Emulsions of aminosiloxanes and silicates

Abstract

To provide oil-in-water emulsions of polydimethylsiloxane containing aminoalkyl groups and silicates.SOLUTION: The present invention relates to oil-in-water emulsions that contain (i) 100 pts.wt. of specific polyorganosiloxane (P) containing aminoalkyl groups and being liquid at 20°C, (ii) protonation agents, (iii) 1 to 80 pts.wt. of a specific tetraalkoxysilicate compound, (iv) water, (v) at most 5 pts.wt. of an emulsifier, and (vi) at least 5 pts.wt. of an organic solvent selected from specific monoalcohols, specific dialcohol monoethers, and mixtures thereof, provided that the emulsion contains at most 10 pts.wt. of a di-, tri- or oligoglycol ether of the general formula XI: R12-O-(CH2CH2)m-OH (XI), wherein R12 is a monovalent hydrocarbon group having 1 to 18 carbon atoms, and m is an integer of 2 or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an oil-in-water emulsion of a polyorganosiloxane containing an aminoalkyl group and a silicate, and a method for treating a substrate using the same.

Background Art

[0002] Emulsions based on aminosiloxanes and silicates are used to repel aqueous soiling on porous or non-porous absorbent or non-absorbent substrates.

[0003] DE102014216380 describes an oil-in-water emulsion of an aminosiloxane used in combination with a silicate, which can be used for the hydrophobization treatment of porous or non-porous absorbent or non-absorbent substrates.

[0004] The formulation described in DE102014216380 uses oligoglycol ethers, such as diethylene glycol butyl ether, as auxiliaries to enhance storage stability. The disadvantage of these auxiliaries is that due to their rather high hydrophilicity caused by two or more glycol groups, the water repellency is not yet good enough, similar to that of a water-alcohol mixture.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

[0006] The present invention is an oil-in-water emulsion, (i) 100 parts by weight of a polyorganosiloxane (P) containing an aminoalkyl group that is liquid at 20 °C and contains at least 80 mol% of units selected from the units of general formulas 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 2R 4 SiO (1 / 2) (IIb), [wherein, a has a value of 0 or 1, R 1 is an alkyl group having 1 to 40 carbon atoms which is unsubstituted or substituted by halogen, R 2 is an aminoalkyl group of general formula III, -R 5 -NR 6 R 7 (III), wherein, R 5 is a divalent hydrocarbon group having 1 to 40 carbon atoms, R 6 is a monovalent hydrocarbon group, hydrogen or an alkanoyl group having 1 to 40 carbon atoms, R 7 is a group of general formula IV, -(R 8 -NR 6 ) x R 6 (IV), wherein, x has a value of 0 or an integer value of 1 to 40, R 8 is a divalent group of general formula V, -(CR 9 R 9 -) y (V), wherein, y has an integer value of 1 to 6, R 9 is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, R 3 is an alkyl group having 1 to 40 carbon atoms which is unsubstituted or substituted by halogen, R 4 is an -OR group or an -OH group, R is an alkyl group having 1 to 40 carbon atoms which is unsubstituted or substituted with halogen, The average ratio of the units of general formulas Ia and IIb to the total of the units of general formulas IIa and IIb in the polyorganosiloxane (P) is from 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) A tetraalkoxysilicate of general formula VI R 10 O4Si(VI) A polyoxysilicate compound containing at least 80 mol% of the units of general formulas VII and VIII, and at least 2 units of general formula VII R 10 O3SiO 1 / 2 (VII), R 10 O2SiO 2 / 2 (VIII) and 1 to 80 parts by weight of a silicate compound selected from the group consisting of those and mixtures thereof, [wherein, R 10 is a hydrocarbon group having 1 to 18 carbon atoms which is unsubstituted or substituted by halogen. (iv) Water, (v) Up to 5 parts by weight of an emulsifier, and (vi) A monoalcohol of general formula IX R 11 -OH(IX), and a dialcohol monoether of general formula X R 12 O-R 13 -OR 14 (X), and at least 5 parts by weight of an organic solvent selected from the group consisting of those and mixtures thereof [wherein, R 11 is a monovalent hydrocarbon group having 2 to 18 carbon atoms, R 12is 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.] which contains, provided that the emulsion relates to an oil-in-water emulsion containing up to 10 parts by weight of a di-, tri- or oligoglycol ether of general formula XI. R 12 -O-(CH2CH2) m -OH (XI), [wherein, R 15 has the definition of R 12 and m is an integer and is 2 or greater than 2.]

