Emulsion of aminosiloxane and silicate

Abstract

The present invention provides an oil-in-water emulsion comprising: (i) 100 parts by weight of the polyorganosiloxane (P) containing aminoalkyl groups that is liquid at 20°C according to claim 1 (ii) a protonating agent; (iii) 1 to 80 parts by weight of the silicate compound of claim 1 (iv) water; (v) up to 5 parts by weight of an emulsifier; and (vi) monoalcohols of general formula IX R 11 -OH(IX), and dialcohol monoethers of general formula X R 12 OR 13 -OR 14 (X), at least 5 parts by weight of an organic solvent selected from [In the formula, R 11 , R 12 , R 13 and R 14 has the definition specified in claim 1.] wherein the emulsion comprises up to 10 parts by weight of the di-, tri- or oligoglycol ether of claim 1, and a method of treating a substrate with said oil-in-water emulsion.

Description

[Technical Field]

[0001] The present invention relates to an oil-in-water emulsion of a polydimethylsiloxane containing aminoalkyl groups and a silicate, and a method for treating a substrate with the same. [Background technology]

[0002] Aminosiloxane and silicate based emulsions are used to repel aqueous stains on porous or non-porous, absorbent or non-absorbent substrates.

[0003] DE 102014216380 describes oil-in-water emulsions of aminosiloxanes in combination with silicates which can be used for the hydrophobic treatment of porous or non-porous, absorbent or non-absorbent substrates.

[0004] The formulation described in DE102014216380 uses oligoglycol ether, for example diethylene glycol butyl ether, as an auxiliary agent to improve storage stability.The disadvantage of these auxiliary agents is that, due to their high hydrophilicity caused by two or more glycol groups, the water repellency is still not good enough, similar to the water repellency of water-alcohol mixtures. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] German Patent Application Publication No. 102014216380 Summary of the Invention

[0006] The present invention provides an oil-in-water emulsion comprising: (i) 100 parts by weight of an aminoalkyl-containing polyorganosiloxane (P) that is liquid at 20°C and contains at least 80 mol% of units selected from units of the general formulae Ia, Ib, IIa and IIb R 1 2SiO (2 / 2)(Ia), R 1 a R 2 SiO (3-a) / 2 (Ib), R 3 3SiO (1 / 2) (IIa), R 3 2nd Round 4 SiO (1 / 2) (IIb), [In the formula, a has a value of 0 or 1; R 1 is an unsubstituted or halogen-substituted alkyl group having 1 to 40 carbon atoms, R 2 is an aminoalkyl group of general formula III, -R 5 -NR 6 R 7 (III), During the ceremony, R 5 is a divalent hydrocarbon group having 1 to 40 carbon atoms, R 6 is a monovalent hydrocarbon group having 1 to 40 carbon atoms, hydrogen, or an alkanoyl group; R 7 is a group of general formula IV, -(R 8 -NR 6 ) x R 6 (IV), During the ceremony, x has a value of 0 or an integer value from 1 to 40; R 8 is a divalent radical of general formula V, -(CR 9 R 9 -) y (V), During the ceremony, y has an integer value from 1 to 6; R 9 is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, R 3 is an unsubstituted or halogen-substituted alkyl group having 1 to 40 carbon atoms; R 4 is an —OR group or an —OH group, R is an unsubstituted or halogen-substituted alkyl group having 1 to 40 carbon atoms; The average ratio of units of general formulae Ia and IIb to the sum of units of general formulae IIa and IIb in the polyorganosiloxane (P) is 0.5 to 500, and the polyorganosiloxane (P) has an average amine value of at least 0.1 mequiv / g. (ii) a protonating agent; (iii) tetraalkoxysilicic acids of general formula VI salt ( R 10 O ) 4Si(VI) one at least 80 mol % of units of general formulae VII and VIII, and Polysilicate compounds containing at least two units of general formula VII ( R 10 O ) 3SiO 1 / 2 (VII), ( R 10 O ) 2SiO 2 / 2 (VIII) and A mixture of them 1 to 80 parts by weight of a silicate compound selected from , [In the formula, R 10 is an unsubstituted or halogen-substituted hydrocarbon group having 1 to 18 carbon atoms. (iv) water; (v) up to 5 parts by weight of an emulsifier; and (vi) monoalcohols of general formula IX R 11 -OH(IX), and dialcohol monoethers of general formula X R 12 OR 13 -OR 14 (X), and mixtures thereof. [In the formula, R 11 is a monovalent hydrocarbon group having 2 to 18 carbon atoms, R 12 is a monovalent hydrocarbon group having 1 to 18 carbon atoms, R 13 is a divalent hydrocarbon group having 2 to 12 carbon atoms, R 14 is hydrogen, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or an acetyl group. with the proviso that the emulsion relates to an oil-in-water emulsion comprising at most 10 parts by weight of a di-, tri- or oligoglycol ether of general formula XI. R 15 - (OC H2CH2) m -OH(XI), [In the formula, R 15 is R 12 has the definition of m is an integer equal to or greater than 2.] DETAILED DESCRIPTION OF THE INVENTION

[0007] The emulsions are homogeneous and stable without further addition of emulsifiers or other stabilizing ingredients such as silicone-polyether copolymer emulsifiers, despite the low or absence of di-, tri-, or oligoglycol ethers of general formula XI. Yes do.

[0008] The emulsions exhibit excellent water repellency on many porous or non-porous, absorbent or non-absorbent substrates, especially on fibers and textiles. Tests according to DIN EN 24920 are very good on textiles treated with the emulsions.

