DE102013210787A1 - Spherical particles and their use - Google Patents

Abstract

Spherical particles with an average diameter (number average) in the range from 1 to 100 μm, comprising at least one organic polymer, the particles having one or more open pores which have a diameter in the range from 1 to 90% of the particle diameter and a depth of at least 10% of the particle diameter and wherein the spherical particles further contains 0.01 to 20% by weight of at least one fluorine-containing compound V.

Description

The present invention relates to spherical particles having a number average molecular weight in the range of 1 to 100 microns, comprising at least one organic polymer, wherein the particles have one or more open pores having a diameter in the range of 1 to 90% of the particle diameter and have a depth of at least 10% of the particle diameter.

Furthermore, the present invention relates to the use of spherical particles according to the invention for coating substrates.

Furthermore, the present invention relates to a process for the preparation of special spherical particles.

Many film-like coatings of substrates, for example of metal, plastics or of fibrous substrates, for example wood, textile or leather, are glossy. In individual applications, however, matt coatings are required, especially when reflections have a disturbing effect. Examples in the case of leather are upholstery leather and automotive interior parts. Glossy leathers are particularly undesirable on the dashboards because they tend to reflect in the sunshine.

Matting can be achieved, for example, by adding particles to the coating mixture. It is placed on a strong matting effect value. Thus, there is a considerable demand for particles having a strong matting effect.

Matt surfaces should also have a pleasant grip, so a pleasant feel.

In the WO 2010/119002 Spherical particles are described which are suitable for matting leather.

In WO 03/095517 discloses particles comprising polyurethane composed of at least one diisocyanate which carries no lateral alkyl groups and at least two different diols, one of which is macromolecular and the other not, and which are suitable for matting. However, their matting effect is in some cases not strong enough and can be improved.

It was therefore the task to provide particles that are particularly suitable for matting. Furthermore, the task was to provide heavily matted substrates. Another object was to provide processes for the production of particles which have strong matting effects. Finally, the object was to provide uses for particles with strong matting properties.

It has furthermore been desirable to provide suitable matting agents which also have good anti-soiling properties and do not or only slightly impair the other mechanical properties of materials coated therewith, such as for example creases or rubbing fastnesses.

Accordingly, the initially defined particles were found, which are also referred to below as particles of the invention.

Particulates according to the invention are spherical. Spherical particles in the context of the present invention are spherical or substantially spherical particles in which the diameters at the widest point and the diameter at the narrowest point deviate from one another by not more than 20%, preferably not more than 15%. Particularly preferred are spherical particles.

Particles according to the invention have an average diameter (volume average) in the range from 1 to 100 μm, preferably from 1 to 50 μm, measured by means of laser diffraction.

In one embodiment of the present invention, particles of the invention have a narrow particle diameter distribution, for example a weight average to diameter ratio (number average) ratio in the range of 3 to 1 to 1.5 to 1 or less.

In another embodiment of the present invention, particles of the invention have a broad particle diameter distribution, for example a weight average to diameter ratio (number average) ratio in the range of 10 to 1 or more to 3.1 to 1.

In one embodiment of the present invention, particles according to the invention have a monomodal particle diameter distribution. In another embodiment of the present invention, particles of the invention may have a bimodal or multimodal particle diameter distribution.

Particles according to the invention have one or more pores which have a diameter in the range from 1 to 90% of the particle diameter, preferably from 2 to 80%, determinable, for example, by microscopic determinations. A particularly suitable determination method is electron microscopy on representative samples, for example on samples of at least 50 particles.

The pores have a depth of at least 10% of the particle diameter, as can be determined for example by microscopic measurements.

In one embodiment of the present invention, particles according to the invention may have on average (number average) from 1 to 100, preferably up to 25, pores, more preferably 2 to 20, pores per particle.

The pores are open pores.

In one embodiment of the present invention, particles of the invention have substantially equal open many pores per particle. In another embodiment of the present invention, the number of open pores per particle deviates greatly from the mean, for example by a factor of 5 to 10 or more.

The shape of pores of particles of the invention may be regular or irregular. Preferably, the shape of open pores of the particles of the invention is regular. In one embodiment of the present invention, pores may have a substantially cylindrical or conical shape. In another embodiment of the present invention, pores may be similar to undercuts, that is, they have a small opening and the cavity under the opening widens.

In one embodiment of the present invention, the pores of particles of the invention are uniform. In another embodiment of the present invention, the pores of particles of the invention may take different forms, for example particles according to the invention may have conical and cylindrically shaped pores.

In one embodiment of the present invention, particles according to the invention have exclusively pores as described above. In another embodiment of the present invention, particles according to the invention may additionally have pores which deviate in shape and / or size from the pores according to the preceding paragraphs.

In one embodiment of the present invention, particles according to the invention may also have one or more closed pores in addition to the open pores.

Particles according to the invention comprise at least one organic polymer. The term "polymer" in the context of the present invention also includes copolymers. For the purposes of the present invention, organic polymers are understood as meaning those high molecular weight compounds whose chains are essentially composed of carbon atoms or of heteroatoms directly bonded with carbon atoms, for example oxygen, nitrogen or sulfur atoms. In one embodiment of the present invention, organic polymers may include, for example, silyl groups, especially Si (CH ₃ ) ₃ groups. In another embodiment of the present invention, organic polymers have no silyl groups.

In one embodiment of the present invention, particles according to the invention consist essentially of organic polymer, for example at least 65% by weight, preferably at least 75% by weight, particularly preferably at least 95% by weight.

In one embodiment of the present invention, particles according to the invention may contain, preferably, one or more inorganic polymers, for example silicates or polysilicic acids as a mass minority component. In another embodiment of the present invention, particles of the invention do not contain inorganic materials such as inorganic polymers. In a further embodiment of the present invention, particles according to the invention contain amounts of up to 25% by weight, preferably up to 5% by weight, of inorganic material, for example polysilicic acid or silica gel.

Preferably, organic polymer is not water soluble.

In one embodiment of the present invention, particles according to the invention comprise only one organic polymer. In another embodiment of the present invention, particles according to the invention comprise at least two organic polymers.

In one embodiment of the present invention, organic polymer is selected from those obtainable by polycondensation, polyaddition or free-radical polymerization, preferred is free-radical polymerization and more preferably polyaddition. In the context of the present invention, the terms polyaddition and polyaddition reactions are used as synonymous.

Preferred examples of organic polymers obtainable by polycondensation are polyesters and polyamides.

Preferred examples of organic polymers obtainable by free radical polymerization are polyolefins, especially polyethylene, where the term polyethylene also includes copolymers of ethylene with up to 30% by weight of one or more comonomers. Examples of suitable comonomers are α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene and 1-dodecene, furthermore ethylenically unsaturated monocarboxylic or dicarboxylic acids such as (meth) acrylic acid, Maleic acid, crotonic acid and itaconic acid and low molecular weight anhydrides of ethylenically unsaturated dicarboxylic acids such as itaconic anhydride and especially maleic anhydride.

Further examples of suitable organic polymers obtainable by free radical polymerization are polyacrylates. In the context of the present invention, polyacrylates are homopolymers of (meth) acrylic acid esters and copolymers of (meth) acrylic acid esters with one another and / or with one or more further comonomers, for example (meth) acrylic acid, (meth) acrylamide, sulfonic acids with a vinyl or allyl group per molecule, amides of sulfonic acids with a vinyl or allyl group per molecule and / or (meth) acrylonitrile understood. Further suitable comonomers may be crosslinkers, for example α, ω-C ₂ -C ₁₀ -alkylenedi (meth) acrylates, for example 1,2-ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate and 1,6-hexanediol (meth) acrylate, and di (meth) acrylates of oligomers or polymers of ethylene glycol, for example diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate and pentaethylene glycol di (meth) acrylate.

In one embodiment of the present invention, organic polymer is a hybrid polymer, for example a hybrid of polyurethane and polyacrylate.

Preferred organic polymers are those which can be obtained by polyaddition. Examples are polyureas and especially polyurethanes.

In one embodiment of the present invention, polyurethanes are selected from those which, in addition to urethane groups, can also have at least one further group selected from allophanate groups, carbodiimide groups, biuret groups and in particular urea groups.

In one embodiment of the present invention, polyurethanes are selected from those in the total range of 0.01 to 10, preferably in the range of 0.02 to 5 further groups selected from allophanate groups, carbodiimide groups, biuret groups and especially urea groups, per urethane group have (number average).

In one embodiment of the present invention, polyurethanes are selected from those having monoalkylpolyalkylene oxide groups. Monoalkylpolyalkyleneoxides are usually obtainable by alkoxylation of low molecular weight monohydric starter molecules, in particular C ₁ -C ₁₀ -alkanols, such as methanol, ethanol or n-butanol, preferably ethylene oxide or mixtures of ethylene oxide with other alkylene oxides, in particular propylene oxide, being used as the alkoxylating agent, and can be incorporated into polyurethanes during polyurethane synthesis. Has used Monoalkylpolyalkylenoxid preferably a number average molecular weight of 250 to 10,000 g / mol, more preferably from 400 to 5,000 g / mol.

Particles according to the invention contain from 0.01 to 20% by weight of at least one fluorine-containing compound V.

