EP1751346A1

EP1751346A1 - Method for the production of structured surfaces

Info

Publication number: EP1751346A1
Application number: EP05750552A
Authority: EP
Inventors: Cédric DIELEMAN; Harald Keller; Wolfgang Schrepp; Thomas Frechen
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-05-19
Filing date: 2005-05-17
Publication date: 2007-02-14
Also published as: US20080014432A1; JP2007538166A; JP4937909B2; CN1957135A; DE102004025368A1; WO2005113885A1; CN100567625C; US7727583B2

Abstract

The invention relates to a method for the production of structured surfaces with high hydrophilicity, characterised in that the surfaces are coated with a) particles with a mean diameter (number mean) in the range of 0.1 to 10 µm and b) particles with a mean diameter (number mean) in the range of 5 nm to 0.5 µm and a surface energy at 20 °C of greater than or equal to 100 mN/m.

Description

Process for the production of structured surfaces

description

The present invention relates to a process for the production of structured surfaces with great hydrophilicity, characterized in that the surfaces with

(a) Particles with an average diameter (number average) in the range from 0.1 to 10 μm and

(b) Particles with an average diameter (number average) in the range from 5 nm to 0.5 μm and a surface energy at 20 ° C. greater than or equal to 100 mN / m

coated

The present invention further relates to surfaces obtainable by the process according to the invention.

It is generally desirable to modify surfaces so that they have little tendency to become dirty. Such surfaces look aesthetic over a long period of time, remain free from bacterial or fungal growth and, when cleaned, are particularly easy to clean.

Modern methods often use the Lotus Effect® to produce surfaces with a low tendency to become dirty, for example WO 96/04123 and EP-B 1 171 529. In order to equip a surface with a Lotus effect, one can proceed, for example, in such a way that surfaces are modeled after the lotus plant with a micro-rough surface, for example with elevations and depressions in dimensions, that the distance of the elevations is in the range from 5 to 200 μm and the height of the elevations is in the range from 5 to 100 μm and at least the elevations consist of, for example, hydrophobic polymers and cannot be removed by water or water with detergents. With surfaces equipped in this way, it is observed that the contact angle with water is large, for example 157 °, see, for example, US 3,354,022, example 9. Dirt particles have a low adhesion to surfaces equipped in this way and can be easily removed by rinsing with water.

A disadvantage of textile surfaces equipped with a lotus effect is, however, that they are not permeable to perspiration. However, perspiration permeability is desirable in many cases, particularly in the case of clothing. It is also desirable that diapers hold urine and do not give rise to urine drops. This applies, for example, to diapers that are manufactured using polypropylene and superabsorbents.

Another method of making surfaces dirt-repellent is to make them very hydrophilic. Water then forms a film and easily removes dirt particles, see. for example WO 03/66710.

From WO 01/83662 it is known that certain particles with a particle size of 5 to 500 nm can be used to treat textiles so that they can be used within a certain time, generally up to 4 washing or cleaning cycles (page 2, last paragraph ) to be dirt-repellent. However, such short equipment lifetimes are undesirable in some applications.

From DE-A 101 16 200 it is known that surfaces can be coated with so-called very finely divided inorganic particles, surface modifiers and, if appropriate, a surfactant, and that the surfaces thereafter have anti-fog properties. However, such coatings cannot withstand a washing cycle without impairments.

The task was therefore to provide a process by which surfaces can be treated, which repel dirt and have good durability. Furthermore, there was the task of providing coated surfaces with great hydrophilicity. Finally, the task was to provide uses for coated surfaces.

Accordingly, the process defined at the outset was found.

For the purposes of the present invention, surfaces with great hydrophilicity are those surfaces which have a non-measurable contact angle with water. Water does not form droplets on the surfaces according to the invention, but spreads to form a film.