[0009] Substrates treated with the emulsion also exhibit improved stain repellency.

[0010] The emulsions further exhibit significant gloss enhancement on many porous or non-porous, absorbent or non-absorbent substrates.

[0011] Alkyl group R 1 , R 3 and R can be linear, cyclic, branched, saturated or unsaturated. The alkyl group R 1 , R 3 and R preferably have 1 to 18 carbon atoms, especially 1 to 6 carbon atoms, and are particularly preferably methyl or ethyl groups. Preferred halogen substituents are fluorine and chlorine. Particularly preferred R 1 , R 3 and the R group is a methyl group.

[0012] Divalent hydrocarbon group R 5 The group R can be halogen-substituted, linear, cyclic, branched, aromatic, saturated or unsaturated. 5 preferably has 1 to 6 carbon atoms and is particularly preferably an alkylene group, especially propylene. Preferred halogen substituents are fluorine and chlorine.

[0013] Monovalent hydrocarbon radical R 6 The group R can be halogen-substituted, linear, cyclic, branched, aromatic, saturated or unsaturated. 6 is preferably an alkyl or alkanoyl group having 1 to 6 carbon atoms, particularly preferably having 1 to 6 carbon atoms. Preferred halogen substituents are fluorine and chlorine. Particularly preferred substituents R 6 is hydrogen, methyl, ethyl, cyclohexyl and acetyl groups.

[0014] Monovalent hydrocarbon radical R 9 The group R can be halogen-substituted, linear, cyclic, branched, aromatic, saturated or unsaturated. 9 is preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably an alkyl group having 1 to 6 carbon atoms. Preferred halogen substituents are fluorine and chlorine. Particularly preferred substituents R 9 are hydrogen, methyl, ethyl and cyclohexyl groups.

[0015] Preferably, x has a value of 0 or a value of 1 to 18, and particularly preferably a value of 1 to 6.

[0016] Particularly preferred groups R 2 is -CH2N(R 6 )2, -(CH2)3N(R 6 )2, -(CH2)3N(R 6 )(CH2)2N(R 6 ) 2, in particular the aminopropyl group, the aminoethylaminopropyl group and the cyclohexylaminopropyl group.

[0017] The polydimethylsiloxane (P) is preferably composed of at least 3, in particular at least 10, and preferably at most 500, in particular at most 200 units of the formulae Ia, Ib, IIa and IIb.

[0018] The polydimethylsiloxane (P) preferably has a chain length of 3 to 1000 repeating units, particularly 10 to 500 repeating units.

[0019] The viscosity of the polydimethylsiloxane (P) at 20°C is preferably 1 to 100,000 mPa·s, particularly 10 to 10,000 mPa·s.

[0020] The ratio of the number of units Ia to the number of units Ib is selected so that the polydimethylsiloxane (P) has an amine value of at least 0.1 mequiv / g of polydimethylsiloxane (P), preferably at least 0.15 mequiv / g of polydimethylsiloxane (P). The amine value of the polydimethylsiloxane (P) is at most 7 mequiv / g, preferably at most 2 mequiv / g, in particular at most 0.6 mequiv / g.

[0021] The polydimethylsiloxane (P) preferably has either only units of formula IIa, only units of formula IIb, or a combination of units of formula IIa and formula IIb.

[0022] Polydimethylsiloxane (P) is produced by known chemical methods such as hydrolysis or equilibration.

[0023] The protonating agent is preferably a monobasic or polybasic, water-soluble or water-insoluble, organic or inorganic acid.

[0024] Suitable protonating agents are, for example, formic acid, acetic acid, propionic acid, malonic acid, citric acid, hydrochloric acid, sulfuric acid, phosphoric acid or mixtures thereof. Preferred protonating agents are formic acid, acetic acid, sulfuric acid or hydrochloric acid. Acetic acid is particularly preferred.

[0025] The protonating agent is generally added undiluted or in the form of an aqueous solution.

[0026] The protonating agent is the group R 2 It is preferable that the amount of protons added is 0.05 to 2 moles per mole of basic nitrogen atom.

[0027] The protonating agent is preferably added in an amount such that the oil-in-water emulsion reaches a pH in the range of 3.5 to 7.0, preferably a pH between 3.5 and 6.0, particularly preferably a pH between 3.5 and 5.0.

[0028] In the context of the present invention, pH is measured at 20° C. with an electrode according to United States Pharmacopeia USP33.

[0029] Monovalent hydrocarbon radical R of silicate compounds 10 The group R can be halogen-substituted, linear, cyclic, branched, aromatic, saturated or unsaturated. 10 has preferably 1 to 6 carbon atoms, and is particularly preferably an alkyl group or a phenyl group. Preferred halogen substituents are fluorine and chlorine. Particularly preferred groups R 10 are methyl, ethyl and propyl.

[0030] The emulsion preferably contains 5 to 50 parts by weight, particularly preferably 10 to 30 parts by weight, of the silicate compound, based on 100 parts by weight of polydimethylsiloxane (P).

[0031] The polysilicate compound preferably comprises at least 90, in particular at least 95 mol % of units of the general formulae VII and VIII.

[0032] The remaining units of the polysilicate compound can be, for example, units of general formulas XII and XIII. R 10 OSiO 3 / 2 (XII), SiO 4 / 2 (XIII), In the formula, R 10 is as defined above.

[0033] The oil-in-water emulsion may also additionally contain silicone oils, silicone waxes and silicone resins, preferably in amounts of up to 5 parts by weight, in particular up to 2 parts by weight.