Preferred fluorine-containing compounds V are, for example, in WO 2007/144283 , P. 2, lines 1 to p. 9, line 20 or in WO 2010/112395 , P. 2, lines 1 to p. 20, line 8, which are incorporated by reference into this application.

wobei,
für n = 1:
R¹ = H, C₁-C₂₅ Alkyl, C₂-C₂₅ Alkenyl, -CO-R⁵, -CH(R¹⁰)CO-R⁵, -C(R¹⁰)₂CO-R⁵, -CO-N(R⁶)-R⁷, -CH(R¹⁰)CO-N(R⁶)-R⁷, -C(R¹⁰)₂CO-N(R⁶)-R⁷, -CH(R¹⁰)COOR⁵ oder -C(R¹⁰)₂CO-OR⁵;
für n = 2:
R¹ = unsubstituiertes oder mit C₁-C₄ Alkyl, Benzyl oder Phenyl substituiertes C₁-C₂₄ Alkylen, durch Sauerstoff oder Schwefel unterbrochenes C₁-C₂₄ Alkylen; -CO-R⁸-CO-, -CH(R¹⁰)CO-R⁸-CO-CH(R¹⁰)-, -C(R¹⁰)₂CO-R⁸-CO-C(R¹⁰)₂, -CO-N(R⁶)-R⁹-N(R⁶)-CO-, -CH(R¹⁰)CO-N(R⁶)-R⁹-N(R⁶)-CO-CH(R¹⁰)-, -C(R¹⁰)₂CO-N(R⁶)-R⁹-N(R⁶)-CO-C(R¹⁰)₂, -CH(R¹⁰)CO-O-R⁹-O-CO-CH(R¹⁰)- oder -C(R¹⁰)2CO-O-R⁹-O-CO-C(R¹⁰)₂;
für n = 3:

R², R³ and R⁴ unabhängig voneinander H, C₁-C₂₅ Alkyl, C₂-C₂₅ Alkenyl, -CH(R¹¹)-

wobei mindestens einer der Reste R², R³ oder R⁴-CH(R¹¹)-S(O)_p-R¹² ist;
R⁵ = C₁-C₂₅ Alkyl, C₁-C₂₅ Alkenyl, unsubstituiertes oder mit C₁-C₄ oder Halogen substituiertes Phenyl oder C₇-C₁₂ Phenylalkyl;
R⁶ = H oder C₁-C₄ Alkyl;
R⁷ = H, C₁-C₂₅ Alkyl, unsubstituiertes oder mit C₁-C₄ Alkyl oder Halogen substituiertes Phenyl;
R⁸ = Phenylen, unsubstituiertes oder mit C₁-C₄ Alkyl, Benzyl oder Phenyl substituiertes C₂-C₂₄ Alkylene oder durch Sauerstoff oder Schwefel unterbrochenes C₂-C₂₄ Alkylen;
R⁹ = eine chemische Bindung, unsubstituiertes oder mit C₁-C₄ Alkyl, Benzyl oder Phenyl substituiertes C₂-C₂₄ Alkylen oder durch Sauerstoff oder Schwefelunterbrochenes C₂-C₂₄ Alkylen;
R¹⁰ = H oder C₁-C₈ Alkyl,
R¹¹ = H, C₁-C₈ Alkyl, unsubstituiertes oder mit C₁-C₄ Alkyl substituiertes Phenyl ist;
R¹² = ein monovalenter perfluorierter Alkyl- oder Alkenyl-Rest oder ein linearer oder verzweigter organischer Rest mit vier bis 20 perfluorierten Kohlenstoffatomen ist;
R¹³ = H, C₁-C₂₅ Alkyl, C₂-C₂₅ Alkenyl, -CO-R⁵, -CO-N(R⁶)-R⁷ oder -CH₂-CO-N(R⁶)-R⁷;
R¹⁴ = H, C₁-C₂₅ Alkyl, C₂-C₂₅ Alkenyl oder -CH(R¹¹)-S(O)_p-R¹²;
R¹⁵ = H, C₁-C₂₅ Alkyl, C₂-C₂₅ Alkenyl oder -CH(R¹¹)-S(O)_p-R¹²;
R¹⁶ = unsubstituiertes oder mit C₁-C₄ Alkyl substituiertes Methylen, -S-, -S(O)-, -S(O)₂ oder -CO-;
R¹⁷ = C₁-C₄ Alkyl;
n = 1, 2 oder 3;
p = 0, 1 oder 2.Preferred fluorine-containing compounds V are, in particular, those according to the general formula I:

in which,
for n = 1:
R ¹ = H, C ₁ -C ₂₅ alkyl, C ₂ -C ₂₅ alkenyl, -CO-R ⁵ , -CH (R ¹⁰ ) CO-R ⁵ , -C (R ¹⁰ ) ₂ CO-R ⁵ , -CO -N (R ⁶ ) -R ⁷ , -CH (R ¹⁰ ) CO-N (R ⁶ ) -R ⁷ , -C (R ¹⁰ ) ₂ CO-N (R ⁶ ) -R ⁷ , -CH (R ¹⁰ ) COOR ⁵ or -C (R ¹⁰ ) ₂ CO-OR ⁵ ;
for n = 2:
R ¹ = unsubstituted or substituted by C ₁ -C ₄ alkyl, benzyl or phenyl substituted C ₁ -C ₂₄ alkylene, which is interrupted by oxygen or sulfur C ₁ -C ₂₄ alkylene; -CO-R ⁸ -CO-, -CH (R ¹⁰ ) CO-R ⁸ -CO-CH (R ¹⁰ ) -, -C (R ¹⁰ ) ₂ CO-R ⁸ -CO-C (R ¹⁰ ) ₂ , -CO-N (R ⁶⁾ -R ⁹ -N (R ⁶⁾ -CO-, -CH (R ¹⁰⁾ CO-N (R ⁶⁾ -R ⁹ -N (R ⁶⁾ -CO-CH (R ¹⁰ ) -, -C (R ¹⁰ ) ₂ CO-N (R ⁶ ) -R ⁹ -N (R ⁶ ) -CO-C (R ¹⁰ ) ₂ , -CH (R ¹⁰ ) CO-OR ⁹ -O-CO -CH (R ¹⁰⁾ - or -C (R ¹⁰⁾ 2 CO-oR ⁹ -O-CO-C (R ¹⁰⁾ _2;
for n = 3:

R ² , R ³ and R ^{4 are} independently H, C ₁ -C ₂₅ alkyl, C ₂ -C ₂₅ alkenyl, -CH (R ¹¹ ) -

wherein at least one of R ² , R ³ or R ^{4 is} -CH (R ¹¹ ) -S (O) _p -R ¹² ;
R ⁵ = C ₁ -C ₂₅ alkyl, C ₁ -C ₂₅ alkenyl, unsubstituted or C ₁ -C ₄ or halogen-substituted phenyl or C ₇ -C ₁₂ phenylalkyl;
R ⁶ = H or C ₁ -C ₄ alkyl;
R ⁷ = H, C ₁ -C ₂₅ alkyl, unsubstituted or C ₁ -C ₄ alkyl or halogen-substituted phenyl;
R ⁸ = phenylene, unsubstituted or C ₁ -C ₄ alkyl, benzyl or phenyl-substituted C ₂ -C ₂₄ alkylenes or interrupted by oxygen or sulfur C ₂ -C ₂₄ alkylene;
R ⁹ = a chemical bond, unsubstituted or C ₁ -C ₄ alkyl, benzyl or phenyl-substituted C ₂ -C ₂₄ alkylene or by oxygen or sulfur interrupted C ₂ -C ₂₄ alkylene;
R ¹⁰ = H or C ₁ -C ₈ alkyl,
R ^{11 is} H, C ₁ -C ₈ alkyl, unsubstituted or C ₁ -C ₄ alkyl substituted phenyl;
R ¹² = a monovalent perfluorinated alkyl or alkenyl radical or a linear or branched organic radical having four to 20 perfluorinated carbon atoms;
R ¹³ = H, C ₁ -C ₂₅ alkyl, C ₂ -C ₂₅ alkenyl, -CO-R ⁵ , -CO-N (R ⁶ ) -R ⁷ or -CH ₂ -CO-N (R ⁶ ) -R ⁷ ;
R ¹⁴ = H, C ₁ -C ₂₅ alkyl, C ₂ -C ₂₅ alkenyl or -CH (R ¹¹ ) -S (O) _p -R ¹² ;
R ¹⁵ = H, C ₁ -C ₂₅ alkyl, C ₂ -C ₂₅ alkenyl or -CH (R ¹¹ ) -S (O) _p -R ¹² ;
R ¹⁶ = unsubstituted or C ₁ -C ₄ alkyl-substituted methylene, -S-, -S (O) -, -S (O) ₂ or -CO-;
R ¹⁷ = C ₁ -C ₄ alkyl;
n = 1, 2 or 3;
p = 0, 1 or 2.

Alkyl groups having 1 to 25 carbon atoms are linear or branched radicals such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, Hexadecyl, heptadecyl, octadecyl, icosyl or docosyl. Alkenyl groups of 2 to 25 carbon atoms are linear or branched radicals such as propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2 Octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl.

Unsubstituted or C ₁ -C ₄ alkyl, benzyl or phenyl-substituted C ₁ -C ₂₄ alkylene are branched or unbranched radicals such as, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, Decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, methylmethylene, ethylmethylene, 2-methylpropylene, 2-phenylpropylene, benzylpropylene, benzylmethylene or phenylmethylene (benzylidene).

Interrupted by oxygen or sulfur, C ₁ -C ₄ alkyl groups are, for example, -CH ₂ -O-CH2-, -CH ₂ -S-CH ₂ -, -CH ₂ -N (CH ₃₎ -CH ₂ -, -CH ₂ -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ - (O-CH ₂ CH ₂ -) ₂ O-CH ₂ CH ₂ -, -CH ₂ CH ₂ - (O-CH ₂ CH ₂ -) ₃ O-CH ₂ CH ₂ -, -CH ₂ CH ₂ - (O -CH ₂ CH ₂ -) ₄ O-CH ₂ CH ₂ - or -CH ₂ CH ₂ -S-CH ₂ CH ₂ -.

Examples of C ₁ -C ₄ -alkyl or halogen-substituted phenyl which preferably contains 1 to 3, in particular 1 or 2, alkyl or halogen groups are o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2, 4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl, 2,6- Diethylphenyl, 2-chlorophenyl, 4-chlorophenyl or 2-methyl-4-chlorophenyl.

C ₇ -C ₁₂ phenylalkyl, substituted or unsubstituted on the phenyl radical by C ₁ -C ₃ alkyl groups, are for example benzyl, alpha-methylbenzyl, alpha, alpha-dimethylbenzyl, 2-phenylethyl, 2-methylbenzyl, 3-methylbenzyl, 4- Methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzyl or 4-tert-butylbenzyl. Benzyl is preferred.

