DE102013209170A1 - Composition useful e.g. for waterproofing of absorbent materials, comprises silicone polymer, wax and/or fatty acid esters, aminoplast, urea derivatives and/or melamine derivatives, solvent, crosslinking agent, and dispersing auxiliaries - Google Patents

Abstract

Composition comprises (a) 1-50 wt.% silicone polymer, (b) 1-50 wt.% wax and/or fatty acid esters, (c) 0-50 wt.% aminoplast, urea derivatives and/or melamine derivatives, (d) 0-98 wt.% solvent, (e) 0-50 wt.% crosslinking agent, and (f) 0-5 wt.% dispersing auxiliaries. Independent claims are also included for: (1) preparing the above composition, comprising providing the component (a), the component (b) and the melamine derivatives optionally with the component (f) and heating to melt, adding the component (d) using additional auxiliaries, and homogenizing using mechanical energy; (2) applying the above composition on textile surfaces by textile engineering processes, preferably exhaust process or by forced application e.g. coating, padding, printing, spraying, single-thread application and/or dyeing; and (3) textiles containing fibers, which is applied with the above composition.

Description

The invention describes a preparation which is applied to textile surfaces, woven fabrics, loops, knits, fibers, nonwovens and knitted fabrics and exhibits a water-repellent effect thereon. Furthermore, the invention comprises a process for the preparation of the preparation and the use of the preparation, including the textiles thus obtained.

Textile materials are used for a variety of applications. However, their absorbency and permeability to water are undesirable in many applications. For outdoor textiles such as rainwear and tarpaulins or permanent outdoor textiles such as awnings and geotextiles, these properties are disadvantageous. Since the sole choice of textile material can not find a technically adequate and economically acceptable solution to the problem, these textiles are treated with water-repellent agents. For a long time, the perfluorinated acrylate systems and the equipment based on them dominated the market. These fluorine-containing surface treatments not only allow excellent water repellency, but also bring along oil and dirt repellent effects. Despite these technical properties, the perfluorinated coatings are now in decline because they are considered persistent and bioaccumulative ( M. Santen, U. Kallee, Chemistry for Any Weather, Greenpeace e. V., 2012, p. 5 ).

The use of waxes in the hydrophobization of textile surfaces has also been known to the skilled person for a long time. However, the equipment is not sufficiently stable to household laundry and must therefore be renewed regularly. A moderate improvement can be achieved by the use of zirconium or aluminum salts of fatty acids ( H.-K. Rouette, Encyclopedia of Textile Finishing, Springer, 2000, p. W91-W95, keyword "water repellent finishing" ). However, such refined fabrics suffer from a very waxy feel, very low air permeability and the associated loss of comfort and increased flammability due to the high wax aggregates on the textile surface.

Therefore, attempts have been made to enhance or supplement waxes in their properties. Thus, waxes are often applied with polymer dispersions. For example, the use of fatty acrylate-based copolymers together with wax emulsions has been known for some time ( C. Tomasino, Chemistry & Technology of Fabric Preparation & Finishing, pp. 158-171, webcast dated 30.04.2013, http://infohouse.p2ric.org/ref/06/05815.pdf ). Solvent-based polyacrylates were initially used in DE 1238215 A1 However, due to their adverse process and environmental influences, such systems can not be used in the textile industry. patent EP 2411575 B1 mentions the use of terpolymers based on alkyl acrylates, chlorine-containing vinyl compounds and styrene derivatives in combination with waxes as aqueous dispersions. However, the use of styrene-containing polymers is unsuitable due to the yellowing tendency of these compounds and also halogen-containing substances are undesirable for environmental reasons in the textile industry. Vinyl esters of the Kochsäuren as a component of copolymer wax dispersions were in EP 1424433 B1 mentioned, but are unfavorable due to the high price.

DE 10211549 B9 describes the preparation of a compound which is obtained from the reaction of a diol, alkanolamine or diamine with a diisocyanate or a dicarboxylic acid and is finally treated with a further isocyanate. In conjunction with waxing, this reaction product is used as a hydrophobic surface finish.

Recently, the use of a polyurethane coatings in DE 10 2009 014 699 A1 described. However, the hydrophobicity described by the authors does not meet current requirements, especially since only contact angles have been tested and no washing tests have been carried out. This is understandable in that comparatively large amounts of emulsifiers are required and they must first be removed.

As an alternative to the wax and polymer-based approaches, those based on silicones are used. Functionalized silicones and siloxanes have long been used for handle optimization (cf. DE 4222483 A1 and writings cited therein).

The use of H-siloxanes for the hydrophobization of textiles is for example out DE 1231663 A1 known. In combination with urea or melamine resins, wrinkle-free equipment can be achieved at the same time (cf US 3,032,442 A ). However, these known systems are known to have the serious disadvantage that during the textile finishing elemental hydrogen can be released, what a represents a significant process risk. In addition, they require anhydrous, flammable solvents and toxicologically questionable catalysts and are therefore not applicable in the textile industry.

Water repellent effects on textile surfaces also describes US 2,758,946 A by equipping the common hydrolysis product of dimethylchlorosilane and alkylmethylchlorosilanes in the finishing liquor with the addition of water-soluble aminoplasts and tin or zinc catalysts. This approach is in no way sufficient today required security requirements.

Likewise, the use of alkyl-modified silicas or their esters is US 2785145 State of the art. However, these finishes suffer from insufficient washing permanence.

EP 2152957 B1 sets the described component DE 10211549 B9 also in conjunction with alkyl-modified organosiloxanes, but can not achieve sufficient hydrophobicity before and after household washes.

The combination of wax and silicone oil emulsion to improve the friction and sliding properties of yarns is the expert from WO 03/078726 A1 and the writings cited therein. The influence of this combination on the water repellency is not mentioned, rather such sizings are generally removed after the weaving processes.

A combination of zirconium paraffin wax and H-siloxane is used in GB 1287745 A1 However, the application of organic, combustible solvent and with highly reactive catalysts is no longer acceptable today for safety reasons.

In JP 2006-124866 A1 For example, the use of a non-functionalized polydimethylsiloxane in compounds with a crosslinker, preferably based on a carbodiimide, has been reported for the hydrophobicization of textile materials.

EP 1108765 B1 describes carboxy-functional silicones as water repellents for furs and leather, optionally together with paraffins. The disadvantage is that these substrates at the latest after the first household wash with a commercial alkaline detergent lose their water-repellent effect, since the present invention according to the necessary acid groups are then deprotonated. The authors also describe a dispersion process in which the silicone is first reacted with a base, then dispersed in a mixture of water and an organic solvent, from which finally this solvent has to be removed by distillation.

Aminoplasts are mostly used in the form of melamine or urea-formaldehyde resins as crease-resistant finishing of cellulosic fibers. Alkyl melamines and their resins as textile hydrophobing agents are made BE 569962 A1 known. Similar approaches can be found in DE 1594977 A1 and DE 1570776 A1 , In DE 60124597 T2 Such melamine derivatives are applied together with waxes on textiles to achieve water-repellent effects. With this non-completely fluorine-free system, however, neither adequate permanence nor the desired handle design can be achieved.

EP 1035200 A2 describes a wiper cloth finished with one or more hydrophobic components for the purpose of producing a water-repellent film on an automotive surface treated therewith, wherein the hydrophobic finish is transferred from the textile to the wiped surface. The authors also state that the amount of emulsifier must not be too high for such a system, since otherwise the hydrophobing effect is lost. Accordingly, the smallest possible amounts of surface-active substances are advantageous.

The object of the present invention is to provide a preparation for producing water-repellent effects on textile surfaces by the combination of suitable active ingredients and the combination of these in the preparation with the lowest possible amounts of emulsifiers available.

It has surprisingly been found that the combination of, on the one hand, silicone polymer and, on the other hand, wax and / or fatty acid ester, and preferably additionally provided with aminoplasts, results in permanent, wash-resistant hydrophobing of textile materials with a pleasant and soft feel and good air permeability. It is particularly advantageous that the plasticizer usually required can be saved.

It has been found, particularly surprisingly, that silicone polymers having a high alkyl density can be formulated particularly advantageously with wax and optionally aminoplast in one step. The process according to the invention describes a production process with the lowest possible amounts of surface-active substances and dispersants.