[0034] The water is demineralized or salt-containing water, preferably demineralized water.

[0035] The oil-in-water emulsion according to the invention preferably comprises at most 3, particularly preferably at most 1, in particular at most 0.1 parts by weight of emulsifier.

[0036] As emulsifiers, all ionic and nonionic emulsifiers known to date can be used, either individually or as mixtures of different emulsifiers, with which aqueous dispersions, in particular aqueous emulsions of organopolysiloxanes, can also be produced today.

[0037] Examples of anionic emulsifiers include: 1. Alkyl sulfates, especially those with a chain length of 8 to 18 carbon atoms, alkyl- and alkaryl ether sulfates with 8 to 18 carbon atoms and 1 to 40 ethylene oxide (EO) or propylene oxide (PO) units in the hydrophobic group.

[0038] 2. Sulfonates, in particular alkylsulfonates having 8 to 18 carbon atoms, alkylarylsulfonates having 8 to 18 carbon atoms, taurides, esters and semi-esters of sulfosuccinic acid with monohydric alcohols or alkylphenols having 4 to 15 carbon atoms, these alcohols or alkylphenols optionally being ethoxylated with 1 to 40 EO units.

[0039] 3. Alkali metal and ammonium salts of carboxylic acids having 8 to 20 carbon atoms in the alkyl, aryl, alkaryl or aralkyl group.

[0040] 4. Partial esters of phosphoric acid and their alkali metal and ammonium salts, in particular alkyl phosphates and alkaryl phosphates having 8 to 20 carbon atoms in the organic radical, alkyl ether phosphates or alkaryl ether phosphates having 8 to 20 carbon atoms and 1 to 40 EO units in the alkyl or alkaryl radical.

[0041] Examples of non-ionic emulsifiers are: 5. Polyvinyl alcohol having a degree of polymerization of 500 to 3000 and containing 5 to 50%, preferably 8 to 20, vinyl acetate units.

[0042] 6. Alkyl polyglycol ethers, preferably those having 3 to 40 EO units and alkyl groups of 8 to 20 carbon atoms.

[0043] 7. Alkylaryl polyglycol ethers, preferably those having 5 to 40 EO units and 8 to 20 carbon atoms in the alkyl and aryl groups.

[0044] 8. Ethylene oxide / propylene oxide (EO / PO) block copolymers, preferably those having 8 to 40 EO or PO units.

[0045] 9. Addition products of alkylamines having alkyl groups with 8 to 22 carbon atoms with ethylene oxide or propylene oxide.

[0046] 10. Fatty acids containing 6 to 24 carbon atoms.

[0047] 11. Alkyl polyglycosides of the general formula R*-O-ZO, where R* is a linear or branched, saturated or unsaturated alkyl group having an average of 8 to 24 carbon atoms, and ZO is an oligoglycosidic group having an average of o=1 to 10 hexose or pentose units or mixtures thereof.

[0048] 12. Natural substances and derivatives thereof such as lecithin, lanolin, saponin, cellulose, cellulose alkyl ethers and carboxyalkylcelluloses, the alkyl groups of which each have up to four carbon atoms.

[0049] 13. Linear organo(poly)siloxanes containing polar groups, in particular polar groups containing the elements O, N, C, S, P, Si, including in particular those containing alkoxy groups with up to 24 carbon atoms and / or up to 40 EO and / or PO groups.

[0050] Examples of cationic emulsifiers include: 14. Salts of primary, secondary and tertiary aliphatic amines containing 8 to 24 carbon atoms with acetic acid, sulfuric acid, hydrochloric acid and phosphoric acid.

[0051] 15. Quaternary alkylammonium salts and alkylbenzeneammonium salts, especially those in which the alkyl group has from 6 to 24 carbon atoms, especially the halides, sulfates, phosphates and acetates.

[0052] 16. Alkylpyridinium salts, alkylimidazolinium salts and alkyloxazolinium salts, especially those in which the alkyl chain has up to 18 carbon atoms, especially the halides, sulfates, phosphates and acetates.

[0053] Suitable amphoteric emulsifiers are in particular: 17. Long chain substituted amino acids such as N-alkyldi(aminoethyl)glycine or N-alkyl-2-aminopropionate.

[0054] 18. Betaines and alkylimidazolium betaines such as N-(3-acylamidopropyl)-N,N-dimethylammonium salts with C8-C18 acyl groups.

[0055] Preferred emulsifiers are nonionic emulsifiers, especially the alkyl polyglycol ethers listed above in 6., and cationic emulsifiers, especially the quaternary alkyl ammonium salts and alkyl benzene ammonium salts listed above in 15. The emulsifier can consist of one of the aforementioned emulsifiers or a mixture of two or more of the aforementioned emulsifiers, which can be used in pure form or in a solution of one or more of the emulsifiers in water or an organic solvent.

[0056] The oil-in-water emulsion preferably comprises an organic solvent selected from the group of monoalcohols of general formula IX or dialcohol monoethers of general formula X, which have a boiling point or boiling range of up to 260° C. at 0.10 MPa.

[0057] Monovalent hydrocarbon radical R 11 The group R can be linear, cyclic, branched, aromatic, saturated or unsaturated. 11 preferably has 2 to 12 carbon atoms, and is particularly preferably an alkyl group or a phenyl group.

[0058] Monovalent hydrocarbon radical R 11Examples are alkyl groups such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, phenyl, 2-butyloctyl and n-dodecyl groups.