Monovalent perfluorinated alkyl or alkenyl groups and linear or branched organic radicals having four to 20 perfluorinated carbon atoms are, for example, -CH ₂ CH ₂ (CF ₂ ) _m CF ₃ , where m is 3 to 19, preferably 3 to 12. The perfluoroalkyl groups may also represent mixtures of perfluoroalkyl groups such that R comprises at the same time a small fraction of perfluoroalkyl groups with a smaller number of carbon atoms and a small fraction of perfluoroalkyl groups with a higher number of carbon atoms in the rule ^12th

R², R³ and R⁴ unabhängig voneinander H, C₁-C₁₈-Alkyl, C₂-C₁₈-Alkenyl, -CH(R¹¹)-S(O)_p-R¹²,

wobei mindestens einer der Reste R2, R3 oder R4-CH(R¹¹)-S(O)_p-R¹² ist;
R⁵ = C₁-C₁₈-Alkyl, C₂-C₁₈-Alkenyl, unsubstituiertes oder mit C₁-C₄-Alkyl oder halogen substituiertes Phenyl; oder C₇-C₁₂-phenylalkyl;
R⁶ = H oder C₁-C₄-Alkyl;
R⁷ = H, C₁-C₁₈-Alkyl, unsubstituiertes oder mit C₁-C₄-Alkyl oder Halogen substituiertes Phenyl;
R⁸ = Phenylen, unsubstituiertes oder mit C₁-C₄-Alkyl, Benzyl oder Phenyl substituiertes C₁-C₂₄-Alkylene; durch Sauerstoff oder unterbrochenes C₂-C₂₄-Alkylen;
R⁹ = eine chemische Bindung oder unsubstituiertes oder mit C₁-C₄-Alkyl, Benzyl oder Phenyl substituiertes C₁-C₁₈-Alkylen;
R¹⁰ = H oder C₁-C₈-Alkyl;
R¹¹ = H, C₁-C₈-Alkyl, unsubstituiertes oder mit C₁-C₄-Alkyl substituiertes Phenyl;
R¹² = ein einwertiger perfluorierter Alkyl- oder Alkenylrest, oder eine linearer oder verzweigter organischer Rest mit 4 bis 20 perfluorierten Kohlenstoffatomen;
R¹³ = H, C₁-C₁₈-Alkyl, C₂-C₁₈-Alkenyl, -CO-R⁵, -CO-N(R⁶)-R⁷ oder -CH₂-CO-N(R⁶)-R⁷;
R¹⁴ = H, C₁-C₁₈-Alkyl, C₂-C₁₈-Alkenyl oder -CH(R¹¹)-S(O)_p-R¹²;
R¹⁵ = H, C₁-C₁₈-Alkyl, C₂-C₁₈-Alkenyl oder -CH(R¹¹)-S(O)_p-R¹².
R¹⁶ = unsubstiuiertes oder mit C₁-C₄-Alkyl substituiertes Methylen, -S-, -S(O)-, -S(O)₂ oder -CO-;
R¹⁷ = C₁-C₄-Alkyl;
n = 1, 2 oder 3;
p = 0, 1 oder 2.In one embodiment, fluorine-containing compounds V are compounds of general formula I wherein
for n = 1:
R ¹ = H, C ₁ -C ₁₈ -alkyl, C ₂ -C ₁₈ -alkenyl, -CO-R ⁵ , -CO-N (R ⁶ ) -R ⁷ or -CH ₂ -CO-N (R ⁶ ) -R ⁷ ;
for n = 2:
R ¹ = unsubstituted or C ₁ -C ₄ alkyl, benzyl or phenyl substituted C ₁ -C ₁₈ alkylenes, oxygen or sulfur interrupted C ₁ -C ₁₈ alkylenes; -CO-R ⁸ -CO-, -CO-N (R ⁶ ) -R ⁹ -N (R ⁶ ) -CO- or -CH (R ¹⁰ ) -CO-N (R ⁶ ) -R ⁹ -N ( R ⁶ ) -CO-CH (R ¹⁰ ) -;
for n = 3:

R ² , R ³ and R ⁴ independently of one another are H, C ₁ -C ₁₈ -alkyl, C ₂ -C ₁₈ -alkenyl, -CH (R ¹¹ ) -S (O) _p -R ¹² ,

wherein at least one of the radicals R2, R3 or R4-CH (R ¹¹⁾ -S (O) _p -R ^12;
R ⁵ = C ₁ -C ₁₈ -alkyl, C ₂ -C ₁₈ -alkenyl, unsubstituted or C ₁ -C ₄ -alkyl or halogen-substituted phenyl; or C ₇ -C ₁₂ phenylalkyl;
R ⁶ = H or C ₁ -C ₄ alkyl;
R ⁷ = H, C ₁ -C ₁₈ -alkyl, unsubstituted or C ₁ -C ₄ -alkyl or halogen-substituted phenyl;
R ⁸ = phenylene, unsubstituted or C ₁ -C ₄ -alkyl, benzyl or phenyl-substituted C ₁ -C ₂₄ -alkylenes; by oxygen or interrupted C ₂ -C ₂₄ alkylene;
R ⁹ = a chemical bond or unsubstituted or C ₁ -C ₄ alkyl, benzyl or phenyl-substituted C ₁ -C ₁₈ alkylene;
R ¹⁰ = H or C ₁ -C ₈ -alkyl;
R ¹¹ = H, C ₁ -C ₈ -alkyl, unsubstituted or C ₁ -C ₄ -alkyl-substituted phenyl;
R ¹² = a monovalent perfluorinated alkyl or alkenyl radical, or a linear or branched organic radical having from 4 to 20 perfluorinated carbon atoms;
R ¹³ = H, C ₁ -C ₁₈ -alkyl, C ₂ -C ₁₈ -alkenyl, -CO-R ⁵ , -CO-N (R ⁶ ) -R ⁷ or -CH ₂ -CO-N (R ⁶ ) -R ⁷ ;
R ¹⁴ = H, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl or -CH (R ¹¹ ) -S (O) _p -R ¹² ;
R ¹⁵ = H, C ₁ -C ₁₈ -alkyl, C ₂ -C ₁₈ -alkenyl or -CH (R ¹¹ ) -S (O) _p -R ¹² .
R ¹⁶ = unsubstituted or C ₁ -C ₄ alkyl-substituted methylene, -S-, -S (O) -, -S (O) ₂ or -CO-;
R ¹⁷ = C ₁ -C ₄ -alkyl;
n = 1, 2 or 3;
p = 0, 1 or 2.

Preferred fluorine-containing compounds V are, in particular, those according to the general formula I, in which:
R ^{12 is} saturated and contains from 4 to 15 carbon atoms, which are perfluorinated and contain at least one terminal perfluoromethyl group.

wobei einer der Reste R², R³ und R⁴ -CH(R¹¹)-S(O)_p-R¹² ist;
R¹¹ = H, C₁-C₈-Alkyl, unsubstituiertes oder mit C₁-C₄-Alkyl substituiertes Phenyl;
R¹² = ein einwertiger perfluoriertes Alkyl oder Alkenylrest oder ein linearer oder verzweigter organischer Rest mit 4 bis 20 perfluorierten Kohlenstoffatomen;
R¹³ = H, C₁-C₁₈-Alkyl, C₂-C₁₈-Alkenyl oder Acetyl,
R¹⁴ = H, C₁-C₁₈-Alkyl, C₂-C₁₈-Alkenyl oder -CH(R¹¹)-S(O)_p-R¹²;
R¹⁵ = H, C₁-C₁₈-Alkyl, C₂-C₁₈-Alkenyl oder -CH(R¹¹)-S(O)_p-R¹²;
R¹⁶ = unsubstituiertes oder mit C₁-C₄-Alkyl substituiertes Methylen, -S-, -S(O)-, -S(O)₂ oder -CO;
p = 0, 1 oder 2.In fluorine-containing compounds, preference is given to VR ² , R ³ and R ⁴ independently of one another being H, C ₁ -C ₄ -alkyl, -CH (R ¹¹ ) -S (O) _p -R ¹² or

wherein one of R ² , R ³ and R ^{4 is} -CH (R ¹¹ ) -S (O) _p -R ¹² ;
R ¹¹ = H, C ₁ -C ₈ -alkyl, unsubstituted or C ₁ -C ₄ -alkyl-substituted phenyl;
R ¹² = a monovalent perfluorinated alkyl or alkenyl radical or a linear or branched organic radical having from 4 to 20 perfluorinated carbon atoms;
R ^{13 is} H, C ₁ -C ₁₈ -alkyl, C ₂ -C ₁₈ -alkenyl or acetyl,
R ¹⁴ = H, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl or -CH (R ¹¹ ) -S (O) _p -R ¹² ;
R ¹⁵ = H, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl or -CH (R ¹¹ ) -S (O) _p -R ¹² ;
R ¹⁶ = unsubstituted or C ₁ -C ₄ alkyl-substituted methylene, -S-, -S (O) -, -S (O) ₂ or -CO;
p = 0, 1 or 2.

R², R³ and R⁴ unabhängig voneinander H, C₁-C₈-Alkyl, C₂-C₁₈-Alkenyl, -CH(R¹¹)-S(O)_p-R¹²,

sind, wobei mindestens einer der Reste R², R³ oder
R⁴ -CH(R¹¹)-S(O)_p-R¹² ist;
R⁵ = C₁-C₁₈-Alkyl, unsubstituiertes oder mit C₁-C₄-Alkyl substituiertes Phenyl oder C₇-C₁₂-Phenylalkyl ist;
R⁶ = H oder C₁-C₄-Alkyl,
R⁷ = H, C₁-C₈-Alkyl, unsubstituiertes oder mit C₁-C₄-Alkyl substituiertes Phenyl;
R⁸ = Phenylene, unsubstituiertes oder mit C₁-C₄-Alkyl substituiertes C₁-C₁₈-Alkylene;
R⁹ = unsubstituiertes oder mit C₁-C₄-Alkyl substituiertes C₂-C₁₈-Alkylene;
R¹⁰ = H oder C₁-C₈-Alkyl,
R¹¹ = H, C₁-C₈-Alkyl, unsubstituiertes oder mit C₁-C₄-Alkyl substituiertes Phenyl;
R¹² = ein gesättigter Rest mit 4-15 C-Atomen, der perfluoriert ist und mindestens eine Perfluormethylgruppe umfasst;
R¹³ = H, C₁-C₁₂-Alkyl, C₂-C₁₈-Alkenyl, -CO-R⁵, -CO-N(R⁶)-R⁷ oder -CH₂-CO-N(R⁶)-R⁷;
R¹⁴ = H, C₁-C₁₂-Alkyl, C₂-C₁₈-Alkenyl oder -CH(R¹¹)-S(O)_p-R¹²;
R¹⁵ = H, C₁-C₁₈-Alkyl oder -CH(R¹¹)-S(O)_p-R¹².
R¹⁶ = unsubstiuiertes oder mit C₁-C₄-Alkyl substituiertes Methylen;
R¹⁷ = C₁-C₄-Alkyl,
n = 1, 2 oder 3, and
p = 0, 1 oder 2.Particularly preferred fluorine-containing compounds V are in particular those of the formula I in which
for n = 1:
R ¹ = H, C ₁ -C ₁₈ -alkyl, C ₂ -C ₁₈ -alkenyl, -CO-R ⁵ , -CO-N (R ⁶ ) -R ⁷ or -CH ₂ -CO-N (R ⁶ ) -R ⁷ ;
for n = 2:
R ¹ = unsubstituted or C ₁ -C ₄ -alkyl-substituted C ₁ -C ₁₈ -alkylenes, -CO-R ⁸ -CO-, -CO-N (R ⁶ ) -R ⁹ -N (R ⁶ ) -CO - or -CH (R ¹⁰ ) -CO-N (R ⁶ ) -R ⁹ -N (R ⁶ ) -CO-CH (R ¹⁰ ) -;
for n = 3:

