EP2807217A1

EP2807217A1 - Mixture composition containing amino-functional siloxanes, hydrophobic particles and high-molecular silicones as well as the use thereof for leather treatment

Info

Publication number: EP2807217A1
Application number: EP12809758.1A
Authority: EP
Inventors: Christian Mund; Joerg Peggau
Original assignee: Evonik Industries AG
Current assignee: Evonik Operations GmbH
Priority date: 2012-01-27
Filing date: 2012-12-18
Publication date: 2014-12-03
Also published as: DE102012201167A1; BR112014018094A2; WO2013110413A1; US20150008355A1; CN103998526A

Abstract

The subject matter of the invention is mixture compositions containing amino-functional siloxanes, hydrophobic particles and high-molecular silicones as well as the use thereof for leather treatment.

Description

E V O N I K I N D U S T R I S S AG

Mixture composition containing amino-functional siloxanes, hydrophobic particles and high molecular weight silicones and its use for leather treatment

Field of the invention

The invention relates to mixture compositions containing amino-functional siloxanes, hydrophobic particles and high molecular weight silicones and their use for leather treatment.

State of the art

The process step of fatliquoring or hydrophobing leather but also the care treatment of leather in everyday life is essential for the equipment and the preservation of leather goods such. of bags, shoes or leather clothing.

Properties and serviceability of the finished products depend essentially on the fatliquoring and treatment agents used.

The treatment agents used are intended to give the leather u.a. Cleaning resistance and water resistance but also good properties with regard to softness,

Suppleness and laxity as well as shine ("Library of the Leather", publisher: Hans Herfeld, volume 4, Frankfurt 1987).

Various types of polymers have been described for the equipment and hydrophobization of leather goods. Polyolefin / poly (meth) acrylates are described for example in EP372746, EP412389 and WO93 / 05188. In DE3438645 fluorocarbon resins are disclosed for use in impregnating sprays.

Silicone compounds are also used as effective leather treatment agents.

DD7286938 uses a silicone oil in admixture with other components

Used leather grease.

DE4139090 describes silicone-chain-containing copolymers for softening and hydrophobicizing leather.

Carboxy-functional siloxanes are disclosed in WO95 / 22627 as emulsifiers for leather water repellency emulsions. EP 350240 describes the superficial coating of leather goods (leather finish) with the aid of aqueous emulsions of silane-containing copolymers.

DE2205143 describes mixtures of (a) 15-50% by weight Ti (OR) ₄ or Zr (OR) ₄ or the corresponding hydrolysates, where R is a long-chain alkyl radical, with (b) 5-70% by weight of an MQ resin and (c) 15-80% of a silicone oil and (d) 0.5-30% by weight of an aminoalkyl-substituted silane or siloxane for the treatment of leather. It describes the improvement of permanently water-repellent properties. DE4126975 describes impregnating and care compositions based on fluorocarbon resins, fluorosilicones and / or organic metal compounds which are formulated in a volatile siloxane as solvent and dispersant.

The products for leather treatment described in the prior art have the disadvantages that they are often difficult to process, do not affect the grip properties positively enough and are halogen-containing in the case of fluorine compounds.

The object of the present invention was to provide compounds for use in the leather trade, which are easy to process and produce a smooth and very pleasant feel of the leather, without losing the good effect of long-lasting water repellency.

Description of the invention

The blend compositions according to the invention containing amino-functional siloxanes, hydrophobic particles and high molecular weight silicones are described below by way of example, without the invention being restricted to these exemplary embodiments. If ranges, general formulas or classes of compounds are given below, these should not only be the

include corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds that can be obtained by removing individual values (ranges) or compounds. If documents are cited in the context of the present description, their content should be completely to the disclosure of the present

Invention. Are in the context of the present invention, compounds such z. B. organomodified polysiloxanes described that may have multiple units multiple, so they can be statistically distributed (statistical

Oligomer) or ordered (block oligomer) occur in these compounds.

Information on the number of units in such compounds is to be understood as an average, averaged over all corresponding compounds. All percentages (%) are by mass unless otherwise specified.

Surprisingly, it was found that the below

Mixing compositions of amino-functional siloxanes, hydrophobic particles and high molecular weight silicone solve the disadvantages of the prior art and thus able to solve the problem set for the invention.

The present invention therefore provides compounding compositions as described in the claims and the use of these for leather care.