Objects with at least one surface are used to produce structured surfaces according to the invention. In the following, such objects are also called substrates, which can consist of a large number of materials, for example

Concrete, stone, solidified mortar, wood, metal, ceramics, paper, cardboard, glass, plastics such as polystyrene, polyethylene, polypropylene, polyamide, polyester, leather, imitation leather and in particular textiles. In the context of the present invention, textile or textile substrates are to be understood as meaning textile fibers, textile semifinished and finished products and finished goods made therefrom which, in addition to textiles for the clothing industry, also include carpets and other home textiles and textile structures serving technical purposes. This also includes unshaped structures such as flakes, line-shaped structures such as twine, threads, yarns, linen, cords, ropes, twists and body structures such as felts, fabrics, nonwovens and wadding. The textiles can be of natural origin, for example cotton, wool or flax, or synthetic, for example polyamide, polyester, modified polyester, polyester blend fabric, polyamide blend fabric, polyacrylonitrile, triacetate, acetate, polycarbonate, polypropylene, polyvinyl chloride, polyester microfiber and glass fiber fabric.

According to the invention, surfaces are structured, namely by using them

(a) Particles with an average diameter (number average) in the range from 0.1 to 10 μm, preferably 0.2 to 5 μm, particularly preferably up to 1 μm and

(b) particles with an average diameter (number average) in the range from 5 nm to 0.5 μm, preferably 10 nm to 400 nm, particularly preferably 20 nm to 300 nm, and a surface energy at 20 ° C. greater than or equal to 80 mN / m

coated.

Common methods can be used to measure the particle diameter, such as transmission electron microscopy.

Particles (a) can be materials which can optionally be hydrophilic or hydrophobic. Particles (b) have a surface energy greater than or equal to 100 mN / m to about 1000 mN / m, determined, for example, by determining contact angles.

In the context of the present invention, hydrophobic is understood to mean that they have a surface energy in the range from 10 mN / m to 70 mN / m, preferably 20 mN / m to 60 mN / m, determined, for example, by determining the contact angle ,

Hydrophilic and hydrophobic materials can be selected from inorganic materials and organic polymers and copolymers.

Hydrophobic materials (a) include hydrophobic organic polymers, for example polyethylene, polypropylene, polyisobutylene and polystyrene, and copolymers thereof with one another or with one or more further olefins, such as for example styrene, methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, maleic anhydride or N-methylmaleinimide. A preferred polyethylene or polypropylene is described for example in EP-A 0 761 696.

In the context of the present invention, silicones which are solid at room temperature are also considered to be hydrophobic organic polymers.

The molecular weight (weight average) M _w of the hydrophobic organic polymer used according to the invention as the hydrophobic material (a) can be in the range from 1000 to 10,000,000 g / mol, preferably in the range from 2500 to 5,000,000 g / mol, determined according to at least one of the following methods: light scattering, gel permeation chromatography (GPC), viscometry. If a polymer from the group of the polyolefins is used, for example polyethylene, polypropylene or polyisobutene and copolymers of ethylene with propylene, butylene or 1-hexene, the molecular weight M _{w is} advantageously in the range from 30,000 to 5,000,000 g / mol. Hydrophobic organic polymers can, for example, have wax-like properties or be thermoplastic.

The breadth of the molecular weight distribution of hydrophobic organic polymer used according to the invention as hydrophobic material (a) is not critical per se and can be in the range from 1.1 to 20. It is usually in the range from 2 to 10.

Hydrophobic inorganic materials (a) are hydrophobic inorganic materials, in particular solid inorganic oxides, carbonates, carbides, phosphates, silicates or sulfates from 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. Silicon dioxide in its modification as silica gel is particularly preferred. Fumed silica gels are very particularly preferred. Solid inorganic oxides and silicate can be made hydrophobic thermally 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 alkyl-lithium compounds such as methyl lithium, n-butyl lithium or n-hexyl lithium; or silanes such as hexamethyldisilazane, octyltrimethoxysilane and in particular halogenated silanes such as trimethylchlorosilane or dichlorodimethylsilane.

In particular, solid inorganic oxides, carbonates, phosphates, silicates or sulfates of groups 3 to 14 can be used as hydrophilic inorganic materials (a) Use periodic table of the elements that have not been made hydrophobic, for example calcium oxide, silicon dioxide or aluminum oxide, calcium carbonate, calcium sulfate or calcium silicate, aluminum oxide and silicon dioxide being preferred, quartz and boehmite, colloidal silica gel and diatomaceous earth. Pyrogenic silicic acid, pyrogenic titanium dioxide and pyrogenic aluminum oxide are preferred.