R ² , R ³ and R ⁴ independently of one another are H, C ₁ -C ₈ -alkyl, C ₂ -C ₁₈ -alkenyl, -CH (R ¹¹ ) -S (O) _p -R ¹² ,

wherein at least one of R ² , R ³ or
R ^{4 is} -CH (R ¹¹ ) -S (O) _p -R ¹² ;
R ⁵ = C ₁ -C ₁₈ alkyl, unsubstituted or C ₁ -C ₄ alkyl substituted phenyl or C ₇ -C ₁₂ phenylalkyl;
R ⁶ = H or C ₁ -C ₄ -alkyl,
R ⁷ = H, C ₁ -C ₈ alkyl, unsubstituted or C ₁ -C ₄ alkyl substituted phenyl;
R ⁸ = phenylenes, unsubstituted or C ₁ -C ₄ -alkyl-substituted C ₁ -C ₁₈ -alkylenes;
R ⁹ = unsubstituted or C ₁ -C ₄ -alkyl-substituted C ₂ -C ₁₈ -alkylenes;
R ¹⁰ = H or C ₁ -C ₈ -alkyl,
R ¹¹ = H, C ₁ -C ₈ -alkyl, unsubstituted or C ₁ -C ₄ -alkyl-substituted phenyl;
R ¹² = a saturated radical having 4-15 C atoms, which is perfluorinated and comprises at least one perfluoromethyl group;
R ¹³ = H, C ₁ -C ₁₂ -alkyl, C ₂ -C ₁₈ -alkenyl, -CO-R ⁵ , -CO-N (R ⁶ ) -R ⁷ or -CH ₂ -CO-N (R ⁶ ) -R ⁷ ;
R ¹⁴ = H, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₈ alkenyl or -CH (R ¹¹ ) -S (O) _p -R ¹² ;
R ¹⁵ = H, C ₁ -C ₁₈ -alkyl or -CH (R ¹¹ ) -S (O) _p -R ¹² .
R ¹⁶ = form unsubstituted or C ₁ -C ₄ alkyl-substituted methylene;
R ¹⁷ = C ₁ -C ₄ -alkyl,
n = 1, 2 or 3, and
p = 0, 1 or 2.

R², R³ and R⁴ unabhängig voneinander H, C₁-C₈-Alkyl, -CH(R¹¹)-S(O)_p-R¹²,

sind, wobei mindestens einer der Reste R², R³ oder
R⁴ -CH(R¹¹)-S(O)_p-R¹² ist;
R⁵ = C₁-C₁₈-Alkyl, unsubstituiertes oder mit C₁-C₄-Alkyl substituiertes Phenyl oder Benzyl;
R⁶ = H;
R⁷ = H, C₁-C₈-Alkyl, unsubstituiertes oder mit C₁-C₄-Alkyl substituiertes Phenyl;
R⁸ = Phenylene, C₁-C₁₈-Alkylene;
R⁹ = C₂-C₁₈-Alkylene;
R¹⁰ = C₁-C₄-Alkyl;
R¹¹ = H, C₁-C₈-Alkyl, unsubstituiertes oder mit C₁-C₄-Alkyl substituiertes Phenyl;
R¹² = CH₂CH₂(CF₂)_mCF₃;
R¹³ = H, -CO-R⁵;
R¹⁴ = H, C₁-C₈-Alkyl;
R¹⁵ = C₁-C₄-Alkyl oder -CH(R¹¹)-S(O)_p-R¹²;
R¹⁶ = Methylen;
m = eine Zahl von 3 bis 12;
n = 1, 2 oder 3, and
p = 0.Particularly preferred fluorine-containing compounds V are in particular those according to the general formula I in which
for n = 1,
R ¹ = H, C ₁ -C ₁₈ alkyl, -CO-R ⁵ , -CO-N (R ⁶ ) -R ⁷ or -CH ₂ -CO-N (R ⁶ ) -R ⁷ ;
for n = 2:
R ¹ = C ₁ -C ₈ -alkylenes, -CO-R ⁸ -CO-, -CO-N (R ⁶ ) -R ⁹ -N (R ⁶ ) -CO- or -CH (R ¹⁰ ) -CO- N (R ⁶ ) -R ⁹ -N (R ⁶ ) -CO-CH (R ¹⁰ ) -;
for n = 3:

R ² , R ³ and R ⁴ independently of one another are H, C ₁ -C ₈ -alkyl, -CH (R ¹¹ ) -S (O) _p -R ¹² ,

wherein at least one of R ² , R ³ or
R ^{4 is} -CH (R ¹¹ ) -S (O) _p -R ¹² ;
R ⁵ = C ₁ -C ₁₈ -alkyl, unsubstituted or C ₁ -C ₄ -alkyl-substituted phenyl or benzyl;
R ⁶ = H;
R ⁷ = H, C ₁ -C ₈ -alkyl, unsubstituted or C ₁ -C ₄ -alkyl-substituted phenyl;
R ⁸ = phenylenes, C ₁ -C ₁₈ -alkylenes;
R ⁹ = C ₂ -C ₁₈ -alkylenes;
R ¹⁰ = C ₁ -C ₄ -alkyl;
R ¹¹ = H, C ₁ -C ₈ -alkyl, unsubstituted or C ₁ -C ₄ -alkyl-substituted phenyl;
R ¹² = CH ₂ CH ₂ (CF ₂ ) _m CF ₃ ;
R ¹³ = H, -CO-R ⁵ ;
R ¹⁴ = H, C ₁ -C ₈ -alkyl;
R ¹⁵ = C ₁ -C ₄ -alkyl or -CH (R ¹¹ ) -S (O) _p -R ¹² ;
R ¹⁶ = methylene;
m = a number from 3 to 12;
n = 1, 2 or 3, and
p = 0.

R², R³ and R⁴ unabhängig voneinander H, C₁-C₄-Alkyl, -CH(R¹¹)-S(O)_p-R¹²,

sind, wobei mindestens einer der Reste R², R³ oder R⁴ -CH(R¹¹)-S(O)_p-R¹² ist;
R⁵ = C₁-C₁₈-Alkyl;
R⁶ = H;
R⁷ = H, C₁-C₆-Alkyl, unsubstituiertes oder mit C₁-C₄-Alkyl substituiertes Phenyl;
R⁸ = Phenylen;
R⁹ = Ethylen;
R¹⁰ = Methyl;
R¹¹ = H, C₁-C₈-Alkyl, unsubstituiertes oder mit Methyl substituiertes Phenyl;
R¹² = CH₂CH₂(CF₂)_mCF₃;
R¹³ = H, Acetyl;
R¹⁴ = C₁-C₄-Alkyl;
R¹⁵ = CH(R¹¹)-S(O)_p-R¹².
R¹⁶ = Methylen;
m = eine Zahl von 3 bis 12;
n = 1, 2 oder 3, and
p = 0.Particularly preferred fluorine-containing compounds V are in particular those according to the general formula I in which
for n = 1,
R ¹ = H, C ₁ -C ₁₂ alkyl, -CO-R ⁵ , -CO-N (R ⁶ ) -R ⁷ or -CH ₂ -CO-N (R ⁶ ) -R ⁷ ;
for n = 2:
R ¹ = methylene, -CO-R ⁸ -CO- or -CH (R ¹⁰ ) -CO-N (R ⁶ ) -R ⁹ -N (R ⁶ ) -CO-CH (R ¹⁰ ) -;
for n = 3:

R ² , R ³ and R ⁴ independently of one another are H, C ₁ -C ₄ -alkyl, -CH (R ¹¹ ) -S (O) _p -R ¹² ,

wherein at least one of R ² , R ³ or R ^{4 is} -CH (R ¹¹ ) -S (O) _p -R ¹² ;
R ⁵ = C ₁ -C ₁₈ alkyl;
R ⁶ = H;
R ⁷ = H, C ₁ -C ₆ -alkyl, unsubstituted or C ₁ -C ₄ -alkyl-substituted phenyl;
R ⁸ = phenylene;
R ⁹ = ethylene;
R ¹⁰ = methyl;
R ¹¹ = H, C ₁ -C ₈ -alkyl, unsubstituted or methyl-substituted phenyl;
R ¹² = CH ₂ CH ₂ (CF ₂ ) _m CF ₃ ;
R ¹³ = H, acetyl;
R ¹⁴ = C ₁ -C ₄ -alkyl;
R ¹⁵ = CH (R ¹¹ ) -S (O) _p -R ¹² .
R ¹⁶ = methylene;
m = a number from 3 to 12;
n = 1, 2 or 3, and
p = 0.

Fluorine-containing compounds of the formula I can be prepared by methods such as US 4,874,885 be revealed.

Particularly preferred fluorine-containing compounds V are those in Examples 1 to 14 of WO 2007/144283 (P. 38, last paragraph to p. 67, last line), and 2010/112395, p. 11, lines 7 to p. 20, line 8.

Particularly preferred fluorine-containing compounds V are:

Another object of the present invention are aqueous dispersions containing particles of the invention.

In one embodiment of the present invention, aqueous dispersions according to the invention contain in the range from 5 to 60% by weight of particles according to the invention.

In one embodiment of the present invention, aqueous dispersions according to the invention contain, in addition to particles according to the invention, those particles which have no pores with a diameter in the range from 1 to 90% of the particle diameter and a depth of at least 10% of the particle diameter.

In one embodiment of the present invention, aqueous dispersions according to the invention contain, in addition to particles according to the invention, particles which have a diameter in the range from 50 nm to less than one micron.

In one embodiment of the present invention, aqueous dispersions according to the invention contain, in addition to particles according to the invention, particles which have a diameter in the range from 50 nm to less than one micron and, furthermore, those particles which do not contain pores with a diameter in the range from 1 to 90% of that Particle diameter and have a depth of at least 10% of the particle diameter.

In one embodiment of the present invention, aqueous dispersions according to the invention contain, in addition to particles according to the invention, particles which have a diameter in the range from 50 nm to less than one micrometer and which have no pores with a diameter in the range from 1 to 90% of the particle diameter and a depth of at least 10% of the particle diameter.

The particles present in addition to particles according to the invention in aqueous dispersions according to the invention are preferably each of an organic polymer. They are particularly preferably also from the same or essentially the same polymer as particles according to the invention.

