Polyorganosiloxane emulsions with large particle size and process for their preparation

Abstract

The invention relates to a process for the preparation of storage-stable, aqueous polyorganosiloxane emulsions comprising (A) at least one polyorganosiloxane (B), at least one alkyl polyglycoside (C), water, optionally (D) further emulsifiers which are different from (B), optionally (E) thickeners and optionally (F) further additives which are usually contained in polyorganosiloxane emulsions, characterised in that (i) a total of 1.5 to 4.5 parts (B) per 100 parts (A) are contained, (ii) a total of 0 to 3 parts (D) per 100 parts (A) are contained, (iii) the sum of parts (B) and (D) is ≤ 4.5 per 100 parts (A) and (iv) the process comprises the following steps: (1) preparing an emulsifier-water mixture comprising at least (B), water (C), optionally (D), optionally (E) and optionally (F); (2) preparing a pre-emulsion by adding at least one (A) to the emulsifier-water mixture, with the proviso that the preparation of the pre-emulsion is carried out under the action of low shear forces by means of stirring devices with maximum peripheral speeds of 4.5 m / s; optionally (3) diluting the pre-emulsion by adding further water (C); and, optionally (4) adding (F), wherein polyorganosiloxane emulsions which have a particle size D(50) of 1 μm to 50 μm are obtained by the process.

Description

[0001]WA12245-S / We Polyorganosiloxane emulsions with large particle sizes and processes for their preparation. The invention relates to storage-stable, aqueous polyorganosiloxane emulsions made from higher-viscosity polyorganosiloxanes that contain alkyl polyglycosides as emulsifiers and have a large particle size, as well as to processes for the preparation of these emulsions. Polyorganosiloxanes have a wide range of applications. The terms "polyorganosiloxane" and "silicone" are used synonymously in the present invention. To facilitate application and dosing, particularly with viscous products, it is desirable for many applications that the organosilicon compounds be in diluted form. The use of organic solvents such as benzene or chlorinated hydrocarbons for this purpose is possible, but disadvantageous from an ecological and occupational health perspective.Therefore, they are usually used in the form of aqueous emulsions or dispersions, usually as oil-in-water emulsions that can be diluted with water. The oil phase refers to the water-immiscible, organosilicon compounds, optionally dissolved in organic solvents. Emulsions containing polyorganosiloxanes and other organosilicon compounds, and processes for their preparation, have long been known in the art and are described, for example, in the textbook W. Noll, Chemistry and Technology of Silicones, 1968, pp. 428-431, Verlag Chemie Weinheim. Emulsifiers typically used for polyorganosiloxane emulsions are ethoxylated synthetic alcohols, ethoxylated fatty alcohols, ethoxylated triglycerides, ethoxylated WA12245-S / We 2 fatty acids and mixtures thereof (for example in EP 200916 B1, EP0463431 A2 and DE 19620405 B4).Emulsifiers based on polyethylene glycol ethers and esters are undesirable, particularly in cosmetic applications, due to potential skin irritation (for example, in US2007178144 AA (corresponding to EP1813251 A2)). There is also an increased demand for products containing emulsifiers based on renewable raw materials. Alkyl polyglycosides are emulsifiers made from renewable raw materials that do not contain polyethylene glycol groups. It is known that silicone oils, e.g., polydimethylsiloxanes, can be emulsified with alkyl polyglycosides (for example, in US5133897 A (corresponding to EP0418479 A1)). These emulsions can be prepared with low shear forces. Two to 40 parts of emulsifier, preferably 5 to 30 parts of emulsifier, based on the oil phase, are used.In the examples, silicone oils are emulsified at up to 2000 mPa.s, using at least 11 parts of emulsifier per 100 parts of polyorganosiloxane to produce stable emulsions. If silicone defoamers, e.g., mixtures of silicone oil and highly dispersed silica, are to be emulsified, higher surfactant contents are required, and the emulsion must be additionally stabilized with thickeners or alcohols (see EP0769548 A1 and EP0774503 A1). EP0769548 A1 uses at least 5 parts, preferably at least 28 parts, of emulsifier, based on the silicone oil. EP0774503 A1 also uses at least 5 parts, preferably at least 10 parts, of emulsifier, based on the polyorganosiloxane. In the examples of these patents, 25 parts or 50 parts of emulsifier are used per 100 parts of silicone oil / SiO2. WA12245-S / We 3 However, high proportions of emulsifiers are economically disadvantageous, particularly for cost reasons.DE102014212725 