It is particularly surprising that excellent Waschpermanenzen the water-repellent effect can be achieved because the silicone polymer has a melting point of in particular -20 to 60 ° C, preferably from 0 to 50 ° C, particularly preferably from 20 to 40 ° C, the expert but it is known that melting points of hydrophobicizing components such as waxes must have a melting range greater than 60 ° C in order to achieve even moderate wash resistance.

• a) 1,0 bis 50,0 Gew-.%, bevorzugt 2 bis 20,0 Gew-.%, Silikonpolymer
• b) 1,0 bis 50,0 Gew-.%, bevorzugt 2 bis 20,0 Gew-.%, Wachs und/– oder Fettsäureester
• c) 0,0 bis 50,0 Gew-.%, vorzugsweise 1,0 bis 50,0 Gew-.%, besonders bevorzugt 2,0 bis 10,0 Gew-.%, Aminoplast, Harnstoffderivat und/oder Melaminderivat
• d) 0,0 bis 98,0 Gew-.% Lösungsmittel
• e) 0,0 bis 50,0 Gew-.% Vernetzer
• f) 0,0 bis 5,0 Gew-.% Dispergierhilfsstoffe.

The preparation according to the invention contains the following constituents:

• a) 1.0 to 50.0% by weight, preferably 2 to 20.0% by weight, silicone polymer
• b) 1.0 to 50.0% by weight, preferably 2 to 20.0% by weight, wax and / or fatty acid esters
• c) from 0.0 to 50.0% by weight, preferably from 1.0 to 50.0% by weight, particularly preferably from 2.0 to 10.0% by weight, of aminoplast, urea derivative and / or melamine derivative
• d) 0.0 to 98.0% by weight of solvent
• e) from 0.0 to 50.0% by weight of crosslinking agent
• f) 0.0 to 5.0% by weight of dispersing aids.

All data are by weight and refer to the entire preparation.

m, n und o sind ganze Zahlen und können unabhängig voneinander gewählt werden und nehmen Werte von 1 bis 100000 an. p_a, p_b, p_c können unabhängig als ganze Zahlen zwischen 0 und 100000 bestimmt werden. Bevorzugt sind solche Silikonpolymere, für die die Beziehung m / 4 < n, insbesondere m / 2 < n, gilt und die einen Stickstoffgehalt zwischen 0,01 bis 4,0 Gew.-%, bevorzugt 0,1 bis 1,0% Gew.-%, bezogen auf das Gesamtpolymer haben. Als Stickstoffgehalt definiert man folgende Beziehung: Stickstoffgehalt [%] = Masse (Stickstoff im Polymer)·100 / Masse (gesamtes Polymer) The silicone polymer according to the invention comprises the necessary units M, N, O as well as the optional units P _a , P _b and also P _c and optionally the end groups X and Y:

m, n and o are integers and can be chosen independently and assume values from 1 to 100,000. p _a , p _b , p _c can be independently determined as integers between 0 and 100,000. Preferred are those silicone polymers for which the relationship m / 4 <n, in particular m / 2 <n, and one applies Nitrogen content between 0.01 to 4.0 wt .-%, preferably 0.1 to 1.0% wt .-%, based on the total polymer have. The nitrogen content is defined as follows: Nitrogen content [%] = mass (nitrogen in polymer) · 100 / mass (total polymer)

The unit M is the base unit of the silicone polymer. R ¹ is selected from the group of saturated or unsaturated, linear, branched and / or cyclic hydrocarbons and the aryls, hydroxy or alkoxy. For R ² , saturated or unsaturated, linear, branched and / or cyclic hydrocarbons and aryls can be used.

Preference is given to those polymers which carry saturated or unsaturated linear, branched and / or cyclic hydrocarbons having 8 to 50 carbon atoms, more preferably those having 16 to 30 carbon atoms.

Particularly preferred is the combination for the unit N, which consists of a methyl radical and a saturated or unsaturated, linear, branched and / or cyclic, aliphatic hydrocarbon having 8 to 50 carbon atoms, very particularly preferably having 16 to 30 carbon atoms.

enthalten mindestens ein Stickstoffatom, das als primäres, sekundäres, tertiäres Amin bzw. als quarternäres Ammonium vorliegt. R⁴ kann ausgewählt werden aus der Gruppe der gesättigten oder ungesättigten, linearen, verzweigten und/oder cyclischen Kohlenwasserstoffe, die zusätzlich noch Amingruppen in der Kette tragen können, wie zum Beispiel Alkylenaminoalkyl, Alkylenaminoalkylenaminalkyl, oder Arylene, besonders bevorzugt werden Alkylene mit 1 bis 6 Kohlenstoffatomen oder Alkylenaminoalkylenamine mit jeweils 1 bis 6 Kohlenstoffatomen in den Ketten eingesetzt. R⁵ und R⁶ können unabhängig voneinander aus den folgenden Substanzklassen ausgesucht werden: Wasserstoff, Alkyl, Amid, Alkylenamin, Alkylenaminoalkyl, Alkylenaminoalkylenamin oder längere Homologe dieser Reihe. Die optionalen Einheiten P_a, P_b und P_c enthalten weitere Funktionalisierungen für R⁷ und R⁸ in Form von organischen Resten, die unmittelbar oder mittelbar über einen Alkylen- oder Arylenspacer an das Siliciumatom gebunden sein können, wie beispielsweise Glycidyl, Epoxyd, Alkylether, Polyalkylenether, Allyl, Hydroxy, Triorganylsilyl (Organyle sind Alkyle und/oder Aryle), Alkyl, Alkoxy, Aryloxy, Vinyl, Mercapto, Phosphato. Auch können für R⁷ und R⁸ weitere Silikonpolymerketten eingesetzt werden, so dass ein querverzweigtes Netzwerk entsteht, das mit den Einheiten M, N, O und/oder P_a, P_b, P_c aufgebaut wird. Erfindungsgemäß sind auch Verknüpfungen von P_b und/oder P_c über Sauerstoffbrücken an weitere Siliziumatome möglich, die wiederum Teil von den vorgenannten Einheiten sein müssen.The unit O carries amino-functional side groups and the radical R ³ . For example, amine-containing silanes from the Dynasylan ^® -Produktgamme can be incorporated into the polymer by equilibration. The radical R ³ may be a hydroxy, alkoxy, alkyl or aryl group in the context of the invention. The amine-containing side groups consisting of

contain at least one nitrogen atom which is present as a primary, secondary, tertiary amine or as quaternary ammonium. R ⁴ can be selected from the group of saturated or unsaturated, linear, branched and / or cyclic hydrocarbons which may additionally carry amine groups in the chain, such as, for example, alkyleneaminoalkyl, alkyleneaminoalkyleneaminalkyl, or arylenes; particularly preferred are alkylenes having 1 to 6 Carbon atoms or Alkylenaminoalkylenamine having in each case 1 to 6 carbon atoms in the chains used. R ⁵ and R ⁶ can be independently selected from the following classes of substance: hydrogen, alkyl, amide, alkyleneamine, Alkylenaminoalkyl, Alkylenaminoalkylenamin or longer homologues of this series. The optional units P _a , P _b and P _c contain further functionalizations for R ⁷ and R ⁸ in the form of organic radicals which may be bonded directly or indirectly via an alkylene or arylene spacer to the silicon atom, such as glycidyl, epoxy, alkyl ethers , Polyalkylene ethers, allyl, hydroxy, triorganylsilyl (organyls are alkyls and / or aryls), alkyl, alkoxy, aryloxy, vinyl, mercapto, phosphato. It is also possible to use further silicone polymer chains for R ⁷ and R ⁸ , so that a cross-branched network is formed which is built up with the units M, N, O and / or P _a , P _b , P _c . According to the invention, linkages of P _b and / or P _c via oxygen bridges to further silicon atoms are possible, which in turn must be part of the abovementioned units.

For linear silicone polymers, the peripheral units in α and ω positions are saturated by the end groups X and Y. X and Y are independently selectable from hydroxy, triorganylsilyl, alkyl, aryl or hydrogen. Organyls in this context are functionalized or non-functionalized hydrocarbons, aryls or mixtures of these classes. With cyclic silicone polymers, these end groups are omitted; with branched or crosslinked silicone polymers, further end groups may be necessary to saturate the valencies.

