DE102005056864A1 - Formulation for use in aqueous bath alone or with fluorocarbon polymer for finishing natural or synthetic fiber textile contains organopolysiloxane modified by terminal cyclic diammonium or branched triammonium and polyether groups - Google Patents

Abstract

Formulation contains (wt.%) (1) 2.60% ammonium- and polyether-modified organopolysiloxane, which has a cyclic diammonium or branched triammonium group at one end of the siloxane chain, to a total nitrogen content of 0.04-3.2%, and an alkoxy-terminated polyether or block, random or partly block and partly random copolyether chain of ethylene oxide and propylene oxide units at the other end, (2) 0-10% emulsifier, (3) 0-15% hydrotropic agent and (4) 20-98% water. Formulation contains (wt.%) (1) 2.60% ammonium- and polyether-modified organopolysiloxane of formula (I), with a total nitrogen content of 0.04-3.2%, (2) 0-10% emulsifier, (3) 0-15% hydrotropic agent and (4) 20-98% water. [Structure, top of page 23; please label (I)] one of R1> and R2>a cyclic diammonium cation (iia) or branched triammonium cation (iib) of the given formulae and the other an alkoxy-terminated (co)polyether of formula (iii) with (OC2H4) and (OC3H6) units in blocks, randomly distributed or partly in blocks and partly random; R3>-(CH2)p-H or phenyl; R4>-(CH)2)3-O-CH2-CH(OH)-CH2-, -(CH2)3-O-CH2-CH(CH2OH)- or a substituted cyclohexylene-alkylene group of formula (iva, ivb, ivc or ivd); R5>-(CH2)q-H; R6>-(CH2)r-; R7>-(CH2)s-; R8>linear or branched 10-18 C alkyl; A->an (in)organic anion; m : 10-1000; n, o : 0-20; p : 1-10; q : 1-18; r : 2-3; s : 2-5; (n+o) : 1 or more . [Sub-structures, second and third formulae on page 23, please label (iia) and (iib)] R4>-(OC2H4)n-(OC3H6)o-O-R8> (iii); [Sub-structures, last four formulae on page 24, please label (iva), (ivb), (ivc) and (ivd)].

Description

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

amino groups containing organopolysiloxanes have been around for quite some time Textile finishes used. The textiles treated with it have good soft-grip effects reached. Often Organopolysiloxanes are used which are in the polymer chain lateral or terminal with aminoethylaminopropyl or aminopropyl radicals are modified. These amino-functional organopolysiloxanes are as described for example in WO 88/08436, by protonation with weak acids and formulated into aqueous microemulsions with the aid of emulsifiers.

disadvantage These emulsions are the low stability under alkaline conditions of use, a poor consistency across from Shear stresses, a pronounced yellowing tendency under temperature stress as well as a strong foaming while the application on modern finishing machines.

Lots Textile finishing processes require the application of high pH values in the watery Treatment baths. Such is the pretreatment, bleaching and dyeing of cellulosic substrates always the use of high amounts of alkalis necessary. Will after such steps are not sufficiently neutralized and careful washed out, it may in the subsequent treatment with soft-grip agents on Basis of amino-functional organopolysiloxanes for destabilization the microemulsions and thus significant deposits of water insoluble Organopolysiloxanes come in the treatment unit. These deposits can then precipitate directly in the form of stains on the textile, which are difficult or impossible to remove.

The Destabilization of the emulsions under alkaline conditions on a deprotonation of the amino-functional groups of the organopolysiloxane due. Without the cationic charges on the organopolysiloxane cause coalescence the microemulsion particles and thus the formation of undesirable Silicone oil drops in the treatment fleet.

Amino-functional Organopolysiloxanes, when applied to finishing machines, show high shear exercise on the treatment fleet, often inadequate stability the preparation. Especially on modern fully or partially flooded Düsenfärbeappa advise kick during the pumping operations high shear stresses, which is why, for example, during a Application in the exhaust process in turn emulsion splitting with the undesirable Silicone stains can occur on the textile substrate.

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

Softeners based on amino-functional organopolysiloxanes usually contain big amount of on nonionic emulsifiers, causing the foaming tendency of the application fleets rises sharply. This makes the universal applicability the fast moving textile equipment machines, such as the nozzle dyeing apparatus limited, because the foam produced in these apparatuses by the strong mechanics the transport of the goods to be treated in the machine, as well as the Mass transfer between treatment liquor and textile substrate considerably impeded.

