EP1776501B1 - Method for finishing absorbent materials - Google Patents

Abstract

A process for finishing absorbent material which comprises it being (A) hydrophilicized in a first step (B) treated in a subsequent step with at least one aqueous liquor comprising (a) at least one organic polymer, (b) at least one organic or inorganic solid in particulate form other than (a), and (c) at least one emulsifier.

Description

1. (A) in einem ersten Schritt hydrophiliert,
2. (B) in einem darauf folgenden Schritt mit mindestens einer wässrigen Flotte behandelt, enthaltend
   1. (a) mindestens ein organisches Polymer,
   2. (b) mindestens einen organischen oder anorganischen Feststoff in partikulärer Form, der von (a) verschieden ist, und
   3. (c) mindestens einen Emulgator.

Process for finishing absorbent materials, characterized in that it

1. (A) hydrophilized in a first step,
2. (B) treated in a subsequent step with at least one aqueous liquor containing
   1. (a) at least one organic polymer,
   2. (B) at least one organic or inorganic solid in particulate form, which is different from (a), and
   3. (c) at least one emulsifier.

Textile equipment is a field of growing economic importance. It is particularly interesting to equip textiles with water and dirt repellent. Modern measures make use of the so-called lotus effect® in some cases and give textiles a water and dirt repellent behavior by applying a rough surface.

WO 96/04123 describes self-cleaning surfaces that have an artificial surface structure, which has elevations and depressions, wherein the structure is characterized in particular by their structural parameters. The structures are produced, for example, by embossing a structure onto a thermoplastically deformable hydrophobic material or by applying Teflon powder to a surface treated with UHU®. Out US 3,354,022 Similarly prepared water-repellent surfaces are known.

Out EP-A 0 933 388 For example, methods for the production of structured surfaces are known in which a negative mold is first produced by photolithography, this mold is used to emboss a plastic film and then the hydrophobicized embossed plastic film is fluorinated with alkylsilanes.

However, the methods described above are unsuitable for the dirt and water repellent finishing of textiles.

In WO 02/84013 It is proposed to hydrophobicize fibers, for example of polyester, by passing them through a Decalin bath heated to 80 ° C. in which 1% hydrophobic silica gel Aerosil 8200 has been suspended.

In WO 02/84016 It is proposed to hydrophobicize polyester fabric by pulling it through a bath of heated to 50 ° C DMSO (dimethyl sulfoxide), in which 1% hydrophobic silica gel Aeroperl 8200 was suspended.

Both methods of hydrophobing have in common that the solvent is chosen so that the fibers are partially dissolved. For this it is necessary to use large amounts of organic solvent, which is undesirable in many cases. In addition, by treatment with organic solvents, the mechanical strength of the fibers can be adversely affected.

In WO 01/75216 It is proposed to provide textile fibers and fabrics with water and dirt repellent by providing them with a two-component layer, one of which is a dispersant and the other, for example, a colloid. Through the in WO 01/75216 In the finishing process described, finishing layers are prepared in which the colloids are anisotropically distributed in the dispersant, whereby accumulation of the colloids is observed at the interface between the finish layer and the surrounding surface. The process uses such equipment fleets containing up to 5 g / l Aerosil 812 S.

Through the in WO 01/75216 however, textiles finished in many cases have unsatisfactory mechanical strength in many cases.

WO 01/83662 describes a process for improving soil release from and / or reducing soil repellency on textile surfaces by treating the surface with particles having a particle size of 5 to 500 nm.

In addition, it is observed that antisoiling-treated absorbent materials and in particular textiles of the prior art in many cases have a high water absorption, detectable for example by Bundesmann, which is undesirable for many applications.

It was therefore an object to provide a method for equipping absorbent materials available, which does not have the above-mentioned disadvantages and at the same time has very good water and dirt repellent effect. It was also the task of providing dirt and water-repellent textiles.

Accordingly, the method defined above was found.

Absorbent materials are for the purposes of the present invention, for example, paper, cardboard, wood, building materials such as brick, concrete, natural stone, sandstone and sand-lime brick, furthermore leather imitations and leather and preferably textile materials. By way of example, textile materials include fibers, rovings, yarn, twine on the one hand, and textile fabrics on the other hand, such as, for example, woven goods, knits, nonwovens and clothing. Particularly preferred are textile fabrics which can be used for example for the production of textile in the outdoor area. Examples include sails, umbrellas and umbrellas, tarpaulins, tarpaulins, tablecloths, awning fabrics, fabrics for watercraft such as sailing and motor boats and furniture covers for example for chairs, swings or benches called.

Absorbent materials in the sense of the present invention can consist of different substances. May include natural fibers and synthetic fibers and mixed fibers. Among natural fibers are, for example, silk, wool and more preferably called cotton. Synthetic fibers include, by way of example, polyamide, polyester, polypropylene, polyacrylonitrile and polyethylene terephthalate. Also modified natural fibers can be coated by the process according to the invention, for example cellulose acetate.

1. (A) in einem ersten Schritt hydrophiliert,
2. (B) in einem darauf folgenden Schritt mit mindestens einer wässrigen Flotte behandelt, enthaltend
   1. (a) mindestens ein organisches Polymer,
   2. (b) mindestens einen organischen oder anorganischen Feststoff in partikulärer Form, der von (a) verschieden ist, und
   3. (c) mindestens einen Emulgator.

The process of the invention comprises two steps of using absorbent material

1. (A) hydrophilized in a first step,
2. (B) treated in a subsequent step with at least one aqueous liquor containing
   1. (a) at least one organic polymer,
   2. (B) at least one organic or inorganic solid in particulate form, which is different from (a), and
   3. (c) at least one emulsifier.

In certain embodiments of the present invention, further optional steps may be performed.

In step (A), absorbent material is hydrophilized. Hydrophilizing in the context of the present invention means treating the surface of absorbent material so that it is wettable by water immediately after step (A). For example, the wettability of the surface of absorbent material pretreated after step (A) can be demonstrated to be effective at Normal conditions have a non-measurable contact angle with water. Preferably, water on surfaces hydrophilized according to step (A) does not form droplets visible to the naked eye, but spreads to form a film.

In a preferred embodiment of the present invention, hydrophilizing and smoothing in step (A). Smoothing is understood in the context of the present invention that protruding fuzz, hairs and other material-related unevenness of absorbent materials are removed or glued to the actual surface that they are not visible to the naked eye of the compensation level.

Step (A) may for example be accomplished by adding absorbent material in dry or preferably water wetted form to one or more articles having a temperature of at least 450 ° C, preferably of at least 500 ° C, more preferably of at least 750 ° C or contacted with one or more flames. As the upper temperature limit for contacting absorbent material with one or more articles having a temperature of at least 450 ° C are 1300 ° C, preferably 900 ° C.

For example, in one embodiment of the present invention, one or more articles having a temperature of at least 450 ° C may be one or more objects having a planar or curved surface, such as one or more rollers, one or more punches, or one or more several plates.

The inventively used in step (A) articles with a temperature of at least 450 ° C are preferably designed so that the surface, which is contacted with absorbent material made of metal or an alloy, preferably made of steel and more preferably of copper or a copper-containing alloy. Very particular preference is given to at least one inventively used in step (A) object is a glowing copper plate.

In one embodiment of the present invention, absorbent material is contacted with one or more articles having a temperature of at least 450 ° C by passing absorbent material over the article (s) which may stand still or, in the case of rolls, rotate. Preferably leads absorbent material having a rate of goods ranging from 20 to 300 m / min, preferably 30 to 200 m / min, over one or more articles having a temperature of at least 450 ° C.

In another embodiment of the present invention, absorbent material is contacted with one or more flames, for example with one or more gas flames, preferably with one or more non-luminous gas flames, the composition of the gas or gas mixture in question not being critical per se. The composition of the gas in question is preferably constant during the performance of step (A). Preferably, the temperature of one or more flames is in the range of 1100 to 1500, preferably 1200 to 1300 ° C.

As a rate of goods, for example, up to 250 m / min are suitable, preferably 30 to 200 m / min.

One can contact absorbent material once or several times with one or more flames.

In another embodiment of step (A), one can proceed by passing absorbent material past one or more hot ceramic bodies having a temperature in the range of 800 ° C to 1300 ° C. On such temperatures heated ceramic body usually radiate z. B. from IR radiation. Suitable apparatuses in which absorbent substrates, and in particular textile, can pass hot ceramic bodies, are commercially available.

Of course, one may combine several of the above-described embodiments of step (A). It is also possible to repeat one or more embodiments, for example by passing absorbent material over two rotating rolls at a temperature of 500 ° C.

The absorbent material to be treated can be contacted on both sides or, preferably, on one side with one or more objects having a temperature of at least 450 ° or with one or more flames, if it is configured flat.

Following the above-described embodiments of step (A), after step (A) and in particular after contacting with one or more Treat absorbent materials, such as baths, in the form of water-cooled rollers or in the form of water vapor, with articles at a temperature of at least 450 ° C or with one or more flames, thus preventing sparks and burning of absorbent material.