A1 describes a process for the production of particularly fine-particle emulsions based on highly viscous silicone oils and alkyl polyglycosides. By applying high shear forces, particle sizes of less than 300 nm are achieved. These emulsions are thus stable even at lower emulsifier concentrations of only approximately 12 parts of emulsifier per 100 parts of silicone oil. However, this process has the disadvantage that it requires corresponding aggregates that can generate high shear forces in highly viscous phases, which also results in high energy consumption and is thus ecologically and economically disadvantageous. For special applications in cosmetics, large particle sizes are preferred (as in WO 03 / 092639 A1). However, with the particle size, the tendency towards separation increases according to Stokes' law (compare H. Schubert et al., Chem. Ing. Techn. 61, 1989, pp. 701-711).The object was therefore to provide emulsions based on highly viscous silicone oils and a process for producing these polyorganosiloxane emulsions, which contain emulsifiers based on renewable raw materials and exhibit excellent stability even with very low emulsifier contents and large particle sizes. This object is achieved by the present invention. The invention provides a process for producing storage-stable, aqueous polyorganosiloxane emulsions comprising (A) at least one polyorganosiloxane of the general formula R. 2 a(R 1 O)bSiO(4-ab) / 2 (I), WA12245-S / We 4 where R 1 may be the same or different and represents a hydrogen atom or a monovalent, substituted or unsubstituted hydrocarbon radical, R 2may be the same or different and represents a monovalent, substituted or unsubstituted hydrocarbon radical having 1 to 30 carbon atoms or a hydrogen atom, a is 0, 1, 2 or 3, b is 0, 1, 2 or 3, with the proviso that the sum a+b is ≤ 3, (B) at least one alkyl polyglycoside of the general formula where A is a linear or branched, saturated or unsaturated alkyl radical having 8 to 24 C atoms, G is a glycoside radical and m is the degree of glycosidation and is an integer from 1 to 5 on average, (C) water, optionally (D) further emulsifiers which are different from the alkyl polyglycosides (B), optionally (E) thickeners and optionally (F) further additives which are usually present in polyorganosiloxane emulsions, characterized in that (i) a total of 1.5 to 4.5 parts of alkyl polyglycoside (B) are present per 100 parts of polyorganosiloxane (A), (ii) a total of 0 to 3 parts of further emulsifiers (D) are present per 100 parts of polyorganosiloxane (A), WA12245-S / We 5 (iii) the sum of the parts of alkyl polyglycoside (B) and other emulsifiers (D) ≤ 4,5 per 100 parts of polyorganosiloxane (A) and (iv) the process comprises the following steps (1) preparation of an emulsifier-water mixture comprising at least one alkyl polyglycoside (B) and water (C) and optionally further emulsifiers (D), optionally thickeners (E) and optionally further additives (F), (2) preparation of a pre-emulsion by adding at least one polyorganosiloxane (A) to the emulsifier-water mixture, with the proviso that the preparation of the pre-emulsion is carried out under the action of low shear forces using stirring devices with maximum peripheral speeds of 4.5 m / s, optionally (3) diluting the pre-emulsion by adding further water (C) and optionally (4) adding further additives (F), wherein the process gives polyorganosiloxane emulsions which have a particle size D(50) of 1 μm to 50 μm Another object of the invention are storage-stable,aqueous polyorganosiloxane emulsions comprising (A) at least one polyorganosiloxane of the general formula R, 2 a(R 1 O)bSiO(4-ab) / 2 (I), where R 1 may be the same or different and represents a hydrogen atom or a monovalent, substituted or unsubstituted hydrocarbon radical, R 2 may be the same or different and represents a monovalent, substituted or unsubstituted hydrocarbon radical having 1 to 30 carbon atoms or a hydrogen atom, WA12245-S / We 6 a is 0, 1, 2 or 3, b is 0, 1, 2 or 3, with the proviso that the sum a+b is ≤ 3, (B) at least one alkyl polyglycoside of the general formula where A is a linear or branched, saturated or unsaturated alkyl radical having 8 to 24 C atoms, G is a glycoside radical and m is the degree of glycosidation and is an integer from 1 to 5 on average, (C) water, optionally (D) further emulsifiers which are different from the alkyl polyglycosides (B), optionally (E) thickeners and optionally (F) further additives which are usually contained in polyorganosiloxane emulsions, characterized in that (i) a total of 1.5 to 4.5 parts of alkyl polyglycoside (B) are present per 100 parts of polyorganosiloxane (A), (ii) a total of 0 to 3 parts of further emulsifiers (D) are present per 100 parts of polyorganosiloxane (A), (iii) the sum of the parts of alkyl polyglycoside (B) and further emulsifiers (D) ≤ 4,5 per 100 parts of polyorganosiloxane (A) and (iv) the emulsions are prepared by a process comprising the steps of (1) preparing an emulsifier-water mixture comprising at least one alkyl polyglycoside (B) and water (C) and WA12245-S / We 7 optionally further emulsifiers (D), optionally thickeners (E) and optionally further additives (F), (2) preparing a pre-emulsion by adding at least one polyorganosiloxane (A) to the emulsifier-water mixture, with the proviso that the pre-emulsion is prepared under the action of low shear forces using stirring devices with maximum peripheral speeds of 4.5 m / s, optionally (3) diluting the pre-emulsion by adding further water (C) and optionally (4) adding further additives (F), with the proviso,that the polyorganosiloxane emulsions have a particle size D(50) of greater than 1 μm up to a maximum of 50 μm. In order to avoid excessive page count for the description of the present invention, only the preferred embodiments of the individual features are listed below. However, the skilled reader should understand this type of disclosure to mean that any combination of different degrees of preference is explicitly disclosed and explicitly desired. Polydimethylsiloxanes with a viscosity of 10,000 mPa s to 3,000,000 mPa s (determined at 25°C according to DIN 53019) are preferably used as polyorganosiloxanes (A). Alkyl polyglycosides (B) with a saturated alkyl radical having an average of 8 to 14 carbon atoms and an average degree of glycosidation m of 1.1 to 3 are preferred.0. In a preferred embodiment, further emulsifiers (D) are not included. WA12245-S / We 8 Preferably, 0.1 to 1 part(s) of xanthan gum per 100 parts of polyorganosiloxane (A) are used as thickeners (E). The instability index of the polyorganosiloxane emulsions, after centrifugation for 8 hours at 2,300xg, is preferably <0.1. In a preferred embodiment, the polyorganosiloxane emulsions have a particle size D(50) of 3 μm to 20 μm. The polyorganosiloxane emulsions preferably have an octamethylcyclotetrasiloxane (D4) content of less than 0.1 wt.% based on the total weight of the polyorganosiloxane emulsion. The polyorganosiloxane emulsions according to the invention and the inventive process for their preparation are described in more detail below: The components (A) to (F) used in the inventive process can each be one type of such a component or a mixture of at least two types of a respective component. Polyorganosiloxanes (A) The polyorganosiloxanes (A) of the general formula (I) used in the inventive emulsions are preferably liquid at 25°C and preferably have viscosities, measured at 25°C according to DIN ISO 53019, of 10 to 50,000,000 mPa s and particularly preferably of 10,000 to 3,000,000 mPa s. The polyorganosiloxanes (A) are preferably those containing 5 to 10,000 units of the formula (I),particularly preferably those comprising units of formula (I) with an average value of a of 1.9 to 2.3 and an average value of b of 0 to 0.2. WA12245-S / We 9 R, 1 may be the same or different and represents a hydrogen atom or a monovalent, substituted or unsubstituted hydrocarbon radical, preferably a hydrogen atom or a monovalent, substituted or unsubstituted hydrocarbon radical having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom. R 2 may be the same or different and represents a monovalent, substituted or unsubstituted hydrocarbon radical having 1 to 30 carbon atoms or a hydrogen atom. Preferably, in the units of formula (I), a maximum of one radical R 2 the meaning of a hydrogen atom. Preferably, the radical R 2a hydrogen atom or a monovalent, substituted or unsubstituted hydrocarbon radical having 1 to 18 carbon atoms, particularly preferably a hydrogen atom or the methyl or phenyl radical. In a preferred embodiment, in particular 80 mol% or more of the radicals R 2 in the polyorganosiloxane (A) the meaning of methyl radicals and 20 mol% or less the meaning of aminopropyl or aminoethylaminopropyl radicals. Non-exhaustive examples of hydrocarbon radicals R 1 or R 2are alkyl radicals such as methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl, hexyl radicals such as n-hexyl, heptyl radicals such as n-heptyl, octyl radicals such as n-octyl and iso-octyl radicals such as 2,2,4-trimethylpentyl, nonyl radicals such as n-nonyl, decyl radicals such as n-decyl, dodecyl radicals such as n-dodecyl, octadecyl radicals such as n-octadecyl, cycloalkyl radicals such as cyclopentyl, Cyclohexyl, cycloheptyl radicals and WA12245-S / We 10 methylcyclohexyl radicals, alkenyl radicals such as the vinyl, 1-propenyl and 2-propenyl radicals, aryl radicals