In DE-OS 19652524 is a synthesis route for the preparation of organopolysiloxanes described with lateral arranged quaternary ammonium groups. These are organopolysiloxanes modified with lateral aminoethylaminopropyl groups, by alkylation with toluene-4-sulfonic acid methyl ester in the presence of emulsifiers and water in microemulsions, which are used as softening agents for the equipment of Textiles are suitable.

In WO 02/10256 mono- or polyquaternary modified polysiloxanes are described in which two polysiloxane units are connected to each other via Alkylenamin- or Alkylenammoniumeinheiten. 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. Use find this Polysiloxane compounds in cosmetic formulations, in surface treatment agents and as softening agents for textiles.

The equipment textiles with fluorocarbon polymers has long been known. While the production of water-repellent effects based on products of paraffins and silicones merely a hydrophobing of Textile fiber causes lead Fluorocarbon polymers in addition for a dirt and oil repellency. Fluorocarbon finishes come for a big Number of items in question. They are used both in clothing and home textile sector, as well as in the sector of technical textiles used.

Usually based products for the fluorocarbon equipment on polyurethanes or polyacrylates, which perfluoroalkyl groups different chain length contain. The application of the preferably aqueous products is usually via the Exhaustion and padding by spraying, foaming or patting, often in Combination with other additives. This can e.g. thermosetting resins based on methylol compounds be, the dimensional stability, Washfastness and stiffness effect. Furthermore, also substances used, which are referred to as extenders. Usually it is thereby to fatty acid-modified Melamine resins, mixtures of wax and zirconium salts or blocked Polyisocyanates. The latter are often used to and oil repellent Effects of fluorocarbon equipment improve and increase the wash permanence.

To the aqueous Application of the mentioned fluorocarbon products takes place in a further Step the drying or thermal treatment of the finished textile at temperatures between 120 ° C and 190 ° C. In this case, an orientation of the Perfluoralkylseitenketten, wherein the fluorocarbon polymer exhibits its optimum level of effect. at Use of blocked polyisocyanates requires elevated temperatures to effect the 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 to a better orientation of the perfluoroalkyl chains and thus to an improvement of the oil and water repellent properties to lead. Furthermore, due to the crosslinking with the textile substrate the washing resistance the equipment improved.

When disadvantageous has been found that the crosslinked polyurethanes the grip, the processing properties and the sewability of the equipped Textile negative affect. Especially based on textiles native fibers is a significant hardening of the grip character too observe.

Around To minimize these negative characteristics would be the use of usual Silicone soft grip agents based on amino-functional organopolysiloxanes conceivable. However, these products lead to a severe deterioration of the water and oil repellent Properties of the fluorocarbon equipment. Another disadvantage the said amino-functional organopolysiloxanes is in one Yellowing tendency, which in the treated, white and light-colored textile substrates at drying temperatures above 120 ° C occur can.

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 It was now the task of a preparation for the treatment of textile To provide substrates that produces a good soft touch effect and in the pH stability, Shear resistance, Low foaming and resistance to yellowing are ensured. Further the preparation should be combinable with fluorocarbon equipment fleets be without the good oil and water-repellent effects of fluorocarbon finish negative influence.

In unexpectedly, it has been found that this object is achieved by the claimed preparations be solved from ammonium and polyether-modified organopolysiloxanes can. The ammonium and polyther groups are terminal on the organopolysiloxane in α, ω position positioned.

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

The with the preparations according to the invention equipped Textiles have a very good softness and a high yellowing resistance.

Furthermore let the preparations of the invention together with watery Fluorocarbon products and other additives such as e.g. Extenders or thermosetting Apply resins in a single-stage exhaustion or padding process. The with the preparations of the invention textiles treated in combination with fluorocarbon polymers in addition to the good water and oil repellency a very good soft touch. Likewise, the sewability across from a pure fluorocarbon kit clearly improved.

One Advantage of the ammonium- and polyether-modified organopolysiloxanes is that they are without or with very low amounts of emulsifier in can be converted stable emulsions. The negative influence of high emulsifier quantities used for emulsification and stabilization of pure amino-functional organopolysiloxanes are necessary, in the inventive preparations be reduced.

Furthermore show the ammonium- and polyether-modified organopolysiloxanes in combination with fluorocarbons a high yellowing resistance at high drying temperatures. This is especially true when using of blocked polyisocyanates (boosters) of advantage. To the deblocking to initiate the isocyanate groups high temperatures are required the at primary Amine-containing organopolysiloxanes to a strong yellowing to lead.

• (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,
• (2) 0 bis 10 Gewichtsprozent eines Emulgators,
• (3) 0 bis 15 Gewichtsprozent eines Hydrotropikums 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),
• (2) 0 to 10% by weight of an emulsifier,
• (3) 0 to 15% by weight of a hydrotrope and
• (4) 20 to 98% by weight of water.