Following the above-described embodiments of step (A), one may treat with one or more fixed or rotating brushes.

In another embodiment of the present invention, it is preferred to treat absorbent material in step (A) with at least one melt or preferably dispersion of at least one (co) polymer selected from anionic polyurethanes, copolymers of (meth) acrylic acid C ₁ - C ₁₀ -alkyl esters and copolymers of (meth) acrylic acid C ₁ -C ₁₀ -alkyl esters with at least one ethylenically unsaturated compound.

Dispersions preferably used in step (A) are preferably aqueous dispersions, for example having a solids content in the range from 30 to 60% by weight, preferably 40 to 55% by weight.

In one embodiment of the present invention, the aqueous dispersion of (co) polymer preferably used in step (A) has a dynamic viscosity in the range of 50 to 500 mPa · s, preferably 70 to 290 mPa · s, measured at 25 ° C.

Anionic polyurethanes for the purposes of the present invention are obtainable, for example, by reacting one or more aromatic or preferably aliphatic or cycloaliphatic diisocyanates or diisocyanates with a polyester diol or several polyester diols.

Suitable aromatic diisocyanates are, for example, 2,4-tolylene diisocyanate and 2,4'-diphenylmethane diisocyanate (2,4'-MDI). Suitable aliphatic diisocyanates are, for example, hexamethylene diisocyanate and dodecamethylene diisocyanate.

Suitable cycloaliphatic diisocyanates are, for example, 2,4'-methylene-bis (cyclohexyl) diisocyanate, 4-methylcyclohexane-1,3-diisocyanate (H-TDI), isophorone diisocyanate (IPDI) and bis-4,4'-cyclohexylmethylene diisocyanate.

Suitable polyester polyols are obtainable by polycondensation of one or more preferably aliphatic or cycloaliphatic diols or diols and one or more aromatic or preferably aliphatic dicarboxylic acids or dicarboxylic acids.

Suitable aliphatic diols are, for example: ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,12-dodecanediol, propylene glycol (1,2-propanediol), butylene glycol (1,2-butanediol ), Neopentyl glycol.

Suitable cycloaliphatic diols are, for example: cis-1,4-cyclohexanedimethanol, trans-1,4-cyclohexanedimethanol, cis-1,3-cyclohexanedimethanol, trans-1,3-cyclohexanedimethanol.

Suitable aromatic dicarboxylic acids are, for example, terephthalic acid, phthalic acid and especially isophthalic acid.

Examples of suitable aliphatic dicarboxylic acids are succinic acid, glutaric acid and, in particular, adipic acid.

Very particularly suitable polyester polyols are obtainable, for example, by polycondensation of at least two different aliphatic or cycloaliphatic diols with at least one aromatic or preferably aliphatic dicarboxylic acid, for example from isophthalic acid, adipic acid and 1,4-cyclohexanedimethanol or from adipic acid, neopentyl glycol and 1,6-hexanediol.

In one embodiment of the present invention, particularly suitable polyester polyols have an acid number in the range from 10 to 200 mg KOH / g polyester polyol, determined according to DIN 53402.

In another embodiment of the present invention, particularly suitable polyester polyols have a hydroxyl number in the range from 10 to 200 mg KOH / g polyester polyol, determined according to DIN 53240.

• 40 bis 95 Gew.-%, bevorzugt 50 bis 90 Gew.-% einen oder mehrere (Meth)acrylsäure-C₁-C₁₀-Alkylester, bevorzugt (Meth)acrylsäure-C₄-C₈-Alkylester, beispielsweise (Meth)acrylsäuremethylester, (Meth)acrylsäureethylester, (Meth)acrylsäure-n-propylester, (Meth)acrylsäure-iso-propylester, (Meth)acrylsäure-n-decylester, bevorzugt (Meth)acrylsäure-n-butylester, (Meth)acrylsäure-iso-butylester, (Meth)acrylsäuren-hexylester, (Meth)acrylsäure-n-octylester, (Meth)acrylsäure-2-ethylhexylester, besonders bevorzugt (Meth)acrylsäure-n-butylester und (Meth)acrylsäure-2-ethylhexylester,
• 0,1 bis 10 Gew.-%, bevorzugt 1 bis 5 Gew.-% einer oder mehrerer ethylenisch ungesättigten Carbonsäure bzw. Carbonsäuren, beispielsweise Methacrylsäure oder insbesondere Acrylsäure,
• 0 bis 50 Gew.-%, bevorzugt 1 bis 40 Gew.-% mindestens einer weiteren ethylenisch ungesättigten Verbindung, gewählt aus vinylaromatischen Verbindungen wie beispielsweise α-Methylstyrol, para-Methylstyrol, para-n-Butylstyrol und insbesondere Styrol, (Meth)acrylnitril, N-Methylol(meth)acrylamid, Vinylestern von aliphatischen Carbonsäuren, beispielsweise Vinylpropionat und insbesondere Vinylacetat.

(Co) polymers of C ₁ -C ₁₀ (meth) acrylic acid esters and copolymers of (meth) acrylic C ₁ -C ₁₀ alkyl ethers with at least one ethylenically unsaturated compound are, for example, block copolymers and preferably random copolymers copolymerized as comonomers contain:

• 40 to 95 wt .-%, preferably 50 to 90 wt .-% one or more (meth) acrylic acid-C ₁ -C ₁₀ -alkyl, preferably (meth) acrylic acid-C ₄ -C ₈ alkyl esters, for example, (meth) methyl acrylate, (meth) acrylic acid ethyl ester, (meth) acrylic acid n-propyl ester, (meth) acrylic acid iso-propyl ester, (meth) acrylic acid n-decyl ester, preferably (meth) acrylic acid n-butyl ester, (meth) acrylic acid iso butyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid n-octyl ester, (meth) acrylic acid 2-ethylhexyl ester, particularly preferably (meth) acrylic acid n-butyl ester and (meth) acrylic acid 2-ethylhexyl ester,
• 0.1 to 10% by weight, preferably 1 to 5% by weight, of one or more ethylenically unsaturated carboxylic acids or carboxylic acids, for example methacrylic acid or, in particular, acrylic acid,
• 0 to 50 wt .-%, preferably 1 to 40 wt .-% of at least one further ethylenically unsaturated compound selected from vinylaromatic compounds such as α-methylstyrene, para-methylstyrene, para-n-butylstyrene and in particular styrene, (meth) acrylonitrile , N-methylol (meth) acrylamide, vinyl esters of aliphatic carboxylic acids, for example vinyl propionate and in particular vinyl acetate.

In a preferred embodiment of the present invention, the copolymer in step (A) is composed of
40 to 95 wt .-%, preferably 50 to 90 wt .-% of at least one (meth) acrylic acid C ₁ -C ₁₀ alkyl ester, preferably ethyl acrylate, n-butyl acrylate and / or 2-ethylhexyl acrylate, 0.1 to 10 wt .-%, preferably 1 to 5 wt .-% of methacrylic acid or acrylic acid in particular, and
0 to 50 wt .-%, preferably 1 to 40 wt .-% of at least one ethylenically unsaturated compound, in particular styrene, vinyl acetate or (meth) acrylonitrile.

In one embodiment of the present invention, a (co) polymer is a self-crosslinking (co) polymer, for example of one or more (meth) acrylic acid C ₁ -C ₁₀ -alkyl esters with acrylic acid and N-methylol (meth) acrylamide ,

In a specific embodiment of the present invention, the absorbent material in step (A) is treated with a mixture of at least two (co) polymers containing from 40 to 99.9% by weight of a thermally crosslinkable (co) polymer of (meth) acrylic acid. C ₁ -C ₁₀ -alkyl esters with (meth) acrylic acid and optionally further ethylenically unsaturated compounds, and 0.1 to 60 wt .-% of anionic polyurethane, wherein in wt .-% in each case on the total weight of the respective melt or on the Solids content of the relevant dispersion are related.

For contacting with at least one melt or, preferably, dispersion of at least one (co) polymer in step (A), it is possible to use, for example, techniques known per se for coating or finishing paper and in particular textile, preferably printing, application and, in particular, doctoring.

In one embodiment of the present invention, for carrying out step (A), at least one (co) polymer in a layer thickness of 10 to 500 μm, preferably 50 to 300 μm, is applied to absorbent material and, in particular, doctored.

In one embodiment of the present invention, to carry out step (A), at least one (co) polymer is applied to absorbent material in the range from 5 to 100 g / m ² , preferably from 8 to 60 g / m ² .

If it is desired to treat in step (A) with at least one (co) polymer in the form of a dispersion which may be present, for example, as an emulsion or suspension, such a dispersion may contain further ingredients, for example defoamers, biocides, thickeners, buffers, binders and emulsifiers.

Defoamers which may be mentioned by way of example are: up to 50 times alkoxylated, preferably ethoxylated or propoxylated polysiloxanes having 3 to 10 silicon atoms per molecule, in particular alkoxylated 2- (3-hydroxypropyl) heptamethyltrisiloxanes which have up to 50 ethylene oxide and / or propylene oxide units per mole and are preferred a block of 7 to 20, preferably 7 to 12, ethylene oxide units and a block of 2 to 20, preferably 2 to 10 propylene oxide units.