such as the phenyl, naphthyl, anthryl and phenanthryl radicals, alkaryl radicals such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals and aralkyl radicals such as the benzyl radical and the ^- and ^-phenylethyl radicals. Non-exhaustive examples of substituted radicals R 1 or R 2are hydrocarbon radicals substituted with halogen, cyano, glycidoxy, polyalkylene glycol, or amino groups, such as trifluoropropyl, cyanoethyl, glycidoxypropyl, polyalkylene glycolpropyl, and hydrocarbon radicals bearing amino groups. Non-exhaustive examples of radicals R substituted with amino groups 2are: H2N(CH2)2NH(CH2)3- H2N(CH2)2- H3CNH(CH2)3- H2N(CH2)4- H2N(CH2)5- H(NHCH2CH2)3- C4H9NH(CH2)2NH(CH2)2- and cyclo-C6H11NH(CH2)3- , with H2N(CH2)3- and H2N(CH2)2NH(CH2)3- being particularly preferred. In formula (I), the sum a+b ≤ 3 and has a value of preferably an average of 1.5 to 2.4, more preferably an average of 1.9 to 2.3, and most preferably an average of 1.95 to 2.05. Non-exhaustive examples of the polyorganosiloxanes (A) used in the emulsions according to the invention are aminopropyldimethylsiloxy, aminoethylaminopropyldimethylsiloxy, WA12245-S / We 11 vinyldimethylsiloxy, trimethylsiloxy, dimethylalkoxysiloxy or dimethylhydroxy group-terminated polydiorganosiloxanes, in particular polydimethylsiloxanes containing pendant aminopropyl, aminoethylaminopropyl or carboxyalkyl groups. Preferred polyorganosiloxanes (A) are those of the formula R 2 3-c (R 1 O) c SiO(R 2SiO) p Si(OR 1 ) c R 2 3-c (III), where R 1 and R 2 have the meaning given above, c is 0, 1 or 2, preferably 0 or 1, and p is 1 to 100,000, preferably 5 to 10,000. Non-exhaustive examples of the preferred polyorganosiloxanes (A) used in the process according to the invention are: (CH3)3Si-O-[Si(CH3)2-O-]n-Si(CH3)3 HO(CH3)2Si-O-[Si(CH3)2-O-]n-Si(CH3)2OH (CH3)3Si-O-[Si(CH3)2-O-] n -[Si(CH3)RO-] m -Si(CH3)3HO(CH3)2Si-O-[Si(CH3)2-O-]n-[Si(CH3)RO-]m -Si(CH3)2OH CH3O(CH3)2Si-O-[Si(CH3)2-O-]n-[Si(CH3)RO-]m -Si(CH3)2OCH3 C2H5O(CH3)2Si-O-[Si(CH3)2-O-] n -[Si(CH3)RO-] m-Si(CH3)2OC2H5, where n is from 50 to 5,000, m is from 1 to 100, and R is, for example, a radical of the formula -C3H6NH2, -C3H6NH-C2H4NH2, or -C10H20COOH. If a reactive polyorganosiloxane, for example with vinyl or OH end groups, is preferably used as the polyorganosiloxane (A), then, for example, a WA12245-S / We 12 chain extension, polycondensation, or crosslinking can occur in the emulsion in the presence of suitable reactants. Such reactions are known to the person skilled in the art and result in the emulsions prepared according to the invention containing polyorganosiloxanes with viscosities greater than 1,000,000 mPa·s (determined at 25°C according to DIN 53019) or crosslinked polyorganosiloxane elastomers. The polyorganosiloxanes (A) used in the emulsions according to the invention are preferably prepared according to relevant processes described in the literature.Alkylpolyglycosides (B) In a preferred embodiment, the alkylpolyglycosides (B) are compounds of the general formula (II), where A has the meaning given above, G is a hexose or pentose unit or mixtures thereof, and m has the meaning given above. Such compounds are described, for example, in US5133897 A (corresponding to EP0418479 A1). The alkylpolyglycosides (B) can be prepared by 1 H-NMR spectroscopy, for example on a Bruker Avance 500 MHz NMR spectrometer, where the average chain length of the alkyl residue A or the average degree of glycosidation m is determined by integrating the areas under the 1H-NMR signals can be determined, as is known to the person skilled in the art and as described, for example, in the textbook H. Fribolin, One- and Two-Dimensional NMR Spectroscopy, 5th edition, 2013, p. 35, Wiley-VHC-Verlag WA12245-S / We 13, and as processed, for example, according to the operating instructions for the NMR data analysis software Bruker Topspin 3.2. Preferably, these are alkyl polyglycosides (B) with a saturated alkyl radical with an average of 8-14 carbon atoms and an average degree of glycosidation of 1.1 to 3.0. Alkyl polyglycosides (B) based on fatty alcohols with 8-10 carbon atoms and an average degree of glycosidation of 1.4 to 2.0 are particularly preferred. Non-exhaustive examples of alkyl polyglycosides (B) are D-glucopyranose, oligomers, decyloctyl glycosides available under the trade name Disponil ® APG 215 at BASF SE or under the trade name TRITON ®CG 110 at Stockmeier GmbH, D-Glucopyranose, oligomer, C10-16-alkyl glycosides available under the trade name Glucopon ® 650 EC and Glucopon ®GD 70 at BASF SE. Water (C) All types of water that have previously been used to produce polyorganosiloxane emulsions can be used as water (C). Partially or fully demineralized water, distilled