The blend compositions of the invention have the advantage of being inexpensive, easily prepared compositions.

Another advantage is that the inventive

Mixing compositions can be processed and applied very easily.

Yet another advantage is that the invention

Mixture compositions can be applied very homogeneously on leather. Yet another advantage of the blend compositions of the invention are their outstanding results in terms of hand properties and sheen on leather.

Another advantage of the blend compositions according to the invention is their and the formulations produced with them increased storage stability.

Another advantage of the blend compositions according to the invention is the excellent hydrophobization of leather achievable with them.

A further advantage of the mixture compositions according to the invention is that the leather hydrophobization achieved with them is long lasting and has a high cleaning resistance.

An object of the present invention are blending compositions containing A) 50% by weight - 96.5% by weight, preferably 65% by weight - 96.5% by weight, of at least one amino-functional siloxane,

B) 3 wt .-% - 40 wt .-%, preferably 3 wt .-% - 30 wt .-%, at least one high molecular weight silicone and

C) 0.5% by weight - 10% by weight, preferably 0.5% by weight - 5% by weight, of hydrophobic particles,

wherein the percentages by weight refer to the sum of components A), B) and C). In connection with the present invention, the term "amino-functional siloxane" is understood to mean a siloxane which has at least one amino group. This term "amino group" includes primary, secondary or tertiary amino groups and their ionic adducts with a protic reactant H ⁺ A ^" In the context of the present invention, the term "high molecular weight silicone" is understood to mean a silicone which has an average molecular weight of at least 20,000 g / mol.

In the context of the present invention, the term "hydrophobic particles" is understood as meaning organic or inorganic particles which have a greater than 50% methanol wettability.

An analytical method for the determination of methanol wettability can

For example, be performed as follows: In transparent

Centrifuge tubes are each weighed into 0.2 g (± 0.005 g) of particles to be measured. 8.0 ml of a methanol / water mixture containing 10, 20, 30, 40, 50, 60, 70 and 80% by volume of methanol are added to each weighing. The sealed tubes are shaken for 30 seconds and then centrifuged for 5 minutes at 2500 min ^-1 The sediment volumes are read off, converted to percent and graphically plotted against the methanol content (% by volume) For example, unless otherwise indicated, pressure and temperature are standard conditions (25 ° C, 1 bar). Percentages are in mass percentages unless otherwise specified.

The amino-containing group characterizing the amino-functional siloxane can be pendant and / or terminal (alpha, omega-modification) on

Siloxane backbone to be bound. The amino-functional siloxane of component A) is preferably one of the general formula 1:

M _a M _b D _c D ' _d T _e T' _f Q _g (general formula 1) with

M = [R ² R ¹ ₂ Si0 _1/2 ]

M '= [R ³ R ¹ ₂ Si0 _1/2 ]

D = [R ² R ¹ Si0 _2/2 ]

D ^' = [R ³ R ¹ Si0 _2/2 ]

T = [R ¹ Si0 _3/2 ]

r = [R ³ Si0 _3/2 ]

Q = [Si0 _4/2 ], where

R ¹ independently of one another identical or different linear or branched, saturated or unsaturated hydrocarbon radicals having 1 to 30

Carbon atoms or aromatic hydrocarbon radicals having 6 to 30 carbon atoms, preferably methyl or phenyl, especially methyl;

R ² independently of one another are identical or different R ¹ , an alkoxy radical or a hydroxy group, preferably R ¹ , in particular methyl;

R ³ independently of one another, identically or differently, a linear or branched hydrocarbon radical substituted by nitrogen atoms, preferably a radical of the formulas - (CH ₂ ) ₃ -NR ⁴ ₂ , -CH ₂ -CHMe-CH ₂ -NR ⁴ ₂ or - (CH ₂ ) ₃ NR ⁴ - (CH ₂ ) ₂ NR ⁴ ₂ ; in particular - (CH ₂ ) ₃ -NH ₂ or - (CH ₂ ) ₃ NH- (CH ₂ ) ₂ NH ₂ ;

R ⁴ independently of one another identical or different linear or branched, saturated or unsaturated hydrocarbon radicals having 1 to 22

Carbon atoms, preferably ethyl or methyl, especially methyl; a = 0 to 20, preferably 0 to 10, in particular 0 or 2,

b = 0 to 20, preferably 0 or 2,

c = 101 to 5000, preferably 170 to 2000, in particular 250 to 1600, d = 0 to 500, preferably 0 to 100, in particular 0 or 2 to 30,

e = 0 to 20, preferably 0 to 10, in particular 0,

f = 0 to 20, preferably 0 to 10, in particular 0,

g = 0 to 20, preferably 0 to 10, in particular 0, with the proviso that at least one of the indices b, d and f Φ is 0.