It is particularly advantageous that due to the low melting point of the silicone polymer and the high density of alkyl functionalities, this polymer dissolves in waxes and / or fatty acid esters, and therefore can be emulsified in one step with these. As a result, the amount of hydrophobicity-disturbing emulsifiers is largely minimized and the water-repellent effects of the finished textiles improved.

For the purposes of the invention, one or more of the group of natural, semisynthetic, synthetic waxes and / or fatty acid esters may be considered as wax / fatty acid esters. Natural waxes can be distinguished into mineral, vegetable and animal waxes, all of which can be used according to the invention. Vegetable waxes are, for example, carnauba or Japan wax, mineral, for example Ceresin or Montan waxes (raw montan waxes, acid waxes, ester waxes, partially hydrolyzed ester waxes, emulsifier-containing ester waxes, fully hydrolyzed montan waxes). Beeswax, lanolin are exemplary listed as animal waxes. Synthetic waxes are those based on polyalkylene (polyethylene, polypropylene, polyolefin waxes), polyol ether esters, Fischer-Tropsch waxes, oxidized PE and HDPE waxes, paraffins, amide waxes such as Ethylenbisstearoyldiamid. Semisynthetic waxes are chemically modified native source waxes such as hydrogenated jojoba waxes and Sasol waxes.

Also higher molecular weight esters of fatty acids, optionally containing still free acid and / or alcohol, can be used as waxes. Suitable acids are the saturated and unsaturated, linear, branched and / or ring fatty acids having 16 to 50 carbon atoms. Preferably, the linear, saturated or unsaturated acids having 16 to 36 carbon atoms in the chain are used. Fatty alcohol residues or polyhydric alcohol residues can be used as the second component of the esters according to the invention. Monofunctional alcohols according to the invention consist of 16 to 50 carbon atoms and one hydroxy group and are composed of saturated or unsaturated and linear, branched and / or rings consisting of rings. Examples are cetyl alcohol, stearyl alcohol, behenyl alcohol, ambrein and betulin.

Suitable polyhydric alcohols are reactive aliphatic alcohols which carry two or more hydroxyl groups and can form compounds having more than one ester group under the conditions known to the person skilled in the art with the abovementioned fatty acids. For example, but not limited to, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, pentaerythritol, trimethylolpropane, glycerin are listed.

Similarly copolymers are mixtures of polyethylene-acrylic acid copolymers, such as are present in Michem ^® emulsion 34935, or polyethylene-maleic acid (anhydride) can be used.

Preferably, such waxes are used with a melting point of greater than 60 ° C, since it is known in the art that the hydrophobicity is often insufficient in low-melting waxes.

The aminoplast preferably to be used according to the invention comprises one or more amine-containing components based on urea, melamine or an aldehyde resin derived therefrom.

The melamine component is composed as shown:

The radicals R ¹ to R ⁶ are independently selectable from the group hydrogen, saturated or unsaturated, linear, branched and / or cyclic hydrocarbons, aryls, preferably saturated or unsaturated aliphatic hydrocarbons having 8 to 50 carbon atoms in the chain, preferably 16 to 30, or the units R - S - T and / or U - V.

For the unit R, an alkylene or arylene can be used, for S an oxygen atom, α, ω-dioxyalkylene, α, ω-dioxyarylene, a carboxyl, carbonate or carbamate group, for T is a hydrogen, a saturated or unsaturated, linear, branched and / or cyclic hydrocarbon or an aryl group, wherein preferably saturated or unsaturated aliphatic hydrocarbons having 8 to 50 carbon atoms, particularly preferably 16 to 30, are used.

For the unit U, a carbonyl or carbamoyl can be used, for V is a saturated or unsaturated, linear, branched or cyclic hydrocarbons or an aryl group, preferably saturated or unsaturated aliphatic hydrocarbons having 8 to 50 carbon atoms, particularly preferably 16 to 30, are used.

The reaction products with aldehydes, the so-called melamine aldehyde resins, here preferably the melamine-formaldehyde resins obtained with formaldehyde, can also be used according to the invention, provided that at least one of R ₁ to R _{6 has} one of the above-mentioned functionalities. It is also possible according to the invention that one or more of the radicals R ¹ to R ⁶ carry a function of the type polyglycol or polyether.

It is further possible for the purposes of the invention that diols or polyhydric alcohols are used in order to achieve crosslinking of various melamine units. For this purpose, at least one of the radicals R ¹ to R ^{6 is} replaced by a polyhydric alcohol, its ether or alkylol ethers and thus binds to a further melamine unit.

As an alternative to the melamine-based compounds described above, it is also possible to use ureas or thioureas and / or their aldehyde resins, which correspond in the following scheme:

The radicals R ⁷ and R ⁸ are independently selectable from the group of saturated or unsaturated, linear, branched or cyclic hydrocarbons, aryls, hydrogen, preferably the saturated or unsaturated aliphatic hydrocarbons having 8 to 50 carbon atoms, particularly preferably 16 to 30, are used, and / or the units R - S - T or U - V.

For the unit R, an alkylene or arylene can be used, for S an oxygen atom, α, ω-dioxyalkylene, α, ω-dioxyarylene, a carboxyl, carbonate or carbamate group, for T is a hydrogen, a saturated or unsaturated, linear, branched and / or cyclic hydrocarbon or an aryl group, wherein preferably saturated or unsaturated aliphatic hydrocarbons having 8 to 50 carbon atoms, particularly preferably 16 to 30, are used.

For the unit U, a carbonyl or carbamoyl can be used, for V is a saturated or unsaturated, linear, branched or cyclic hydrocarbons or an aryl group, preferably saturated or unsaturated aliphatic hydrocarbons having 8 to 50 carbon atoms, particularly preferably 16 to 30, are used.

Z can be either an oxygen or a sulfur atom. W represents a hydroxyl-functionalized or a non-functionalized alkylene bridge, preferably ethylene, 1,2-dihydroxyethylene or 1,2-dialkoxyethylene. Mixtures of several aminoplasts are also inventive.

The reaction products with aldehydes, the so-called urea-aldehyde resins, here preferably the urea-formaldehyde resins obtained with formaldehyde, can also be used according to the invention if at least one of the radicals R ₇ / R _{8 has} one of the abovementioned functionalities. Likewise, according to the invention, it is possible that one of the radicals R ⁷ or R ⁸ carries a function of the type polyglycol or polyether.

Furthermore, it is possible for the purposes of the invention that diols or polyhydric alcohols are used in order to achieve crosslinking of different urea units. For this purpose, at least one of the radicals R ⁷ to R ^{8 is} replaced by a polyhydric alcohol, its ether or alkylol ethers and thus binds to a further urea moiety.

It is particularly advantageous if a high density of alkyl functionalities is present in the aminoplast, so that this compound is soluble in waxes, and can therefore be emulsified in one step with these. As a result, the amount of hydrophobicity-disturbing emulsifiers is largely minimized and the water-repellent effects of the finished textiles improved.

For further improvement of the washing permanence of the effect described, fixers and / or crosslinkers from the group of blocked and unblocked isocyanates, diisocyanates, oligoisocyanates and also polyisocyanates, melamine-formaldehyde resins, zirconium salts, urea-formaldehyde resins, glycidyl- or epoxy groups-bearing crosslinking agents, for example according to the invention functionalized polyethyleneimines or polyvinylamines, aziridine-based crosslinkers such as Tubassist FIX 104 W, available from CHT R. Seitlich GmbH, and / or di-, oligo- or polycarboxylic acids, optionally in combination with suitable catalysts which increase the reactivity and / or selectivity of the crosslinking used.

In the group of di-, oligo- or polyfunctional carboxylic acids are compounds of the type L _l (CO ₂ H) _k wherein L is an organic radical selected from the group of optionally functionalized alkyl, aryl, alkenyl, alkylaryl, arylalkyl, arylalkenyl, alkenylaryl, l as a number is either 0 or 1 and k is a number between 2 and 100,000. Alkanedicarboxylic acids are particularly preferred, in particular malonic acid, maleic acid, derivatives of succinic acid and oxalic acid. Particularly suitable oligo- and polycarboxylic acids are alkyloligo-, alkylpoly- or aryloligocarboxylic acids, particular preference is given to butanetetracarboxylic acid, all-cis-1,2,3,4-cyclopentanetetracarboxylic acid, tricarballylic acid, citric acid, 1,2,3-trans-propentricarboxylic acid, Succinic acid and derivatives of polyacrylic acid and polymethacrylic acid as homopolymers or copolymers.