Particles (b) can be composed, for example, of hydrophilic inorganic materials and of hydrophilic polymers. Solid inorganic oxides, carbonates, phosphates, silicates or sulfates from groups 3 to 14 of the periodic table of the elements which have not been rendered hydrophobic, for example calcium oxide, silicon dioxide or aluminum oxide, calcium carbonate, calcium sulfate or calcium silicate, can be mentioned as hydrophilic inorganic materials (b). alumina and silicon dioxide are preferred, quartz and boehmite, colloidal silica gel and diatomaceous earth. Pyrogenic silica, pyrogenic titanium dioxide and pyrogenic aluminum oxide are preferred.

In one embodiment of the present invention, particles (a) and particles (b) do not differ in their composition, but only in their mean particle diameter. The particle diameter distribution of a mixture of particles (a) and (b) is then bimodal.

In another embodiment of the present invention, particles (a) and particles (b) differ not only in their average particle diameter, but also in their composition.

In one embodiment of the present invention, (a) or (b) is selected from the above-mentioned organic polymers or copolymers.

In one embodiment of the present invention, particles (a) and (b) are coated in a weight ratio in the range from 1:99 to 99: 1, preferably 1: 9 to 9: 1, particularly preferably 3: 7 to 7: 3.

In one embodiment of the process according to the invention, particles (a) and (b) are each used in an aqueous liquor, preferably in a common aqueous liquor.

In the following, aqueous liquors are understood not only to mean fleets which have water as the only medium which is liquid at room temperature, but also those which have a mixture of water and one or more non-aqueous medium which is liquid at room temperature, for example

Alcohols such as ethanol, isopropanol, butanol, tert-butanol, 3-octanol, 1-decanol, 2-decanol, 2-dodecanol, 2-hexadecanol, Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, ethers such as THF, di n-propyl ether, dioxanes such as 1,4-dioxane.

In one embodiment of the present invention, one or more aqueous liquors are used to carry out the process according to the invention, each in the range from 0.1 to 500 g / l particles, preferably 1 to 250 g / l and particularly preferably 10 to 100 g / l Contain particles, calculated from the sum of particles (a) and (b).

In one embodiment of the present invention, in the range from 0.1 to 30 g of particles, ie the sum of (a) and (b), are applied per m ² of surface to be coated, preferably 0.5 to 20 gg / m ^{2 of} particles, particularly preferably 1 to 15 g / m ² .

In one embodiment of the present invention, the application is followed by a fixing step, which can be thermal, for example at 80 to 250 ° C., preferably 100 to 210 ° C. Preferred times are 10 to 24 minutes. Other variants of the fixing step are the addition of a crosslinking agent, especially when working with binder (c), or fixing using actinic radiation.

In one embodiment of the present invention, the process according to the invention is carried out with one or more aqueous liquors, of which at least one contains one or more emulsifiers, selected, for example, from the group of the ionic and nonionic emulsifiers.

Suitable nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C ₄ -C ₁₂ ) and ethoxylated fatty alcohols (degree of ethoxylation: 3 to 80; alkyl radical: C ₈ -C ₃₆ ). Examples include the Lutensol ^® brands from BASF Aktiengesellschaft or the Triton ^® brands from Union Carbide. Alcohols to be ethoxylated can be of synthetic or natural origin, for example coconut oil alcohol, palm oil alcohol, tallow oil alcohol and oleyl alcohol.

Suitable anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C ₈ to C ₁₂ ), of sulfuric acid semiesters of ethoxylated alkanols (degree of ethoxylation: 4 to 30, alkyl radical: C ₁ -C ₁₈ ) and ethoxylated alkylphenols (ethoxylation Grade: 3 to 50, alkyl radical: C ₄ -C ₁₂ ), of alkyl sulfonic acids (alkyl radical: C ₁₂ -C ₁₈ ), CC ₁₀ mono- or dialkyl esters of sulfosuccinic acid and of alkyl aryl sulfonic acids (alkyl radical: C _θ -Cι ₈ ) ,

Suitable cationic emulsifiers are generally a primary, secondary, tertiary or quaternary C ₆ -C ₁₈ alkyl, aralkyl or heterocyclic radical 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- (Λ /, Λ /, Λ / -trimethylammonium) ethyl paraffinic acid ester, Λ / -cetylpyridinium chloride, Λ / -laurylpyridinium sulfate as well as -C / -cetyl- / v Λ /, Λ / -trimethylammoniumbromid, Λ / -dodecyl- Λ /, / V, Λ / -trimethylammonium bromide, Λ /, Λ / -distearyl-Λ /, Λ / -dimethylammonium chloride and the gemini surfactant Λ / .Λ / '^ lauryldimethy ethylenediamine dibromide. Numerous other examples can be found in H. Stächen, Tensid-Taschenbuch, Carl-Hanser-Verlag,

Munich, Vienna, 1981 and in McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989. Further suitable cationic emulsifiers are C ₁₀ -C ₀ -alkyl amines mono- to ten-fold alkoxylated, preferably mono- to quadruple-ethoxylated.