In the context of the present invention, essentially identical polymers may differ from one another in the composition, for example in the relative proportions of incorporated comonomers or in the molecular weight of the relevant organic polymer.

If aqueous dispersions according to the invention contain additional particles in addition to particles according to the invention, they preferably have a solids content in the range from 5 to 80% by weight in total.

If aqueous dispersions according to the invention contain additional particles in addition to particles according to the invention, it is preferred that the proportion of particles according to the invention is at least 10% by weight, preferably at least 20% by weight, particularly preferably at least 30% by weight and very particularly preferably at least 40 wt .-%, based on the total amount of particles contained in the inventive aqueous dispersion.

In one embodiment of the present invention, aqueous dispersions according to the invention may also comprise one or more additives, for example biocides, film-forming (co) polymers (binders), thickeners or surfactants.

Suitable biocides are for example 1,2-benzisothiazolin-3-one ( "BIT") (commercially available as Proxel ^® brands from Avecia Lim..) And its alkali metal salts; other suitable biocides are 2-methyl-2H-isothiazol-3-one ("MIT") and 5-chloro-2-methyl-2H-isothiazol-3-one ("CIT"). In general, 10 to 150 ppm of biocide are sufficient, based on the total aqueous dispersion according to the invention.

Suitable binders are, for example, film-forming polyacrylates and polyurethanes, for example those polyacrylates which comprise (meth) acrylic acid in copolymerized form and at least one comonomer, such as N-methylol (meth) acrylamide, glycidyl (meth) acrylamide or acetoacetyl (meth) acrylate. Examples of particularly suitable binders can be found in WO 2003/23071 , Examples of suitable polyurethanes can be found in EP-A 0 437 742 and in DE-A 42 31 034 ,

Suitable thickeners are, for example, crosslinkable copolymers based on acrylic acid and acrylamide and thickeners based on polyurethane or polyvinylpyrrolidone or acrylate (co) polymers. Furthermore, so-called associative thickeners are suitable, for example based on hydrophobic / hydrophilic-built polyurethanes, polyureas and polyether polyols.

mit Molekulargewichten M_W im Bereich von 100.000 bis 200.000 g/mol, in denen R¹ gewählt wird aus Methyl und vorzugsweise Wasserstoff.Preferred examples of thickeners are copolymers with 85 to 95 wt .-% acrylic acid, 4 to 14 wt .-% acrylamide and optionally up to 1 wt .-%, preferably 0.01 to 0.5 wt .-% of a (meth) acrylamide derivative of formula II

with molecular weights M _W in the range of 100,000 to 200,000 g / mol, in which R ^{1 is} selected from methyl and preferably hydrogen.

Other suitable ingredients may be one or more surfactants, which may be anionic, cationic, zwitterionic or preferably nonionic.

Suitable anionic surfactants are, for. B. Alkali metal and ammonium salts of alkyl sulfates (alkyl: C ₈ to C ₁₂ ), of sulfuric monoesters of ethoxylated alkanols (degree of ethoxylation: 4 to 30, alkyl: C ₁₂ -C ₁₈ ) and ethoxylated alkylphenols (degree of ethoxylation: 3 to 50, alkyl: 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 surfactants 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-cetylpyridinium chloride, N-Laurylpyridiniumsulfat and N-cetyl-N, N, N-trimethylammonium bromide, 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, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989 ,

Suitable nonionic surfactants are, for. B. 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 are the Lutensol from BASF SE ^® brands and the Triton ^® grades from Union Carbide.

In a preferred embodiment of the present invention, aqueous dispersions according to the invention comprise one or more further constituents, for example urea-formaldehyde condensates, melamine-formaldehyde resins, proteins or fillers based on inorganic or preferably organic substances.

In one embodiment of the present invention, aqueous dispersions according to the invention may contain one or more pigments, preferably one or more black pigments.

In a preferred embodiment of the present invention, aqueous dispersions according to the invention contain less than 2% by weight of inorganic particles. It is particularly preferred to add no inorganic particles to aqueous dispersions according to the invention.

In one embodiment of the present invention, aqueous dispersions according to the invention contain
From 5 to 30, preferably at least 10% by weight of particles according to the invention,
optionally 1 to 20, preferably at least 3 wt.% of film-forming polymer,
0.05 to 5, preferably 0.2 to 2 wt .-% thickener,
in each case based on the total aqueous dispersion according to the invention.

In one embodiment of the present invention, aqueous dispersions according to the invention have a solids content in the range from 10 to 50%, preferably 15 to 40%.

Another object of the present invention is the use of particles according to the invention or of aqueous dispersions according to the invention for coating substrates. Another object of the present invention is a process for coating substrates with particles of the invention or with aqueous dispersions.

Substrates can be selected, for example, from metals, glass, plastics and preferably from fibrous substrates, for example paper, cardboard, cardboard, wood, textile and in particular from leather and imitations of leather, wherein the term imitation leather also includes Lefa and Alcantara and the term leather also includes split leather , Leather refers to the tanned, hydrophobized and greased skin of dead animals, for example of cattle, veal, deer, pig, goats, kangaroos or sheep. Leather may be made from skins of slaughtered animals or from skins of animals that have been whipped or have died of natural causes, such as illnesses, accidents or fights with other animals.

It is irrelevant in the context of the present invention, whether it is leather tanned with the aid of chrome tanning or chromium-free tanning leather.

By coating, it is to be understood that particles according to the invention influence the surface topography of coated substrate and that a significant proportion of particles according to the invention is located on the coated surface. Surfaces coated in accordance with the invention thus have an extremely matt effect.

In one embodiment of the present invention, only the surface of substrate which is the visible side when using coated substrate is coated, leaving the other surfaces substantially uncoated. If, for example, leather is to be coated according to the invention, it is preferable to coat the grain side of leather and leave the meat side uncoated.

The coating according to the invention can be carried out by methods known per se, for example rollcoats (roller application), brushing, spraying, so-called "airless spraying", printing, laminating, plushing, brushing, casting or spraying. After applying particles of the invention can be dried, for example at temperatures in the range of 60 to 80 ° C, and then iron, for example at temperatures in the range of 90 to 160 ° C. You can also iron hydraulically, for example, at temperatures in the range of 70 to 100 ° C. There are conventional devices for ironing in question, such as continuous ironing machines.

In one embodiment of the present invention, 2 to 30 g of aqueous dispersion according to the invention are applied per m ^{2 of} substrate surface, in particular leather surface, the amount / m ² of aqueous dispersion being adapted to the intended use of the substrate, in particular leather, and the information in g / m ^{2 are} each based on the solids content of the relevant aqueous dispersion according to the invention. Thus, for upholstery leather 2 to 15 g / m ² and preferably for leather for automobile interior parts from 5 to 30 g / m ^2.

A further subject of the present invention is a process for the production of particles according to the invention, also referred to in the context of the present invention as a preparation process according to the invention. Particulates according to the invention can be prepared, for example, by polycondensation, by free-radical polymerization or, preferably, by polyaddition reactions.

In one embodiment of the present invention, the preparation process according to the invention can be carried out by preparing an organic polymer in the presence of a second organic polymer, for example by free radical polymerization or by complex catalysis, the two organic polymers being incompatible. By suitable choice of polymerization processes, for example emulsion polymerization, suspension polymerization and polymerization with the aid of a supported catalyst, and process parameters such as, for example, temperature, mixing and, if appropriate, use of surfactants, it is possible to adjust the desired particle size. After completion of the actual preparation, one of the two polymers can be removed, for example by extraction with a solvent. The pore (s) are located in the corresponding particle according to the invention at the location of the particle on which the second polymer was located during the synthesis.

In a preferred embodiment of the preparation process according to the invention, the procedure is such that a polyaddition, preferably a multistage polyaddition, is carried out to produce particles according to the invention.

• (a) Umsetzung von mindestens einem polymeren Diol mit einem Überschuss an Diisocyanat und gegebenenfalls mindestens einem weiteren Diol,
• (b) gegebenenfalls Umsetzung mit mindestens einem aliphatischen oder cycloaliphatischen Diamin,
• (c) Umsetzung mit mindestens einem Diamin oder Diol, welches mindestens eine ionische oder in wässrigem Medium ionisierbare Gruppe aufweist,
• (d) Zugabe von Wasser,
• (e) gegebenenfalls Umsetzung mit mindestens einem wasserdispergierbaren Di- oder Polyisocyanat,
• (f) gegebenenfalls Umsetzung mit mindestens einem aliphatischen Polyamin.

For example, one can proceed by carrying out a process comprising the following steps:

• (a) reaction of at least one polymeric diol with an excess of diisocyanate and optionally at least one further diol,
• (b) if appropriate, reaction with at least one aliphatic or cycloaliphatic diamine,
• (c) reaction with at least one diamine or diol which has at least one ionic or ionizable group in aqueous medium,
• (d) adding water,
• (e) if appropriate, reaction with at least one water-dispersible di- or polyisocyanate,
• (f) optionally reaction with at least one aliphatic polyamine.

The addition of the at least one fluorine-containing compound V can be carried out at any time. In a preferred embodiment, compounds V are already present at step (a). In other embodiments, compound V is added before step (b), (c), (d), (e) or (f). In one embodiment, compound V is added after step (f).

In one embodiment of the present invention, polymeric diols have an average molecular weight M _n of at least 500 g / mol.

As polymeric diols there may be mentioned dihydric or polyhydric polyester polyols and polyether polyols, the divalent ones being preferred. Suitable polyether polyols are preferably polyether diols, as they are, for. B. by boron trifluoride catalyzed linkage of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself or with one another or by addition of these compounds, individually or in admixture, to starter components with reactive hydrogen atoms such as water, polyhydric alcohols or amines such as 1,2 Ethanediol, propanediol (1,3), 1,2- or 2,2-bis (4-hydroxyphenyl) propane or aniline are contemplated. Furthermore, polyether-1,3-diols, z. B. the alkoxylated at an OH group trimethylolpropane, the alkylene oxide is completed with an alkyl radical containing 1 to 18 carbon atoms, preferably used polymeric diols.

Preferred polymeric diols are: polyethylene glycol, polypropylene glycol, polytetrahydrofuran (poly-THF).

Particular preference is given to polyether polyols selected from: polyethylene glycol having an average molecular weight (M _n ) in the range from 500 to 9,000 g / mol, preferably in the range from 500 to 6,000 g / mol, poly-1,2-propylene glycol or poly-1,3 propanediol having an average molecular weight (M _n ) in the range from 500 to 6,000, preferably 600 to 4,000 g / mol, poly-THF having an average molecular weight (M _n ) in the range from 500 to 5,000, preferably from 600 to 3,000 g / mol, more preferably in the range of 750 to 2,500 g / mol.