Suitable catalysts for the fixers are generally Lewis acids or bases. Magnesium chloride is particularly preferably used alone or in combination with Bronsted acids, preferably ortho-phosphoric acid, citric acid, sulfuric acid. Alternatively, Brönsted acids, preferably ortho-phosphoric acid, citric acid, sulfuric acid without Lewis acid can be used. Also known is the use of basic catalysts such as amines, hypophosphites, phosphonates, pyro and polyphosphates or alkali.

The preparation is in the form of a solution, dispersion or emulsion in a solvent. Preference is given to using water, possibly in mixtures with alcohols, esters, glycols, polyols, glycol ethers, polyvinyl alcohols or polyol ethers.

To prepare the preparation in the form of dispersions, emulsions or solutions, it is possible, for example, to use dispersants from the group of anionic, cationic or nonionic surfactants, optionally in combination with acids or bases. To adjust the viscosity of the preparation, it is possible to add rheological additives, such as carboxyalkyl polysaccharides or suitable polyacrylates.

• – Gemeinsames Schmelzen der wesentlichen Bestandteile Silikonpolymer, Wachs und/oder Fettsäureestern sowie vorzugsweise Aminoplast einschließlich eventuell notwendiger Dispergierhilfsstoffe
• – Zeitversetzter Lösungsmitteleintrag enthaltend optional Dispergierhilfsstoffe, Säure und/oder Base oberhalb des Schmelzpunktes der vorgenannten Mischung
• – Verringerung der Partikelgröße der Zubereitung durch Eintrag von mechanischer Energie

The process for dispersing the ingredients comprises the steps

• - Common melting of the essential constituents silicone polymer, wax and / or fatty acid esters and preferably aminoplast including any necessary dispersing aids
• - Time-shifted solvent entry containing optionally dispersants, acid and / or base above the melting point of the aforementioned mixture
• - Reduction of the particle size of the preparation by input of mechanical energy

Silicone polymer, wax and / or fatty acid esters and optionally aminoplast are brought to the melt with dispersing aids at elevated temperature and successively mixed with the solvent optionally containing further dispersing aids, acids or bases at elevated temperature, the temperature between the melting point of the mixture and the Boiling temperature of the solvent should be. For the subsequent or simultaneous comminution of the particle size, methods and systems known to the person skilled in the art can be used. This includes the use of rotor-stator systems, rotor-rotor systems, pressure homogenizers, ultrasonic probes, homogenizers and porous membrane emulsifier units.

Particularly preferred for the purposes of the invention are those building blocks which are soluble in each other, optionally with the aid of elevated temperature. As a result, the preparations can be produced with a minimum amount of emulsifiers. This is particularly advantageous because larger amounts of these auxiliaries interfere with the water-repellent effects of the finishes, as known to those skilled in the art DE 1135418 A1 is known.

The preparation on which the invention is based and the preparation forms contained therein can also be combined with customary textile auxiliaries known to the person skilled in the art and applied together in standard textile processes. These include, for example, plasticizers, high-performance resins, brighteners, dyes, hydrophilizing or other water repellents, fluorocarbons, anti-pilling additives, fixers, crosslinkers, zirconium salts, surfactants, polymeric binders, adhesives, slip resistance and / or pigments. The way Textile auxiliaries obtained can be used as liquors, foams or pastes for the textile finishing of fibers, woven fabrics, knitted fabrics, knitted fabrics or nonwovens. Also, the combination of these additives and the aforementioned components to a preparation for the finishing of textiles is according to the invention. Suitable textile-technological processes include, for example, exhaust processes or forced applications such as coating, equipment by padding, printing, spray processes, monofilament application and / or dyeing. Optionally, common emulsifiers, wetting agents and / or deaerators can be added to stabilize finishing solutions.

The textile material used in the present invention may be made of natural fibers such as cotton, bast fibers, hard fibers, wool, silk, mineral fibers and / or synthetic fibers such as regenerated cellulose fibers, polylactic acid, polyester, polyamide, polyimide, polyamideimide, polyphenylene sulfide, aramid, polyvinyl chloride, polyacrylonitrile , Polyvinyl acetal, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, elastane, carbon fibers, silicate fibers, glass fibers, basalt fibers, metal fibers, these contain or consist of mixtures of the materials mentioned. Also, laminated fibers or fibers cast in a composite material are according to the invention.

Examples:

All percentages in the examples are percentages by weight. The water repellency was after DIN EN 24920 determined by the so-called spray test. In addition to the values 50, 70, 80, 90 and 100 specified in the standard, a complete, double-sided wetting of the textile sample, whereby the adhering water also penetrates the non-irrigated areas by capillary forces, is given the value 0. The finished textiles were to a number of household laundry after DIN EN ISO 6330 at 40 ° C to check the washing permanence. The air permeability was after ISO 9237 determines the breathability after ISO 15496 , The haptic assessment was divided into five softness levels (very soft, soft, moderate, stiff, very stiff).

The dispersions were stabilized by introduction of mechanical energy on a homogenizer of the type LAB 100 from A.P.V. Schröder GmbH, Lübeck. The air permeability was carried out on a test rig of the type "material testing machine" Karl Schröder KG.

The equipment was a laboratory tampon Walter Mathis AG used, the samples were dried in a laboratory clamping frame "Mathis Labdryer" the same company provided with a control unit "Programmer LTE". All finishing liquors were 2 g / L Kollasol SD added to improve the wetting of the textile pattern.

The liquor pick-up of the samples is defined as the percentage increase in mass by the liquor and was determined by weighing the samples before and after the finish. It was about 75% for both materials.

• 1. dunkelblauer Polyester, Warengewicht von 115 g/m², Flachgewebe
• 2. ungefärbte Baumwoll-Popeline, 115 g/m², Flachgewebe

The textile patterns used included

• 1. dark blue polyester, fabric weight of 115 g / m ² , flat fabric
• 2. undyed cotton poplin, 115 g / m ² , flat weave

The following compounds were used:
Bayhydur BL XP 2706: blocked aliphatic isocyanate available from Bayer Materials Science AG
Dynasilan 1505: 3-aminopropylmethyldiethoxysilane, available from Evonik Industries AG
Freepel 1200 BASE: paraffinized melamine derivative, available from Emerald Performance Materials
Genamin O-020: oleylamine with 2 ethylene oxide, available from Clariant SE
Geniosil GF 95: N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, available from Wacker Chemie AG
Hansa SW 3020: C ₁₆ -containing silicone wax, available from CHT R. Seitlich GmbH
Hansa ASE 6630C: Silicone macro emulsion with approx. 50% active and 0.4% nitrogen content from the company CHT R. Seitlich GmbH
Hansa SW 3020: Silicone polymer with C16 side chains, available from CHT R. Seitlich GmbH
Hansa SW 3068: Silicone polymer with C18 side chains, available from CHT R. Seitlich GmbH
Kollasol SD: Breather, available from CHT R. Seitlich GmbH
Lamethane ADH 1: adhesive, available from CHT R. Seitlich GmbH
Lamethan LB 25: membrane film, available from CHT R. Seitlich GmbH
Licowax KPS: Montan wax with acid number 30, available from Clariant SE
Licowax LP: Montan wax with acid number 122, available from Clariant SE
Lutensol AT 25: stearyl alcohol with ethylene oxide, BASF SE
Mulsifan RT 258: fatty alcohol ethoxylate, available from Zschimmer & Schwarz GmbH & Co. KG
PMX-156: OH siloxane, 80 mPas and an OH / silanol content of 2.5%, available from Xiameter
Radia 7500: cetyl stearate, Oleon NV, Belgium
Radia 7501: stearyl stearate, Oleon NV, Belgium
Sasolwax 6403: paraffin wax available from Sasol Wax GmbH, solidification temperature 63-66 ° C
Tubicoat FIX FC: blocked isophorone diisocyanate, aqueous dispersion with about 30% active content, available from CHT R. Seitlich GmbH
Tubiguard 21: fluorocarbon, available from CHT R. Seitlich GmbH
Tubicoat Fixer FA: Melamine aldehyde resin based crosslinker, available from CHT R. Seitlich GmbH

Examples:

Preparation of Silicone Polymer 1

A four-necked flask equipped with stirrer, dropping funnel, thermometer and reflux condenser was charged with 606 g of PMX-156 (OH-siloxane with a viscosity of about 80 mPas and an OH / silanol content of 2.5%) and 28.8 g of N-siloxane. Presented (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and stirred homogeneously. Subsequently, a mixture of 2.7 g of water, 0.91 g of sodium hydroxide solution (50% in water) and 0.88 g of tetrabutylphosphonium hydroxide (40% in water) was added. At 90 ° C was stirred for 30 min and then the resulting alcohol was distilled off. Thereafter, 423.29 g HANSA SW 3020 were added and stirred at 90 ° C for 3h. Subsequently, 1.42 g of lactic acid (80% in water) was added and stirred for a further 30 min. Thereafter, the temperature was raised to 140 ° C. Under vacuum 64 g volatile components were separated within 2 h. 1000 g of a slightly yellow liquid with about 0.4% of nitrogen and a viscosity of about 1000 mPas were obtained.