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, methylene malonic acid, maleic anhydride , Itaconic anhydride. The carboxyl groups can 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.

The proportion of emulsifier can be selected within wide limits and can be 0.1 to 200 g / l aqueous liquor, preferably 0.2 to 100 g / l, particularly preferably 1 to 50 g / l.

The process according to the invention is preferably carried out by treating substrate with (a) and (b), for example in an aqueous liquor. Suitable procedures are spraying, dipping, roller application, foam application and knife application and in particular application using one or more foulards.

The process according to the invention can be carried out by treating substrates and in particular textile substrates with at least one aqueous liquor. It is also possible to carry out several treatment steps with the same or different liquors.

In one embodiment of the present invention, the process according to the invention is carried out by treating substrates and in particular textiles Substrates are first treated with a liquor which contains (b) and, if appropriate, at least one emulsifier, and then a further treatment with a new liquor which (a) and optionally contains at least one emulsifier. In one embodiment of the present invention, the process according to the invention is carried out by first treating substrates to be treated and in particular textile substrates with a liquor which contains (a) and, if appropriate, at least one emulsifier, and then a further treatment with a new liquor , which (b) and optionally contains at least one emulsifier. The temperature for carrying out the method according to the invention is not critical per se. The liquor temperature can be in the range from 10 to 100 ° C., preferably 15 to 60 ° C.

The method according to the invention can be carried out in conventional machines which are used for finishing substrates and in particular textiles, for example foulards. Foulards with vertical textile feed are preferred, which contain two pressed rollers as an essential element, through which the textile is guided. The liquid is filled in above the rollers and wets the textile. The textile is squeezed off by the pressure and a constant application is guaranteed.

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

The liquor absorption can be selected so that the process according to the invention results in a liquor absorption of 25% by weight to 85% by weight, preferably 40 to 70% by weight.

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

After the treatment according to the invention, annealing can be carried out continuously or discontinuously. The duration of the annealing can be chosen within wide limits. Usually one can anneal over a period of about 10 seconds to about 30 minutes, in particular 30 seconds to 5 minutes. To carry out an annealing, the mixture is heated to temperatures of up to 180 ° C., preferably up to 150 ° C. Of course, it is necessary to adapt the temperature of the tempering to the sensitivity of the substrate.

A suitable method for tempering is, for example, hot air drying. If one wishes to coat textile, in one embodiment of the present invention the textile material can be provided with an adhesive layer before the actual coating. One or more so-called primers can be used for this. The application of primers is preferred if you want to finish synthetic fibers.

In one embodiment of the present invention, one or more polymers, for example, can be applied as an adhesive layer to the textile material to be treated, wherein the polymer synthesis can also be carried out on the textile material. Polymers which are particularly suitable are those which have crosslinked or crosslinkable groups, for example natural or synthetic polymers with free hydroxyl groups, carbonyl groups, primary or secondary amino groups or thiol groups. Examples of suitable polymers are lignin, polysaccharides, polyvinyl alcohol and polyethyleneimine. Crosslinking can be achieved, for example, by subsequent reaction with, for example, isocyanates, dimethyl urea or N, N-dimethylol-4,5-dihydroxyethylene urea (DMDHEU). Other particularly preferred crosslinkers are melamine-formaldehyde resins, which can be etherified with alcohols such as methanol, n-butanol or ethylene glycol.

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

In one embodiment of the present invention, at least one aqueous liquor used in the process according to the invention contains at least one binder (c).

In principle, all binders customary in coating technology are suitable as binders (c).