Other preferred polymeric diols are polyester polyols (polyester diols) and polycarbonate diols.

Suitable polyester polyols are, in particular, the reaction products of polyhydric alcohols with polybasic carboxylic acids which are known per se, the alcoholic component being used in excess. Polybasic carboxylic acids may be aliphatic, cycloaliphatic, aromatic, heterocyclic or ethylenically unsaturated and optionally bear halogen atoms as substituents. Instead of polybasic carboxylic acids and their anhydrides can be esterified. Preference is given to polyester polyols of diols and dicarboxylic acids. Examples of suitable polybasic carboxylic acids which may be mentioned are: succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endo-methylene tetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride or fumaric acid. As excess polyhydric alcohols to be mentioned are:
1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,4-but-2-endiol, 1,4- But-2-indiol, 1,5-pentanediol and its positional isomers, 1,6-hexanediol, 1,8-octanediol, 1,4-bis-hydroxymethylcyclohexane, 2,2-bis- (4-hydroxycyclohexyl) propane, 2-methyl- 1,3-propanediol, 2,2-dimethylpropane-1,3-diol (neopentyl glycol), glycerol, 1,1,1-trimethylolpropane ("TMP"), 1,1,1-trimethylolethane, 1,2,6- Hexane triol, 1,2,4-butanetriol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having an average molecular weight (M _n ) in the range from 375 to 900 g / mol, preferably from 375 to 700 g / mol, poly-1,2- propylene glycol or poly-1,3-propanediol having an average molecular weight (M _n ) in the range of 134 to 1200 g / mol, preferably in the range of 134 to 900 g / mol, poly-THF having an average molecular weight (M _n ) im Range of 162 to 2000 g / mol, preferably in the range of 375 to 1500 g / mol, particularly preferably 375 to 700 g / mol.

In one embodiment of the present invention, the polyester diol used is a polyester prepared from at least two different dicarboxylic acids and at least one polyhydric alcohol. In one embodiment of the present invention, the polyester diol used is a polyester prepared from a dicarboxylic acid and at least two different polyhydric alcohols. In a further embodiment of the present invention, the polyester diol used is a polyester which is prepared from at least two dicarboxylic acids and at least two polyhydric alcohols.

Further suitable polyester polyols are the addition products of lactones or lactone mixtures to dihydric alcohols used as starter molecules. Examples of preferred lactones are ε-caprolactone, δ-valerolactone, β-propiolactone, γ-butyrolactone or methyl ε-caprolactone. Suitable starter molecules are, in particular, the low molecular weight dihydric alcohols already mentioned as synthesis components for the polyesterpolyols, in particular 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4 Butanediol, 1,4-but-2-endiol, 1,4-but-2-indiol, 1,2-pentanediol, 1,5-pentanediol and its positional isomers, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,4-bis-hydroxymethylcyclohexane, 2,2-bis (4-hydroxycyclohexyl) propane, 2-methyl-1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol and tetraethylene glycol.

In one embodiment of the present invention, polycarbonate diols are selected from those which are obtained e.g. B. from phosgene or diphenyl carbonate and an excess of at least one of the structural components mentioned for the aforementioned polyester polyols low molecular weight dihydric alcohols can be obtained.

In one embodiment of the present invention, polyester diol or polycarbonate diol has an average molecular weight M _n in the range of 500 and 5,000 g / mol, preferably in the range of 800 to 3,000 g / mol.

Reactant in step (a) is diisocyanate, hereinafter also called diisocyanate (A), in excess of isocyanate groups, based on the sum of hydroxyl groups of polymeric diol and amino groups of diamine (B) and diamine (C) or diol ( C).

In one embodiment of the present invention, the term diisocyanate (A) also includes polyisocyanates.

In one embodiment of the present invention, the excess of isocyanate groups, based on the sum of hydroxyl groups of polymeric diol and optionally further diol, in the range from NCO / (OH + NH) 2 to 1 to 1.1 to 1, preferably 1.5 to 1 to 1.15 to 1.

Diisocyanates (A) can be aromatic, aliphatic or cycloaliphatic. Examples of aromatic diisocyanates (A) are 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate.

In one embodiment of the present invention, diisocyanates (A) are selected from aliphatic and cycloaliphatic diisocyanates. Examples are tetramethylxylylene diisocyanates (TMXDI), hexamethylene diisocyanate (HDI), trimethylhexane diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI) and carbodiimide, allophanate, isocyanurate, urethane or biuret groups derived therefrom having polyisocyanates. Particularly preferred are hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI).

In one embodiment of the present invention, one or more monoisocyanates can be used in addition to diisocyanate (A), for example phenyl isocyanate. However, it is preferred to use only a small amount, for example from 1 to 5 mol% monoisocyanate, based on diisocyanate (A). It is particularly preferred to use no monoisocyanate.

In one embodiment of the present invention, in step (a), in addition to polymeric diol, at least one further diol is employed. Further diol may preferably be low molecular weight diol, for example having a molecular weight in the range from 50 to 499 g / mol. Suitable further diols for step (a) are selected from 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,4 But-2-endiol, 1,4-but-2-indiol, 1,5-pentanediol and its positional isomers, 1,6-hexanediol, 1,8-octanediol, 1,4-bishydroxymethylcyclohexane, 2,2-bis- (4-hydroxycyclohexyl) propane, 2-methyl-1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and tripropylene glycol.

In one embodiment of the present invention, in step (a), 0.1 to 10 moles of additional diol are employed per mole of polymeric diol, preferably 0.2 to 5 moles.

In one embodiment of the present invention, in step (a), in addition to polymeric diol and diisocyanate (A), at least one triol or at least one alcohol having at least 4 hydroxyl groups per molecule is used. Examples are glycerol, 1,2,4-butanetriol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane and 1,1,1-trimethylolbutane.

In one embodiment of the present invention, in step (a), in addition to polymeric diol and diisocyanate (A), 0.1 to 10% by weight of triol or alcohol having at least 4 hydroxyl groups per molecule, based on polymeric diol.

In one embodiment of the present invention, in step (a), in addition to polymeric diol and diisocyanate (A), at least one monoalkyl polyalkylene oxide is employed. Monoalkylpolyalkylene oxides are usually obtainable by alkoxylation of low molecular weight monohydric starter molecules, in particular C ₁ -C ₁₀ -alkanols, such as methanol, ethanol or n-butanol, preferably ethylene oxide or mixtures of ethylene oxide with other alkylene oxides, in particular propylene oxide, as the alkoxylating agent. be used. In the case of an alkoxylation with alkylene oxide mixtures, these advantageously contain at least 40, with particular advantage at least 65 mol% of ethylene oxide, based on alkylene oxide. Monoalkylpolyalkylene oxide used preferably has a number-average molecular weight of 500 to 10,000 g / mol, more preferably of 1,000 to 5,000 g / mol.

In one embodiment of the present invention, in step (a), in the range of 0.01 to 10 mol% of monoalkylpolyalkylene oxide, based on polymeric diol.

If, in addition to polymeric diol, additional diol, triol, monoalkylpolyalkylene oxide and / or alcohol having at least 4 hydroxyl groups per molecule are used in step (a), the term "excess" refers to the sum of all hydroxyl groups of the reactants of diisocyanate (A).

The reaction in step (a) is preferably carried out in a solvent or solvent mixture. Preferred solvents are organic solvents, for example ethers, ketones or aromatic hydrocarbons. Suitable solvents are preferably aprotic. Suitable examples are acetone, tetrahydrofuran, butanone, diethyl ketone, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), cyclic or open-chain organic carbonates, for example diethyl carbonate, or N-alkylpyrrolidone, in particular N-methylpyrrolidone or N-ethylpyrrolidone. Furthermore, dimethylformamide, dimethylacetamide and diethylformamide are suitable.

In one embodiment of the present invention, the reaction in step (a) is carried out at temperatures of 20 to 160, preferably 50 to 100 ° C.

In one embodiment of the present invention, the reaction in step (a) is initiated by mixing together polymeric diol and diisocyanate (A) and optionally further reactants, such as monoalkylpolyethyleneglycol, and optionally with solvent and / or catalyst. In this case, it is possible to add various reaction partners such as polymeric diol and diisocyanate (A) and also solvents in one or more portions. The mixing can be done for example by stirring.

In one embodiment of the present invention, the reaction time in step (a) is in the range of one to 24 hours, preferably 2 to 10 hours.

Preferably, the reaction in step (a) is carried out in the presence of a catalyst. Suitable catalysts are catalysts known from polyurethane chemistry, for example organotin compounds such as dibutyltin dilaurate or esters of titanic acid such as tetra-n-butylorthotitanate. Particularly suitable catalysts are carboxylic acid salts of alkali metals, in particular monocarboxylic acid salts of alkali metals. Very particular preference is given to rubidium acetate and cesium acetate. Suitable amounts are for example amounts of 10 to 100 ppm, based on the solvent-free reaction mixture of diisocyanate.

Carboxylic acid salts of alkali metals can be added in solid form, but preferably in dissolved form. Suitable solvents are polar aprotic solvents or protic solvents. Examples of suitable solvents are alcohols; very particularly suitable are polyols, as they are also used as building blocks for polyurethanes, such as. For example, ethane, propane and butane diols.

In step (b) it is possible to react with at least one aliphatic or cycloaliphatic diamine, preferably with a diamine having two primary amino groups per molecule, also called diamine (B). It is preferred in the context of the present application to carry out step (b).

In one embodiment of the present invention, diamine (B) is selected from aliphatic and preferably cycloaliphatic diamines. In this context, in the context of the present invention, diamines (B) which denote an amino group bonded directly to a cyclic hydrocarbon radical and an amino group which is bonded to an alkyl group or alkylene group are termed cycloaliphatic diamines (B). Diamines (B), whose amino groups are each bonded to alkyl groups or to alkylene groups which are not part of a ring, are referred to as aliphatic diamines (B).

Examples of aliphatic diamines (B) are ethylenediamine, 1,3-propanediamine, 1,6-diaminohexane and 1,12-dodecanediamine.

Examples of cycloaliphatic diamines (B) are 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA), cyclohexane-1,4-diamine and 4,4'-di (aminocyclohexyl) -methane.

In one embodiment of the present invention, diamine (B) is added to the reaction mixture of step (a).