In a preferred embodiment, at least 50%, preferably at least 70% of the radicals R ² = R ¹ .

Corresponding examples of amino-functional siloxanes are in almost all

Commercially available to silicone manufacturers such as DC 2-8566 (Dow Coming), SF 1708 (Momentive), KF-8015 or KF-8008 (Shin-Etsu).

These can be prepared by known methods of equilibration or

Condensation can be prepared, as described for example in EP1972330 (Sections 0154 and 0155), US7238768 and DE102010062676.

As high molecular weight silicone of component B) in particular halogen-free compounds are used.

A high molecular weight silicone of component B) has a molecular weight average Mw of at least 20,000 g / mol, preferably 50,000 g / mol, particularly preferably at least 100,000 g / mol.

The average molecular weight Mw of the high molecular weight silicone can be determined by gel permeation chromatography (GPC). For this purpose, as usual, e.g. calibrated against commercially available polystyrene standards of different molecular weights (see also standard DIN 55072-1 / ISO 13885-1). The high molecular weight silicone of component B) is preferably one which has a high viscosity; In particular, it preferably has viscosities of at least 50,000 mPa.s, more preferably at least 70,000 mPa.s, more preferably at least 100,000 mPa.s, measured at 25 ° C.

The viscosity of the high molecular weight silicone can be determined by means of a rheometer at a shear rate of 10 s ^-1 at 25 ° C.

According to preferred, high molecular weight silicones are selected from the group of linear silicone oils, which preferably have an average molecular weight of more than 50,000 g / mol, or from the group of branched silicone resins, which preferably has a viscosity of more than 20,000 mPa-s, measured at 25 ° C, exhibit. Preferred silicone oils are selected from the group of methyl- and / or phenyl-substituted, optionally also hydroxy-terminated polysiloxanes with middle

Molecular weights of more than 50,000 g / mol.

As high-molecular-weight silicones of component B), particular preference is given to dimethylpolysiloxane oils having viscosities of> 100 000 cSt, measured at 25.degree. Exemplary, preferred high molecular weight silicone oils are the commercially available products SS4267 or Baysilone Oel M 2000000 (Momentive), KF-96H-300000 (Shin-Etsu), PMX-200 Silicone Fluid, 500000 cSt. (Dow Corning) and Rhodorsil oil 47 V 300000 (Bluestar). Exemplary, preferred hydroxy-terminated polysiloxanes (PDM siloxanes) are the Bays products commercially available under CAS number 70131-67-8. Abhesive / Release Coat. ZW PR / OH (Momentive) or UC 107 (UChem).

Preferred branched silicone resins consisting essentially of R ⁵ ₂ R ⁶ SIOI _{/ 2} ( "M") - and Si0 _{_4/2} ( "Q") - and / or R ⁶ SI03 / 2 ( "T") - units,

in which

R ^{5 may be the} same or different and is a hydrogen atom or a monovalent, optionally substituted, optionally unsaturated SiC-bonded

Hydrocarbon radical having 1 to 16 carbon atoms, preferably methyl and R ^{6 has} the meaning of the radical R ⁵ or is an alkoxy radical having 1 to 4 carbon atoms or a hydroxy radical.

These resins are also called "MQ" or "MT" resins The molar ratio of M to Q and T units (M / (Q + T)) is preferably in the range of 0.5 / 1 to 1 , 5/1, in particular in the range of 0.5 / 1 to 1, 0/1, the quotient of T to M units preferably in the range of 0/1 to 0.4 / 1, in particular 0/1 Silicone resins may also contain up to 10% by weight of free hydroxy or alkoxy groups.

Exemplary, preferred silicone resins are the commercially available products PA 51 (Dow Corning) or Wacker MQ 803 TF (Wacker). The high molecular weight silicones can be prepared by methods such as described in W. Noll, Chemistry and Technology of Silicones, Verlag Chemie, Weinheim, 1968.