So-called self-crosslinking binders are particularly suitable for textile substrates. In the context of the present invention, these include polymers, preferably in the form of aqueous polymer dispersions, which undergo intra- and / or intermolecular crosslinking reactions when the coating produced according to the invention is dried. Crosslinking reactions are brought about by the fact that the polymers used as binders either have different functional groups which react with one another to form ionic or covalent bonds, or by adding one or more crosslinkers to the polymers used which have functional groups as binders can be, for example, low molecular weight, ie its molecular weight M _w can be, for example, 500 g / mol or lower. The crosslinker (s) have at least two functional groups per molecule, each of which can be the same or different and which can be linked to the radio tional groups of the polymer can react. Suitable reactive groups in polymers are, for example

Carboxyl groups which can react, for example, with hydroxyl groups, amino groups, epoxy groups or aziridine groups or with polyvalent metal ions such as Ca ²⁺ , Al ³⁺ , Mg ²⁺ , Mn ²⁺ and Zn ²⁺ ,

Hydroxyl groups which can react, for example, with carboxyl groups, isocyanate, epoxy, carboxylic anhydride groups, epoxy groups or aldehyde groups,

Aldehyde or keto groups that can react with amino groups and hydrazines, N-methylolamino and N-methoylolamido groups that can react with another N-methylolamino or N-methoylolamido group, isocyanate groups that are blocked, i.e. reversibly blocked with, for example, phenol, tert-butanol, 1,3-diketones, malonic esters, cyclic amides such as ε-caprolactam, nitriles, aldehydes or oximes, or which can be uncapped and which - capped or uncapped - can react with, for example, amino groups and hydroxyl groups.

The theoretical crosslinking density of suitable self-crosslinking binders, expressed in mol of crosslinking points per kg of binder which arise on complete reaction on the polymer which serves as the binder, is preferably in the range from 0.1 to 1 mol / kg of binder.

Examples of suitable crosslinking agents are diols and polyols such as, for example, ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, propane-1, 3-diol, butane-1, 4-diol, hexane-1, 6- diol, secondary or preferably primary diamines such as C ₂ -C ₁₂ alkylene diamines, in which up to 5 non-adjacent C atoms can be replaced by oxygen, for example hexamethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, N, N bis- (aminopropyl) aminoethane, 3,6-dioxaoctane-1,8-diamine, 3,7-dioxanonane-1,9-diamine, 3,6,9-trioxaundecane-1,11-diamine, furthermore Jeffamine such as 4,4'-diamaminodicyclohexylmethane

and, 4'-diamino-3,3'-dimethyldicyclohexylmethane,

Amino alcohols such as B. ethanolamine, 3-hydroxypropylamine, mono- and poly-ethoxylated di- and oligoamines, dihydrazides of aliphatic and aromatic dicarboxylic acids such as adipic acid dihydrazide, dialdehydes such as glyoxal, partially or completely O-methylolated melamines, salts of divalent metals, especially magnesium chloride, for example as hydrate (MgCl ₂ 6 H ₂ O), and also compounds which have an average (number average) of 2 or more, preferably 3 or more isocyanate groups or blocked isocyanate groups per molecule.

In one embodiment, aqueous liquors used in the process according to the invention contain 100 to 800 g / l of binder, preferably 200 to 500 g / l.

In one embodiment of the present invention, one or more adhesion promoters (d) can be added.

Hydrophilic organic polymers are very particularly preferably used as adhesion promoters (d).

In one embodiment of the present invention, hydrophilic organic polymers used as adhesion promoters (d) are polymers or copolymers which have structural elements 1.1 to I.4

1.1 I.2 I.4

exhibit.

In one embodiment of the present invention, the sum of nitrogen atoms and oxygen atoms to the carbon atoms in hydrophilic organic polymers or copolymers is in the range from 2: 1 to 1: 5, in particular from 3: 2 to 1: 3.

In another embodiment of the present invention, the adhesion promoter (d) chosen is a hydrophilic organic polymer which, at pH values from 3 to 12, contains non-ionizable polar structural elements, for example polyurethane units. ten, polyethylene glycol units, polyvinylpyrrolidone units, polyvinyl alcohol units, polyvinylformamide units or polysaccharide units.

Of course, such copolymers are also suitable which have different structural elements 1.1 to I.4.