All Weight specifications of the preparations according to the invention relate on the overall composition of the preparation according to the invention. As preferred range for the component (1) is a range of 10-40% by weight. If component (3) is added, its concentration is preferably in the range of 1-10, especially from 3-7 Weight. The preferred range of component (4) is at 60-90, but especially between 70-90 Weight.

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 for organic anions are tosylate, formate and acetate; preferred is tosylate.

The Preparation of the modified organopolysiloxanes is carried out by methods which are known in the art. The claimed component (1) is in particular through the synthetic route described below accessible.

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

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

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

is.

In In the following synthesis steps, the epoxide groups with amines and alkyl alcohol alkoxylates with ring opening to the 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 (IIIa) and (IIIb)

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 ⁸ , n and o have the abovementioned meanings.

The Order of Addition of Amine and Alkyl Alcohol Alkoxylate is variable. The stoichiometry is chosen so in each case after the first step, an epoxy group in the organopolysiloxane remains.

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

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 quaternized analogously to DE-OS 1493384 (Example 2) with, for example, methyl iodide or methyl tosylate. 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 analogous to DE-OS 1493384 (Example 2) by quaternization with eg methyl iodide or methyl tosylate the ammonium and to obtain polyether-modified organopolysiloxanes.

The aforementioned writings and their specified passages are Components 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 become more aliphatic Alcohols having 6 to 22 carbon atoms used, containing up to 50 moles of ethylene oxide attached. The alcohols preferably contain 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, 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.

Examples of preferred cationic emulsifiers are 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-methylammonium-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 in the preparations according to the invention optionally present component (3), a hydrotrope, may be the group of polyfunctional alcohols are selected. So can dialcohols with 2-10, preferred 2-6, in particular however 2-4 Carbon atoms per molecule be used. Also suitable are their mono- and diethers as well as the mono- and diesters of these dialcohols. As particularly preferred Examples to be used for Component (3) is butyl diglycol, 1,2-propylene glycol and dipropylene glycol to call.

The Preparation of the preparations according to the invention is generally done by tapping the ammonium- and polyether-modified organopolysiloxanes (component (1)), the emulsifier (component (2)), the hydrotopic (component (3)) and the water (component (4)) at 70 ° C. The claimed ammonium and polyether-modified organopolysiloxanes (component 1) due to their structure usually already a good emulsifiability. If these are insufficient in individual cases should be, it may be appropriate the preparations of the components (1) to (4) with stirring 70 ° C in Presence of small amounts of organic acids (for example, acetic acid or Lactic acid) to prepare the polymer in the aqueous medium form to bring an emulsion.

Another The invention relates to the use of the preparations according to the invention in the finishing of textile substrates in aqueous baths and application fleets.

at The textile substrates are woven, knitted or braided and textile composites of native fibers, such as cotton or wool, but also of synthetic fibers, such as Viscose, polyester, polyamide or polyacrylonitrile. In the application on textile substrates the preparations according to the invention also with the textile auxiliaries customary in the textile industry be combined. Noteworthy are agents that the Entknitterungseigenschaften improve, for example, methylol compounds of Dihydroxyethylenharnstoffes or Methylolmelaminether different degrees of methylolation.

One Another object of the invention is the use of the preparations according to the invention in combination with fluorocarbon polymer formulations. In the formulations these are aqueous preparations of fluorocarbon polymers based on perfluorinated polyacrylates or perfluorinated polyurethanes, optionally with others Aids such as blocked polyisocyanates (boosters) or extenders are mixed. All components of these formulations can also be used separately in the application fleet.

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 in the desired concentration by means of a forced application of aqueous medium by padding, spraying, Pflatsch-, foam application made. The fleet takes between 40 and 100%. This is followed by a pre-drying at 80-110 ° C and then a hot treatment at 130-170 ° C for 1-5 minutes. The duration of the heat treatment depends on the temperatures used.

A further application possibility on textile fabrics is given by the exhaust process known in the art.

The 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).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 analogously 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 quaternized with 28.2 grams (0.2 mol) of methyl iodide analogously to DE-OS 1493384 (Example 2). 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 made from 15 grams of ammonium and so produced polyether-modified organopolysiloxane (component (1)) stir 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)) added with 2 grams of acetic acid (60%).