The high molecular weight silicones can also be directly penetrated in an emulsion

Condensation of low molecular weight organosilicon compounds, as described for example in EP 0093310 B2. The emulsions thus obtained can be in the context of the present invention also directly with A) and C) to obtain the inventive

Mix mixture composition. Hydrophobic particles which have a maximum particle size distribution in the range from 0.5 to 30 μm, preferably 0.7 to 15 μm, in particular 0.8 to 1 μm, are preferably used as component C).

As component C) it is preferred to use hydrophobic particles which have a methanol wettability of greater than 55%, preferably greater than 60%, particularly preferably greater than 65%, in particular greater than 70%.

The particle size distribution of the particles can be determined with a measuring system such as the company Sympatec, consisting of the modules VIBRI, RODOS and HELOS. The particles are predispersed by vibration and with compressed air, preferably with an overpressure of 2 to 3 bar, dispersed and by a

Blown measuring chamber. There, the particle size distribution is determined by means of laser diffraction. The evaluation is carried out with the associated WINDOX software. Suitable inorganic particles are hydrophobic or hydrophobized metal oxides such as silicas and alumina, metal soaps, alkaline earth carbonates or similar finely divided solids known in the art. As organic fine particulate substances, known alkaline earth salts of long-chain fatty acids having 12 to 22 carbon atoms, the amides of these fatty acids, micronized waxes such as e.g.

Polyethylene, PTFE waxes and their copolymers, and mixtures of such waxes are used, which are solid under conditions of use. Likewise, oligoureas can be used, as described by way of example in DE 19917186. Particularly suitable hydrophobic particles are hydrophobized metal oxides such as

Silica or alumina, in particular with a methanol wettability of greater than 55%, and organic waxes with a melting point> 80 °.

Preferred, hydrophobized metal oxides are hydrophobized, pyrogenically prepared silicas, such as those sold under the trade name "AEROSIL R" by EVONIK INDUSTRIES AG (eg AEROSIL R 972, AEROSIL R 805, AEROSIL R 8200, AEROSIL RX 200). Preferred organic waxes are, for example

Polyethylene-based waxes (LANCO WAX PE 1544, LUBRIZOL), amide waxes (e.g., LICOWAX C P, CLARIANT), and partially fluorinated waxes (such as VESTOWAX FM 1012, EVONIK INDUSTRIES)

In particular, mixture compositions are preferred according to the invention in which

Component A) is selected from amino-functional siloxanes of formula 1, wherein R ¹ is methyl and R ³ is - (CH ₂ ) ₃ -NH ₂ or - (CH ₂ ) ₃ NH- (CH ₂ ) ₂ NH ₂ , and component B) is selected from the group of methyl- and / or phenyl-substituted, optionally hydroxy-terminated polysiloxanes with middle

Molecular weights of more than 50,000 g / mol or from the group of branched silicone resins consisting essentially of R ⁵ ₂ R ⁶ SiOi _{/ 2} ("M") - and Si0 _4/2 ("Q") - and / or R ⁶ Si03 / 2 ("T") units where R ⁵ = methyl and the molar ratio of M to Q and T units (M / (Q + T)) in the range of 0.5 / 1 to 1, 5/1 and the quotient of T to M units is in the range of 0/1 to 0.4 / 1, and

Component C) is selected from hydrophobic particles which have a maximum particle size distribution in the range from 0.7 to 15 μm and a methanol wettability of greater than 55%.

The blend compositions of the present invention are advantageously useful for the care of leather and for the manufacture of leather care formulations. Exemplary leather goods are bags, shoes, leather clothing, hats, furniture,

Leather seats.

Thus, such uses are also the subject of the present invention, as well as the leather care formulations containing at least one

Blend composition of the present invention for leather itself. The term "care formulation" is understood here to mean a formulation which serves the purpose of preserving an object in its original form, the effects of external influences (eg time, light, temperature, pressure, contamination, chemical reaction with others, with the object contacting reactive compounds) such as aging, fouling, material fatigue,

Dulling, embrittling, fading, mitigating or avoiding or even to improve desired positive properties of the article. For the last point, let's say a gloss of the considered object.

Preferred leather care formulations are shoe creams, impregnating agents or leather cleaners.

The care formulations according to the invention are preferably in the form of aqueous dispersions, in particular emulsions.

In this case, the care formulations according to the invention preferably comprise water, at least one emulsifier and optionally at least one organic solvent and optionally at least one preservative.