Mode for Carrying Out the Invention

[0007] The emulsion is homogeneous, stable and stable to dilution without further addition of other stabilizing components such as emulsifiers or silicone-polyether copolymer emulsifiers, despite the low or absent amount of the di-, tri- or oligoglycol ether of general formula XI.

[0008] The emulsion exhibits excellent water repellency on many porous or non-porous, absorbent or non-absorbent substrates, particularly fibers and fiber products. Tests according to DIN EN 24920 are very good on fiber products treated with the emulsion.

[0009] The substrate treated with the emulsion also shows an improvement in stain repellency.

[0010] The emulsion further shows a significant enhancement of gloss on many porous or non-porous, absorbent or non-absorbent substrates.

[0011] The alkyl group R 1 、R 3and 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, particularly 1 to 6 carbon atoms, and are particularly preferably a methyl group or an ethyl group. Preferred halogen substituents are fluorine and chlorine. Particularly preferred R 1 , R 3 and the R group are methyl groups.

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

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

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

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

[0016] Particularly preferred group R2 is -CH2N(R 6 )2, -(CH2)3N(R 6 )2, -(CH2)3N(R 6 )(CH2)2N(R 6 )2, and in particular an aminopropyl group, an aminoethylaminopropyl group and a cyclohexylaminopropyl group.

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

[0018] Polydimethylsiloxane (P) preferably has a chain length of 3 to 1000 repeating units, in particular 10 to 500 repeating units.

[0019] The viscosity of polydimethylsiloxane (P) is preferably 1 to 100000 mPa·s at 20°C, in particular 10 to 10000 mPa·s.

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

[0021] 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 base R 2 preferably added in an amount of 0.05 to 2 moles of protons per mole of basic nitrogen atoms.

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

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

[0029] The monovalent hydrocarbon group R of the silicate compound 10 can be halogen-substituted, linear, cyclic, branched, aromatic, saturated or unsaturated. The group R 10 preferably has 1 to 6 carbon atoms and is particularly preferably an alkyl group and a phenyl group. Preferred halogen substituents are fluorine and chlorine. Particularly preferred group R 10 is 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 contains at least 90, in particular at least 95 mol% of the units of general formulas VII and VIII.

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

[0033] The oil-in-water emulsion can also additionally contain silicone oil, silicone wax and silicone resin, preferably in an amount of up to 5 parts by weight, in particular up to 2 parts by weight.

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

[0035] The oil-in-water emulsion according to the invention preferably contains up to 3, particularly preferably up to 1, in particular up to 0.1 part by weight of an emulsifier.

[0036] As the emulsifier, all ionic and non-ionic emulsifiers known to date can be used individually or as a mixture of different emulsifiers, and with it, aqueous dispersions, in particular aqueous emulsions of organopolysiloxanes, can also be produced at present.

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

[0038] 2. Sulfonates, particularly alkyl sulfonates having 8 to 18 carbon atoms, alkyl aryl sulfonates having 8 to 18 carbon atoms, taurides, esters and half-esters of sulfosuccinic acid with a monohydric alcohol or alkylphenol having 4 to 15 carbon atoms, these alcohols or alkylphenols being optionally ethoxylated with 1 to 40 EO units.

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

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

[0041] Examples of nonionic emulsifiers are as follows. 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 an alkyl group of 8 to 20 carbon atoms.

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

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

[0045] 9. An addition product of an alkylamine having an alkyl group with 8 to 22 carbon atoms and ethylene oxide or propylene oxide.

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

[0047] 11. An alkyl polyglycoside 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 oligoglycoside group having an average of o = 1 to 10 hexose or pentose units or a mixture thereof.

[0048] 12. Natural substances such as lecithin, lanolin, saponin, cellulose, cellulose alkyl ether, and carboxyalkyl cellulose and derivatives thereof, wherein the alkyl groups each have up to 4 carbon atoms.

[0049] 13. Polar groups, in particular linear organo(poly)siloxanes containing polar groups containing the elements O, N, C, S, P, Si, in particular those having an alkoxy group with a maximum of 24 carbon atoms and / or a maximum of 40 EO and / or PO groups.