or (multiply) redistilled water, and water for medical or pharmaceutical purposes, such as purified water (aqua purificata according to Pharm. Eur.), are preferably used as water (C). The water (C) used according to the invention preferably has a conductivity of less than 50 µS / cm, particularly preferably less than 10 µS / cm, in particular less than 1.3 µS / cm, in each case at 25°C and 1,010 hPa. Water (C) is used in amounts of preferably 10 to 1,000 parts by weight, particularly preferably 40 to 500 parts by weight, based on 100 parts by weight of polyorganosiloxane (A). Further emulsifiers (D) The polyorganosiloxane emulsions according to the invention may optionally contain further emulsifiers (D).All non-ionic, anionic or cationic emulsifiers known to the person skilled in the art can be used here. Emulsifiers based on renewable raw materials are preferred. The further emulsifiers (D) are preferably commercially available emulsifiers. Non-exhaustive examples of substance classes of further emulsifiers (D) are sorbitan esters, glycerol esters, polyglycerol esters, alkyl sulfates and alkyl phosphates. The further emulsifiers (D) optionally used according to the invention can preferably be used in pure form or as a solution of one or more emulsifiers in water or organic solvents. Thickeners (E) The emulsions according to the invention can optionally contain thickeners as component (E), these are preferably cellulose ethers and polysaccharides, such as xanthan gum, particularly preferably xanthan gum.WA12245-S / We 15 If thickeners (E) are used, the amounts used are preferably from 0.01 to 2 parts, based on 100 parts of polyorganosiloxane (A). Further additives (F) In addition to components (A) to (E), further additives (F) that are usually added to silicone emulsions can optionally be used. Non-exhaustive examples of further additives (F) are other siloxanes that are different from the polyorganosiloxanes (A), such as polyether siloxanes or silanes, in particular alkoxysilanes, fillers, additives such as preservatives, disinfectants, wetting agents, corrosion inhibitors, dyes and fragrances, and mixtures thereof. If further siloxanes other than the polyorganosiloxanes (A) are used, they are preferably used in amounts of 0.1 to 1 part based on 100 parts of polyorganosiloxane (A).If silanes are used, they are preferably used in amounts of 0.1 to 50 parts based on 100 parts of polyorganosiloxane (A). Non-exhaustive examples of additives that can be used according to the invention are preservatives, dyes, or fragrances known to those skilled in the art, in particular preservatives such as methylisothiazolinone, chloromethylisothiazolinone, benzylisothiazolinone, phenoxyethanol, methylparaben, ethylparaben, propylparaben, butylparaben, isobutylparaben, alkali benzoates, benzoic acid, alkali sorbates, sorbic acid, iodopropynyl butylcarbamate, benzyl alcohol, and 2-bromo-2-nitropropane-1,3-diol. If additives are used, they are preferably used in amounts of 0.0005 to 2 parts, based on 100 parts of WA12245-S / We 16 polyorganosiloxane (A). Additives (F), in particular preservatives, are preferably used in the process according to the invention.The emulsions according to the invention have particle sizes (median value of the volume distribution) of 1 µm to 50 µm, in particular particle sizes of 3 µm to 20 µm, whereby these figures refer to the D(50) value of the volume distribution measured according to the principle of Fraunhofer diffraction (according to ISO 13320). The parameter assumed for the measurement is a spherical model with a refractive index of the continuous phase of 1.33, a refractive index of the disperse phase of 1.39, and an absorption of 0.01. The emulsions produced according to the invention preferably have a non-volatile content, measured according to DIN EN ISO 3251, of preferably 1 to 80 wt.%, particularly preferably 50 to 70 wt.%. The pH of the emulsions produced according to the invention is preferably 3 to 10, particularly preferably 3 to 8.Storage-stable emulsions are those in which no visible separation into two phases occurs after 30 days of storage at 50°C, preferably in a drying cabinet. The polyorganosiloxane emulsions according to the invention can preferably be prepared batchwise or continuously, e.g., according to US2018193808 (equivalent to EP3349888 B1). The peripheral speed v (speed of a point on the edge of the rotor or disk) (in meters per second) is calculated using the following formula: v = U · π · d. R(IV), WA12245-S / We 17 where U is the rotational speed (in revolutions per second) and dR is the diameter of the dispersing tool (in meters). The higher the peripheral speed v, the stronger the shear forces acting on the product to