As biocides, fungicides are exemplified, in particular 1,2-benzisothiazolin-3-one (commercially available as Proxel brands from Avecia Lim.) And its alkali metal salts, glutardialdehyde, tetramethylolacetylenediurea, 2-methoxycarbonylaminobenzimidazole.

mit Molekulargewichten M_w im Bereich von 100.000 bis 200.000 g/mol, in denen R⁷ für Methyl oder vorzugsweise Wasserstoff steht. Als Beispiele für Verdicker natürlichen Ursprungs seien genannt: Agar-Agar, Carrageen, modifizierte Stärke und modifizierte Cellulose.As thickeners thickeners of natural or synthetic origin may be mentioned. Suitable synthetic thickeners are poly (meth) acrylic compounds, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes, in particular copolymers with 85 to 95% by weight of acrylic acid, 4 to 15% by weight of acrylamide and about 0.01 to 1% by weight. % of the (meth) acrylamide derivative of the formula V

with molecular weights M _w in the range of 100,000 to 200,000 g / mol, in which R ^{7 is} methyl or preferably hydrogen. Examples of thickeners of natural origin include: agar-agar, carrageenan, modified starch and modified cellulose.

Examples of buffers include, for example, ammonia / ammonium halide buffer, acetic acid / acetate buffer and citric acid / citrate buffer.

Examples of emulsifiers which may be mentioned are mono- to 50-fold alkoxylated, in particular ethoxylated, nC ₁₀ -C ₃₀ -alkanols and mono- to 50-times alkoxylated, in particular ethoxylated, alkylphenols.

Examples of binders which may be mentioned are melamine-formaldehyde condensation products, for example melamine with preferably up to 6 equivalents of formaldehyde, and urea-glyoxal-formaldehyde condensation products of glyoxal with urea and 2 equivalents of formaldehyde.

In one embodiment of the present invention, in addition to binders, one or more crosslinking catalysts may be added as an ingredient, for example Zn (NO ₃ ) ₂ or MgCl ₂ , for example in the form of their hydrates, or NH ₄ Cl

In one embodiment of the present invention, the total amount of the other ingredients mentioned above is in the range of 0.5 to 20% by weight to melt used in step (A) or preferably dispersion, preferably 1 to 10 wt.%.

Following the treatment of absorbent material with at least one melt or preferably dispersion of at least one (co) polymer in step (A), it is possible to thermally treat, for example, over a period of 10 seconds to 60 minutes, preferably 0.5 minutes to thermally treat at temperatures in the range of 50 to 300 ° C, preferably 100 to 160 ° C, more preferably 110 to 130 ° C for 7 minutes. Polyamide, polyester, polyvinyl chloride, modified polyester, polyester blend fabrics, polyamide blends, polyacrylonitrile, cotton are treated thermally advantageous at temperatures in the range of 130 to 250 ° C. Polypropylene fabric preferably between 80 and 130 ° C, preferably 110 and 130 ° C. In this case, the temperature is generally to be understood as meaning the temperature of the medium, for example air, which surrounds the flexible substrate to be treated.

In a special variant you combine two steps (A). For example, it is possible first to contact absorbent material with one or more articles having a temperature of at least 450 ° C., or with one or more flames, and then with at least one melt or preferably dispersion of at least one (co) polymer selected from anionic polyurethanes, copolymers of (meth) acrylic acid C ₁ -C ₁₀ -alkyl esters and copolymers of (meth) acrylic acid C ₁ -C ₁₀ -alkyl esters with at least one ethylenically unsaturated compound. It is also possible to use absorbent material first with at least one melt or preferably dispersion of at least one (co) polymer selected from anionic polyurethanes, copolymers of (meth) acrylic acid C ₁ -C ₁₀ -alkyl esters and copolymers of (meth) acrylic acid C ₁ -C ₁₀ -alkyl esters with at least one ethylenically unsaturated compound, and then contact with one or more objects having a temperature of at least 450 ° C or with one or more flames.

Hereinafter, absorbent material treated after step (A) is also referred to as pretreated absorbent material.

1. (a) mindestens ein organisches Polymer,
2. (b) mindestens einen organischen oder anorganischen Feststoff in partikulärer Form, und
3. (c) mindestens einen Emulgator.

To carry out the process according to the invention, the procedure further comprises treating pretreated absorbent material in step (B) following step (A) with at least one aqueous liquor containing

1. (a) at least one organic polymer,
2. (b) at least one organic or inorganic solid in particulate form, and
3. (c) at least one emulsifier.

For the purposes of the present invention, aqueous liquors are to be understood as meaning those liquors which, based on the proportions which are liquid at room temperature, may contain at least 5% by weight of water. Preferably, aqueous liquors contain at least 25% by weight of water, more preferably at least 50% by weight and most preferably at least 75% by weight. The maximum water content, based on components which are liquid at room temperature, is 100% by weight, preferably 97% by weight, particularly preferably 95% by weight.

Aqueous liquors used in accordance with the invention may contain, in addition to water, organic solvents, for example methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, acetic acid, n-butanol, isobutanol, n-butanol. Hexanol and isomers, n-octanol and isomers, n-dodecanol and isomers. Organic solvents may constitute from 0.2 to 50% by weight, preferably from 0.5 to 35% by weight, of the aqueous liquor used according to the invention. Aqueous liquors with a water content of 100% by weight, based on portions which are liquid at room temperature, accordingly contain no organic solvents.

At least one of the liquors used in the process according to the invention contains at least one organic polymer (a). Organic polymers (a) can serve as binders. The effect of a binder may, for example, be such that the organic polymer (a) forms a film and bonds the particles together and to the absorbent and preferably textile material to be coated.

In one embodiment of the present invention, at least one organic polymer (a) is a polymer or copolymer of ethylenically unsaturated hydrophobic monomers having a solubility in water of less than 1 g / l, determined at 25 ° C. In copolymers, hydrophobic monomers constitute at least 50% by weight, preferably at least 75% by weight of the copolymer.

Preferred monomers are selected from the groups of
C ₂ -C ₂₄ -olefins, in particular α-olefins having 2 to 24 carbon atoms, for example ethylene, propylene, 1-butene, isobutene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene or 1-octadecene;
Vinylaromatics, for example styrene, α-methylstyrene, cis-stilbene, trans-stilbene, diolefins such as 1,3-butadiene, cyclopentadiene, chloroprene or isoprene, C ₅ -C ₁₈ -cycloolefins such as cyclopentene, cyclohexene, norbornene, dimeric cyclopentadiene,
Vinyl esters of linear or branched C ₁ -C ₂₀ -alkanecarboxylic acids, such as, for example, vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl n-hexanoate, vinyl n-octanoate, vinyl laurate and vinyl stearate,
(Meth) acrylic esters of C ₁ -C ₂₀ -alcohols, for example methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate), tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-eicosyl (meth) acrylate
and most preferably from the groups of the halogenated monomers and the monomers with siloxane groups.

Halogenated monomers include chlorinated olefins such as vinyl chloride and vinylidene chloride.

Very particularly preferred halogenated monomers are fluorine-containing olefins such as, for example, vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropylene, vinyl esters of fluorinated or perfluorinated C ₃ -C ₁₁ -carboxylic acids, such as, for example, in US Pat US 2,592,069 and US 2,732,370 describe (meth) acrylic esters of fluorinated or perfluorinated alcohols, such as, for example, fluorinated or perfluorinated C ₃ -C ₁₄ -alkyl alcohols, for example (meth) acrylate esters of HO-CH ₂ -CH ₂ -CF ₃ , HO-CH ₂ -CH ₂ -C ₂ F ₅ , HO-CH ₂ -CH ₂ -nC ₃ F ₇ , HO-CH ₂ -CH ₂ -iso-C ₃ F ₇ , HO-CH ₂ -CH ₂ -nC ₄ F ₉ , HO-CH ₂ -CH ₂ -nC ₆ F ₁₃ , HO-CH ₂ -CH ₂ -nC ₈ F ₁₇ , HO-CH ₂ -CH ₂ -nC ₁₀ F ₂₁ , HO-CH ₂ -CH ₂ -nC ₁₂ F ₂₅ , described for example in US 2,642,416 . US 3,239,557 . BR 1,118,007 . US 3,462,296 ,

in denen die Variablen wie folgt definiert sind:

R⁴

Wasserstoff, CH₃, C₂H₅,

R⁵

CH₃, C₂H₅,

x

eine ganze Zahl im Bereich von 4 bis 12, ganz besonders bevorzugt 6 bis 8

y

eine ganze Zahl im Bereich von 1 bis 11, bevorzugt 1 bis 6,

oder Glycidyl(meth)acrylat mit Vinylestern von fluorierten Carbonsäuren sind geeignet.Also copolymers of, for example, glycidyl (meth) acrylate with esters of the formula III

where the variables are defined as follows:

R ⁴

Hydrogen, CH ₃ , C ₂ H ₅ ,

R ⁵

CH ₃ , C ₂ H ₅ ,

x

an integer in the range of 4 to 12, most preferably 6 to 8

y

an integer in the range of 1 to 11, preferably 1 to 6,

or glycidyl (meth) acrylate with vinyl esters of fluorinated carboxylic acids are suitable.