[0050] Examples of cationic emulsifiers are as follows. 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, in particular those having an alkyl group with 6 to 24 carbon atoms, in particular halides, sulfates, phosphates, and acetates.

[0052] 16. Alkylpyridinium salts, alkylimidazolinium salts, and alkyloxazolinium salts, in particular those having an alkyl chain with up to 18 carbon atoms, in particular halides, sulfates, phosphates, and acetates.

[0053] Particularly suitable as amphoteric emulsifiers are the following. 17. Long-chain substituted amino acids such as N-alkyldi(aminoethyl)glycine or N-alkyl-2-aminopropionate.

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

[0055] As emulsifiers, nonionic emulsifiers, particularly the alkyl polyglycol ethers listed in 6. above, and cationic emulsifiers, particularly the quaternary alkylammonium salts and alkylbenzeneammonium salts listed in 15. above, are preferred. The emulsifier can consist of one of the aforementioned emulsifiers, or a mixture of two or more of the aforementioned emulsifiers that can be used in pure form or as a solution of one or more emulsifiers in water or an organic solvent.

[0056] The oil-in-water emulsions preferably contain 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] The monovalent hydrocarbon radical R 11 can be straight-chain, cyclic, branched, aromatic, saturated or unsaturated. The radical R 11 preferably has 2 to 12 carbon atoms and is particularly preferably an alkyl group and a phenyl group.

[0058] The monovalent hydrocarbon radical R 11 Examples 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] The monovalent hydrocarbon radical R 12can be linear, cyclic, branched, aromatic, saturated or unsaturated. The group R 12 preferably has 1 to 12 carbon atoms, and particularly preferably is an alkyl group and a phenyl group.

[0060] Examples of the monovalent hydrocarbon group R 12 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] Examples of the divalent hydrocarbon group R 13 can be linear, cyclic, branched, saturated or unsaturated. The group R 13 preferably has 2 to 6 carbon atoms, and particularly preferably is an alkylene group, particularly 1,2-ethylene group, 1,3-propylene group, 1,2-propylene group, 1,2-butylene group, 1,3-butylene group and 1,4-butylene group.

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

[0063] Examples of the monoalcohol of general formula IX are ethanol, n-propanol, isopropanol, butanol, pentanol, hexanol, heptanol or n-octanol, or a garbet alcohol such as 2-ethylhexanol, 2-butyloctanol or 2-hexyldecanol.

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

[0065] Examples of the dialcohol monoethers of general formula X and their derivatives 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 the dialcohol monoethers of general formula X and their derivatives 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 contains at least 10 parts by weight, particularly preferably at least 20 parts by weight, especially 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 consisting of monoalcohols of general formula IX or dialcohol monoethers of general formula X.

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

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

[0070] The oil-in-water emulsion preferably contains at most 8 parts by weight, particularly preferably at most 5 parts by weight, especially preferably at most 2 parts by weight, especially at most 1 part by weight of the di-, tri- or oligoglycol ether of 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 isothiazolinone.

[0072] The oil-in-water emulsion can further contain other additives such as non-silicone-containing oils, resins and waxes. These examples include non-silicone-containing waxes such as rapeseed oil, olive oil, mineral oil, paraffin oil or carnauba wax and candelilla wax or montanic acid and montanic acid ester waxes, non-oxidizing synthetic paraffin, polyethylene wax, polyvinyl ether wax and waxes containing metal soaps, with carnauba wax, paraffin wax and polyethylene wax being preferred, and paraffin wax being particularly preferred.

[0073] In any case, the oil-in-water emulsion preferably contains such additives in a maximum amount of 30.0 parts by weight, particularly preferably a maximum of 10 parts by weight, and preferably a maximum of 0.1 parts by weight, based on 100 parts by weight of the polyorganosiloxane (P).

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

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

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

[0077] Techniques for manufacturing emulsions of organopolysiloxanes are known. For example, intensive mixing and dispersion can be carried out using rotor - stator stirrers, colloid mills, high - pressure homogenizers, microchannels, membranes, jet nozzles and the like, or ultrasound. Homogenizing devices 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] Oil - in - water emulsions can be diluted with water in any ratio. The emulsions can contain water in an amount of at least 10.0 parts by weight, particularly at least 100.0 parts by weight, preferably at most 5000 parts by weight, particularly at most 1000 parts by weight.