[0059] Monovalent hydrocarbon radical R 12 The group R can be linear, cyclic, branched, aromatic, saturated or unsaturated. 12 preferably has 1 to 12 carbon atoms, and is particularly preferably an alkyl group or a phenyl group.

[0060] Monovalent hydrocarbon radical R 12 Examples are alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, phenyl, 2-butyloctyl and n-dodecyl groups.

[0061] Divalent hydrocarbon group R 13 The group R can be linear, cyclic, branched, saturated or unsaturated. 13 preferably has 2 to 6 carbon atoms and is particularly preferably an alkylene group, in particular a 1,2-ethylene group, a 1,3-propylene group, a 1,2-propylene group, a 1,2-butylene group, a 1,3-butylene group and a 1,4-butylene group.

[0062] R 14 When R is a monovalent hydrocarbon group, it can be linear, cyclic, branched, aromatic, saturated, or unsaturated. 14 is preferably hydrogen, an alkyl group, in particular a methyl or ethyl group, a phenyl group or an acetyl group. 14 is particularly preferably hydrogen.

[0063] Examples of monoalcohols of general formula IX are ethanol, n-propanol, isopropanol, butanol, pentanol, hexanol, heptanol or n-octanol, or Guerbet alcohols such as 2-ethylhexanol, 2-butyloctanol or 2-hexyldecanol.

[0064] Preferred examples of monoalcohols of general formula IX are n-hexanol, n-heptanol, n-octanol and 2-ethylhexanol.

[0065] Examples of dialcohol monoethers of general formula X and derivatives thereof are monoethylene glycol monoalkyl ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether.

[0066] Examples of dialcohol monoethers of general formula X and derivatives thereof are monopropylene glycol monoalkyl ethers, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, propylene glycol monobutyl ether or propylene glycol monophenyl ether.

[0067] The oil-in-water emulsion preferably comprises at least 10 parts by weight, particularly preferably at least 20 parts by weight, in particular at least 30 parts by weight and at most 150 parts by weight, preferably at most 100 parts by weight, of an organic solvent selected from the group of monoalcohols of general formula IX or dialcohol monoethers of general formula X.

[0068] An oil-in-water emulsion can include an organic solvent or a combination of two or more organic solvents. In particular, an oil-in-water emulsion can include a single organic solvent.

[0069] The oil-in-water emulsion may contain additional substances such as preservatives, fragrances, rust inhibitors and dyes.

[0070] The oil-in-water emulsion preferably comprises at most 8 parts by weight, particularly preferably at most 5 parts by weight, particularly preferably at most 2 parts by weight, in particular at most 1 part by weight of a di-, tri- or oligoglycol ether of the general formula XI.

[0071] Examples of preservatives are alcohol, phenoxyethanol, quaternary ammonium compounds such as N-alkyl(C12-18)-N,N-dimethyl-N-benzylammonium chloride, formaldehyde, parabens, benzyl alcohol, propionic acid and its salts, and isothiazolinones.

[0072] The oil-in-water emulsion may further contain other additives such as non-silicon-containing oils, resins and waxes. Examples of these are rapeseed oil, olive oil, mineral oil, paraffin oil or non-silicon-containing waxes such as carnauba wax and candelilla wax or Montan acid and Montan acid ester waxes, non-oxidized synthetic paraffins, polyethylene waxes, polyvinyl ether waxes and waxes including metal soaps, with carnauba wax, paraffin wax and polyethylene wax being preferred, and paraffin wax being particularly preferred.

[0073] The oil-in-water emulsion preferably contains at most 30.0 parts by weight, in particular at most 10 parts by weight, preferably at most 0.1 parts by weight of such additives, in each case based on 100 parts by weight of polyorganosiloxane (P).

[0074] The oil-in-water emulsion is prepared by mixing the polyorganosiloxane (P), the protonating agent, the silicate compound, water, and an organic solvent, and optionally further components. Mixing is preferably carried out at a temperature of 10 to 80°C, particularly preferably 15 to 40°C, and at a pressure of preferably 900 to 1100 hPa. However, mixing can also be carried out at higher or lower pressures.

[0075] In a preferred procedure, the polyorganosiloxane (P) and the silicate compound are premixed. This premix is ​​then incorporated into a mixture of water, a protonating agent, an organic solvent, and optionally further ingredients, and then diluted with more water to obtain an oil-in-water emulsion.

[0076] The production can be carried out discontinuously or continuously.

[0077] Techniques for producing emulsions of organopolysiloxanes are known. For example, intensive mixing and dispersion can be achieved using rotor-stator agitators, colloid mills, high-pressure homogenizers, microchannels, membranes, jet nozzles, and the like, or ultrasound. Homogenization equipment and methods are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, CD-ROM edition 2003, Wiley-VCH Verlag, under the heading "Emulsions."

[0078] The oil-in-water emulsion can be diluted with water in any proportion. The emulsion can contain water in an amount of at least 10.0 parts by weight, in particular at least 100.0 parts by weight, preferably at most 5000 parts by weight, in particular at most 1000 parts by weight.

[0079] The oil-in-water emulsion preferably has a viscosity of 5 to 10,000 mm at 25°C, regardless of the water fraction. 2 / s, particularly preferably 5 to 1000 mm 2 / s, particularly preferably 10 to 500 mm 2 It is a clear to opaque liquid with a pH of 1.