Further suitable copolymers are copolymers of (meth) acrylic acid esters of fluorinated or perfluorinated C ₃ -C ₁₂ -alkyl alcohols, for example HO-CH ₂ -CH ₂ -CF ₃ , HO-CH ₂ -CH ₂ -C ₂ F ₅ , HO-CH ₂ -CH ₂ -nC ₃ F ₇ , HO-CH ₂ -CH ₂ -iso-C ₃ F ₇ , HO-CH ₂ -CH ₂ -nC ₄ F ₉ , HO-CH ₂ -CH ₂ -nC ₅ F ₁₁ , HO-CH ₂ -CH ₂ -nC ₆ F ₁₃ , HO-CH ₂ -CH ₂ -nC ₇ F ₁₅ ; with (meth) acrylic acid esters of non-halogenated C ₁ -C ₂₀ -alcohols, for example methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, n-propyl (meth) acrylate, 2-ethylhexyl (meth ) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-eicosyl (meth) acrylate.

An overview of suitable fluorinated polymers and copolymers can be found for example in Lewin, M., et al., Chemical Processing of Fibers and Fabrics, Part B, Volume 2, Marcel Dekker, New York (1984), pp. 172 ff., And pp. 178-182 ,

Further suitable fluorinated polymers are, for example, in DE 199 120 810 disclosed.

genannt, in denen die Variablen wie folgt definiert sind:

• R⁶ ist gewählt aus C₁-C₁₈-Alkyl, beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, iso-Heptyl, n-Octyl, n-Nonyl, n-Decyl, n-Dodecyl, n-Tetradecyl, n-Hexadecyl, n-Octadecyl; bevorzugt C₁-C₆-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl und ganz besonders Methyl.
• C₆-C₁₄-Aryl, beispielsweise Phenyl, 1-Naphthyl, 2-Naphthyl, 1-Anthryl, 2-Anthryl, 9-Anthryl, 1-Phenanthryl, 2-Phenanthryl, 3-Phenanthryl, 4-Phenanthryl und 9-Phenanthryl, bevorzugt Phenyl, 1-Naphthyl und 2-Naphthyl, besonders bevorzugt Phenyl
• C₃-C₁₂-Cycloalkyl, beispielsweise Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclooctyl, Cyclononyl, Cyclodecyl, Cycloundecyl und Cyclododecyl; bevorzugt sind Cyclopentyl, Cyclohexyl und Cycloheptyl oder Si(CH₃)₃.

From the group of olefins with siloxane groups are olefins of the general formulas IV a to IV c

in which the variables are defined as follows:

• R ⁶ is selected from C ₁ -C ₁₈ -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isobutyl Pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl; preferably C ₁ -C ₆ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, more preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso-propyl , n-butyl, iso-butyl, sec-butyl and tert-butyl and most especially methyl.
• C ₆ -C ₁₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , preferably phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl
• C ₃ -C ₁₂ cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl or Si (CH ₃ ) ₃ .

a is an integer in the range of 2 to 10,000, especially up to 100.

b is an integer in the range of 0 to 6, especially 1 to 2;

Furthermore, suitable organic polymers are (a): polyethers such as, for example, polyethylene glycol, polypropylene glycol, polybutylene glycols, polytetrahydrofuran; Polycaprolactone, polycarbonates, polyvinyl butyral, partially aromatic polyesters of aliphatic or aromatic dicarboxylic acids and / or aliphatic or aromatic dialcohols, e.g. Polyester, composed of aliphatic dialcohols having 2 to 18 carbon atoms such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol or bisphenol A, and aliphatic dicarboxylic acids with 3 to 18 C atoms such as succinic acid, glutaric acid, adipic acid and α, ω-decanedicarboxylic acid; Polyester, composed of terephthalic acid and aliphatic dialcohols having 2 to 18 carbon atoms such as ethylene glycol, propanediol, 1,4-butanediol, 1,6-hexanediol or 1,8-octanediol.

The abovementioned polyesters can be terminated, for example, with monoalcohols, for example 4 to 12 C atoms, for example n-butanol, n-hexanol, n-octanol, n-decanol or n-dodecanol.

The abovementioned polyesters may be terminated, for example, with monocarboxylic acids such as, for example, stearic acid.

Other suitable polymers (a) are melamine-formaldehyde resins, urea-formaldehyde resins, N, N-dimethylol-4,5-dihydroxyethylenhamstoffe, which may be etherified with C ₁ -C ₅ alcohols.

The molecular weight of the organic polymer or polymers (a) can be chosen within wide ranges. The weight average molecular weight M _w may range from 1000 to 10,000,000 g / mol, preferably from 2,500 to 5,000,000 g / mol, determined by at least one of the following methods: light scattering, gel permeation chromatography (GPC), viscometry , If one uses an organic polymer from the group of polyolefins, for example polyethylene, polypropylene or polyisobutene and copolymers of ethylene with propylene, butylene or 1-hexene, the molecular weight is advantageously in the range of 30,000 to 5,000,000 g / mol.

The breadth of the molecular weight distribution is not critical per se and can range from 1.1 to 20. It is usually in the range of 2 to 10.

In one embodiment of the present invention, the proportion of or of the above-described organic polymers (a) may be at least 0.1 g / l of the aqueous liquor, preferably at least 1 g / l and more preferably at least 10 g / l. The maximum proportion is, for example, 500 g / l, preferably 250 g / l and particularly preferably 100 g / l.

In one embodiment of the present invention, the organic polymer or polymers (a) is not soluble in the aqueous liquor, and in the context of the present invention, insoluble in the context of organic polymers means that less than 1 g / l is soluble in the liquor at room temperature are, preferably less than 0.1 g / l.

In one embodiment of the present invention, at least two different organic polymers (a) are used.

In one embodiment of the present invention, at least one organic polymer (a) may be present in the form of particles having an average particle diameter of 0.1 to 50 μm, preferably 0.5 to 30 μm and particularly preferably up to 20 μm (median value, number average).

At least one of the aqueous liquors used in the process according to the invention contains an organic or inorganic solid (b) in particulate form which is different from the organic polymer (s) described above, for example in an amount of at least 5.5 g / l, preferably at least 7 g / l, more preferably at least 10 g / l. The maximum proportion can be about 150 g / l. Solid (b) may be inorganic or organic in nature, preferably inorganic. The organic or inorganic solid (b) is preferably hydrophobic.

Examples of suitable materials are polyethylene, polypropylene, polyisobutylene and polystyrene and copolymers thereof with each other or with one or more other olefins such as styrene, methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, maleic anhydride or N-methylmaleimide , A preferred polyethylene or polypropylene, for example, in EP-A 0 761 696 described.

Particularly suitable materials are inorganic materials, in particular solid inorganic oxides, carbonates, phosphates, silicates or sulfates of groups 3 to 14 of the Periodic Table of the Elements, for example calcium oxide, silicon dioxide or aluminum oxide, calcium carbonate, calcium sulfate or calcium silicate, with aluminum oxide and silicon dioxide being preferred. Particularly preferred is silica in its modification as silica gel. Very particular preference is given to pyrogenic silica gels. Solid inorganic oxides can be thermally rendered hydrophobic by heating to 400 to 800 ° C or preferably by physisorbed or chemisorbed organic or organometallic compounds. For this purpose, particles are reacted before the coating step, for example, with organometallic compounds which contain at least one functional group, for example alkyllithium compounds such as methyllithium, n-butylithium or n-hexyllithium; or silanes such as hexamethyldisilazane, octyltrimethoxysilane and in particular halogenated silanes such as trimethylchlorosilane or dichlorodimethylsilane.

In one embodiment of the present invention, a mixture of hydrophobized solid inorganic oxide with corresponding non-hydrophobic inorganic oxide is used, for example in proportions by weight of 100: 0 to 0: 100, preferably 99: 1 to 60: 40, particularly preferably 99: 1 to 80 : 20.

Hydrophobic in the context of the hydrophobic solid (s) in particulate form is understood to mean that its solubility in water is below 1 g / l, preferably below 0.3 g / l, determined at room temperature.

Inorganic solids may preferably be porous in nature. The porous structure is best characterized by the BET surface area, measured according to DIN 66131. Inorganic solids used may preferably have a BET surface area in the range from 5 to 1000 m ² / g, preferably from 10 to 800 m ² / g and particularly preferably from 20 to 500 m ² / g.

In one embodiment of the present invention, at least one of the hydrophobic solids is in particulate form. The mean particle diameter (median value, number average) is at least 1 nm, preferably at least 3 nm and particularly preferably at least 6 nm. The maximum particle diameter (median value, number average) is 1000 nm, preferably 350 nm and particularly preferably 100 nm Measurement of the particle diameter can be used in common methods such as transmission electron microscopy.