Production of silicone polymer 2

A four-necked flask equipped with stirrer, dropping funnel, thermometer and reflux condenser was charged with 56.4 g of 3-aminopropylmethyldiethoxysilane and heated to 75.degree. Subsequently, 11.7 g of water were added. At 85 ° C was stirred for 3 h and then the cleavage alcohol distilled off. Thereafter, 1013 g HANSA SW 3068 were added and stirred homogeneously. Subsequently, 2 g of tetrabutylphosphonium hydroxide (40% in water) were added and stirred at 90 ° C for 5 h. Subsequently, 0.33 g of lactic acid (80% in water) was added and stirred for a further 30 min. Thereafter, the temperature was raised to 140 ° C. Under vacuum 50 g volatile components were separated within 2 h. There were obtained 1000 g of a slightly yellowish solid (melting point about 30 ° C) with about 0.3% nitrogen.

Reference Example 1:

In a sufficiently dimensioned steel bucket with anchor stirrer, which was heated in with a water bath, 700 g of Radia 7501, 57.75 g Licowax KPS, 420 g of Freepel 1200 Base and 57.75 g of Genamin O-020 were submitted together. The mixture was heated to 90 ° C and stirred until the components were homogeneously dissolved in each other. Then, while stirring, a mixture of 42 g of 60% acetic acid in 2908.5 g of hot water was added slowly. After complete addition, the preemulsion thus obtained was mixed with 168 g of a 15% Lutensol AT 25 in water, circulated for 15 minutes in a homogenizer (200 bar, 80 ° C) and drained through the plate heat exchanger in a separate vessel. Then 910 g of Hansa ASE 6630C in 560 g of cold water were added. From this emulsion finishing liquors were prepared with the below concentrations and additives in soft water (pH 5.5, adjusted with acetic acid) and thus equipped the textile samples on a laboratory pad. These samples were tested for their water repellency with the spray test before and after household washes. The results are shown in Table 1 below. Table 1: polyester cotton liquor concentration 50 g / L 80g / L 50 g / L 80g / L Tubicoat FIX FC 10 g / L 16 g / L 10 g / L 16 g / L start value 70 70 70 70 1 household linen 70 70 70 70 5 household linen 70 70 70 70 10 household washes 70 70 50 70 Haptic assessment very soft soft very soft very soft

The example did not meet the required water rejections.

Reference Example 2:

60 g of Licowax KPS, 1100 g of Freepel 1200 Base and 60 g of Genamin O-020 were initially taken together in a sufficiently dimensioned steel bucket with anchor stirrer, which was heated in a water bath. The mixture was heated to 90 ° C and stirred until the components were homogeneously dissolved in each other. Then, while stirring, a mixture of 48 g of 60% acetic acid in 2772 g of hot water was added slowly. After complete addition, the preemulsion thus obtained was mixed with 120 g of a 15% Lutensol AT 25 in water, circulated for 15 minutes in a homogenizer (200 bar, 80 ° C) and drained via the plate heat exchanger in a separate vessel. From this emulsion finishing liquors were prepared with the below concentrations and additives in soft water (pH 5.5, adjusted with acetic acid) and thus equipped the textile samples on a laboratory pad. These samples were tested for their water repellency with the spray test before and after household washes. The results are listed in Table 2 below. Table 2: polyester cotton liquor concentration 50 g / L 80g / L 50 g / L 80g / L start value 50 90 70 100 1 household linen 50 70 0 70 5 household linen 50 70 0 50 10 household washes 50 50 0 0 Haptic assessment stiff stiff stiff stiff

The example did not meet the required grip requirements, since the textile character was largely lost.

Reference Example 3:

500 g Radia 7501, 56.7 g Licowax KPS, 300 g Freepel 1200 Base, 300 g Hansa SW 3068 and 56.7 g Genamin O-020 were combined in a sufficiently dimensioned steel bucket with anchor stirrer, which was heated in a water bath submitted. The mixture was heated to 90 ° C and stirred until the components were homogeneously dissolved in each other. Then, while stirring, a mixture of 33 g of 60% acetic acid in 2793.6 g of hot water was added slowly.

After complete addition, the preemulsion thus obtained was mixed with 120 g of a 15% Lutensol AT 25 in water, circulated for 15 minutes in a homogenizer (200 bar, 80 ° C) and drained via the plate heat exchanger in a separate vessel. From this emulsion finishing liquors were prepared with the below concentrations and additives in soft water (pH 5.5, adjusted with acetic acid) and thus equipped the textile samples on a laboratory pad. These samples were tested for their water repellency with the spray test before and after household washes. The results are listed in Table 3 below. Table 3: polyester cotton liquor concentration 50 g / L 80g / L 50 g / L 80g / L Tubicoat FIX FC 10 g / L 16 g / L 10 g / L 16 g / L start value 100 100 100 100 1 household linen 70 70 70 70 5 household linen 70 70 50 70 10 household washes 70 70 50 70 Haptic assessment soft soft soft soft

The example did not meet the required water rejections.

Embodiment 1

In a sufficiently dimensioned steel bucket with anchor stirrer, which was tempered in with a water bath, 500 g Sasolwax 6403, 56.7 g Licowax LP, 300 g Freepel 1200 Base, 300 g silicone polymer 2 and 42 g of Genamin O-020 were submitted together. The mixture was heated to 90 ° C and stirred until the components were homogeneously dissolved in each other. Then, while stirring, a mixture of 33 g of 60% acetic acid in 2808.3 g of hot water was added slowly. After complete addition, the preemulsion thus obtained was mixed with 120 g of a 15% Lutensol AT 25 in water, circulated for 15 minutes in a homogenizer (200 bar, 80 ° C) and drained via the plate heat exchanger in a separate vessel. From this emulsion finishing liquors were prepared with the below concentrations and additives in soft water (pH 5.5, adjusted with acetic acid) and thus equipped the textile samples on a laboratory pad. These samples were tested for their water repellency with the spray test before and after household washes. The results are shown in Table 4 below. Table 4: polyester cotton liquor concentration 50 g / L 80g / L 50 g / L 80g / L start value 100 100 100 100 1 household linen 100 100 90 90 5 household linen 90 100 70 80 10 household washes 70 90 50 70 Haptic assessment very soft soft very soft soft

The example showed sufficient water repellency with a pleasant full grip. The addition of a cross-linker further improved the washing permanence of the cotton effect (see Table 5 below). Table 5: polyester cotton liquor concentration 50 g / L 80g / L 50 g / L 80g / L Tubicoat FIX FC 10 g / L 16 g / L 10 g / L 16 g / L start value 100 100 100 100 1 household linen 100 100 90 100 5 household linen 100 100 80 90 10 household washes 90 100 50 90 Haptic assessment soft soft soft soft

By adding the cross-linking agent, the washing permanence of the effect, especially on cotton, could be further improved with slight manipulation.

