophobizing agent based on a perfluorinated polyacrylate, 20 g / l booster based on a blocked polyisocyanate and 0.5 g / l acetic acid (60%) impregnated on a laboratory pad with a wet pickup of 80% and then dried for 2 minutes at 120 ° C and condensed for 2 minutes at 170 ° C. (Table 2: Grip assessment II.)

Subsequently, the evaluation of the handle character of the treated test fabric. This is subject to different criteria. In order to obtain meaningful results, an assessment is made by at least 5 test persons. The evaluation of the results was done according to statistical methods, where grade 1 represents the softest, most comfortable grip, grade 10 the hardest, least smooth and uncomfortable touch within the test series. Table 1: Handle assessment I. Preparation according to Example 1 (not according to the invention) 20 g / l untreated Preparation according to Example 2 (not according to the invention) 20 g / l untreated Preparation according to Example 3 (not according to the invention) 20 g / l untreated Preparation according to Example 4 (according to the invention) 20 g / l untreated Preparation according to Example 5 (according to the invention) 20 g / l untreated Preparation according to Example 6 (according to the invention) 20 g / l untreated Grip evaluation grade within the test series 7 2 5 2 2 1 10 Table 2: Handle assessment II. Water repellent based on a perfluorinated polyacrylate 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l untreated Booster based on a blocked polyisocyanate 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l untreated Preparation according to Example 1 (not according to the invention) 20 g / l untreated Preparation according to Example 2 (not according to the invention) 20 g / l untreated Preparation according to Example 3 (not according to the invention) 20 g / l untreated Preparation according to Example 4 (according to the invention) 20 g / l untreated Preparation according to Example 5 (according to the invention) 20 g / l untreated Preparation according to Example 6 (according to the invention) 20 g / l untreated Grip evaluation grade within the test series 9 4 7 2 2 2 10 10

alkali resistance

1 liter of an aqueous liquor containing 20 g / l of the preparations prepared according to the examples is used. This is adjusted to a pH of 12 with sodium hydroxide solution (w (NaOH) = 10%). Subsequently, the liquor is stirred for twenty minutes with a paddle stirrer at two thousand revolutions per minute. At the end of this time, the stirrer was stopped and the liquid surface was evaluated for deposition after 1 hour. Table 3: Alkali resistance Preparation according to Example 1 (not according to the invention) 20 g / l Preparation according to Example 2 (not according to the invention) 20 g / l Preparation according to Example 3 (not according to the invention) 20 g / l Preparation according to Example 4 (according to the invention) 20 g / l Preparation according to Example 5 (according to the invention) 20 g / l Preparation according to Example 6 (according to the invention) 20 g / l Assessment after 1 hour slight deposits no deposits no deposits no deposits no deposits no deposits

foam test

For the evaluation of the foaming behavior, 1 liter of a liquor with 3 g / l of the preparations prepared according to the examples is used. This is filled in a laboratory jet from MATHIS and circulated at 40 ° C and 1000 rpm. After 10 minutes, the foam height is measured. The maximum foam height is 10 cm, the minimum is 0 cm. A low foam height is positive. Table 4: Foaming behavior Preparation according to Example 1 (not according to the invention) 3 g / l Preparation according to Example 2 (not according to the invention) 3 g / l Preparation according to Example 3 (not according to the invention) 3 g / l Preparation according to Example 4 (according to the invention) 3 g / l Preparation according to Example 5 (according to the invention) 3 g / l Preparation according to Example 6 (according to the invention) 3 g / l Foam height after 10 min 7 cm 9 cm 10 centimeters 2 cm 4 cm 3 cm

Determination of hydrophobicity and oleophobicity

Sections of a bleached, non-optically brightened cotton woven fabric were coated with an aqueous liquor containing 20 g / l of the formulations prepared according to the examples, 20 g / l of a perfluorinated polyacrylic based water-repellent, 20 g / l of a blocked polyisocyanate-based booster 0.5 g / l acetic acid (60%) impregnated on a laboratory pad with a wet pickup of 80% and then dried for 2 minutes at 120 ° C and condensed for 2 minutes at 170 ° C.

The examination of the hydrophobic and optionally oleophobic effects did not take place immediately after the application, but only after a conditioning of the substrates in a standard atmosphere for 24 hours in order to level influences on these properties by overdrying.