[0080] The present invention further relates to a method for treating a substrate with said oil-in-water emulsion, the treatment preferably being water- and stain-repellent impregnation and gloss enhancement of porous or non-porous, absorbent or non-absorbent substrates, preferably cellulose, paper, natural and / or synthetic fibers, mineral building materials, stone, tile, marble, metal, painted metal, glass, ceramic, glass-ceramic, plastic, coated plastic, wood, laminate, cork, rubber, imitation leather, leather as well as skin and hair for cosmetic applications.

[0081] Particularly preferred is the treatment and impregnation of any textile, especially natural and synthetic textile products and functional materials.

[0082] The oil-in-water emulsion is highly suitable for impregnating fabrics in commercial washing machines, in addition to the fabric softener chamber. In this case, laundry is washed in the wash cycle and contacted with the oil-in-water emulsion in the fabric softening cycle. A time-consuming second treatment step in the washing machine or subsequent treatment of the fabrics by spraying for impregnation is no longer necessary.

[0083] Furthermore, oil-in-water emulsions can not only be used to waterproof and enhance the shine of textiles and general porous or non-porous, absorbent or non-absorbent substrates, but also (particularly in combination with other additives) can achieve other effects such as resistance to environmental influences such as heat, sunlight, especially UV radiation, oxidizing agents, acidic environments, or finishing effects on textiles, especially color protection, fabric resistance, wrinkle resistance, stain repellency, shrinkage protection, flame retardancy, moth protection, anti-felt finish or antibacterial finish.

[0084] All symbols above the formula are defined independently of each other. The silicon atom is tetravalent in all formulas. The amounts in parts by weight refer to 100 parts by weight of polydimethylsiloxane (P).

[0085] In the following examples, all amounts and percentages are by weight, all pressures are 0.10 MPa (absolute) and all temperatures are 20° C. unless otherwise stated in any case.

[0086] All components of the silicone mixture add up to 100% by weight.

[0087] Unless otherwise stated, the following examples are carried out at ambient atmospheric pressure, i.e., about 1000 hPa, at room temperature, i.e., about 20°C, or at the temperature set when the reactants are mixed at room temperature without additional heating or cooling.

[0088] Dynamic viscosity was measured in accordance with DIN EN ISO 3219:1994 and DIN 53019 on an Anton Paar "MCR 302" rheometer using a cone-plate system (cone CP50-2) with an opening angle of 2°. The instrument was calibrated with 10,000 standard oils from the German National Metrology Institute. The measurement temperature was 25.00°C ± 0.05°C, and the measurement time was 3 minutes. The viscosity value (expressed in mPas) is the arithmetic mean of three independent measurements. The measurement uncertainty for dynamic viscosity is 1.5%. The shear rate gradient was selected depending on the viscosity and was specified separately for each viscosity value.

[0089] The kinematic viscosity is measured with a Schott ViscoSystem® AVS 350 viscosity measuring system using an Ubbelohde viscometer tube with constants (e.g., from Windaus or VWR) according to DIN 51562 Section 1 or ISO / DIS 3105 (including their calibration). Measurements are carried out at 25.0°C (±0.1°C). Viscosity values ​​(mm 2 The kinematic viscosity (specified in / s) is the arithmetic mean of three separate measurements carried out independently. The measurement uncertainty of the kinematic viscosity is 1.05%. Depending on the measurement range, different viscometer tubes with corresponding directional constants are used.

[0090] [Table 1]

[0091] Information on measuring range, appropriate capillary numbers and constants according to VWR Laboratory Catalogue, 2011-2013, p. 645.8.

[0092] 1 H-NMR spectra are recorded as solutions in CDCl 3 on a Bruker Avance III HD-NMR spectrometer (5 mm broadband probe with ATMA and Z-gradient) at a measurement frequency of 500.13 MHz.

[0093] 29 Si-NMR was recorded as a solution in C6D6-toluene on a Bruker Avance III HD-NMR spectrometer (5 mm broadband probe with ATMA and Z-gradient) at a measurement frequency of 90.34 MHz.

[0094] The following documents are known to those skilled in the art: 1 H-, 13 C- und 29 Si-NMR chemischen Verschiebungen einiger linearer, verzweigter und cyclischer Methyl-Siloxan-Verbindungen”, [of some linear, branched, and cyclic methylsiloxane compounds 1 H-, 13 C- and 29 Regarding Si-NMR chemical shifts] G. Engelhardt, H. Jancke; J. Organometal. Chem. 28 (1971), 293-300; "Chapter 8 - NMR spectroscopy of organosilicon compounds", Elizabeth A. Williams, The Chemistry of Organic Silicon Compounds, 1989 John Wiley and Sons Ltd, 511-533, evaluate the spectrum.

[0095] The amine number indicates the number of mmol of KOH equivalent to a gram of the substance to be determined. The amine number is determined in accordance with DIN 16945 1989-03 edition. [Example]

[0096] To demonstrate the advantages of an oil-in-water emulsion with a polysilicate compound using an organic solvent, it is tested in comparison with a formulation with a polysilicate compound using the organic solvent diethylene glycol butyl ether or a formulation with an MQ methyl silicone resin (as prior art).

[0097] The aminoalkyl-containing polydimethylsiloxane (P-1) used in the test examples was a mixed hydroxy- / methoxydimethylsilyl-terminated copolymer composed of aminoethylaminopropylmethylsiloxane units and dimethylsiloxane units, with a viscosity of 982 mPas (25°C, shear rate of 10 1 / s) and an amine value of 0.287 mmol / g.