The weight ratio of organic polymer (a) to organic or inorganic solid (b) in particulate form is generally 9: 1 to 1: 9, preferably 4: 1 to 1: 4 and more preferably 7: 3 to 4: 6.

In one embodiment of the present invention, at least one of the organic or inorganic solids (b) is present in the form of predominantly spherical particles, which should comprise those particulate solids of which at least 75% by weight, preferably at least 90% by weight. be present in spherical form and other particles may be in granular form.

In one embodiment of the present invention, at least one of the organic or inorganic solids (b) may form aggregates and / or agglomerates in particulate form. In the presence of one or more organic or inorganic solids (b) in the form of aggregates and / or agglomerates, which may consist of 2 to several thousand primary particles and may in turn have spherical shape, the information on the shape and size of the particles refer to the primary particles ,

At least one liquor used in the process according to the invention comprises at least one emulsifier (c) selected, for example, from the group of ionic and nonionic emulsifiers.

Suitable nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: from 3 to 50, alkyl radical: C ₄ -C ₁₂ ) and ethoxylated fatty alcohols (degree of ethoxylation: from 3 to 80, alkyl radical: C ₈ -C ₃₆ ). Examples are the Lutensol ^® grades from BASF AG or the Triton ^® grades from Union Carbide.

Suitable anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C ₈ to C ₁₂ ), of sulfuric monoesters of ethoxylated alkanols (degree of ethoxylation: from 4 to 30, alkyl radical: C ₁₂ -C ₁₈ ) and ethoxylated alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C ₄ -C ₁₂ ), of alkylsulfonic acids (alkyl radical: C ₁₂ -C ₁₈ ) and of alkylarylsulfonic acids (alkyl radical: C ₉ -C ₁₈ ).

Suitable cationic emulsifiers are generally C ₆ -C ₁₈ -alkyl-, aralkyl- or heterocyclic radical-containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, Morpholinium salts, thiazolinium salts and salts of amine oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts. Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- ( N, N, N- trimethylammonium) ethylparaffinsäureester, N -Cetylpyridiniumchlorid, N-Laurylpyridiniumsulfat and N -Cetyl- N, N, N -trimethylammoniumbromid, N- Dodecyl- N, N, N- trimethylammonium bromide, N, N -distearyl- N, N -dimethylammonium chloride and the gemini-surfactant N, N '- (lauryldimethyl) ethylenediamine dibromide. Numerous other examples can be found in H. Stache, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981 and in McCutcheon's, Emulsiflers & Detergents, MC Publishing Company, Glen Rock, 1989 ,

Very particularly suitable emulsifiers are, for example, copolymers of ethylene and at least one α, β-unsaturated mono- or dicarboxylic acid or at least one anhydride of an α, β-unsaturated mono- or dicarboxylic acid, for example acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, methylenemalonic acid, maleic anhydride , Itaconic anhydride. The carboxyl groups may be partially or preferably completely neutralized, for example with alkali metal ions, alkaline earth metal ions, ammonium or amines, for example amines such as triethylamine, diethylamine, ethylamine, trimethylamine, dimethylamine, methylamine, ethyldiisopropylamine, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N- ( n-butyl) diethanolamine or N, N-dimethylethanolamine.

und II,

in denen die Variablen wie folgt definiert sind:

R¹

gewählt ausC₆-C₄₀-Alkyl, beispielsweise n-Hexyl, iso-Hexyl, n-Heptyl, iso- Heptyl, n-Octyl, iso-Octyl, n-Nonyl, n-Decyl, iso-Decyl, n-Undecyl, n-Dodecyl, iso-Dodecyl, n-Tridecyl, n-Tetradecyl, iso-Tetradecyl, n-Pentadecyl, n- Hexadecyl, n-Octadecyl, n-Eicosyl, n-C₃₀H₆₁, n-C₄₀H₈₁, C₃-C₄₀-Alkenyl mit einer bis fünf C-C-Doppelbindungen, wobei die C-C- Doppelbindungen beispielsweise isoliert oder konjugiert sein können. Beispiel- haft seien genannt: Allyl, -(CH₂)₂-CH=CH₂, all-cis-(CH₂)₈-(CH=CH-CH₂)₃CH₃, all- cis-(CH₂)₈-(CH=CH-CH₂)₂(CH₂)₄CH₃, all-cis-(CH₂)₈-CH=CH-(CH₂)₇CH₃,

R²

gleich oder verschieden und gewählt aus Wasserstoff und Methyl, bevorzugt Methyl,

m, n

gleich oder verschieden und gewählt aus ganzen Zahlen im Bereich von 0 bis 10, bevorzugt 1 oder 2 und besonders bevorzugt 2,

R³

gleich oder verschieden und gewählt aus Wasserstoff und C₆-C₂₀-Alkyl, beispielsweise n-Hexyl, iso-Hexyl, n-Heptyl, iso-Heptyl, n-Octyl, iso-Octyl, n-Nonyl, n-Decyl, iso-Decyl, n-Undecyl, n-Dodecyl, iso-Dodecyl, n- Tridecyl, n-Tetradecyl, iso-Tetradecyl, n-Pentadecyl, n-Hexadecyl, n-Octadecyl, n-Eicosyl;

M

Alkalimetall oder Ammonium.

Very particularly preferred emulsifiers are selected from emulsifiers of the general formula I.

and II,

where the variables are defined as follows:

R ¹

selected fromC ₆ -C ₄₀ -alkyl, for example n-hexyl, iso-hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl, iso-decyl, n-undecyl, n-dodecyl, iso-dodecyl, n-tridecyl, n-tetradecyl, iso-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-eicosyl, nC ₃₀ H ₆₁ , nC ₄₀ H ₈₁ , C ₃ -C ₄₀ alkenyl having one to five CC double bonds, wherein the CC double bonds may for example be isolated or conjugated. Examples include: allyl, - (CH ₂ ) ₂ -CH = CH ₂ , all-cis- (CH ₂ ) ₈ - (CH = CH-CH ₂ ) ₃ CH ₃ , allcis- (CH ₂ ) ₈ - (CH = CH-CH ₂ ) ₂ (CH ₂ ) ₄ CH ₃ , all-cis- (CH ₂ ) ₈ -CH = CH- (CH ₂ ) ₇ CH ₃ ,

R ²

identical or different and selected from hydrogen and methyl, preferably methyl,

m, n

the same or different and selected from integers in the range from 0 to 10, preferably 1 or 2 and particularly preferably 2,

R ³

identical or different and selected from hydrogen and C ₆ -C ₂₀ -alkyl, for example n-hexyl, iso-hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl, iso Decyl, n-undecyl, n-dodecyl, iso-dodecyl, n-tridecyl, n-tetradecyl, iso-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-eicosyl;

M

Alkali metal or ammonium.

The proportion of emulsifier (c) can be selected within wide limits and can be 0.1 to 200 g / l, preferably 0.2 to 100 g / l and particularly preferably up to 50 g / l of aqueous liquor.

Aqueous liquors used in step (B) may contain (d) at least one resin capable of crosslinking.

Suitable resins (d) are melamine-formaldehyde resins, urea-formaldehyde resins, N, N-dimethylol-4,5-dihydroxyethyleneureas, which may be etherified with C ₁ -C ₅ -alcohols.

If one wishes to use one or more resins (d), aqueous liquor (B) can be added to one or more crosslinking catalysts in addition to resin (d), for example Zn (NO ₃ ) ₂ or MgCl ₂ , for example in the form of their hydrates, or NH ₄ cl.

Aqueous liquors used in step (B) may further contain one or more additives.

mit Molekulargewichten M_w im Bereich von 100.000 bis 200.000 g/mol, in denen R⁷ für Methyl oder vorzugsweise Wasserstoff steht. Als Beispiele für Verdicker natürlichen Ursprungs seien genannt: Agar-Agar, Carrageen, modifizierte Stärke und modifizierte Cellulose.In the process according to the invention used aqueous liquors can be added to adjust the viscosity of one or more thickeners, which may be of natural or synthetic origin, for example. Suitable synthetic thickeners are poly (meth) acrylic compounds, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes, in particular copolymers with 85 to 95% by weight of acrylic acid, 4 to 15% by weight of acrylamide and about 0.01 to 1% by weight. % of the (meth) acrylamide derivative of the formula V

with molecular weights M _w in the range of 100,000 to 200,000 g / mol, in which R ^{7 is} methyl or preferably hydrogen. Examples of thickeners of natural origin include: agar-agar, carrageenan, modified starch and modified cellulose.

For example, from 0 to 10% by weight, based on the liquor used in the process according to the invention, of thickener may be used, preferably from 0.05 to 5% by weight and more preferably from 0.1 to 3% by weight.

At room temperature, liquors used in the process according to the invention preferably have a dynamic viscosity in the range from 50 to 5000 mPa.s, preferably 100 to 4000 mPa.s and particularly preferably 200 to 2000 mPa.s, measured for example with a Brookfield viscometer according to DIN 51562. 1 to 4.