be dispersed. According to the invention, peripheral speeds v are to be selected which are a maximum of 4.5 m / s, preferably a maximum of 3 m / s, more preferably a maximum of 2 m / s and most preferably a maximum of 1 m / s. The process according to the invention is preferably carried out at a pressure of the ambient atmosphere, i.e. at about 1,010 hPa. The process according to the invention is preferably carried out at temperatures of 0 to 80°C, preferably from 2 to 50°C, and more preferably from 5 to 30°C. The process according to the invention is preferably carried out at room temperature, i.e. about 25°C ora temperature which is established when the components are combined at room temperature without additional heating or cooling. The present invention further relates to the use of the polyorganosiloxane emulsions produced by the process according to the invention in cosmetic compositions such as, for example, body or hair care products. The emulsions produced according to the invention can in principle be used for all other purposes for which emulsions containing polyorganosiloxanes have previously been used, such as, for example, as release agents, lubricants, water repellents WA12245-S / We 18 and for textile impregnation, in the processing of rubber and plastics or in metal processing and as water repellents for glass and mineral building materials.The process according to the invention has the advantage that, despite very low proportions of emulsifier and the action of low shear forces, very storage-stable and high-performance emulsions with average particle sizes of 1 µm to 50 µm, in particular 3 µm to 20 µm (D(50) value of the volume distribution) can be obtained. In this way, the process according to the invention is energetically favorable and thus economically and ecologically advantageous. The large particle sizes of the polyorganosiloxane emulsions according to the invention accessible via the process according to the invention also offer particular application advantages in cosmetic hair care products. The use of alkyl polyglycosides (B) as emulsifiers based on renewable raw materials is resource-saving.In addition, the use of polysaccharide-based emulsifiers in cosmetic applications can minimize potential skin irritations and intolerances caused by conventional emulsifiers based on polyethylene glycol ethers and esters. The polyorganosiloxane emulsions according to the invention also have excellent application properties, such as, for example, a good conditioning effect in hair care products, ie a significant reduction in wet and dry combing force, as well as a good effect as a release agent and lubricant, and good wettability on different substrates. Examples The subject matter of the present invention is to be illustrated by the following examples, without, however, restricting the latter to the contents disclosed therein. WA12245-S / We 19 In the following examples, all parts and percentages are by weight unless stated otherwise.Unless otherwise stated, the following examples are carried out at ambient atmospheric pressure, i.e., at approximately 1,010 hPa, and at room temperature, i.e., at approximately 25°C, or a temperature that occurs when the components are combined at room temperature without additional heating or cooling. All viscosity data given in the examples refer to a temperature of 25°C. The particle size measurement of the polyorganosiloxane emulsions according to the invention is carried out using a Malvern Mastersizer 2000 (Malvern Instruments GmbH, Herrenberg, Germany; measuring principle: Fraunhofer diffraction according to ISO 13320). The parameter assumed for the measurement is a spherical model with a refractive index of the continuous phase of 1.33, a refractive index of the disperse phase of 1.39, and an absorption of 0.01. The measured value is D(50), the median value of the volume distribution.To determine oil viscosity, 20 g of polyorganosiloxane emulsion are mixed with 30 g of acetone, causing the emulsion to separate. The acetone-water phase is separated, and the process is repeated once. The polymer is then washed three times with water and dried at 110°C with stirring until no more water droplets are visible. The mixture is then post-treated in a drying cabinet at 110°C for a further 8 hours. The viscosities of the polyorganosiloxane emulsions and the separated oil for determining oil viscosity are determined according to DIN 53019 using an MCR 302 rheometer from Anton Paar GmbH Graz at 25°C. The CP-50-2 cone-plate system is used, and a flow curve is measured with shear rates ranging from 0.1 to 100 / s. In the examples, the viscosity is given at 10 / s.WA12245-S / We 20 To determine the octamethylcyclotetrasiloxane (D4) content, 0.5 g of the sample is mixed with 10 ml of ultrapure acetone containing 120 ppm n-dodecane as an internal standard. After shaking for 16 hours, two phases form. 10 µl of the supernatant clear phase is injected into a gas chromatograph. A duplicate determination is carried out. The D4 content in the emulsion is determined using a previously recorded calibration curve. From this, the D4 content can then be calculated. To determine the instability index, the emulsions are centrifuged for 8 h at 4,000 rpm (corresponding to approx. 