[0098] The polydimethylsiloxane (P-2) containing aminoalkyl groups used in the test example was 69 mm 2 A mixed hydroxy- / methoxydimethylsilyl-trimethylsilyl terminated copolymer (68 mol% SiMe3 end groups, 29 mol% SiMe2OH end groups, 3 mol% SiMe2OMe end groups) composed of aminoethylaminopropylsiloxane units and dimethylsiloxane units with a viscosity of 0.05 / s (measured at 25°C in capillary tube number II) and an amine value of 0.12 mmol / g was obtained. 29 (Measured by Si-NMR).

[0099] The silicate compound (S-1) used in the test examples was a mixture of tetraethoxysilicate of general formula VI and a polysilicate compound having 2 units of general formula VII and 1 to 7 units of general formula VIII [where R 10 is an ethyl group.] and has an SiO2 content of 40% by weight.

[0100] Preparation of various formulations: <Composition E-1 according to the present invention> 95.0 g of polydimethylsiloxane (P-1) containing an aminoalkyl group and 5.0 g of silicate compound (S-1) are mixed at room temperature to obtain a clear, colorless oily mixture (M-1).

[0101] 7.0 g of demineralized water, 12.0 g of n-butyl glycol (available from Sigma-Aldrich under the trade name Ethylene Glycol Butyl Ether), and 0.9 g of acetic acid (80% aqueous solution available from Brenntag) are initially charged and mixed at room temperature. 17.0 g of oily mixture (M-1) and 63.1 g of demineralized water are continuously stirred at room temperature using a propeller stirrer. A translucent, colorless emulsion (E-1) is obtained. This emulsion is homogeneous and stable after storage at room temperature and at 40°C for 6 months.

[0102] <Comparative example VE-2, non-inventive and similar to DE 10 2014 216 380> 7.0 g of demineralized water, 2.9 g of ethylene glycol monohexyl ether (commercially available from BASF), 6.0 g of diethylene glycol monobutyl ether (commercially available from BASF), and 0.4 g of acetic acid (80% aqueous solution available from Brenntag) are initially charged and mixed at room temperature. 17.0 g of oily mixture (M-1), 64.1 g of demineralized water, 0.5 g of acetic acid, and 2.1 g of diethylene glycol monobutyl ether are continuously stirred at room temperature using a propeller stirrer. A clear, colorless emulsion is obtained (VE-2).

[0103] <Comparative example VE-3, non-inventive and similar to DE 10 2014 216 380> 7.0 g of demineralized water, 9.0 g of n-butyl glycol (available from Sigma-Aldrich under the trade name Ethylene Glycol Butyl Ether), 3.0 g of diethylene glycol monobutyl ether (commercially available from BASF), and 0.3 g of acetic acid (80% aqueous solution available from Brenntag) are initially charged and mixed at room temperature. 17.0 g of oily mixture (M-1), 63.5 g of demineralized water, and 0.2 g of acetic acid are continuously stirred at room temperature using a propeller stirrer. A clear, colorless emulsion (VE-3) is obtained.

[0104] <Composition E-4 according to the present invention> 80.0 g of polydimethylsiloxane (P-2) containing an aminoalkyl group and 20.0 g of silicate compound (S-1) are mixed at room temperature to obtain a clear, colorless oily mixture (M-2).

[0105] 7.0 g of demineralized water, 12.0 g of n-butyl glycol (available from Sigma-Aldrich under the trade name Ethylene Glycol Butyl Ether), and 0.3 g of acetic acid (80% aqueous solution available from Brenntag) are initially charged and mixed at room temperature. 25.0 g of oily mixture (M-2) and 55.7 g of demineralized water are continuously stirred at room temperature using a propeller stirrer. A translucent whitish emulsion (E-4) is obtained. This emulsion is homogeneous and stable after 6 months of storage at room temperature and 40°C.

[0106] <Composition E-5 according to the present invention> 10.0 g of demineralized water, 17.0 g of n-butyl glycol (available from Sigma-Aldrich under the trade name Ethylene Glycol Butyl Ether), and 0.4 g of acetic acid (80% aqueous solution available from Brenntag) are initially charged and mixed at room temperature. 35.0 g of oily mixture (M-2) and 37.6 g of demineralized water are continuously stirred at room temperature using a propeller stirrer. A slightly cloudy emulsion (E-5) is obtained. This emulsion is homogeneous and stable after 6 months of storage at room temperature and 40°C.

[0107] <Application example> <Application example 1> Water repellency test (water / alcohol drop test) This test method is useful for measuring the hydrophobic finish of leather or textiles.

[0108] For the purpose of impregnating leather or textiles, emulsions (E-1) and (VE-2) are diluted with deionized water to an active ingredient ratio of 5%.

[0109] The treated sample (leather or textile) to be tested is placed on the dish without touching the bottom of the test area of ​​the test sample.

[0110] Starting with test liquid W (distilled water), carefully place a 40 μl drop on each of three locations on the test specimen. These locations should be at least 2 cm apart from each other. The pipette should not touch the specimen while depositing the test liquid. To avoid excessive evaporation during the test, cover the test specimen with a Petri dish. Observe the specimen from an angle of approximately 45° until the drop is completely absorbed. This is the rewet time. If a drop remains on the specimen after 5 hours, the test is terminated and the time recorded as >300 minutes (for textiles). If the test specimen is leather, the time is specified in seconds (seconds). The test is then carried out with the next test liquid.

[0111] [Table 2]

[0112] evaluation The result of a hydrophobic finished leather or textile is called the rewet time: the longer the time, the more hydrophobic the finish.

[0113] [Table 3]

[0114] Surprisingly, the inventive formulations (E-1) and (E-4) appear to be significantly superior to the non-inventive formulation (VE-2) containing diethylene glycol butyl ether.