Step (B) of the process according to the invention is carried out by treating the absorbent material with at least one aqueous liquor. It is also possible to carry out several treatment steps with similar or different aqueous liquors.

In one embodiment of the present invention, step (B) of the process according to the invention is carried out by first treating an absorbent material, and in particular a textile, with an aqueous liquor containing at least one organic polymer (a) and furthermore an organic or preferably inorganic Solid (b) in particulate form and at least one emulsifier (c) and then followed by a further treatment with a new aqueous liquor containing organic polymer (a), but no further organic or inorganic solid (b) in particulate form.

In another embodiment of the present invention, step (B) of the process according to the invention is carried out by first treating an absorbent material, and in particular a textile, with an aqueous liquor which contains at least one organic polymer (a) and furthermore an organic or preferred one inorganic solid (b) in particulate form and at least one emulsifier (c) and optionally at least one resin (d) followed by further treatment with a new aqueous liquor containing another organic polymer (a) and at least one emulsifier (c) contains, but no further organic or inorganic solid (b) in particulate form.

In a specific embodiment of the present invention, step (B) of the process according to the invention is carried out by first treating the textile to be treated with an aqueous liquor containing at least one organic polymer (a) and furthermore an organic or preferably inorganic solid ( b) in particulate form and at least one emulsifier (c) followed by further treatment with a new aqueous liquor which contains no further polymer (a) but the inorganic solid (b) already used in the first step in particulate form and at least an emulsifier (c) and optionally at least one resin (d).

Preferably, step (B) of the process according to the invention is carried out in such a way that the absorbent material to be treated and in particular textile with only one treated aqueous liquor containing at least one organic polymer (a) and further an organic or preferably inorganic solid (b) in particulate form and at least one emulsifier (c) and optionally at least one resin (d).

The temperature for carrying out step (B) of the process according to the invention is not critical per se. The liquor temperature may be in the range of 10 to 80 ° C, preferably 15 to 50 ° C.

Step (B) of the method according to the invention can be carried out with conventional machines which are used for the finishing of absorbent materials and in particular textiles, for example with one or more foulards. In the case of textile to be treated, preference is given to fabrics with vertical textile infeed, which as an essential element contain two rollers which are pressed onto one another and through which the textile is guided. Above the rollers, the liquid is filled in and wets the textile. The pressure squeezes off the textile and ensures a constant application. In other preferred foulards textile is first passed through a dip and then up through two pressed rollers. In the latter case one speaks also of foulards with vertical Textileinzug from below.

In one embodiment of the present invention, a padder is used, which is operated with a textile feed in the range of 1 to 40 m / min, preferably up to 30 m / min.

The liquor pickup can be chosen so that by step (B) of the process according to the invention a liquor uptake of 25 wt .-% to 85 wt.%, Preferably 40 to 70 wt .-% results. The liquor pick-up can be adjusted, for example, by applying pressure to the rollers of the foulard.

In a specific embodiment of the present invention, foam application of aqueous liquor is combined with a padder. In another embodiment of the present invention, doctor blade application of aqueous liquor is combined with a padder. In another embodiment of the present invention, a spray application of aqueous liquor is combined with a padder. In a further embodiment of the present invention, a roll application of aqueous liquor with a padder is combined.

Following the treatment according to the invention, the treated absorbent material and in particular textile can be dried by methods customary in the textile industry.

After the treatment according to the invention, it is possible to temper, continuously or discontinuously. The duration of tempering can be chosen within wide limits. Usually, one can over the duration of about 10 seconds to about 30 minutes, in particular 30 seconds to 5 minutes annealing. To carry out a heat treatment is heated to temperatures of up to 180 ° C, preferably up to 160 ° C. Of course, it is necessary to adjust the tempering temperature to the sensitivity of the fabric.

Suitable method for annealing is for example a hot air drying. Another suitable method for tempering uses one or more IR emitters.

In one embodiment, 0.01 to 1% by weight, preferably 0.1 to 0.5% by weight, of the textile is saponified in the case of polyesters or polyamides to be treated by partial saponification with strong alkalis, such as aqueous sodium hydroxide solution or potassium hydroxide solution.

Another object of the present invention are absorbent materials and in particular textile, equipped by the method according to the invention. By means of the provisioning according to the invention, the absorbent materials according to the invention and in particular textiles are provided with one or more layers. The absorbent materials according to the invention and in particular textiles show particularly good dirt and water-repellent behavior. Furthermore, absorbent materials according to the invention and in particular textiles show very good mechanical strength. In absorbent materials coated according to the invention, and in particular textiles, the solid (s) used is preferably isotropic or substantially isotropically distributed over the finish layer, i. no measurable concentration difference is detected in the boundary layer between the finish layer and the surrounding atmosphere.

In one embodiment, absorbent materials according to the invention and in particular textiles contain 0.5 to 50 g / m ^{2 of} coating, resulting from treatment with aqueous liquor, preferably 1 to 20 g / m ² and more preferably 1.5 to 17 g / m ² .

The invention will be illustrated by examples.

example 1

Example 1.1 Pretreatment of textiles by singeing (step A) Polyacrylonitrile fabric having a weight per unit area of 300 g / m ² was pretreated on a machine Pyrotrop XIS (with 4 burners with propane gas and fire-extinguishing roll) from Xetma Gematex GmbH on the front and rear side by: it was passed on hot ceramics. Settings: goods speed 70 m / min, 6.5 m ³ / h and burner, gas pressure 60 mbar, air consumption 0.01 m ³ / h.

Pre-treated polyacrylonitrile fabric 1.1 was obtained. An examination of pretreated polacrylonitrile fabric 1.1 according to DIN EN 24920 determined a grade of 1, that is, pretreated polacrylonitrile fabric 1.1 was completely wettable.

With the naked eye, pretreated polacrylonitrile tissue 1.1 did not show any hairs that protrude from the compensation plane.

Example 1.2 Pretreatment with Copolymer (Step A)

9 g wässrige Ammoniaklösung (25 Gew.-%) 15 g Melamin-Formaldehyd-Harz, hergestellt durch Kondensation von 3 Äquivalenten Formaldehyd pro Äquivalent Melamin, mit Methanol erschöpfend verethert 12 g wässrige NH₄Cl-Lösung (20 Gew.-%). An aqueous dispersion of a copolymer was prepared containing per liter: 923 g Aqueous dispersion of a random copolymer of n-butyl acrylate / vinyl acetate / acrylic acid in the weight ratio 50: 48: 2, solids content 50 wt .-%, dynamic viscosity: 50 mPa · s 5 g H (OCH ₂ CH ₂ ) ₇ O- (CH ₂ ) ₃ -Si [OSi (CH ₃ ) ₃ ] ₂ 3 g alkyl phenol ethoxylate) 25 g 2-methoxycarbonylamino 20 g Thickener (copolymer of 85% by weight of acrylic acid, 14.9% by weight of acrylamide and 0.1% by weight of compound V.1, M _w about 200,000 g / mol)

9 g aqueous ammonia solution (25% by weight) 15 g Melamine-formaldehyde resin prepared by condensation of 3 equivalents of formaldehyde per equivalent of melamine, exhaustively etherified with methanol 12 g aqueous NH ₄ Cl solution (20% by weight).

Dynamic viscosity at 25 ° C: 130 mPa · s.

The above-described dispersion was spread on polyacrylonitrile fabric having a basis weight of 300 g / m ² , in an amount of 25 g / m ² . It was then dried for 2 minutes at 160 ° C in a drying oven. Pre-treated polacrylonitrile fabric 1.2 was obtained.

With the naked eye, pretreated polacrylonitrile tissue 1.2 showed no hairs that protrude from the compensation plane.

An examination of pretreated polacrylonitrile fabric 1.2 according to DIN EN 24920 determined a grade of 1, that is, pretreated polacrylonitrile fabric 1.2 was completely wettable.

Example 2: Production of aqueous liquors Example 2.1: Preparation of the aqueous liquor B-2.1

• 624 g destilliertes Wasser,
• 120 g einer wässrigen Dispersion (30Gew.-% Feststoffgehalt) eines statistischen Copolymeren aus 10 Gew.-% Methacrylsäure und 90 Gew.-% CH₂=C(CH₃)COO-CH₂-CH₂-n-C₆F₁₃ mit M_n 3000 g/mol (Gelpermeationschromatographie),
• 200 g einer wässrigen Dispersion (8 Gew.-% Feststoffgehalt) aus 135 g Wasser, 43 g Ethylenglykol-mono-n-Butylether, 16 g mit Dimethylsiloxangruppen modifizierte pyrogene Kieselsäure mit einer BET-Oberfläche von 225 m²/g, bestimmt nach DIN 66131, Primärpartikelgröße: 10 nm (Medianwert, Zahlenmittel), und 6 g Amin der Formel I.1
  
  neutralisiert mit 32 Gew.-% wässriger HCl, zugegeben und 10 Minuten dispergiert (Ultraturrax-Rührer).
• 56 g eines Melamin-Formaldehyd-Harzes mit Methanol verethert (Feststoffgehalt 50%).
• 8 g einer 20%igen Lösung von Ammoniumchlorid.