2,300xg) using a LUMiFuge. ®110.2-69 (LUM GmbH Berlin) and cuvettes with path lengths of 2 mm are used. The stability is characterized by the instability index output by the device software. If this is 0, the emulsion is stable, if it is 1, the emulsion is completely separated (cf. Dispersion Letters Technical, T4 (2013) 1-4, Update 2014). This means that the smaller this value, the more stable the emulsion. To determine the combing force of wet hair, hair tresses from damaged, Caucasian hair from Kerling International Haarfabrik GmbH (hair tresses damage grade B, double drawn) with a weight of 2 g and a length of 20 cm are used. The combing force is measured using the double comb method according to YK Kamath and Hans-Dietrich Weigmann, J. Soc. Cosmet. Chem., 37, 111-124, 1986 is carried out using an Instron 3343 tensile-elongation machine. First, the wet combing force is determined along the measuring section on untreated hair strands.The hair tresses are then treated with a cosmetic composition according to the invention, and the force absorbed during the combing process is determined. The measured value is the reduction in combing force along the measured distance (work) that results between the treated and untreated hair tresses. WA12245-S / We 21 the average value from five hair tresses is calculated. The combing force reduction is given as a percentage. Raw materials used Polyorganosiloxane A1: A polydimethylsiloxane terminated with trimethylsiloxy groups with a viscosity of 60,000 mPa s Polyorganosiloxane A2 Mixture of polydimethylsiloxanes terminated with trimethylsiloxy groups with a viscosity of 300,000 mPa s and 1,000 mPa s; the mixture has a viscosity of 60,000 mPa s. Polyorganosiloxane A3: A hydroxyl-terminated polydimethylsiloxane with a viscosity of 80.000 mPa·s Polyorganosiloxane A4: A polydimethylsiloxane terminated with trimethylsiloxy groups and having a viscosity of 20,000 mPa·s Polyorganosiloxane A5: A polydimethylsiloxane terminated with trimethylsiloxy groups and having a viscosity of 330,000 mPa·s Alkylpolyglycoside B1: A 63% aqueous solution of a caprylyl / decyl glycoside, with a surface tension (1g / l) of 29 mN / m and a pour point below 0°C, available under the name DISPONIL. ® APG 215 at BASF SE Alkylpolyglycoside B2: A 53% aqueous solution of an alkyl polyglycoside C10-16 with a surface tension (1g / l) of 28 mN / m and a pour point of 5°C, available under the name Glucopon ® 600 CSUP at BASF SE Alkylpolyglycoside B3: A 50% aqueous solution of a decyloctylpolyglycoside with a surface tension (1g / l) of 29 mN / m and a pour point of 0°C, available under the name TRITON WA12245-S / We 22 ®CG-50 at Stockmeier Chemie GmbH Co KG Bielefeld Additional emulsifier D1: Sorbitan monolaurate available under the name SPAN ® 20 at Croda GmbH Nettetal Additional emulsifier D2: Octyldecyl phosphate (acid number 330 mg KOH / g) available under the name CRODAFOS ® 810 A at Croda GmbH Nettetal Thickener E: Xanthan Gum available under the name Xanthan FN at Jungbunzlauer Ladenburg GmbH Ladenburg Further additives (preservatives) F1: K-sorbates, benzoic acid and Na-benzoate available at CSC JÄKLECHEMIE GmbH & Co. KG Nuremberg Further additives (preservatives) F2: Phenoxyethanol available at Thor GmbH Speyer Production of the polyorganosiloxane emulsions The emulsions are produced in an IKA laboratory mixer ® magic PLANT by IKA ®Werke GmbH & Co. KG Staufen using an anchor stirrer with a scraper. The batch size in each case is 1,500 g at 25°C. The recipes for inventive examples 1 to 9 and comparative examples V1 to V3 can be found in Table 1 below. 