[0115] Even the formulation (VE-3) containing only 18.6 parts by weight of diethylene glycol butyl ether based on 100 parts by weight of polydimethylsiloxane (P-1) exhibits significantly shorter rewet times in the rewet test with 80 / 20 water / isopropanol compared to the inventive formulations (E-1) and (E-4).

[0116] [Table 4]

[0117] The formulation (E-1) according to the invention is also excellent for impregnating the lining leather.

[0118] <Application example 2> <Water repellency measurement (spray method)> Cotton treated similarly to Application Example 1 is stretched on a petri dish.

[0119] 250 ml of demineralized water is continuously sprayed onto the test cloth from a height of 150 mm using a nozzle. Immediately after spraying, the test cloth is vigorously shaken, and then the surface appearance is evaluated according to the following evaluation criteria.

[0120] evaluation: Template evaluation criteria: 100 No adhesion to or wetting of the surface 90 Slight, randomly distributed adhesion to or wetting of surfaces 80 Surface wetting at spray point 70 Partial wetting of the entire surface 50 Complete wetting of the entire surface

[0121] [Table 5]

[0122] Surprisingly, the inventive formulations (E-1) and (E-4) are clearly superior to the non-inventive formulation (VE-2) containing diethylene glycol butyl ether.

[0123] <Application example 3> <Measurement of water repellency in a washing machine> For soaking in a washing machine, use the following cloths: Polyester material: wfk 30A from wfk Testgewebe GmbH, 100% polyester, width: 100cm, item no. 30000, fabric weight approx. 170g / m 2 Polyamide material: wfk 40A from wfk Testgewebe GmbH, 100% polyamide 6.6, width: 80cm, item no. 40000, fabric weight approx. 75g / m 2

[0124] In each case, 600 g of fabric to be tested are placed in the drum of a washing machine (Novotronic® W 941, Miele). 100 g of the formulation to be tested are placed in the fabric conditioner compartment. The main wash cycle is then started at 40°C with spin (1200 rpm). After the wash program is complete, the fabrics are removed from the washing machine and immediately dried before being conditioned overnight in a climate-controlled room at 23°C and 60% relative humidity.

[0125] The impregnation effect is tested by measuring the time it takes for colored water droplets to penetrate into the fabric. The droplet application, the test liquid used and the evaluation are carried out as described for the textile product of Application Example 1.

[0126] [Table 6]

[0127] [Table 7]

[0128] Surprisingly, the inventive formulations (E-1) and (E-5) have excellent impregnation effects, clearly superior to the non-inventive formulation (VE-2) containing diethylene glycol butyl ether.

[0129] <Application Example 4> <Measurement of water repellency on porous substrates> Measurement of water repellency for wood by weight gain

[0130] The test materials used are wooden cubes made of beech and spruce with sides 3 cm long.

[0131] One end of a wooden cube is immersed in the test solution to a depth of approximately 1 cm for 5 seconds and then tapped with tissue paper.

[0132] After drying at room temperature (3 days), the weight (g1) of the cube was measured using an analytical balance (AE 200 model, Mettler-Toledo GmbH, Germany).Then, the treated surface of the cube was placed in water to a depth of about 0.5 cm, removed, and tapped with tissue paper to determine the weight (g2).

[0133] Weight increase [%]: Δg = (g2 - g1) / g1 x 100

[0134] The smaller the weight gain, the better the impregnation effect.

[0135] For the purpose of impregnating the wooden cubes, the emulsion (E-1) is diluted with deionized water to a concentration of 5% active ingredient.

[0136] [Table 8]

[0137] The formulation (E-1) according to the invention shows an excellent impregnation effect in the case of wood as a porous substrate.

[0138] Marble properties Marble (yellow Jura limestone, polished on one side, 5 x 5 x 1 cm, Herbst-Berghausen) processing:

[0139] For the purpose of impregnating marble, emulsion (E-1) is diluted with deionized water to an active ingredient rate of 2% or 5%.

[0140] A bowl was filled with the 2% or 5% test solution to a depth of approximately 0.2-0.5 cm. The polished side of the marble slab was placed in the solution for approximately 1-5 seconds, then removed and gently wiped with cosmetic tissue until no droplets were visible on the surface. The marble slab was left to dry at room temperature (20°C). After three days, the hydrophobicity of the marble was measured by water droplet contact angle measurement, stain repellency was measured using soybean oil and ink, and gloss change was measured using a gloss measuring device.

[0141] Water repellency measurement The water resistance of the treated marble is measured by measuring the contact angle of a water droplet on the surface of untreated and treated marble with a contact angle measuring device (Rame-hart Inc., USA). The droplet size of the demineralized water used is 0.01 ml.

[0142] [Table 9]

[0143] The formulation according to the invention (E-1) exhibits an excellent water repellency effect on marble as a porous substrate, as evidenced by a clearly increased contact angle compared to the untreated marble slab.

[0144] Measurement of stain repellency A 0.4 ml drop of soybean oil (Rapunzel Organic Soybean Oil, available from Amazon) and blue ink (Pelican 4001 ink cartridge for pen, available from Amazon) was placed on the surface of the untreated and treated marble. After 5 minutes, the marble was wiped with tissue paper and the appearance of any remaining stain was visually assessed.

[0145] [Table 10]

[0146] The formulation (E-1) according to the invention exhibits excellent stain repellency on marble as a porous substrate, especially compared to untreated marble slabs.