[0079] Oil - in - water emulsions are preferably transparent to opaque liquids with a viscosity at 25 °C of 5 - 10000 mm 2 / s, particularly preferably 5 - 1000 mm 2 / s, particularly preferably 10 - 500 mm 2 / s, regardless of the water fraction.

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

[0081] Particularly preferably, it is the treatment and impregnation of any fiber, particularly natural and synthetic fiber products and functional materials.

[0082] Oil-in-water emulsions are very suitable for impregnating fibers in a commercially available washing machine in addition to the fabric softener chamber. In this case, the laundry is washed in a washing cycle and brought into contact with the oil-in-water emulsion in a fabric softening cycle. There is no longer a need for a time-consuming second treatment step in the washing machine or subsequent treatment of the fiber product by spraying for impregnation.

[0083] Furthermore, oil-in-water emulsions can be used not only to waterproof fiber products and common porous or non-porous, absorbent or non-absorbent substrates and enhance their luster. Rather, oil-in-water emulsions (some in combination with other additives) can further achieve resistance to environmental influences such as heating, sunlight, especially ultraviolet irradiation, oxidizing agents, acidic environments, etc., or other effects such as finishing effects in fiber products such as color protection, fiber resistance, wrinkle-free, stain repellency, shrinkage protection, flame retardancy, moth protection, anti-felt finish or antibacterial finish.

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

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

[0086] The sum of all components of the silicone mixture is 100% by weight.

[0087] Unless otherwise specified, 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] The dynamic viscosity is measured with an Anton Paar "MCR 302" rheometer in accordance with DIN EN ISO 3219:1994 and DIN 53019, where a cone-plate system with an opening angle of 2° (cone CP50-2) is used. This device is calibrated with 10000 standard oils from the German National Metrology Institute. The measurement temperature is 25.00 °C ± 0.05 °C, and the measurement time is 3 minutes. The viscosity value (displayed in mPas) is the arithmetic mean of three individually performed measurements. The measurement uncertainty in dynamic viscosity is 1.5%. The shear rate gradient is selected according to the viscosity and is specified separately for each viscosity value.

[0089] The kinematic viscosity is measured with a Schott ViscoSystem(R) AVS 350 viscosity measurement system using a Ubbelohde viscometer tube with a constant (e.g., from Windaus or VWR) in accordance with DIN 51562 section 1 or ISO / DIS 3105 (including its calibration). The measurement is carried out at 25.0 °C (± 0.1 °C). The viscosity value (specified in mm 2 / s) is the arithmetic mean of three individually performed measurements. The measurement uncertainty in kinematic viscosity is 1.05%. Depending on the measurement range, different viscometer tubes with corresponding direction constants are used.

[0090]

Table 1

[0091] Information on the measurement range, appropriate capillary number, and constants according to the VWR Laboratory Catalog, 2011 - 2013, page 645.8.

[0092] 1 The 1H-NMR spectrum is recorded as a solution in CDCl3 with 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] 29The 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 gradients) at a measurement frequency of 90.34 MHz.

[0094] The following literature, known to those skilled in the art, namely, "Ueber die 1 H-, 13 C- und 29 Si-NMR chemical shifts of some linear, branched and cyclic methyl-siloxane compounds", [for the 1 H-, 13 C- and 29 Si-NMR chemical shifts of] 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, was used to evaluate the spectra.

[0095] The amine value indicates the number of mmol of KOH corresponding to the grams of the substance to be measured. The amine value is measured according to DIN 16945 Edition 1989 - 03.

Examples

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

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

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

[0099] The silicate compound (S-1) used in the test example is 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: <Formulation 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 colorless and clear oily mixture (M-1).

[0101] First, charge 7.0 g of deionized water, 12.0 g of n-butyl glycol (available under the trade name ethylene glycol butyl ether from Sigma-Aldrich), and 0.9 g of acetic acid (80% aqueous solution available from Brenntag), and mix at room temperature. Continuously stir 17.0 g of the oily mixture (M-1) and 63.1 g of deionized water at room temperature using a propeller stirrer. A translucent colorless emulsion (E-1) is obtained. Also, this emulsion is homogeneous and stable after storage at room temperature and 40 °C for 6 months.

[0102] <Comparative example formulation VE-2, which is similar to DE 10 2014 216 380 and is not an invention> First, charge 7.0 g of deionized 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), and mix at room temperature. Continuously stir 17.0 g of the oily mixture (M-1), 64.1 g of deionized water, 0.5 g of acetic acid, and 2.1 g of diethylene glycol monobutyl ether at room temperature using a propeller stirrer. A colorless and clear emulsion (VE-2) is obtained.