Diamine (B) can be added in pure form. Preferably, however, diamine (B) is added dissolved in a solvent. The solvents used are the abovementioned solvents. Preferably, acetone, MEK and THF are used. Furthermore, water is suitable as a solvent. The amount of solvent is 10 to 1000 wt .-%, based on diamine (B), preferably 50 to 500 wt .-%.

In one embodiment of the present invention, the reaction in step (b) is carried out at temperatures of 20 to 160, preferably 25 to 80 ° C.

In one embodiment of the present invention, during step (b), additional diisocyanate may be added which is different or preferably equal to diisocyanate (A).

In step (c), at least one diamine or diol is reacted, in the context of the present invention also diamine (C) or diol (C), which has at least one ionic or ionizable group in an aqueous medium.

Preferably, diamine (C) is an aliphatic diamine. Preferably, diol (C) is an aliphatic diol.

In one embodiment of the present invention, ionic groups are anionic groups. Preferred example is the sulfonic acid group.

In one embodiment of the present invention, groups which are ionizable in an aqueous medium are groups which can cleave a proton in an aqueous medium, for example at pH values in the range of 7 or above. Particularly preferred is the carboxylic acid group.

In one embodiment of the present invention, diamine (C) or diol (C) is present as the free acid. In another embodiment of the present invention, diamine (C) or diol (C) is present as a salt. Suitable counterions are, for example, the cations of alkali metals, preferably K ⁺ and in particular Na ⁺ . Further suitable counterions are the cations of tertiary amines, for example the cations of tri-C ₁ -C ₁₀ -alkylamines and the cations of tertiary ethanolamines such as cations of NC ₁ -C ₄ -alkyldiethanolamines, of N, N-di-C ₁ C ₄ -alkylethanolamine and triethanolamine.

Examples of suitable diamines (C) are N- (2-aminoethyl) -2-aminoethanecarboxylic acid and N- (2-aminoethyl) -2-aminoethanesulfonic acid or their alkali metal salts, in particular sodium salts.

Examples of suitable diols (C) are 1,1-dimethylolpropionic acid, 1,1-dimethylolbutyric acid and tartaric acid.

In one embodiment of the present invention, diamine (C) or diol (C) is used in amounts such that organic polymer in the range of 30 to 150 mmol / kg, based on the total mass of the organic polymer, diamine (C) or Diol (C) incorporated, preferably 50 to 120, more preferably 50 to 100 mmol / kg.

In one embodiment of the present invention, diamine (C) or diol (C) is added to the reaction mixture of step (b).

In one embodiment of the present invention, during step (c), additional diisocyanate may be added which is different or preferably equal to diisocyanate (A).

In one embodiment of the present invention, the reaction in step (c) is carried out at temperatures of 20 to 160, preferably 25 to 80 ° C.

The reaction in step (a), (b) or (c) can be carried out in each case at atmospheric pressure or at elevated pressure, for example at 1.1 to 10 bar. Preference is given to atmospheric pressure.

In one embodiment of the present invention, solvent may be added during step (b) and / or during step (c) that is the same or different than the solvent used in step (a). The solvent added in step (b) and / or step (c) is preferably a polar aprotic solvent, in particular ketone, for example acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK) or diethyl ketone.

In step (d), water is added.

After the addition of water, the solvent used can be removed, for example by distillation. In another embodiment of the present invention, the solvent used is not removed until after step (f), which is described below.

In one embodiment of the present invention, mixing is vigorous during the addition of water, for example by stirring.

In one embodiment of the present invention, mixing is vigorous during the addition of water and the removal of solvent, for example by stirring.

The added amount of water in step (d) is usually measured so that the final, in particular after step (f) (see below) available aqueous dispersion has a solids content of 5 to 60 wt .-%.

In optional step (e), it is possible to react with at least one water-dispersible di- or preferably polyisocyanate, also referred to below briefly as polyisocyanate (E).

In one embodiment of the present invention, polyisocyanate (E) is selected from isocyanurates, biurets or allophanates of aliphatic diisocyanates such as hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI), which are reacted with a hydrophilic compound, for example a C ₁ -C ₄ -alkyl ether of polyethylene glycol, for example, with polyethylene glycol monomethyl ether having a number average molecular weight in the range of 500 to 10,000 g / mol, preferably to 2,000 g / mol.

In one embodiment of the present invention, polyisocyanate (E) is selected from isocyanurates, biurets or allophanates of aliphatic diisocyanates, such as HDI or IPDI, with a hydrophilic compound, for example a polyethylene glycol, for example with a polyethylene glycol having a number average molecular weight in the range from 250 to 10,000 g / mol, preferably in the range of 1,000 to 5,000 g / mol and then reacted with a further diisocyanate, for example TDI, IPDI or HDI.

In one embodiment of the present invention, polyisocyanate (E) is selected from isocyanurates, biurets or allophanates of aliphatic diisocyanates, such as hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI), with a urethane of a diisocyanate, such as TDI or IPDI, and a hydrophilic compound, e.g. C ₁ -C ₂₀ alkyl ethers of polyethylene glycol, for example with polyethylene glycol monomethyl ether having a number average molecular weight in the range of 500 to 10,000 g / mol, preferably up to 2,000 g / mol, are mixed or reacted.

In one embodiment of the present invention, from 0 to 20% by weight, preferably from 0.1 to 15% by weight, based on the total weight of the polymer, of polyisocyanate (E) is used.

In optional step (f), at least one aliphatic or cycloaliphatic polyamine is reacted. In the context of the present application, aliphatic or cycloaliphatic polyamines are aliphatic or cycloaliphatic diamines, aliphatic or cycloaliphatic triamines and aliphatic or cycloaliphatic compounds having 4 or more amino groups per molecule; preference is given to aliphatic or cycloaliphatic compounds having two or three amino groups per molecule. Examples of suitable aliphatic and cycloaliphatic polyamines are diethylenetriamine, triethylenetetramine, isophoronediamine and hexamethylenediamine.

In one embodiment of the present invention, the amount of polyamine in step (f) is selected such that from 0.01 to 0.5, preferably from 0.01 to 0.4, moles of aliphatic or cycloaliphatic amino groups are obtained per mole of isocyanate groups from diisocyanate (A) Polyamine can be used.

The sequence of steps (a) to (f) of the production process according to the invention can be varied within certain limits. Care should be taken to perform step (a) before step (d).

In one embodiment of the present invention, the preparation process according to the invention is carried out by carrying out the steps in the following order: step (a), step (c), step (d).

In one embodiment of the present invention, the preparation process according to the invention is carried out by carrying out the steps in the following order: step (a), step (b), step (c), step (d).

In another embodiment of the present invention, the manufacturing method of the present invention is carried out by carrying out the steps in the following order: step (a), step (b), step (c), step (d), step (f).

In another embodiment of the present invention, the preparation process according to the invention is carried out by carrying out the steps in the following order: step (a), step (b), step (c), step (d), step (e).

In another embodiment of the present invention, the manufacturing method of the present invention is carried out by carrying out the steps in the following order: step (a), step (c), step (d), step (e), step (f).

Preferably, one carries out the six steps (a) to (f).

In a preferred embodiment of the present invention, the preparation process according to the invention is carried out by carrying out the steps in the following order: step (a), step (b), step (c), step (d), step (e), Step (f).

In another preferred embodiment of the present invention, the production process of the present invention is carried out by carrying out the steps in the following order: step (a), step (c), step (b), step (d), step (e) , Step (f).

In another preferred embodiment of the present invention, the preparation process according to the invention is carried out by carrying out the steps in the following order: step (a), step (b), step (c), step (d), step (f) , Steps).

In another preferred embodiment of the present invention, the manufacturing method of the present invention is carried out by carrying out the steps in the following order: step (a), step (c), step (b), step (d), step (f) , Steps).

In another embodiment of the present invention, the preparation process according to the invention is carried out by carrying out the steps in the following order: step (a), step (c), step (d), step (b), step (f), Steps).

In another embodiment of the present invention, the preparation process according to the invention is carried out by carrying out the steps in the following order: step (a), step (c), step (d), step (b), step (e), Step (f). By carrying out the preparation process according to the invention, aqueous dispersions according to the invention are obtained.

In one embodiment of the present invention, it is possible to isolate particles according to the invention from aqueous dispersions according to the invention, for example by filtration or by evaporation of the water, in particular by spray drying. In many cases, however, it is preferable to use aqueous dispersions according to the invention-optionally provided with additives-without further isolation of the particles according to the invention for coating substrates.

Another object of the present invention are substrates coated with particles of the invention. The coated substrates according to the invention are preferably fibrous substrates, in particular leather or imitations of leather. Coated substrates according to the invention, in particular coated leather according to the invention have a particularly strong matting and are therefore suitable especially good for automotive interior parts, either as such or as a component. In addition, they have a particularly pleasant grip. In addition, they have good anti-soiling properties, oil-repellent properties and anti-graffiti properties, are easy to clean, self-cleaning and solvent-stable. In addition, the other mechanical properties such as kink fastness or rubbing fastness are not or only slightly affected.

The invention will be explained by working examples.

I.1 Preparation of particles P.1 according to the invention in the form of aqueous dispersion D.1 according to the invention

gegeben und 5 Minuten gerührt. Dann wurde eine Lösung von 51,0 g (0,30 mol) Isophorondiamin (IPDA), gelöst in 50 g Wasser, zugegeben und 5 Minuten gerührt. Danach wurden 20,5 g PUD-Salz (Natriumsalz von N-(2-Aminoethyl)-2-aminoethancarbonsäure) gegeben und 5 Minuten gerührt. Hernach wurde 750 g Wasser zugesetzt und anschließend 120 g einer 50 Gew.-%igen wässrigen Emulsion eines wasseremulgierbaren modifizierten trimeren Hexamethylendiisocyanats nach DE 40 36 927 A1 , Beispiel 4 zugefügt.In a 3 L flask equipped with stirrer, thermometer and reflux condenser, 400 g (0.20 mol) of poly-THF having a number average molecular weight of 2,000 g / mol, 2.25 g of a n-butanol-started polyethylene oxide having a number average molecular weight of 3,000 g / mol, 110 g of acetone and 0.2 g of a 10 wt .-% solution of cesium acetate in 1,4-butanediol and heated to 50 ° C. To this was added 112.6 g (0.67 mol) of HDI and stirred at 77 ° C for 150 minutes. It was then diluted with 840 g of acetone and cooled to 30 ° C. The NCO content was determined titrimetrically to 2.60 wt .-% (calculated: 2.68 wt .-%). To the reaction mixture was added an additional 4.75 g of HDI and stirred for 5 minutes. Then, to the solution was 40.6 g

added and stirred for 5 minutes. Then, a solution of 51.0 g (0.30 mol) of isophoronediamine (IPDA) dissolved in 50 g of water was added and stirred for 5 minutes. Thereafter, 20.5 g of PUD salt (sodium salt of N- (2-aminoethyl) -2-aminoethanecarboxylic acid) were added and stirred for 5 minutes. Thereafter, 750 g of water were added and then 120 g of a 50 wt .-% aqueous emulsion of a water-emulsifiable modified trimeric hexamethylene diisocyanate after DE 40 36 927 A1 Example 4 added.