100

= Kein Anhaften von Wassertropfen oder Benetzung der oberen Oberfläche

90

= Vereinzeltes Anhaften von Wassertropfen oder Benetzung der oberen Oberfläche

80

= Benetzung der oberen Oberfläche an den Auftreffpunkten des Wassers

70

= Teilweise Benetzung der ganzen oberen Oberfläche

50

= Vollständige Benetzung der ganzen oberen Oberfläche

0

= Vollständige Benetzung der ganzen oberen und unteren Oberfläche (Durchnetzung).

The water repellency was performed on the fabrics by spray test according to AATCC Standard Test Method 22. The test according to AATCC Standard Test Method 22 is carried out by spraying distilled water under controlled conditions onto the textile substrate to be tested and then visually comparing the wetting pattern with images of an evaluation standard listed in the test method. The numerical values given here refer to the appearance of the surface after spraying the water and have the following meaning:

100

= No adhesion of water droplets or wetting of the upper surface

90

= Isolated adhesion of drops of water or wetting of the upper surface

80

= Wetting of the upper surface at the points of impact of the water

70

= Partial wetting of the whole upper surface

50

= Complete wetting of the whole upper surface

0

= Complete wetting of the whole upper and lower surface (Durchnetzung).

The oil rejection is tested according to AATCC Standard Test Method 118. The ability of the textile substrate is assessed to withstand the wetting by liquid hydrocarbons with different surface tensions. The test provides an index of the ability of a substrate to repel oily soils, where on the rating scale the higher marks mean a better rejection of such soils, especially oily liquids. In the test, drops of standardized test liquids consisting of a selected series of hydrocarbons having different surface tensions are successively applied to the surface of the test sample to be tested by gentle dripping and the wetting is assessed visually after a defined contact time. The oil repellency value corresponds to the highest numbered test fluid at which no surface wetting occurs. The standard test liquids have the following composition: oil repellency composition Grade 1 = "Nujol" Grade 2 = 65% by volume of "Nujol" to 35% by volume of n-hexadecane Grade 3 = n-hexadecane Grade 4 = n-tetradecane Grade 5 = n-dodecane Grade 6 = n-decane Grade 7 = n-octane Grade 8 = n-heptane.

With commonly used FC polymers of the prior art, oil repellency values of 6 are currently achieved; however, grade 5 is usually considered excellent. Table 5: Spray test according to AATCC Method 22 and oil rejection according to Method 118 Water repellent based on a perfluorinated polyacrylate 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l untreated Booster based on a blocked polyisocyanate 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l untreated Preparation according to Example 1 (not according to the invention) 20 g / l untreated Preparation according to Example 2 (not according to the invention) 20 g / l untreated Preparation according to Example 3 (not according to the invention) 20 g / l untreated Preparation according to Example 4 (according to the invention) 20 g / l untreated Preparation according to Example 5 (according to the invention) 20 g / l untreated Preparation according to Example 6 (according to the invention) 20 g / l untreated Spray repellent spray test AATCC 0 70 50 100 100 100 100 0 Oil repellency grade AATCC Method 118 1 2 2 4 5 5 5 0

Determination of yellowing

Sections of a bleached, optically brightened cotton woven fabric were impregnated with an aqueous liquor containing 20 g / l of the formulations prepared according to the examples and 0.5 g / l acetic acid 60% on a laboratory pad with a wet pickup of 80% and then 2 Dried minutes at 120 ° C and condensed at 170 ° C for 2 min. (Table 6: yellowing 1)

Likewise, the formulations prepared according to the examples were tested in combination with a fluorocarbon polymer and a booster. For this purpose, sections of a bleached, non-visually brightened cotton woven fabric with an aqueous liquor containing 20 g / l of the preparations prepared according to the examples, 20 g / l water repellents based on a perfluorinated polyacrylate, 20 g / l booster based on a blocked polyisocyanate and 0.5 g / l acetic acid (60%) impregnated on a laboratory pad with a wet pickup of 80% and then dried for 2 minutes at 120 ° C and condensed for 2 minutes at 170 ° C. (Table 7: yellowing II.)