Examples of suitable hydrophilic polymers or copolymers are those with the following polar groups A ¹ or A ¹ ':

-SO ₃ H, -SO ₃ - X ⁺ , -PO ₃ H ₂ , -PO ₃ ² - 2 X ⁺ , -O-PO ₃ H ₂ , -COOH, -COOR ¹ , -COO ^" X ⁺ , -C (O) NR ¹ R ² , -OC (O) NR ¹ R ² , -OH, -OCH ₃ .

In the chain of suitable hydrophilic organic polymers or copolymers, for example, one or more of the following divergent groups A ² can be found:

-O-, -C (O) O-, -OC (O) O-, -NR ¹ -C (O) NR ² -, -OC (O) NR ¹ -, -CH ₂ CH ₂ O-, - C (O) NR ¹ C (O) -, -OC (O) NR ¹ C (O) -, -OC (O) NR ¹ C (O) -O-, -C (O) NR ¹ C (O ) NR ² -, -OC (O) NR ¹ C (O) NR ² -, -OC (O) NR ¹ C (O) -O-,

X represents ü, Na, K, Rb, Cs or ammonium ions of the formula N (R ³ ) ₄ ;

R ¹ to R ² are in each case identical or different and stand for H, C ₁ -C ₄ alkyl, selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl;

n is an integer in the range of 8 to 80,000, preferably 10 to 16,000.

R ³ are each the same or different and selected from

Hydrogen;

-CC ₄ alkyl, selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl;

-CH ₂ -CH ₂ -OH

Benzyl or C ₆ -C ₁₄ aryl, preferably phenyl.

The following ammonium ions may be mentioned as examples: NH ⁺ , CH ₃ NH ₃ ⁺ ,

(CH ₃ ) ₂ NH ₂ ⁺ , (CH ₃ ) ₃ NH ⁺ , (CH ₃ ) ₄ N ⁺ , C ₂ H ₅ NH ₃ ⁺ , H ₂ N (CH ₂ CH ₂ OH) ₂ ⁺ , HN (CH ₂ CH ₂ OH) ₃ ⁺ , CH ₃ NH (CH ₂ CH ₂ OH) ₂ ⁺ , nC ₄ H ₉ NH (CH ₂ CH ₂ OH) ₂ ⁺ . Very particularly preferred polar groups are the a.1.1 to a.1.7 simply bonded to the polymer chain

1.1.1 1.1.2 1.1.3 1.1.4

.1.5 1.1.6 1.1.7

1.1.8 1.1.9

Groups 1.1.1 to 1.1.9 can be in the polymer main chain or copolymer main chain or - for example, a branched or crosslinked polymer or copolymer - in the polymer side chains of hydrophilic organic polymer or copolymer.

Groups 1.1.1 to 1.1.9 can be uniformly, ie statistically or alternately, distributed over the polymer molecule of hydrophilic organic polymer or copolymer, or non-uniformly, as is the case, for example, with block copolymers and in particular with graft copolymers.

Polymers or copolymers used according to the invention can also be groups 1.1.1a and / or 1.1.2a

1.1.1a 1.1.2a

contain, wherein polymers or copolymers used according to the invention preferably form branched or crosslinked structures via these groups.

Groups 1.1.1a and 1.1.2a can be in the main polymer chain or main copolymer chain or - for example, a branched or crosslinked polymer or copolymer - in the polymer side chains. Groups 1.1.1a and 1.1.2a can be uniform over the polymer molecule, i.e. random or alternating, distributed or uneven, as is the case with block copolymers, for example.

In one embodiment of the present invention, 1 to 150 g / l of adhesion promoter is added to the aqueous liquor, preferably at least 4 g / l and particularly preferably at least 5 g / l.

Aqueous liquors used in the process according to the invention can be added to adjust the viscosity, one or more thickeners, which can 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 14% by weight of acrylamide and about 0.01 to 1% by weight. % of the (meth) acrylamide derivative of the formula II

with molecular weights M _w in the range from 100,000 to 200,000 g / mol, in which R ^{4 represents} methyl or preferably hydrogen. As examples of natural thickeners Origin are: agar-agar, carrageenan, modified starch and modified cellulose.

For example, 0 to 10% by weight, based on the liquor used in the process according to the invention, of thickeners can be used, preferably 0.05 to 5% by weight and particularly preferably 0.1 to 3% by weight.