After 5 minutes, a solution of 21.0 g (0.12 mol) of IPDA and 8.2 g (0.08 mol) of diethylenetriamine (DETA) in 65 g of water was added. Subsequently, the acetone was distilled off under reduced pressure. Aqueous dispersion (D.1) according to the invention was obtained with a solids content of 36.7% by weight.

I.2 Preparation of particles in the form of comparative aqueous dispersion V.1 according to the teaching of WO 2010/119002

In a 3 L flask equipped with stirrer, thermometer and reflux condenser, 400 g (0.20 mol) of poly-THF having a number average molecular weight of 2,000 g / mol, 2.25 g of a n-butanol-started polyethylene oxide having a number average molecular weight of 3,000 g / mol, 110 g of acetone and 0.2 g of a 10 wt .-% solution of cesium acetate in 1,4-butanediol and heated to 50 ° C. To this was added 112.6 g (0.67 mol) of HDI and stirred at 77 ° C for 150 minutes. It was then diluted with 840 g of acetone and cooled to 30 ° C. The NCO content was determined titrimetrically to 2.60 wt .-% (calculated: 2.68 wt .-%). To the reaction mixture was added an additional 4.75 g of HDI and stirred for 5 minutes. Then, a solution of 51.0 g (0.30 mol) of isophoronediamine (IPDA) dissolved in 50 g of water was added and stirred for 5 minutes. Thereafter, 20.5 g of PUD salt (sodium salt of N- (2-aminoethyl) -2-aminoethanecarboxylic acid) were added and stirred for 5 minutes. Thereafter, 750 g of water were added and then 120 g of a 50 wt .-% aqueous emulsion of a water-emulsifiable modified trimeric hexamethylene diisocyanate after DE 40 36 927 A1 Example 4 added.

After 5 minutes, a solution of 21.0 g (0.12 mol) of IPDA and 8.2 g (0.08 mol) of diethylenetriamine (DETA) in 65 g of water was added. Subsequently, the acetone was distilled off under reduced pressure. This gave aqueous comparative dispersion (V.1) with 40 wt .-% solids content.

I.3 Mixing Dispersion A.1

In a 3 l flask equipped with stirrer, thermometer and reflux condenser, 400 g (0.20 mol) of a polyesterol of adipic acid, 1,6-hexanediol and neopentyl glycol having a number average molecular weight of 2,000 g / mol, 30.0 g of dimethylolpropionic acid, 50 g of acetone and 0.2 g of a 10 wt .-% solution of cesium acetate in 1,4-butanediol and heated to 50 ° C. To this was added 112.0 g (0.50 mol) of IPDI and stirred at 100 ° C for 180 minutes. It was then diluted with 750 g of acetone and cooled to 30 ° C. The NCO content was determined titrimetrically to 0.51 wt .-% (calculated: 0.50 wt .-%). To the reaction mixture was added 21.4 g of triethylamine and stirred for 5 minutes. Then, 1000 g of water was added and then a solution of 5.5 g of water was added, followed by distilling off the acetone under reduced pressure. This gave an aqueous blend dispersion (A.1) with 30.5 wt .-% solids content.

There were those in Table 1 of WO 2010/119002 prepared mixtures and aufgerakelt on cardboard.

The measurement of the gloss level shows the superiority of the dispersion according to the invention in terms of reduced gloss. In addition, samples coated with the dispersion of the present invention had excellent anti-soiling properties.

QUOTES INCLUDE IN THE DESCRIPTION

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

Cited patent literature

• WO 2010/119002 [0007, 0177]
• WO 03/095517 [0008]
• WO 2007/144283 [0041, 0056]
• WO 2010/112395 [0041]
• US 4874885 [0055]
• WO 2003/23071 [0070]
• EP 0437742 A [0070]
• DE 4231034A [0070]
• DE 4036927 A1 [0172, 0174]

Cited non-patent literature

• H. Stache, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981 [0075]
• McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989 [0075]

Claims (14)

Spherical particles having a number average molecular weight in the range of 1 to 100 microns comprising at least one organic polymer, said particles having one or more open pores having a diameter in the range of 1 to 90% of the particle diameter and a depth of at least 10% of the particle diameter and wherein the spherical particles further contains 0.01 to 20% by weight of at least one fluorine-containing compound V. Particle according to Claim 1, characterized in that the at least one fluorine-containing compound V is a compound of the formula I,

where, for n = 1: R ¹ = H, C ₁ -C ₂₅ alkyl, C ₂ -C ₂₅ alkenyl, -CO-R ⁵ , -CH (R ¹⁰ ) CO-R ⁵ , -C (R ¹⁰ ) ₂ CO-R ⁵ , -CO-N (R ⁶ ) -R ⁷ , -CH (R ¹⁰ ) CO-N (R ⁶ ) -R ⁷ , -C (R ¹⁰ ) ₂ CO-N (R ⁶ ) -R ⁷ , -CH (R ¹⁰ ) COOR ⁵ or -C (R ¹⁰ ) ₂ CO-OR ⁵ ; for n = 2 R ¹ = unsubstituted or substituted by C ₁ -C ₄ alkyl, benzyl or phenyl substituted C ₁ -C ₂₄ alkylene, which is interrupted by oxygen or sulfur C ₁ -C ₂₄ alkylene; -CO-R ⁸ -CO-, -CH (R ¹⁰ ) CO-R ⁸ -CO-CH (R ¹⁰ ) -, -C (R ¹⁰ ) ₂ CO-R ⁸ -CO-C (R ¹⁰ ) ₂ , -CO-N (R ⁶ ) -R ⁹ -N (R ⁶ ) -CO-, -CH (R ¹⁰ ) CO-N (R ⁶ ) -R ⁹ -N (R ⁶ ) -CO-CH (R ¹⁰ ) -, -C (R ¹⁰ ) ₂ CO-N (R ⁶ ) -R ⁹ -N (R ⁶ ) -CO-C (R ¹⁰ ) ₂ , -CH (R ¹⁰ ) CO-OR ⁹ -O-CO -CH (R ¹⁰⁾ - or -C (R ¹⁰⁾ 2 CO-oR ⁹ -O-CO-C (R ¹⁰⁾ _2; for n = 3:

and where R ² , R ³ and R ⁴ independently of one another are H, C ₁ -C ₂₅ -alkyl, C ₂ -C ₂₅ -alkenyl-CH (R ¹¹ )

wherein at least one of R ² , R ³ or R ^{4 is} -CH (R ¹¹ ) -S (O) _p -R ¹² ; R ⁵ = C ₁ -C ₂₅ alkyl, C ₁ -C ₂₅ alkenyl, C ₇ -C ₁₂ phenylalkyl or unsubstituted or C ₁ -C ₄ or halogen-substituted phenyl; R ⁶ = H or C ₁ -C ₄ alkyl: R ⁷ = H, C ₁ -C ₂₅ alkyl, unsubstituted or C ₁ -C ₄ alkyl or halogen-substituted phenyl; R ⁸ = phenylene, unsubstituted or with C ₁ -C ₄ alkyl, benzyl or phenyl substituted C ₂ -C ₂₄ alkylene or by oxygen or sulfur interrupted C ₂ -C ₂₄ alkylene; R ⁹ = a chemical bond, unsubstituted or C ₁ -C ₄ alkyl, benzyl or phenyl-substituted C ₂ -C ₂₄ alkylene or interrupted by oxygen or sulfur C ₂ -C ₂₄ alkylene; R ¹⁰ = H or C ₁ -C ₈ alkyl; R ¹¹ = H, C ₁ -C ₈ alkyl, unsubstituted or C ₁ -C ₄ alkyl-substituted phenyl; R ¹² = a monovalent perfluorinated alkyl or alkenyl radical or a linear or branched organic radical having four to 20 perfluorinated carbon atoms; R ¹³ = H, C ₁ -C ₂₅ alkyl, C ₂ -C ₂₅ alkenyl, -CO-R ⁵ , -CO-N (R ⁶ ) -R ⁷ or -CH ₂ -CO-N (R ⁶ ) -R ⁷ ; R ¹⁴ = H, C ₁ -C ₂₅ alkyl, C ₂ -C ₂₅ alkenyl or -CH (R ¹¹ ) -S (O) _p -R ¹² ; R ¹⁵ = H, C ₁ -C ₂₅ alkyl, C ₂ -C ₂₅ alkenyl or -CH (R ¹¹ ) -S (O) _p -R ¹² ; R ¹⁶ = unsubstituted or C ₁ -C ₄ alkyl-substituted methylene, -S-, -S (O) -, -S (O) ₂ or -CO-; R ¹⁷ = C ₁ -C ₂₅ alkyl; n = 1, 2 or 3; p = 0, 1 or 2. Particles according to at least one of the preceding claims, characterized in that the pores have a substantially cylindrical or conical shape. Particles according to at least one of the preceding claims, characterized in that organic polymer is selected from polymers which are obtainable by polycondensation, polyaddition or free-radical polymerization. Particles according to at least one of the preceding claims, characterized in that organic polymer is selected from polyurethanes. Particles according to at least one of the preceding claims, characterized in that they are polyurethanes which are prepared essentially using aliphatic or cycloaliphatic diisocyanates. Aqueous dispersions containing spherical particles according to any one of claims 1 to 7. Aqueous dispersions according to claim 8, characterized in that they further contain particles which have no pores with a diameter in the range of 1 to 90% of the particle diameter and a depth of at least 10% of the particle diameter. Aqueous dispersions according to claim 8 or 9, characterized in that they further contain particles having a diameter in the range of 50 nm to less than a micrometer. Use of spherical particles according to at least one of Claims 1 to 7 or of aqueous dispersions according to one of Claims 8 to 10 for coating substrates. Use according to claim 11, characterized in that substrates are selected from metal, glass, plastic and fibrous substrates. Use according to claim 12, characterized in that fibrous substrates are selected from paper, textile, leather and imitations of leather. Leather coated with spherical particles according to one of claims 1 to 7. Use of leather according to claim 15 for automotive interior parts.