Embodiment 2:

In a sufficiently dimensioned steel bucket with anchor stirrer, which was heated in a water bath, 700 g of Radia 7501, 57.68 g of Licowax KPS, 420 g of silicone polymer 2 and 57.68 g of Genamin O-020 were submitted together. The mixture was heated to 90 ° C and stirred until the components were homogeneously dissolved in each other. Then, with stirring, a mixture of 42 g of 60% acetic acid in 2908.64 g of hot water was added slowly. After complete addition, the preemulsion thus obtained was mixed with 168 g of a 15% Lutensol AT 25 in water, circulated for 15 minutes in a homogenizer (200 bar, 80 ° C) and drained through the plate heat exchanger in a separate vessel. From this emulsion finishing liquors were prepared with the below concentrations and additives in soft water (pH 5.5, adjusted with acetic acid) and thus equipped the textile samples on a laboratory pad. These samples were tested for their water repellency with the spray test before and after household washes. The results are shown in Table 6 below. Table 6: polyester cotton liquor concentration 50 g / L 80g / L 50 g / L 80g / L Tubicoat FIX FC 10 g / L 16 g / L 10 g / L 16 g / L start value 100 100 90 100 1 household linen 100 100 90 100 5 household linen 100 100 70 100 10 household washes 100 100 70 80 Haptic assessment very soft soft very soft soft

The example showed very good water-repellent effects with a full, soft feel.

Embodiment 3

700 g Radia 7501, 57.68 g Licowax KPS, 420 g silicone polymer 2 and 57.68 g Genamin O-020 were initially taken together in a sufficiently dimensioned steel bucket with anchor stirrer, which was heated in a water bath. The mixture was heated to 90 ° C and stirred until the components were homogeneously dissolved in each other. Then, with stirring, a mixture of 42 g of 60% acetic acid in 2908.64 g of hot water was added slowly. After complete addition, the preemulsion thus obtained was mixed with 168 g of a 15% Lutensol AT 25 in water, circulated for 15 minutes in a homogenizer (200 bar, 80 ° C) and drained through the plate heat exchanger in a separate vessel. In this mixture was incorporated 1470 g of Persistol HP. From this emulsion finishing liquors were prepared with the below concentrations and additives in soft water (pH 5.5, adjusted with acetic acid) and thus equipped the textile samples on a laboratory pad. These samples were tested for their water repellency with the spray test before and after household washes. The results are listed in Table 7 below. Table 7: polyester cotton liquor concentration 50 g / L 80g / L 50 g / L 80g / L Tubicoat FIX FC 10 g / L 16 g / L 10 g / L 16 g / L start value 100 100 90 100 1 household linen 100 100 80 100 5 household linen 100 100 70 90 10 household washes 100 100 50 80 Haptic assessment soft moderate soft moderate

The example showed very good water-repellent effects with a full, soft feel even at low application rates. For higher quantities, the feel slightly deteriorated.

Embodiment 4

300 g of Radia 7501, 56.7 g of Licowax KPS, 300 g of silicone polymer 2, 500 g of Freepel 1200 Base and 56.7 g of Genamin O-020 were initially taken together in a sufficiently dimensioned steel bucket with anchor stirrer which was heated in a water bath , The mixture was heated to 90 ° C and stirred until the components were homogeneously dissolved in each other. Then, while stirring, a mixture of 45 g of 60% acetic acid in 2901.6 g of hot water was added slowly. After complete addition, the mixture was circulated for 15 minutes in a homogenizer (200 bar, 80 ° C) and drained via the plate heat exchanger in a separate vessel. From this emulsion finishing liquors were prepared with the below concentrations and additives in soft water (pH 5.5, adjusted with acetic acid) and thus equipped the textile samples on a laboratory pad. These samples were tested for their water repellency with the spray test before and after household washes. The results are shown in Table 8 below. Table 8: polyester cotton liquor concentration 50 g / L 80g / L 50 g / L 80g / L Tubicoat FIX FC 10 g / L 16 g / L 10 g / L 16 g / L start value 100 100 100 100 1 household linen 100 100 90 100 5 household linen 100 100 70 90 10 household washes 100 90 50 80 Haptic assessment soft moderate moderate moderate

The example showed very good water-repellent effects on polyester with a soft feel even at low application rates. At higher quantities, the haptics deteriorated slightly. On cotton permanence and grip were slightly worse than on polyester.

Embodiment 5:

In a sufficiently dimensioned steel bucket with anchor stirrer, which was tempered in with a water bath, 1100 g paraffin type 6403, 90 g Licowax LP, 25 g Mulsifan RT 258 and 450 g silicone polymer 2 were submitted together. The mixture was heated to 90 ° C and stirred until the components were homogeneously dissolved in each other.

Then, with stirring, a mixture of 27.5 g of ammonia (25%) in 2397.5 g of hot water was added slowly. After complete addition, the preemulsion thus obtained was mixed with 120 g of a 15% Lutensol AT 25 in water, circulated for 15 minutes in a homogenizer (200 bar, 80 ° C) and drained via the plate heat exchanger in a separate vessel. From this emulsion finishing liquors were prepared with the below concentrations and additives in soft water and thus equipped the textile samples on a laboratory pad. These samples were tested for their water repellency with the spray test before and after household washes. The results are shown in Table 9 below. Table 9: polyester cotton liquor concentration 50 g / L 80g / L 50 g / L 80g / L Bayhydur BL XP 2706 8 g / L 12g / L 8 g / L 12g / L start value 100 100 100 100 1 household linen 100 100 100 100 5 household linen 100 100 80 100 10 household washes 90 100 70 90 Haptic assessment very soft soft very soft soft

The example showed very good water-repellent effects on polyester with a full, soft feel even at low application rates. Higher levels were slightly worse for cotton, which is still acceptable on cotton.

Embodiment 6:

500 g of pentaerythritol tetrastearate, 56.7 g of Licowax KPS, 300 g of silicone polymer 2, 300 g of Freepel 1200 Base and 42 g of Genamin O-020 were initially taken together in a sufficiently dimensioned steel bucket with an anchor stirrer. The mixture was heated to 90 ° C and stirred until the components were homogeneously dissolved in each other. Then, while stirring, a mixture of 33 g of 60% acetic acid in 2808.3 g of hot water was added slowly. After complete addition, the preemulsion thus obtained was mixed with 120 g of a 15% Lutensol AT 25 in water, circulated for 15 minutes in a homogenizer (200 bar, 80 ° C) and drained via the plate heat exchanger in a separate vessel. From this emulsion finishing liquors were prepared with the below concentrations and additives in soft water (pH 5.5, adjusted with acetic acid) and thus equipped the textile samples on a laboratory pad. These samples were tested for their water repellency with the spray test before and after household washes. The results are shown in Table 10 below. Table 10: polyester cotton liquor concentration 50 g / L 80g / L 50 g / L 80g / L Tubicoat FIX FC 10 g / L 16 g / L 10 g / L 16 g / L start value 100 100 100 100 1 household linen 100 100 80 100 5 household linen 100 100 70 80 10 household washes 80-90 90 70 70 Haptic assessment very soft soft very soft soft

The example showed very good water-repellent effects on polyester with a full, soft feel even at low application rates. At higher quantities, the haptics deteriorated slightly. On cotton the water repellent effect was not so pronounced.

Embodiment 7:

In a sufficiently dimensioned steel bucket with anchor stirrer, which was tempered in with a water bath, 500 g paraffin type 6403, 56.7 g Licowax LP, 300 g Freepel 1200 base, 300 g silicone polymer 1 and 42 g of Genamin O-020 were submitted together. The mixture was heated to 90 ° C and stirred until the components were homogeneously dissolved in each other. Then, while stirring, a mixture of 33 g of 60% acetic acid in 2808.3 g of hot water was added slowly. After complete addition, the preemulsion thus obtained was mixed with 120 g of a 15% Lutensol AT 25 in water, circulated for 15 minutes in a homogenizer (200 bar, 80 ° C) and drained through the plate heat exchanger in a separate vessel. From this emulsion finishing liquors were prepared with the below concentrations and additives in soft water (pH 5.5, adjusted with acetic acid) and thus equipped the textile samples on a laboratory pad. These samples were tested for their water repellency with the spray test before and after household washes. The results are shown in Table 11 below. Table 11: polyester cotton liquor concentration 50 g / L 80g / L 50 g / L 80g / L Tubicoat FIX FC 10 g / L 16 g / L 10 g / L 16 g / L start value 100 100 90 100 1 household linen 90 100 80 90 5 household linen 80 90 70 80-90 10 household washes 80 90 50 80 Haptic assessment soft soft soft soft

The example showed very good water-repellent effects on polyester with a full, soft feel. On cotton the water repellent effect was not so pronounced.