[0103] <Comparative example formulation VE-3, which is similar to DE 10 2014 216 380 and is not an invention> First, charge 7.0 g of deionized water, 9.0 g of n-butyl glycol (available under the trade name ethylene glycol butyl ether from Sigma-Aldrich), 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), and mix at room temperature. Continuously stir 17.0 g of the oily mixture (M-1), 63.5 g of deionized water, and 0.2 g of acetic acid at room temperature using a propeller stirrer. A colorless and clear emulsion (VE-3) is obtained.

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

[0105] First, charge 7.0 g of deionized water, 12.0 g of n-butyl glycol (available under the trade name ethylene glycol butyl ether from Sigma-Aldrich), and 0.3 g of acetic acid (80% aqueous solution available from Brenntag), and mix at room temperature. Continuously stir 25.0 g of the oily mixture (M-2) and 55.7 g of deionized water at room temperature using a propeller stirrer. A translucent, whitish emulsion (E-4) is obtained. Also, this emulsion is homogeneous and stable after storage at room temperature and 40 °C for 6 months.

[0106] <Formulation E-5 according to the present invention> First, charge 10.0 g of deionized water, 17.0 g of n-butyl glycol (available under the trade name ethylene glycol butyl ether from Sigma-Aldrich), and 0.4 g of acetic acid (80% aqueous solution available from Brenntag), and mix at room temperature. Continuously stir 35.0 g of the oily mixture (M-2) and 37.6 g of deionized water at room temperature using a propeller stirrer. A slightly turbid emulsion (E-5) is obtained. Also, this emulsion is homogeneous and stable after storage at room temperature and 40 °C for 6 months.

[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 textile products.

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

[0109] Place the treated sample (leather or textile product) to be tested on a petri dish so as not to contact the bottom of the test area of the test sample.

[0110] Start with the test liquid W (distilled water) and carefully place 40 μl droplets at each of three locations on the test sample. These positions must be at least 2 cm apart from each other. During the placement of the test liquid, ensure that the pipette does not touch the sample. To avoid excessive evaporation during the test, cover the test sample with a petri dish. Observe the sample at an angle of approximately 45° until the droplets are completely absorbed. This is the rewetting time. If droplets remain on the sample after 5 hours, end the test and record time > 300 minutes (in the case of textile products). If the test sample is leather, the time is specified in seconds. Then, conduct the test with the next test liquid.

[0111]

Table 2

[0112] Evaluation The results for leather or textile products finished with hydrophobicity are referred to as the rewetting time. The longer the time, the more hydrophobic the finish.

[0113]

Table 3

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

[0115] Even a 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) shows a considerably shorter rewetting time in the rewetting test with water / isopropanol 80 / 20 compared to the formulations (E-1) and (E-4) of the invention.

[0116]

Table 4

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

[0118] <Application Example 2> <Measurement of Water Repellency (Spray Method)> The cotton treated similarly to Application Example 1 is spread out on a petri dish.

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

[0120] Evaluation: Evaluation Criteria by Template: 100 No adhesion to the surface or wetting of the surface 90 Slight and randomly distributed adhesion to the surface or wetting of the surface 80 Wetting of the surface at the spray point 70 Partial wetting of the entire surface 50 Complete wetting of the entire surface

[0121]

Table 5

[0122] Surprisingly, it is clear that the formulations (E-1) and (E-4) of the present invention 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 impregnation in a washing machine, the following cloths are used. Polyester material: wfk 30A from wfk Testgewebe GmbH, 100% polyester, width: 100 cm, product number 30000, cloth weight approximately 170 g / m 2 Polyamide material: wfk 40A from wfk Testgewebe GmbH, 100% polyamide 6.6, width: 80 cm, product number 40000, cloth weight approximately 75 g / m2

[0124] In each case, 600 g of the fabric to be tested is placed in the drum of a washing machine (Novotronic(R) W 941, Miele). 100 g of the formulation to be tested is placed in the fabric conditioner compartment. Then, a main wash cycle at 40 °C is started with spin (1200 revolutions per minute). After completion of the washing program, the fabric is taken out of the washing machine, dried immediately, and then conditioned in a climate-controlled chamber at 23 °C and 60% relative humidity overnight.