Aqueous liquors used in the process according to the invention preferably have a dynamic viscosity in the range from 10 to 5000 mPa-s, preferably 20 to 4000 mPa-s and particularly preferably 50 to 2000 mPa-s, measured at room temperature, for example using a Brookfield viscometer according to DI 51562 -1 to 4.

In one embodiment of the present invention, one or more pigments can be added to the aqueous liquors used in the process according to the invention, for example inorganic or organic pigments, preferably in the form of pigment preparations containing surfactants.

The present invention further relates to surfaces, for example surfaces of substrates, obtainable by the process according to the invention. The surfaces according to the invention are preferably textile surfaces. Surfaces according to the invention are distinguished by good cleaning behavior with respect to dirt, wherein dirt can be selected, for example, from solid and liquid substances. Examples of solid substances are earth, mud, soot, dust, pollen; Examples of liquid substances are urine, oil such as olive oil and coffee, tea, fruit juices, beer and red wine. Dirt can be easily removed from surfaces according to the invention. Furthermore, good durability of surfaces according to the invention is observed. Textile surfaces according to the invention can be washed more than 5 times in conventional washing machines without their advantageous properties being lost. Surfaces according to the invention also have very good optical properties, for example high transparency.

Water forms very heavily on surfaces according to the invention and ideally does not form any drops. The contact angle of water is usually less than 10 °, preferably less than 5 °; ideally they are not measurable. It is therefore easy to dry wet surfaces according to the invention. Dry surfaces according to the invention show little tendency towards fogging.

The present invention further provides articles of clothing with surfaces according to the invention and in particular articles of clothing with outer surfaces which have been produced by the method according to the invention.

Another object of the present invention are diapers with surfaces according to the invention. They hold urine particularly well. The invention is illustrated by working examples.

working examples

General preliminary remarks

The measurements for determining the surface energy (corresponds to the surface tension) were carried out as described in WO 01/96433, p. 19.

The absorbency was determined in accordance with DIN 53924. A 0.5% by weight aqueous solution of the substantive dye lurant turquoise blue GL was used as the rising liquid. The climbing height was 1 cm in each case and was determined in the warp direction in the case of fabrics. With a stamp standardized according to DIN 53924, a marking was applied to a sample of coated or uncoated textile fabric (fabric) that had a size of at least

8 cm '4 cm. The sample was clamped vertically and the lower end was weighted with a hat clip so that the lower end was immersed in the rising liquid. The rising fluid then began to rise in the tissue. As soon as the rising liquid crossed the finish line over the mean width, the time was taken.

The drip test was carried out as a TEGEWA drip test in accordance with Melliand Textile Reports 1987, 68, 581-3.

Production of surfaces according to the invention

1.1 Manufacture of aqueous liquors

1.1.1 Production of aqueous liquor 1

The following were mixed in a bottle: 601, 15 g of distilled water, 200 g of ethanol,

(a.1): 60 g of a 10% by weight aqueous dispersion of amorphous silica, particle diameter 5.5 μm (median, number average), determined by laser diffraction with a Beckman Coulter LS 230; BET surface area according to DIN 66131: 750 m ² / g, surface energy 150 mN / m, produced by mixing the above-mentioned amorphous silica and water using an Ultraturrax; (b.1): 60 g of a 10% by weight aqueous dispersion of amorphous silica, particle diameter 22 nm (median, number average), determined by laser diffraction with a Beckman Coulter LS 230; BET surface area according to DIN 66131: 140 m ² / g, surface energy 150 mN / m, produced by stirring the above-mentioned amorphous silica and water;

(c.1): 18.85 self-crosslinking binder, composed of 17.14 of a 70% by weight aqueous solution 1, 3-dimethylol-4,5-dihydroxyethylene urea (DMDHEU) and 1.71 crystalline magnesium chloride (MgCl ₂ 6 H ₂ O)

(d.1): 60 g of a 10% by weight aqueous solution of polyvinylpyrrolidone with M _w of 50,000 g / mol, determined by gel permeation chromatography, and a K value according to Fikentscher of 30, measured according to H. Fikentscher at 25 ° C in water and a polyvinylpyrrolidone concentration of 1% by weight.

Aqueous liquor 1 was obtained.

1.1.2 Production of further aqueous liquors 2 to 8

The procedure was as described under 1.1.1, but the amounts of distilled water, ethanol, (a.1), (b.1), (c.1) and (d.1) were selected according to Table 1. Amounts of ( a.1), (b.1), (c.1) and (d.1) each relate to aqueous dispersions / mixtures as stated under 1.1.1. The results are summarized in Table 1.