Emulsifiers preferred in this context are selected from

Fatty alcohol ethoxylates and polyglycerol esters; in particular fatty alcohol ethoxylates. For example, as emulsifiers, representatives of the Tergitol product line from Dow Chemicals may be used, e.g. Tergitol 15-S-7, Tergitol TMN-6 or Tergitol 15-S-5.

Preferred, care formulations according to the invention additionally contain one or more ingredients from the group of surfactants, builders, perfumes,

Perfume carriers, dyes, antimicrobial agents, germicides, fungicides,

Antioxidants, preservatives, corrosion inhibitors, other phobic and

Impregnating, swelling and anti-slip agents, neutral filler salts and UV absorbers. In particular, the leather care formulations according to the invention may contain 0.001 and 90, more preferably 0.01 to 45 wt .-% of one or more of the other ingredients mentioned herein, wherein the wt .-% refer to the entire formulation.

Examples of surfactants which can be used are described in WO 2007/1 15872, page 17, line 28 to page 21, line 24. Examples of builders are described in WO 2007/1 15872, page 22, line 7 to page 25, line 26. Examples of antimicrobial agents, germicides, fungicides, antioxidants,

Preservatives, UV absorbers are described in WO 2007/1 15872 on pages 28, line 14 to page 30, line 22. Their explicit explicit disclosure content becomes part of this disclosure by this reference.

The amounts of the respective ingredients in the formulation according to the invention depend on the intended use.

Typical recipes for the respective applications are known in the art and are for example in the brochures of the manufacturers of the respective Basic and active ingredients included. These existing formulations can usually be adopted unchanged. If necessary, for adaptation and optimization, the desired modifications can be made without complications by simple experiments.

In the examples given below, the present invention is described by way of example, without the invention, the scope of application of which is apparent from the entire description and the claims, to be limited to the embodiments mentioned in the examples.

Examples:

Example 1 mixture of amino-functional polydimethylsiloxane of formula II with a silicone oil and 300000 cSt Aerosit ^® RX 200:

79% of an amino-functional polydimethylsiloxane according to formula II (prepared as example 4 from DE102010062676.7 but without guanidinomodifiziert.es silane) with 18% of a polydimethylsiloxane having a viscosity of 300000 cSt (Rhodorsil oil 47 V 300000, Bluestar) and with 3% of a hydrophobic silica (Aerosil ^® RX 200, Evonik Industries AG) blended.

Me ₃ SiO- [Me ₂ SiO] 3 ₅ o- [MeRSiO] 7-SiMe ₃ , R = - (CH ₂ ) ₃ -NH ₂ (Formula II)

Example 2. mixture of amino-functional polydimethylsiloxane of formula III with an emulsion of silicone oil and 300000 cSt Vestowax FM ^® 1012:

A prepared using a homogenizer emulsion of 25 parts of a polydimethylsiloxane having a viscosity of 300,000 cSt (Rhodorsil oil 47 V 300 000, Blue Star), 5 parts of a micronized hard wax (Vestowax ^® FM 1012 Evonik Industries AG), 17 parts of emulsifier Tergitol 15 -S-7 (Dow Chemicals) and 20 parts of water with 70 parts of an aminopropyl-functional polydimethylsiloxane according to formula III (prepared similar to Example 4 of DE102010062676.7 but without gunidinomodifiziertem silane and with Dynasylan ^® 141 1 (Evonik Industries AG)) mixed. Me ₃ SiO [Me 2 SiO] iooo- [MeRSiO] 2o-SiMe _3! R = - (CH ₂ ) ₃ -NH- (CH ₂ ) ₂ -NH ₂ (Formula III)

Example 3. Mixture of amino-functional polydimethylsiloxane of the formula IV with a silicone oil 200,000 cSt and Aerosif RX 200:

75% of an aminofunctional polydimethylsiloxane according to formula IV (prepared via alkaline equilibration of 1,3-bis (aminopropyl) tetramethyldisiloxane and decamethylcyclopentasiloxane D5) is mixed with 22% of a polydimethylsiloxane having a viscosity of 100,000 cSt (KF-96L-100,000, Shin-Etsu) and with 3% of a hydrophobic silica (Aerosil ^® RX 200, Evonik Industries AG) blended.