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 mol) of bis [3- (dimethylamino) -propyl] amine analogously 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 quaternized with 42.3 grams (0.3 mol) of methyl iodide analogously to DE-OS 1493384 (Example 2). 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 made from 15 grams of ammonium and so produced polyether-modified organopolysiloxane (component (1)) stir with 3 grams of isotridecyl alcohol with 6 ethylene oxide groups (component (2)) and 5 grams of butyldiglycol (component (3)) in 75 grams of water (Component (4)) added 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 analogously 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 quaternized with 28.2 grams (0.2 mol) of methyl iodide analogously to DE-OS 1493384 (Example 2). 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 made from 15 grams of ammonium and so produced polyether-modified organopolysiloxane (component (1)) stir with 6 grams of isotridecyl alcohol with 6 ethylene oxide groups (component (2)) and 4 grams of butyl diglycol (component (3)) in 73 grams of water (Component (4)) added with 2 grams of acetic acid (60%).

equipment

The Application of the finishes on textile fabrics was done on a Laboratory padder type LFV 350/2 "RFA" (Benz, Switzerland) with following Drying and hot treatment on a laboratory clamping frame type TKF 15 / M 350 (Benz, Switzerland). The determination of the liquor pickup was carried out by weighing the finished test samples before and after application.

Carrying out the handle assessment

to Handle assessment were sections of a bleached, not optical brightened cotton woven fabric with an aqueous liquor containing 20 g / l of the examples according to the examples Prepared preparations and 0.5 g / l acetic acid (60%) on a laboratory pad impregnated with a wet pickup of 80% and then 2 minutes at 120 ° C dried and 2 minutes at 170 ° C. condensed. (Table 1: Grip assessment I.)

As well were the according to the examples Preparations prepared in combination with a Fluorcarbonpolymer and a booster tested. For this purpose, sections of a bleached, non-visually brightened cotton woven fabric with an aqueous Liquor containing 20 g / l of the prepared according to the examples Preparations, 20 g / l of water-repellent 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 subsequently 2 minutes at 120 ° C dried and 2 minutes at 170 ° C. condensed. (Table 2: Grip assessment II.)

Tabelle 2: Griffbeurteilung 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.

Table 2: Handle assessment II.

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

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

Determination of hydrophobicity and oleophobia

sections a bleached, non-visually brightened cotton woven fabric with an aqueous Liquor containing 20 g / l of the prepared according to the examples Preparations, 20 g / l of water-repellent based on a perfluorinated Polyacryaltic, 20 g / l booster based on a blocked polyisocyanate and 0.5 g / L acetic acid (60%) on a laboratory foulard impregnated with a wet pickup of 80% and subsequently 2 minutes at 120 ° C dried and 2 minutes at 170 ° C. condensed.

The exam the hydrophobic and optionally oleophobic effects did not occur immediately after application, but only after conditioning of substrates in standard climate during 24 hours to influences on these properties by overdrying to level.

• 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 sticking of water drops 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 test fluid with the highest number, at which no wetting of the surface takes place.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

Determination of yellowing

sections bleached, optically brightened cotton woven fabric with an aqueous fleet, containing 20 g / l of the examples Prepared preparations, and 0.5 g / l acetic acid 60% on a laboratory pad impregnated with a wet pickup of 80% and then 2 minutes dried at 120 ° C. and 2 min at 170 ° C condensed. (Table 6: yellowing I.)

As well were the according to the examples Preparations prepared in combination with a Fluorcarbonpolymer and a booster tested. For this purpose, sections of a bleached, non-visually brightened cotton woven fabric with an aqueous Liquor containing 20 g / l of the prepared according to the examples Preparations, 20 g / l of water-repellent 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 subsequently 2 minutes at 120 ° C dried and 2 minutes at 170 ° C. condensed. (Table 7: yellowing II.)

Tabelle 7: Vergilbung 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.

Table 7: Yellowing II.

Determination of sewability

sections a bleached, not optically brightened cotton knitwear were with an aqueous Liquor containing 20 g / l of the prepared according to the examples Preparations, 20 g / l of water-repellent 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 pick-up of 80% and then 2 minutes at 120 ° C dried without voltage and condensed at 170 ° C for 2 minutes.

The sewability was checked with a Dürkopp industrial sewing machine. The equipped Tex The til is sewn on top of each other 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

Claims (3)

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 -HR 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 one 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 to the total composition of component (1), (2) 0 to 10% by weight of an emulsifier, (3) 0 to 15% by weight of a hydrotrope and (4) 20 to 98% by weight of water. Use of the preparation according to claim 1 in the refinement textile substrates in aqueous bathrooms and application fleets. Use of the preparations according to claim 1 in combination with fluorocarbon polymers.