Subsequently, the whiteness of the samples was measured whole on the whiteness meter "texflash 2000" from the company "datacolor international" (Switzerland). Table 6: Yellowing I. Preparation according to Example 1 (not according to the invention) 20 g / l untreated Preparation according to Example 2 (not according to the invention) 20 g / l untreated Preparation according to Example 3 (not according to the invention) 20 g / l untreated Preparation according to Example 4 (according to the invention) 20 g / l untreated Preparation according to Example 5 (according to the invention) 20 g / l untreated Preparation according to Example 6 (according to the invention) 20 g / l untreated Whiteness to whole 181 172 173 178 179 176 186 Table 7: Yellowing II. Water repellent based on a perfluorinated polyacrylate 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l untreated Booster based on a blocked polyisocyanate 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l untreated Preparation according to Example 1 (not according to the invention) 20 g / l untreated Preparation according to Example 2 (not according to the invention) 20 g / l untreated Preparation according to Example 3 (not according to the invention) 20 g / l untreated Preparation according to Example 4 (according to the invention) 20 g / l untreated Preparation according to Example 5 (according to the invention) 20 g / l untreated Preparation according to Example 6 (according to the invention) 20 g / l untreated Whiteness to whole 175 170 171 176 177 175 176 186

Determination of sewability

Sections of a bleached, non-optically brightened cotton knitted fabric were treated with an aqueous liquor containing 20 g / l of the formulations prepared according to the examples, 20 g / l of a perfluorinated polyacrylate-based water repellent, 20 g / l of a blocked polyisocyanate-based booster 0.5 g / l acetic acid (60%) impregnated on a laboratory pad with a wet pickup of 80% and then dried for 2 minutes at 120 ° C without voltage and condensed at 170 ° C for 2 minutes.

The sewability was checked with a Dürkopp industrial sewing machine. The finished textile is sewn together in four layers. The measuring distance is 50 cm. The needle size used is 80R. The number of damage caused by the machine gives information about the sewability of the finished textile. Table 8: Sewability Water repellent based on a perfluorinated polyacrylate 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l untreated Booster based on a blocked polyisocyanate 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l 20 g / l untreated Preparation according to Example 1 (not according to the invention) 20 g / l untreated Preparation according to Example 2 (not according to the invention) 20 g / l untreated Preparation according to Example 3 (not according to the invention) 20 g / l untreated Preparation according to Example 4 (according to the invention) 20 g / l untreated Preparation according to Example 5 (according to the invention) 20 g / l untreated Preparation according to Example 6 (according to the invention) 20 g / l untreated Number of machine damage 18 5 10 2 3 2 33 25

Claims (4)

Preparations, characterized by a content, based on the total composition, of (1) 2 to 60% by weight of an ammonium- and polyether-modified organopolysiloxane of the general formula

wherein one of the two radicals R ¹ and R ^{2 is} the meaning

has, and the other of the radicals R ¹ and R ^{2 is} the meaning R ⁴ -OC ₂ H ₄ ) _n - (OC ₃ H ₆ ) _o -OR ⁸ with said units (OC ₂ H ₄ ) and (OC ₃ H ₆ ) being present in blocks, randomly distributed or partially in blocks and partly statistically distributed,

R ⁵ = - (CH ₂ ) _q -H- R ⁶ = - (CH ₂ ) _r -, R ⁷ = - (CH ₂ ) _s -, R ⁸ = linear or branched C ₁₀ -C ₁₈ -alkyl radical, A ^- inorganic or organic anions, m is an integer of 10-1000, n is an integer of 0-20, o is an integer of 0-20, p is an integer of 1-10, q is an integer of 1-18, r is an integer of 2-3, s is an integer of 2-5, with the proviso that the sum of n and o is at least 1 and the total nitrogen content of component (1) is 0.04 to 3.2% by weight , based on the total composition of component (1), and (4) 20 to 98 weight percent water. Preparations according to claim 1, characterized by a content, based on the total composition, of the additional components (2) to 10 wt .-% of an emulsifier and / or (3) to 15% by weight of a hydrotrope. Use of the preparation according to claim 1 in aqueous baths and application liquors for finishing textile substrates Use according to claim 3, wherein in this use aqueous preparations of fluorocarbon polymers based on perfluorinated polyacrylates or perfluorinated polyurethanes are added as separate formulations of the application liquor.