RMe ₂ SiO- [Me ₂ SiO] ₃₅ o-SiMe ₂ R, R = - (CH ₂ ) ₃ -NH ₂ (Formula IV)

Example 4. Mixture of amino-functional polydimethylsiloxane of the formula V with an MQ resin PA 51 and Aerosif RX 200: 69% of an amino-functional polydimethylsiloxane according to formula V (prepared similarly to example 4 from DE102010062676.7 but without gunidinomodified silane and with Dynasylan 141 1 ( Evonik Industries AG)) is mixed (with 26% of an MQ resin PA 51, Dow Corning) and 5% of a hydrophobic silica (Aerosil ^® RX 200, Evonik Industries AG).

Me ₃ SiO- [Me ₂ SiO] ₄ oo- [MeRSiO] io-SiMe ₃ , R = - (CH ₂ ) ₃ -NH- (CH ₂ ) ₂ -NH ₂ (Formula V)

Comparative Example 5 (not according to the invention):

Mixture as Example 1 but without Aerosil ^® RX 200.

Comparative Example 6 (not according to the invention):

Mixture as Example 1, but without silicone oil 300,000 cSt and without Aerosil ^® RX 200. Comparative Example 7 (not according to the invention): Mixture as Example 1, but without silicone oil 300,000 cSt. Application properties:

In the following, the product examples described above for use on leather were tested.

Examples 1 -7 were diluted with mineral spirits to 10% active ingredients (aminosiloxane + silicone oil + hydrophobic particles). Of the solutions / mixtures obtained, 1 g per 2 g grained full chrome leather was spread evenly. The treated leather samples were allowed to dry under controlled conditions (23 ° C, 50% relative humidity) for 3 days.

An expert panel of 4 persons then evaluated the grip characteristics of the leather (grades from 1 = bad to 5 = very good). The summarized results are shown in Table 1. Tab. 1: Evaluation of the handling properties of the treated leather samples.

The results of the panel test show that, surprisingly, the

Inventive Examples 1 to 4 perform better on all the handle properties of the leather than Comparative Examples 5, 6 and 7. Especially in softness and

Smoothness of the leather, the positive effect of the mixtures according to the invention is very clear. Further formulation examples:

Tab. 2: Mixtures which serve, for example, as 10% dilutions with mineral spirits for leather treatment.

a b c d e f g h i j

Aminosiloxane according to formula II 59% 10% 40%

Aminosiloxane according to formula III 95% 10%

Aminosiloxane according to formula IV 80% 65% 50% 45%

Aminosiloxane according to formula V 70% 35% 30%

Aminosiloxane KF-8015

85% 5% (Shin-Etsu)

Aminosiloxane SF 1708

75% 5% (Momentive)

Silicone oil Rhodorsil Ol 47 V

3% 9% 5% 300000 (Bluestar)

Silicone oil KF-96L - 100,000

17% 15% 16% 10% (Shin-Etsu)

Silicone oil Baysilone oil M

19%

2000000 (Momentive)

PDM Siloxane Bays.

Abhesive / Release Coat. TW 28% 5%

PR / OH (Momentive)

MQ resin PA 51 (Dow

12% 5% 10% Corning)

Wacker MQ 803 TF (Wacker) 5% 1%

PE wax LAN CO WAX PE

1% 1, 5% 1544 (Lubrizol)

Hydrophobic silica

2% 1% 1% AEROSIL ^® R 972 (Evonik)

Amide wax LICOWAX C P

5% 0.5% (Clariant)

Micronized hard wax

VESTOWAX ^® FM 1012 2% 3% 1% 2.5% (Evonik)

Hydrophobic silica

3% 4% 3% 1% 2.5% AEROSIL ^® RX 200 (Evonik)

Tergitol 15-S-7 (Dow

7.5% 5.5% 6% Chemicals)

Water 1 1% 7% 8,5%

Preservative Acticide

0.5% 0.5% 0.5% MBS

Claims

claims

Containing mixture composition

A) 50% by weight - 96.5% by weight of at least one amino-functional siloxane,

B) 3 wt .-% - 40 wt .-% of at least one high molecular weight silicone and

C) 0.5% by weight to 10% by weight of hydrophobic particles,

wherein the percentages by weight refer to the sum of components A), B) and C).