[0147] Measurement of gloss change The gloss is measured on the untreated and treated surfaces of the marble with a gloss measuring device (Micro Trigloss, Byk Gardner) at a beam angle of 20°. The difference in gloss values ​​between untreated and treated marble is the gloss change specified in the table.

[0148] [Table 11]

[0149] On marble porous substrates, treatment with formulation (E-1) according to the invention results in a surprisingly clear increase in gloss.

[0150] <Application example 5> Measuring properties on smooth substrates For the purpose of impregnating the smooth substrate, a black matt plastic sheet (material: ABS, Narbung 3, 150×100×3 mm, commercially available from Merck & Partner GmbH, Ulm) is used.

[0151] 0.5 ml of emulsion (E-4) is placed on the plastic sheet and rubbed with cosmetic tissue. The sheet is left at room temperature (20°C) for 24 hours. The change in gloss is measured using a gloss measuring device, and the waterproof test is performed by briefly rinsing the sheet with drinking water (about 10 seconds).

[0152] Measurement of gloss change The gloss is measured on the untreated and treated surfaces of the plastic sheet using a gloss measuring device (Micro Trigloss, Byk Gardner) at a beam angle of 85°. The difference in gloss value between the untreated and treated plastic sheet is the gloss change specified in the table.

[0153] [Table 12]

[0154] On smooth plastic substrates, treatment with the formulation of the present invention (E-4) results in a surprisingly clear increase in gloss, which remains even after treatment with water.

Claims

1. An oil-in-water emulsion comprising: (i) 100 parts by weight of an aminoalkyl-containing polyorganosiloxane (P) that is liquid at 20°C and contains at least 80 mol% of units selected from units of the general formulae Ia, Ib, IIa, and IIb R １ ２ Yes （２／２） (Ia) R １ ａ R ２ SiO （３－ａ）／２ (Ib)、 R ３ ３ SiO （１／２） (IIa) R ３ ２ R ４ SiO （１／２） (IIb)、 [In the formula, a has a value of 0 or 1; R １ is an alkyl group having 1 to 40 carbon atoms, unsubstituted or substituted by halogen, R ２ is an aminoalkyl group of general formula III, -R ５ -NR ６ R ７ (III)、 During the ceremony, R ５ is a divalent hydrocarbon group having 1 to 40 carbon atoms, R ６ is a monovalent hydrocarbon group having 1 to 40 carbon atoms, hydrogen, or an alkanoyl group; R ７ is a group of general formula IV, -(R ８ -NR ６ ) ｘ R ６ (IV) During the ceremony, x has a value of 0 or an integer value from 1 to 40; R ８ is a divalent group of general formula V, -(CR ９ R ９ -) ｙ (V)、 During the ceremony, y has an integer value from 1 to 6; R ９ is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, R ３ is an unsubstituted or halogen-substituted alkyl group having 1 to 40 carbon atoms; R ４ is an —OR group or an —OH group, R is an unsubstituted or halogen-substituted alkyl group having 1 to 40 carbon atoms; The average ratio of units of general formulae Ia and IIb to the sum of units of general formulae IIa and IIb in the polyorganosiloxane (P) is 0.5 to 500, and the polyorganosiloxane (P) has an average amine number of at least 0.1 mequiv / g and an amine number of at most 0.6 mequiv / g. (ii) a protonating agent; (iii) tetraalkoxysilicates of general formula VI (R) １０ O) ４ Si (VI), Polysilicate compounds comprising at least 80 mol % of units of general formulas VII and VIII and at least 2 units of general formula VII (2 １０ 9) ３ 3iｯ １／２ (699)、 () １０ .) ２ 3) ２／２ ((==).、 and 1 to 80 parts by weight of a silicate compound selected from the group consisting of silicates, ... [In the formula, R １０ is an unsubstituted or halogen-substituted hydrocarbon group having 1 to 18 carbon atoms. (iv) Water; (v) up to 5 parts by weight of an emulsifier; and (vi) a dialcohol monoether selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether, and ethylene glycol monohexyl ether; and at least 30 parts by weight of an organic solvent selected from the group consisting of However, the dialcohol monoether has a boiling point or boiling range of up to 260°C at 0.10 MPa. Including, provided that the emulsion contains up to 2 parts by weight of a di-, tri- or oligoglycol ether of general formula XI, R １５ -(OCH ２ CH ２ ) ｍ -OH(XI) [In the formula, R １５ is a monovalent hydrocarbon radical selected from n-butyl, isobutyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, phenyl, 2-butyloctyl, and n-dodecyl radicals; m is an integer and is 2 or greater. Oil-in-water emulsion.

2. group R １ and R ３ 2. The emulsion of claim 1, wherein is an alkyl group having 1 to 6 carbon atoms.

3. group R ６ 3. The emulsion of claim 1, wherein is an alkyl group having 1 to 6 carbon atoms, hydrogen, or acetyl.

4. group R ２ But -CH ２ N (R ６ ) ２ , -(CH ２ ) ３ N (R ６ ) ２ and (CH ２ ) ３ N (R ６ ) (CH ２ ) ２ N (R ６ ) ２ The emulsion according to any one of claims 1 to 3, wherein the emulsion is selected from

5. 5. The emulsion according to claim 1, wherein the protonating agent is selected from formic acid, acetic acid, sulfuric acid and hydrochloric acid.

6. group R １０ An emulsion according to any one of claims 1 to 5, wherein is selected from methyl, ethyl and propyl.

7. A method of treating a substrate with the oil-in-water emulsion of any one of claims 1 to 6.

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