In a flask were mixed with mechanical stirring:

• 624 g of distilled water,
• 120 g of an aqueous dispersion (30 wt .-% solids content) of a random copolymer of 10 wt .-% methacrylic acid and 90 wt .-% CH ₂ = C (CH ₃ ) COO-CH ₂ -CH ₂ -nC ₆ F ₁₃ with M _n 3000 g / mol (gel permeation chromatography),
• 200 g of an aqueous dispersion (8 wt .-% solids content) of 135 g of water, 43 g of ethylene glycol mono-n-butyl ether, 16 g with dimethylsiloxane modified fumed silica having a BET surface area of 225 m ² / g, determined according to DIN 66131, primary particle size: 10 nm (median, number average), and 6 g of amine of formula I.1
  
  neutralized with 32 wt .-% aqueous HCl, added and dispersed for 10 minutes (Ultraturrax-stirrer).
• 56 g of a melamine-formaldehyde resin etherified with methanol (solids content 50%).
• 8 g of a 20% solution of ammonium chloride.

The aqueous liquor B-2.1, which had a pH of 6.1, was obtained.

Example 2.2: Preparation of the aqueous liquor B-2.2

• 872,8 g destilliertes Wasser,
• 68,1 g einer wässrigen Dispersion (20 Gew.-% Feststoffgehalt) eines statistischen Copolymeren aus 10 Gew.-% Methacrylsäure und 90 Gew.-% CH₂=C(CH₃)COO-CH₂-CH₂-n-C₆F₁₃ mit M_n 3000 g/mol (Gelpermeationschromatographie),
• 86,5 g einer wässrigen Dispersion (20 Gew.-% Feststoffgehalt) eines statistischen Copolymers aus 20 Gew.-% Acrylsäure, 80 Gew.-% Ethylen, M_w: 20.000 g/mol, neutralisiert mit N,N-Dimethylethanolamin, pH-Wert zwischen 8,5 und 9,5.
• Anschließend wurden 12,8 g mit Dimethylsiloxangruppen modifizierte pyrogene Kieselsäure mit einer BET-Oberfläche von 225 m²/g, bestimmt nach DIN 66131 zugegeben, Primärpartikelgröße: 10 nm (Medianwert, Zahlenmittel), und
• 8,8 g Amin der Formel I.1
  
  neutralisiert mit 32 Gew.-% wässriger HCl, zugegeben und 10 Minuten dispergiert (Ultraturrax-Rührer). Man erhielt die wässrige Flotte B-2.2, die einen pH-Wert von 6,5 hatte.

In a flask were mixed with mechanical stirring:

• 872.8 g of distilled water,
• 68.1 g of an aqueous dispersion (20 wt .-% solids content) of a random copolymer of 10 wt .-% methacrylic acid and 90 wt .-% CH ₂ = C (CH ₃ ) COO-CH ₂ -CH ₂ -nC ₆ F. ₁₃ with M _n 3000 g / mol (gel permeation chromatography),
• 86.5 g of an aqueous dispersion (20% by weight solids content) of a random copolymer of 20% by weight of acrylic acid, 80% by weight of ethylene, M _w : 20,000 g / mol, neutralized with N, N-dimethylethanolamine, pH Value between 8.5 and 9.5.
• Subsequently, 12.8 g of fumed silica modified with dimethylsiloxane groups having a BET surface area of 225 m ² / g, determined in accordance with DIN 66131, primary particle size: 10 nm (median value, number average), and
• 8.8 g of the amine of the formula I.1
  
  neutralized with 32 wt .-% aqueous HCl, added and dispersed for 10 minutes (Ultraturrax-stirrer). The aqueous liquor B-2.2, which had a pH of 6.5, was obtained.

Example 2.3: Preparation of the aqueous liquor B-2.3

• 872,8 g destilliertes Wasser,
• 68,1 g einer wässrigen Dispersion (20 Gew.-% Feststoffgehalt) eines statistischen Copolymeren aus 10 Gew.-% Methacrylsäure und 90 Gew.-% CH₂=C(CH₃)COO-CH₂-CH₂-n-C₆F₁₃ mit M_n 3000 g/mol (Gelpermeationschromatographie),
• 86,5 g einer wässrigen Dispersion (20 Gew.-% Feststoffgehalt) eines statistischen Copolymers aus 20 Gew.-% Acrylsäure, 80 Gew.-% Ethylen, M_w: 20.000 g/mol, neutralisiert mit N,N-Dimethylethanolamin, pH-Wert zwischen 8,5 und 9,5.
• Anschließend wurden 12,8 g mit Dimethylsiloxangruppen modifizierte pyrogene Kieselsäure mit einer BET-Oberfläche von 225 m²/g, bestimmt nach DIN 66131 zugegeben, Primärpartikelgröße: 10 nm (Medianwert, Zahlenmittel), und
• 8,8 g Amin der Formel I.2
  
  neutralisiert mit 32 Gew.-% wässriger HCl, zugegeben und 10 Minuten dispergiert (Ultraturrax-Rührer). Man erhielt die wässrige Flotte B-2.3, die einen pH-Wert von 6,5 hatte.

In a flask were mixed with mechanical stirring:

• 872.8 g of distilled water,
• 68.1 g of an aqueous dispersion (20 wt .-% solids content) of a random copolymer of 10 wt .-% methacrylic acid and 90 wt .-% CH ₂ = C (CH ₃ ) COO-CH ₂ -CH ₂ -nC ₆ F. ₁₃ with M _n 3000 g / mol (gel permeation chromatography),
• 86.5 g of an aqueous dispersion (20% by weight solids content) of a random copolymer of 20% by weight of acrylic acid, 80% by weight of ethylene, M _w : 20,000 g / mol, neutralized with N, N-dimethylethanolamine, pH Value between 8.5 and 9.5.
• Subsequently, 12.8 g of fumed silica modified with dimethylsiloxane groups having a BET surface area of 225 m ² / g, determined in accordance with DIN 66131, primary particle size: 10 nm (median value, number average), and
• 8.8 g of the amine of the formula I.2
  
  neutralized with 32 wt .-% aqueous HCl, added and dispersed for 10 minutes (Ultraturrax-stirrer). The aqueous liquor B-2.3, which had a pH of 6.5, was obtained.

Example 2.4: Preparation of the aqueous liquor B-2.4 according to the invention

• 872,8 g destilliertes Wasser,
• 68,1 g einer wässrigen Dispersion (20 Gew.-% Feststoffgehalt) eines statistischen Copolymeren aus 10 Gew.-% Methacrylsäure und 90 Gew.-% CH₂=C(CH₃)COO-CH₂-CH₂-n-C₆F₁₃ mit M_n 3000 g/mol (Gelpermeationschromatographie),
• 86,5 g einer wässrigen Dispersion (20 Gew.-% Feststoffgehalt) eines statistischen Copolymers aus 20 Gew.-% Acrylsäure, 80 Gew.-% Ethylen, M_w: 20.000 g/mol, neutralisiert mit N,N-Dimethylethanolamin; pH-Wert zwischen 8,5 und 9,5.
• Anschließend wurden 12,8 g mit Dimethylsiloxangruppen modifizierte pyrogene Kieselsäure mit einer BET-Oberfläche von 225 m²/g, bestimmt nach DIN 66131 zugegeben, Primärpartikelgröße: 10 nm (Medianwert, Zahlenmittel), und
• 8,8 g Amin der Formel I.2
  
  neutralisiert mit 32 Gew.-% wässriger HCl, zugegeben und 10 Minuten dispergiert (Ultraturrax-Rührer). Man erhielt die wässrige Flotte B-2.4, die einen pH-Wert von 6,7 hatte.

In a flask were mixed with mechanical stirring:

• 872.8 g of distilled water,
• 68.1 g of an aqueous dispersion (20 wt .-% solids content) of a random copolymer of 10 wt .-% methacrylic acid and 90 wt .-% CH ₂ = C (CH ₃ ) COO-CH ₂ -CH ₂ -nC ₆ F. ₁₃ with M _n 3000 g / mol (gel permeation chromatography),
• 86.5 g of an aqueous dispersion (20% by weight solids content) of a random copolymer of 20% by weight of acrylic acid, 80% by weight of ethylene, M _w : 20,000 g / mol, neutralized with N, N-dimethylethanolamine; pH between 8.5 and 9.5.
• Subsequently, 12.8 g of fumed silica modified with dimethylsiloxane groups having a BET surface area of 225 m ² / g, determined in accordance with DIN 66131, primary particle size: 10 nm (median value, number average), and
• 8.8 g of the amine of the formula I.2
  
  neutralized with 32 wt .-% aqueous HCl, added and dispersed for 10 minutes (Ultraturrax-stirrer). The aqueous liquor B-2.4, which had a pH of 6.7, was obtained.