Embodiment 8:

500 g of Radia 7501, 210 g of Sasolwax 6403, 52 g of Licowax KPS, 300 g of silicone polymer 2 and 52 g of Genamin O-020 were initially taken together in a sufficiently dimensioned steel bucket with anchor stirrer, which was heated in a water bath. The mixture was heated to 90 ° C and stirred until the components were homogeneously dissolved in each other. Then, while stirring, a mixture of 34 g of 60% acetic acid in 2592 g of hot water was added slowly. After complete addition, the preemulsion thus obtained was mixed with 120 g of a 15% Lutensol AT 25 in water, circulated for 15 minutes in a homogenizer (200 bar, 80 ° C) and drained via the plate heat exchanger in a separate vessel. In this emulsion, 100 g of Tubicoat fixer FA mixed in 200 g of water. From this emulsion finishing liquors were prepared with the below concentrations and additives in soft water (pH 5.5, adjusted with acetic acid) and thus equipped the textile samples on a laboratory pad. These samples were tested for their water repellency with the spray test before and after household washes. The results are shown in Table 12 below. Table 12: polyester cotton liquor concentration 50 g / L 80g / L 50 g / L 80g / L Tubicoat FIX FC 10 g / L 16 g / L 10 g / L 16 g / L start value 90 100 90 100 1 household linen 100 100 90 100 5 household linen 100 100 70 90 10 household washes 100 100 50 80 Haptic assessment soft moderate soft moderate

The example showed very good water-repellent effects on polyester with a full, soft feel even at low application rates. For higher quantities, the haptic deteriorates slightly. The poor starting value at 50 g / L was due to emulsifiers, which could be removed by the first wash. On cotton the water repellent effect was not so pronounced.

Embodiment 9:

500 g of Radia 7501, 210 g of Sasolwax 6403, 52 g of Licowax KPS, 300 g of silicone polymer 2 and 52 g of Genamin O-020 were initially taken together in a sufficiently dimensioned steel bucket with anchor stirrer, which was heated in a water bath. The mixture was heated to 90 ° C and stirred until the components were homogeneously dissolved in each other. Then, while stirring, a mixture of 34 g of 60% acetic acid in 2892 g of hot water was added slowly. After complete addition, the preemulsion thus obtained was mixed with 120 g of a 15% Lutensol AT 25 in water, 15 minutes in a homogenizer in a circle run (200 bar, 80 ° C) and drained through the plate heat exchanger in a separate vessel. From this emulsion finishing liquors were prepared with the below concentrations and additives in soft water (pH 5.5, adjusted with acetic acid) and thus equipped the textile samples on a laboratory pad. These samples were tested for their water repellency with the spray test before and after household washes. The results are listed in Table 13 below. Table 13: polyester cotton liquor concentration 50 g / L 80g / L 50 g / L 80g / L Tubicoat FIX FC 10 g / L 16 g / L 10 g / L 16 g / L start value 80 100 100 100 1 household linen 100 100 90 100 5 household linen 100 100 70 100 10 household washes 100 100 70 80 Haptic assessment soft soft soft soft

The example showed very good water-repellent effects on polyester and cotton with a full, soft feel.

Embodiment 10:

500 g Radia 7501, 210 g Paraffin Type 6403, 52 g Licowax KPS, 300 g Silicone Polymer 2 and 52 g Genamin O-020 were initially taken together in a sufficiently dimensioned steel bucket with anchor stirrer which was heated in a water bath. The mixture was heated to 90 ° C and stirred until the components were homogeneously dissolved in each other. Then, while stirring, a mixture of 34 g of 60% acetic acid in 2592 g of hot water was added slowly. After complete addition, the preemulsion thus obtained was mixed with 120 g of a 15% Lutensol AT 25 in water, circulated for 15 minutes in a homogenizer (200 bar, 80 ° C) and drained via the plate heat exchanger in a separate vessel. 200 g of Tubicoat Fixer FA are mixed into 100 g of water in this emulsion. From this emulsion finishing liquors were prepared with the below concentrations and additives in soft water (pH 5.5, adjusted with acetic acid) and thus equipped the textile samples on a laboratory pad. These samples were tested for their water repellency with the spray test before and after household washes. The results are shown in Table 14 below. Table 14: polyester cotton liquor concentration 50 g / L 80g / L 50 g / L 80g / L Tubicoat FIX FC 10 g / L 16 g / L 10 g / L 16 g / L start value 80 100 90 100 1 household linen 100 100 80 100 5 household linen 100 100 80 100 10 household washes 100 100 70 90 Haptic assessment moderate moderate soft moderate

The example showed very good water-repellent effects on polyester with a full, soft feel even at low application rates. At higher quantities, the haptics deteriorated slightly. The poor starting value at 50 g / L was due to emulsifiers, which could be removed by the first wash. On cotton, the water-repellent effect was not as pronounced as on the synthetic fiber.

Embodiment 11:

Analogously to the preparation procedure in Example 5, the silicone polymer 2 was replaced by the silicone polymer 1 and the textile pattern finishing was carried out. The spray values obtained are shown in Table 15 below. TABLE 15 polyester cotton liquor concentration 50 g / L 80g / L 50 g / L 80g / L Bayhydur BL XP 2706 8 g / L 12g / L 8 g / L 12g / L start value 90 100 80 80 1 household linen 90 100 70 90 5 household linen 70 80 50 70 10 household washes 50 70 0 50 Haptic assessment very soft soft very soft soft

From this example it could be seen that a high alkyl density on the silicone polymer was advantageous for the water-repellent effect.

Exemplary Embodiment 12 Variation of Emulsifier Quantity

As described in Example 10, further dispersions and equipment liquors were prepared and made the changes listed in Table 16 below. These were applied to polyester materials as described above to study the influence of the amount of emulsifier. Table 16: Embodiment 10 Genamin O-020 26 g 26 g 52 g 52 g Lutensol AT 25 (15% solution) 0 g 120 g 0 g 120 g Spray before washing (50 g / L + 10 g / l Tubicoat FIX FC on polyester) * 100 90 80 Spray after 5 washes (50 g / L + 10 g / l Tubicoat FIX FC on polyester * 100 100 100 * The dispersion was not fine enough.

From this example it was easy to see that the amount of emulsifier must be chosen as low as possible in order to obtain good initial values in particular.

Embodiment 13 - Determination of Air Permeability

Textile patterns were based on their air permeability with 1 bar air pressure DIN EN ISO 9237 tested in comparison to the unfinished goods. The results obtained can be found in Table 17: Table 17: cotton polyester commodity 225 ± 5 mm / s 55 ± 5 mm / s Reference Example 2 206 ± 6 mm / s 48 ± 3 mm / s Embodiment 2 223 ± 2 mm / s 60 ± 1 mm / s Embodiment 5 235 ± 1 mm / s 65 ± 5 mm / s

The embodiments show an improvement of the air permeability over the raw material, while the reference example shows a deterioration.

Embodiment 14 - Determination of Breathability:

To check the influence of breathability, a reference pattern was first created. On a polyester sample, a thin membrane film was laminated to achieve the desired windproofness with simultaneous breathability. For this purpose, the material was preimpregnated with 5 g / l TUBIGUARD 21 by padding. Subsequently, the now preimpregnated goods on the tenter frame for 2.5 min at 105 ° C was dried. The adhesive used was LAMETHAN ADH1, which was mechanically foamed to a foam weight of 200 g / l. The foamed adhesive composition was applied to the preimpregnated textile by means of a doctor blade with a layer thickness of 0.5 mm. It was then dried at 105 ° C. for 2.5 minutes on the tenter. The breathable membrane film LAMETHAN LB 25 was laminated to the adhesive side of the textile with the aid of a press shop. Subsequently, the resulting textile / membrane composite was fixed to the tenter frame at 145 ° C for 2.5 min.