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

[0126] [Table 6]

[0127] [Table 7]

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

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

[0130] Wooden cubes with a side length of 3 cm made of beech wood and fir are used as test materials.

[0131] After immersing one end face of the wooden cube in the test liquid to a depth of about 1 cm for 5 seconds, it is tapped with a tissue paper.

[0132] After drying at room temperature (for 3 days), measure the weight (g1) of the cube using an analytical balance (AE 200 type, Germany, Mettler-Toledo GmbH). Then, place the treated surface of the cube in water to a depth of about 0.5 cm, take it out, pat it with a tissue paper, and determine the weight (g2).

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

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

[0135] For the purpose of impregnating the wooden cube, dilute the emulsion (E-1) with deionized water to an active ingredient ratio of 5%.

[0136]

Table 8

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

[0138] Properties of marble Treatment of marble (yellow Jurassic limestone, one-sided polished, 5 × 5 × 1 cm, Herbst·Berghausen):

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

[0140] Fill the bowl with a 2% or 5% test solution to a depth of about 0.2 - 0.5 cm. Immerse the polished side of the marble slab in the solution for about 1 - 5 seconds and then take it out. Gently wipe the polished side with a cosmetic tissue paper until no liquid droplets are visible on the surface. Leave the marble slab to dry at RT (20°C). After 3 days, measure the hydrophobicity of the marble by measuring the contact angle of water droplets, measure the stain repellency with soybean oil and ink, and measure the change in gloss with a gloss measuring device.

[0141] Measurement of water repellency The water resistance of the treated marble is measured by measuring the contact angle of water droplets on the surfaces of the untreated and treated marbles using a contact angle measuring device (Rame-hart Inc., USA). The droplet size of the deionized water used is 0.01 ml.

[0142]

Table 9

[0143] The formulation (E-1) according to the present invention shows an excellent water repellent effect on marble as a porous substrate, which is indicated by a clearly increased contact angle compared to the untreated marble slab.

[0144] Measurement of stain repellency 0.4 ml drops of soybean oil (Lapunzel organic soybean oil, commercially available from Amazon) and blue ink (Pelikan 4001 ink cartridge for pens, commercially available from Amazon) are placed on the surfaces of the untreated and treated marbles. After 5 minutes, the marbles are wiped with tissue paper, and the appearance of the remaining stains is visually evaluated.

[0145]

Table 10

[0146] The formulation (E-1) according to the present invention shows an excellent stain repellent effect on marble as a porous substrate, especially compared to the untreated marble slab.

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

[0148]

Table 11

[0149] In the case of a porous marble substrate, the gloss increases remarkably clearly by the treatment with the formulation (E-1) according to the present invention.

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

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

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

[0153]

Table 12

[0154] In the case of a smooth plastic substrate, the gloss increases remarkably clearly by the treatment with the formulation (E-4) of the present invention, and this increase in gloss does not change even after treatment with water.

Claims

1. 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 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 from 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) a tetraalkoxysilicic acid salt of the 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 mixtures thereof, [In the formula, R １０ is a hydrocarbon group having 1 to 18 carbon atoms, unsubstituted or substituted by halogen. (iv) water; (v) up to 5 parts by weight of an emulsifier; and (vi) monoalcohols of general formula IX ( １１ H(︉、 and dialcohol monoethers of the general formula X R １２ O-R １３ -OR １４ (X)、 and at least 5 parts by weight of an organic solvent selected from the group consisting of [In the formula, R １１ is a monovalent hydrocarbon radical 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. Including, provided that the emulsion contains up to 10 parts by weight of a di-, tri- or oligoglycol ether of general formula XI, R １２ -O-(CH ２ CH ２ ) ｍ -OH(XI)、 [In the formula, R １５ is R １２ has the definition of 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 or 2, 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, which is selected from

5. The emulsion according to any one of claims 1 to 4, 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. group R １１ The emulsion of any one of claims 1 to 6, wherein is an alkyl group having from 2 to 12 carbon atoms.

8. group R １２ is an alkyl group having 1 to 12 carbon atoms, and the group R １３ is an alkylene group having 2 to 6 carbon atoms, and the group R １４ The emulsion according to any one of claims 1 to 7, wherein is a hydrogen atom.

9. A method of treating a substrate with an oil-in-water emulsion according to any one of claims 1 to 8.

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