Example 3 Equipment of pretreated textile Example 3.1. Treatment with aqueous liquor B-2.1

Example 3.1.1. Treatment of pretreated polyacrylonitrile fabric 1.1 (step B) Pretreated polyacrylonitrile fabric 1.1 was treated with liquor B-2.1 on a padder (manufactured by Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 60%. The application speed was 2 m / min. It was then dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 2 min at 160 ° C. under circulating air in a drying oven. The treated polyacrylonitrile fabric PAN3.1.1 according to the invention was obtained.

Example 3.1.2. Treatment of pretreated polyacrylonitrile fabric 1.2 (step B) Pretreated polyacrylonitrile fabric 1.2 was treated with liquor B-2.1 on a padder (manufacturer: Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 60%. The application speed was 2 m / min. It was then dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 2 min at 160 ° C. under circulating air in a drying oven. The treated polyacrylonitrile fabric PAN3.1.2 according to the invention was obtained.

Example 3.2. Treatment with aqueous liquor B-2.2

Example 3.2.1. Treatment of pretreated polyacrylonitrile fabric 1.1 (Step B) Pretreated polyacrylonitrile fabric 1.1 was treated with Fleet B-2.2 on a padder (manufactured by Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 60%. The application speed was 2 m / min. It was then dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 2 min at 160 ° C. under circulating air in a drying oven. The treated polyacrylonitrile fabric PAN3.2.1 according to the invention was obtained.

Example 3.2.2. Treatment of pretreated polyacrylonitrile fabric 1.2 (step B)

Pretreated polyacrylonitrile fabric 1.2 was treated with liquor B-2.2 on a padder (manufacturer: Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 60%. The application speed was 2 m / min. It was then dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 2 min at 160 ° C. under circulating air in a drying cabinet. The treated polyacrylonitrile fabric PAN3.2.2 according to the invention was obtained.

Example 3.3. Treatment with aqueous liquor B-2.3 Example 3.3.1. Treatment of pretreated polyacrylonitrile fabric 1.1 (step B)

Pretreated polyacrylonitrile fabric 1.1 was treated with liquor B-2.3 on a padder (manufacturer Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 60%. The application speed was 2 m / min. It was then dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 2 min at 160 ° C. under circulating air in a drying oven. The treated polyacrylonitrile fabric PAN3.3.1 according to the invention was obtained.

Example 3.3.2. Treatment of pretreated polyacrylonitrile fabric 1.2 (step B)

Pretreated polyacrylonitrile fabric 1.2 was treated with liquor B-2.3 on a padder (manufacturer Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 60%. The application speed was 2 m / min. It was then dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 2 min at 160 ° C. under circulating air in a drying oven. The treated polyacrylonitrile fabric PAN3.3.2 according to the invention was obtained.

Example 3.4. Treatment with aqueous liquor B-2.4 Example 3.4.1. Treatment of pretreated polyacrylonitrile fabric 1.1 (step B)

Pretreated polyacrylonitrile fabric 1.1 was treated with Fleet B-2.4 on a padder (manufacturer Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 60%. The application speed was 2 m / min. It was then dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 2 min at 160 ° C. under circulating air in a drying oven. The treated polyacrylonitrile fabric PAN3.4.1 according to the invention was obtained.

Example 3.4.2. Treatment of pretreated polyacrylonitrile fabric 1.4 (step B)

Pretreated polyacrylonitrile fabric 1.2 was treated with liquor B-2.4 on a padder (manufacturer Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 60%. The application speed was 2 m / min. It was then dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 2 min at 160 ° C. under circulating air in a drying oven. The treated polyacrylonitrile fabric PAN3.4.2 according to the invention was obtained.

Comparative Examples: Comparative Example V4

Polyacrylonitrile fabric having a weight per unit area of 300 g / m ² was treated with liquor B-2.1 on a padder (manufacturer Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 60%. The application speed was 2 m / min. It was then dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 2 min at 160 ° C. under circulating air in a drying oven. Comparative fabric V4 was obtained.

Comparative Example V5

An aqueous liquor V5.1 was prepared by adding 68.1 g of an aqueous dispersion (20% by weight solids) of a random copolymer of 10% by weight methacrylic acid and 90% by weight CH ₂ = C (CH ₃ ) COO-CH ₂ -CH ₂ -nC ₆ F ₁₃ with M _n 3000 g / mol (gel permeation chromatography) diluted to one liter with distilled water.

Polyacrylonitrile fabric having a weight per unit area of 300 g / m ² was treated with liquor V5.1 on a padder (manufacturer: Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 60%. The application speed was 2 m / min. It was then dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 2 min at 160 ° C. under circulating air in a drying oven. Comparative fabric V5 was obtained.

Example 4 Investigation of the textile samples treated according to the invention and comparative fabrics V4 and V5 for performance properties

Each examined according to the invention treated polyacrylonitrile or the comparative fabric was manually clamped and fixed with needles on a flat wooden board whose inclination could be adjusted continuously from 1 ° to 90 °. Then, with the aid of a cannula from a height of 10 mm, individual drops of water were dropped onto the polyacrylonitrile fabric treated according to the invention. The drops had a mass of 4.7 mg. By gradually lowering the inclination angle was the angle of inclination at which the drops just bared and no adhesion was observed. The results are shown in Table 1.

The water absorption after 60 minutes or 24 hours was determined by determining the weight of the fabric before and after the immersion of a tissue pattern in demineralised water for 24 hours or 24 hours and tested according to Bundesmann, DIN 53888. Table 1: Performance properties of polyacrylonitrile fabrics according to the invention and not according to the invention test method V4 V5 PAN3.1.1 (according to the invention) PAN3.1.2 (according to the invention) Self-cleaning according to DIN 24920 [Note] 3-4 2 5 5 Inclination angle [°] 7 12 6 6 Handle soft hard soft hard wrinkles little little little very little Water absorption after 60 minutes 27% by weight 55% by weight 23% by weight 19% by weight Water absorption after 60 minutes 62% by weight 69% by weight 42% by weight 57% by weight Water absorption according to Bundesmann: grade 4-5 4-5 5 5 water absorption 17.7% 23.3% 8.4% 11.5% permeability 0 0 0 0

The self-cleaning was investigated in accordance with DIN 24920 by the respective fabric with 0.5 g of a standard dirt, consisting of 50 wt .-% silica, 24 wt .-% olive oil, 24 wt .-% mineral oil and 2 wt .-% Treated carbon black and then rinsed with 800 ml of water. Grades were awarded depending on the amount of dirt left (grade 1: very bad, grade 2: poor, grade 3: sufficient, grade 4: satisfactory, grade 5: good).

Grip and wrinkles were determined by a test team.

Claims (13)

1. A process for finishing absorbent material, which comprises it being

   (A) hydrophilicized in a first step,

   (B) treated in a subsequent step with at least one aqueous liquor comprising

   (a) at least one organic polymer,

   (b) at least one organic or inorganic solid in particulate form other than (a), and

   (c) at least one emulsifier.
2. The process according to claim 1 wherein step (A) comprises contacting absorbent material with one or more objects having a temperature of not less than 450°C or with one or more flames.
3. The process according to claim 1 or claim 2 wherein a glowing plate of copper is an object having a temperature of not less than 450°C.
4. The process according to claim 1 wherein step (A) comprises leading absorbent material past one or more ceramic bodies having a temperature in the range from 800 to 1300°C.
5. The process according to claim 1 wherein step (A) comprises treating absorbent material with at least one melt or dispersion of at least one (co)polymer selected from anionic polyurethanes, copolymers of C₁-C₁₀-alkyl (meth)acrylates and copolymers of C₁-C₁₀-alkyl (meth)acrylates with at least one ethylenically unsaturated compound.
6. The process according to claim 1 or 5 wherein step (A) comprises applying at least one (co)polymer in a layer thickness in the range from 10 to 500 µm atop absorbent material.
7. The process according to any one of claims 1 to 6 wherein the or at least one of the organic or inorganic solids (b) is hydrophobic.
8. The process according to any one of claims 1 to 7 wherein at least one aqueous liquor (B) comprises (d) at least one resin capable of crosslinking.
9. The process according to any one of claims 1 to 8 wherein the organic or inorganic solid or solids (b) have a particle diameter (median value, number average) in the range from 10 to 1000 nm.
10. The process according to any one of claims 1 to 9 wherein absorbent material comprises textile material.
11. The process according to any one of claims 1 to 10 wherein absorbent material comprises material composed of polyacrylonitrile, polyester or cotton.
12. The process according to any one of claims 1 to 11 wherein at least one emulsifier (c) is selected from emulsifiers of the general formula I

    

    and II

    

    where

    R¹ is selected from C₆-C₄₀-alkyl and C₃-C₄₀- alkenyl having one to five carbon-carbon double bonds,

    R² is at each instance the same or different and selected from hydrogen and methyl,

    m and n are the same or different and each selected from integers in the range from 0 to 10,

    R³ is at each instance the same or different and selected from hydrogen and C₆-C₂₀-alkyl,

    M is an alkali metal or ammonium.
13. Absorbent material finished by a process according to claims 1 to 12.