These operations described above for the reference pattern have also been used to create a textile impregnated with a water-repellent finish. For this purpose, a preimpregnation was carried out with 160 g / L of a liquor from application example 1 and 40 g / l Tubicoat FIX FC. The spray value obtained was 100. The breathability of the samples was based on ISO 15496 checked. The found Re values of the reference sample and that impregnated with Application Example 1 were identical.

By means of this example, it can be shown that no negative change in the breathability results from the finish according to the invention.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 1238215 A1 [0004]
• EP 2411575 B1 [0004]
• EP 1424433 B1 [0004]
• DE 10211549 B9 [0005, 0011]
• DE 102009014699 A1 [0006]
• DE 4222483 A1 [0007]
• DE 1231663 A1 [0008]
• US 3,032,442 A [0008]
• US 2758946A [0009]
• US 2785145 [0010]
• EP 2152957 B1 [0011]
• WO 03/078726 Al [0012]
• GB 1287745 A1 [0013]
• JP 2006-124866 A1 [0014]
• EP 1108765 B1 [0015]
• BE 569962 A1 [0016]
• DE 1594977 A1 [0016]
• DE 1570776 A1 [0016]
• DE 60124597 T2 [0016]
• EP 1035200 A2 [0017]
• DE 1135418 A1 [0058]

Cited non-patent literature

• M. Santen, U. Kallee, Chemistry for Any Weather, Greenpeace e. V., 2012, p. 5 [0002]
• H.-K. Rouette, Encyclopedia of Textile Finishing, Springer, 2000, p. W91-W95, keyword "water repellent finishing" [0003]
• C. Tomasino, Chemistry & Technology of Fabric Preparation & Finishing, pp. 158-171, webcast dated 30.04.2013, http://infohouse.p2ric.org/ref/06/05815.pdf [0004]
• DIN EN 24920 [0061]
• DIN EN ISO 6330 [0061]
• ISO 9237 [0061]
• ISO 15496 [0061]
• DIN EN ISO 9237 [0102]
• ISO 15496 [0105]

Claims (15)

Containing preparation a) 1 to 50 wt .-% silicone polymer b) 1 to 50 wt .-% wax and / or fatty acid esters c) 0 to 50 wt .-% aminoplast, urea derivative and / or melamine derivative d) 0 to 98% by weight of solvent e) 0 to 50 wt .-% crosslinker f) 0 to 5 wt .-% dispersants. Preparation according to claim 1 containing a) 2 to 20 wt .-% silicone polymer b) 2 to 20 wt .-% wax and / or fatty acid esters c) 1 to 50 wt .-%, in particular 2 to 10 wt .-% aminoplast, urea derivative and / or melamine derivative. Preparation according to claim 1 or 2, characterized in that the silicone polymer contains the following units

where m, n and o are independently integers from 1 to 100,000, for p _a , p _b and p _c of these independently each integers of 0 and 100,000 can be used, preferred are those silicone polymers for which the relationship m / 4 <n, in particular m / 2 <n, and having a nitrogen content of 0.01 to 4.0 wt .-%, more preferably between 0.1 to 1.0 wt .-%, and for the radicals R ¹ to R ^{8 are} independently selectable from the following groups: - R ¹ from the group of saturated or unsaturated, linear, branched and / or cyclic hydrocarbons, and the aryls, hydroxy or alkoxy, - R ² from the group of saturated or unsaturated, linear, branched and / or cyclic hydrocarbons and the aryls, - R ³ from the group of hydroxy, alkoxy, aryl and / or alkyl, - R ⁴ from the group of saturated or unsaturated, linear, branched and / or cyclic hydrocarbons, which may optionally be additionally functionalized by amino groups in the chain, in particular for example Alkylenaminoalkyl, Alkylenaminoalkylenaminalkyl, or arylenes, particularly preferably from alkylenes with 1 to 6 carbon atoms or Alkylenaminoalkylen each having 1 to 6 carbon atoms in the chains, - R ⁵ and R ^{6 are} independently selected from the group consisting of: hydrogen, alkyl, amide, Alkylenamin, Alkylenaminoalkyl, Alkylenaminoalkylenamin, - R ⁷ and R ⁸ are organic Radicals which may be bonded directly or indirectly via an alkylene or arylene spacer to the silicon atom, for example glycidyl, epoxide, alkyl ether, polyalkylene ether, allyl, hydroxy, trialkylsilyl, in particular trimethylsilyl, alkyl, alkoxy, aryloxy, vinyl, mercapto, phosphato. Preparation according to one of claims 1 to 3, characterized in that it contains one or more waxes and / or fatty acid esters, wherein the waxes from the group of natural, semi-synthetic and / or synthetic waxes are selected and the fatty acid esters of fatty acids and alcohols are constructed wherein the fatty acids are saturated and unsaturated, linear, branched and / or ring acids having 16 to 50 carbon atoms, preferably linear or unsaturated acids having 16 to 36 carbon atoms, and the alcohols are selected from fatty alcohols or polyhydric alcohols, wherein the fatty alcohols consist of 16 to 50 carbon atoms and one hydroxy group and are composed of saturated or unsaturated and linear, branched and / or ring hydrocarbon skeletons and the polyhydric alcohols are aliphatic hydrocarbons having at least two hydroxyl groups, which correspond to those mentioned above Fatty acids may form compounds with more than one ester group. Preparation according to one of claims 1 to 4, characterized in that it is 0.0 to 50.0 wt .-%, preferably 1.0 to 50.0 wt .-%, particularly preferably 2.0 to 10.0 wt. %, one or more aminoplasts, urea derivatives and / or melamine derivative of the following types

the radicals R ¹ to R ^{8 are} each independently selectable from the group consisting of hydrogen, saturated or unsaturated, linear, branched and / or cyclic hydrocarbons, aryls or the radicals composed of the units R - S - T and / or U - V , wherein for the units in each case the following groups are available for selection - R from alkylene or arylene, - S from oxygen atom, α, ω-dioxyalkylene, α, ω-dioxyarylene, carboxyl, carbonate or carbamate group, - T from hydrogen atoms, saturated or unsaturated, linear, branched and / or cyclic hydrocarbons or aryl group, - U of carbonyl or carbamate, - V of saturated or unsaturated, linear, branched and / or cyclic hydrocarbons or aryl group, - W of hydroxyl-functionalized or non-functionalized alkylene bridges , in particular 1,2-ethylene, 1,2-dihydroxyethylene or 1,2-dialkoxyethylene, - Z from oxygen or sulfur saturated, unsaturated, linear or branched aliphatic hydrocarbons having 8 to 50 carbon atoms, more preferably those having 16 to 30, and wherein also derived from these compounds aldehyde resins and oligomeric and polymeric Umetherungsprodukte be used with diols are. Preparation according to one of claims 1 to 5, characterized in that optionally a fixer / crosslinker from the group of the group of blocked and / or unblocked isocyanates, diisocyanates, oligoisocyanates and polyisocyanates, melamine-formaldehyde resins, urea-formaldehyde resins, epoxy-based crosslinkers, especially glycidyl-functionalized polyethylenimines / glycidylfunktionalisierten polyvinylamines . aziridine-based crosslinkers and / or di-, oligo- or polycarboxylic acids, optionally in combination with suitable catalysts, the preparation or the application finish is added. Preparation according to one of claims 1 to 6, characterized in that the preparation contains one or more solvents, preferably water. Preparation according to one of claims 1 to 7, characterized in that the preparation contains one or more dispersing aids. Preparation according to one of claims 1 to 8, characterized in that the silicone polymer has a melting point of less than 60 ° C, more preferably between 0 and 50 ° C, most preferably between 20 and 40 ° C. A preparation according to any one of claims 1 to 9, comprising at least one wax and / or fatty acid ester having a melting point greater than 60 ° C. A process for preparing a preparation according to any one of claims 1 to 10, characterized in that silicone polymer, wax and / or fatty acid ester and melamine derivative optionally present with dispersants and heated to melt, solvent possibly with additional adjuvants successively enters and finally homogenized by mechanical energy input. Use of the preparation according to the preceding claims by application of textile-technical processes, in particular by exhaust processes or forced applications such as coating, equipment by padding, printing, spray processes, monofilament application and / or dyeing. Use of the preparation according to claim 12 for the finishing of textile materials. Use of the preparation according to the preceding claims for the hydrophobic treatment of absorbent materials and surfaces. Textiles containing fibers according to one of the preceding claims.