Mixture composition according to claim 1 comprising as component A) an amino-functional siloxane of the general formula 1:

M _a M _b D _c D ' _d T _e T' _f Q _g (general formula 1) with

M = [R ² R ¹ ₂ Si0 _1/2 ]

M '= [R ³ R ¹ ₂ Si0 _1/2 ]

D = [R ² R ¹ Si0 _2/2 ]

D ^" = [R ³ R ¹ Si0 _2/2 ]

T = [R ¹ Si0 _3/2 ]

r = [R ³ Si0 _3/2 ]

Q = [Si0 _4/2 ], where

R ^{1 are} independently the same or different linear or

branched, saturated or unsaturated hydrocarbon radicals having 1 to 30 carbon atoms or also aromatic hydrocarbon radicals having 6 to 30 carbon atoms, preferably methyl or phenyl, in particular methyl;

R ³ independently of one another, identically or differently, a linear or branched hydrocarbon radical substituted by nitrogen atoms, preferably a radical of the formulas - (CH ₂ ) ₃ -NR ⁴ ₂ , -CH ₂ -CHMe-CH ₂ -NR ⁴ ₂ or - (CH ₂ ) ₃ NR ⁴ - (CH ₂ ) ₂ NR ⁴ ₂ ; in particular - (CH ₂ ) ₃ -NH ₂ or - (CH ₂ ) ₃ NH- (CH ₂ ) ₂ NH ₂ ; R ⁴ independently of one another are identical or different linear or branched, saturated or unsaturated hydrocarbon radicals having 1 to 22 carbon atoms, preferably ethyl or methyl, in particular methyl; a = 0 to 20, preferably 0 to 10, in particular 0 or 2,

b = 0 to 20, preferably 0 or 2,

e = 0 to 20, preferably 0 to 10, in particular 0,

f = 0 to 20, preferably 0 to 10, in particular 0,

g = 0 to 20, preferably 0 to 10, in particular 0, with the proviso that at least one of the indices b, d and f + 0.

3. Mixture composition according to claim 2, characterized in that at least 50%, preferably at least 70% of the radicals R ² = R ¹ are.

4. Blend composition according to any one of claims 1 to 3, comprising as component B) high molecular weight silicones selected from the group of linear silicone oils and the branched silicone resins.

5. mixture composition according to any one of claims 1 to 4, comprising as component C) hydrophobic particles having a maximum of the particle size distribution in the range of 0.5 to 30 μηη.

6. Mixture composition according to any one of claims 1 to 5, comprising as component C) hydrophobic particles selected from

hydrophobic or hydrophobized metal oxides such as silicas and

Alumina, metal soaps, alkaline earth carbonates and

Alkaline earth salts of long-chain fatty acids having 12 to 22 carbon atoms, the amides of these fatty acids,

micronized waxes such as e.g. Polyethylene, PTFE waxes and their

Copolymers, as well as mixtures of such waxes

and oligoureas.

7. Mixture composition according to any one of claims 1 to 6 wherein

Component A) is selected from amino-functional siloxanes of the formula 1, wherein R ¹ is methyl and R ³ is - (CH ₂ ) 3-NH ₂ or - (CH ₂ ) ₃ NH- (CH ₂ ) ₂ NH ₂ , and

Component B) is selected from the group of methyl- and / or phenyl-substituted, optionally also hydroxy-terminated polysiloxanes having average molecular weights of more than 50,000 g / mol or from the group of branched silicone resins consisting essentially of R ⁵ ₂ R ⁶ SiOi _{/ 2} ("M") and Si0 _4/2 ("Q") and / or R ⁶ Si03 / 2 ("T") units, wherein R ⁵ = methyl and the molar ratio of M- to Q and T units (M / (Q + T)) in the range of 0.5 / 1 to 1.5 / 1 and the quotient of T to M units in the range of 0/1 to 0.4 / 1, and

Component C) is selected from hydrophobic particles which have a maximum of the particle size distribution in the range of 0.7-15 μηη and a

Methanol wettability greater than 55%.

8 Use of at least one of the mixture compositions according to any one of claims 1 to 7 for leather care.

9. Use of at least one of the blend compositions according to any one of claims 1 to 7 for the preparation of leather care formulations.

10. Leather care formulation containing at least one of

Mixture compositions according to any one of claims 1 to 7.

1 1. Leather care formulation according to claim 10 in the form of an aqueous

Dispersion, in particular emulsion.

12. leather care formulation according to claim 1 1 containing

Water,

at least one emulsifier and optionally

at least one organic solvent and optionally

at least one preservative. Leather care formulation according to claim 12 as an emulsifier containing selected from fatty alcohol ethoxylates and polyglycerol esters.