Table 1: Composition of the aqueous liquors 1 to 5

1.1.3 Production of the aqueous liquor 9

940 g of distilled water and 60 g of a 10% by weight aqueous di-n-octylsulfosuccinate solution were mixed.

Aqueous liquor 9 was obtained. 1.2. Coating of surfaces

1.2.1. Coating of polyester fabric

Polyester fabric with a weight per unit area of 220 g / m ² was treated with a liquor in accordance with Table 1 or 2 on a padder (manufacturer Mathis, type no. HVF12085). The application speed was 1 m / min. The contact pressure was 10 bar. This resulted in an occupancy rate in the range of 1.8 to 2.7 g / m ² . The treated polyester fabric was then dried at 120 ° C. on a tenter. The final tempering was carried out over a period of 3 minutes at 150 ° C. under circulating air. Coated polyester fabric according to Table 2 was obtained.

Table 2: Coated polyester fabrics 1.2.1 to 1.2.3 and comparative fabrics V1.2.4 to V1.2.5 according to the invention

1.2.2 Coating of polypropylene fleece

Polypropylene nonwoven with a weight per unit area of 10 g / m ² was treated with a liquor according to Tables 1 and 3 on a padder (manufacturer Mathis, type no. HVF12085). The application speed was 1 m / min. The contact pressure was 10 bar. This resulted in an occupancy rate in the range of 0.08 to 0.12 g / m ² . Subsequently the treated polypropylene fleece was dried at 80 ° C. on a tenter. Coated polypropylene fleece according to Table 3 was obtained.

Table 3: Coated polypropylene nonwovens 1.2.6 to 1.2.8 and comparative nonwoven V1.2.9 according to the invention

nb: not determined

Studies on coated surfaces and comparison surfaces according to the invention

Surfaces coated according to the invention and comparison surfaces were examined for their application properties. The data can be found in Tables 2 and 3.

Polypropylene nonwovens were tested according to the Edana RUN-OFF test (152.0-99), a test recommended by the EDANA (European Nonwoven Association).

Coated fleece was fixed on an inclined plane (inclination: 25 °). An absorbent cardboard was fixed underneath the fleece to absorb the liquid that passed through. 25 g of artificial urine (aqueous NaCl solution, 0.9% by weight) were then passed in 4x (1st surge, 2nd surge, 3rd surge, 4th surge) over the fleece, the carton in each case between two Swell was exchanged. The amount of water that ran over the fleece was collected at the foot of the inclined plane and its volume was determined in each case. The less artificial urine ran over the fleece, the better the hydrophilicity.

The surface tension relates to the trapped artificial urine. The higher the surface tension, the better propylene nonwovens are suitable for or for the production of diapers.

The results are shown in Table 3.

Claims

claims

1. Process for the production of structured surfaces with great hydrophilicity, characterized in that the surfaces with

(b) Coated particles with an average diameter (number average) in the range from 5 nm to 0.5 μm and a surface energy at 20 ° C. greater than or equal to 80 mN / m.

2. The method according to claim 1, characterized in that the particles (a) are one or more hydrophobic polymers.

3. The method according to claim 1 or 2, characterized in that it is particles (b) is one or more inorganic materials.

4. The method according to any one of claims 1 to 3, characterized in that the surface containing one or more dispersions

(b) particles with an average diameter (number average) in the range from 5 nm to 0.5 μm and a surface energy greater than or equal to 80 mN / m.

5. The method according to any one of claims 1 to 4, characterized in that it is carried out in an aqueous liquor.

6. The method according to any one of claims 1 to 5, characterized in that at least one aqueous liquor contains at least one emulsifier.

7. The method according to any one of claims 1 to 6, characterized in that surfaces to be coated are provided with an adhesive layer before coating.

8. The method according to any one of claims 1 to 7, characterized in that (c) uses at least one binder.

9. The method according to any one of claims 1 to 8, characterized in that (d) uses at least one coupling agent.

10. Surfaces obtainable by a process according to at least one of claims 1 to 9.

11. Surfaces according to claim 10, characterized in that they are textile surfaces.

12. Garments with outer surfaces according to one of claims 9 or 10.