82.5 g of deionized water (C) are initially charged, and components (B) and, if desired, (D) and, if desired, (E) are added. They are mixed for 10 minutes at a stirrer speed of 75 rpm (corresponding to a peripheral speed of 0.63 m / s). Component (A) is metered in over the course of 60 minutes, and the mixture is mixed for a further 60 minutes at 75 rpm. The remaining water is added over the course of 60 minutes, and WA12245-S / We 23 is stirred in at 75 rpm. In all experiments, 1.5 g of potassium sorbate, 1.95 g of benzoic acid, and 4.5 g of sodium benzoate were added as component (F) (preservative F1) at the end and stirred for 30 minutes. Table 1: Recipes 1)Examples 1 to 9 and comparative examples V1 to V3 for components (A), (B), (D) and (E) Component Example (A) (B) 2) Parts (B) each (D) (E) 100 parts (A) 1 75% A1 2.90% B1 3.87 - - 2 60% A1 2.52% B1 4.20 - 0.35% 3 60% A2 2.52% B1 4.20 0.12% 0.25% D1 3)4 60% A1 2.65% B2 4.42 - 0.20% 5 60% A1 0.94% B1 1.57 - 0.35% 6 60% A3 1.89% B1 3.15 - 0.35% 7 60% A4 1.89% B1 3.15 - 0.35% 8 60% A5 1.89% B1 3.15 - 0.35% 9 60% A1 1.89% B3 3.15 - 0.35% V1 60% A1 9.45% B1 15.75 - - V2 60% A1 15.75% B1 26.25 - - V3 60% A1 15.75% B1 26.25 - 0.10% Preservative F1 Use amounts as described above; water (C) must be made up to 100% in each case. Amount based on 100% active content corresponds to 0.2 parts (D) per 100 parts (A). Examples 1 to 9 according to the invention in Table 2 below show only very slight signs of incipient separation (instability indices less than 0.1) when measuring the instability index after 8 hours at 2,300xg, while non-inventive examples V1 to V3 with higher emulsifier proportions, although they have a similar viscosity, show clear signs of separation with instability indices greater than 0.3 or even greater than 0.5.Table 2: Testing of emulsion properties Example D(50) in µm Viscosity in Instability index mPa s 1 2.75 1.344 0.075 2 6.48 2.310 0.026 3 4.62 1.510 0.080 4 4.08 2.070 0.052 5 8.00 2.350 0.016 6 5.91 2.610 0.020 7 3.36 2.310 0.013 8 9.89 2.740 0.029 9 6.53 2.360 0.021 V1 1.09 1.580 0.305 V2 1.20 1.740 0.540 V3 7.34 2.810 0.518 Example 10: Emulsion polymerization with a polyorganosiloxane emulsion according to the invention 82.5 g of deionized water (C) are initially introduced, 60 g of B1 (corresponding to 37.8 g active content) and 5.25 g of E are added and mixed for 10 minutes at a stirrer speed of 75 / min (corresponding to a peripheral speed of 0.63 m / s). 895.65 g of component A3 are metered in over the course of 60 minutes and mixed for a further 60 minutes at 75 / min. This means that 4.22 parts (B) are used per 100 parts (A). The remaining water is added over the course of 60 minutes and stirred in at 75 / min. Then 1.79 g of component D2 are added and stirred in for 30 minutes.The emulsion is stored at 4°C for 48 hours and neutralized with 31.5 g of triethanolamine. 13.5 g of phenoxyethanol are then added as component (F) (preservative F2). WA12245-S / We 25 Comparative Example V4: Emulsion Polymerization with a Non-Inventive Polyorganosiloxane Emulsion 82.5 g of deionized water (C) are initially charged, and 375 g of B1 (corresponding to 236.2 g of active content) are added, and the mixture is mixed for 10 minutes at a stirrer speed of 75 rpm (corresponding to a peripheral speed of 0.63 m / s). 895.65 g of component A3 are metered in over 60 minutes, and the mixture is mixed for a further 60 minutes at 75 rpm. Thus, 26.37 parts of (B) are used per 100 parts of (A). The remaining water is added over 60 minutes and stirred at 75 rpm. Then, 35 g of component D2 are added and stirred for 30 minutes. The emulsion is stored at 4°C for 48 hours and neutralized with 31.5 g of triethanolamine.13.5 g of phenoxyethanol are then added as component (F) (preservative F2). Table 3: Testing of the emulsion properties of Example 10 and Comparative Example V4 Example D(50) Viscosity Viscosity Instability D4in wt.% in µm of the emulsion oil phase in mPa·s in mPa·s total weight of the emulsion 10 5.53 2,680 2,165,000 0.019 0.018 V4 1.76 2,880 110,372 0.158 not determined As Table 3 shows, the polyorganosiloxane emulsion according to the invention from Example 10 enables the formation of a very high viscosity oil without impairing the stability of the emulsion and without forming significant amounts of octamethylcyclotetrasiloxane (D4). In the non-inventive polyorganosiloxane emulsion from Comparative Example V4, only a slight increase in WA12245-S / We 26 oil viscosity occurs. Therefore, no testing for D4 content is performed.The instability index is significantly worse despite the significantly smaller particle size and slightly higher viscosity. Example 11: Application example as a hair care product. A shampoo is formulated from the components shown in Table 4: Table 4: Formulation components Shampoo ingredients (INCI). * -Name) Quantity in wt.% Citric Acid 1) 0.05 Cocamidopropyl Betaine 2) 5.00 Sodium Laureth Sulfate 3) 29.90 Guar Hydroxypropyltrimonium Chloride 4) 0.20 Sodium Lauryl Sulfate 5) 6.06 Aqua (DI Water) 33.65 Carbomer 6) 0.60 Lactic Acid 7) 0.06 Aqua (DI Water) 20.00 Phenoxyethanol, Ethylhexylglycerin 8) 0.95 C12-13 Alkyl Lactates 9) 0.30 Polyorganosiloxane emulsion from Example 2 or V2 2.17 Sodium Hydroxide 10) 0.40 Sodium Chloride 11) 0.66 International Nomenclature of Cosmetic Ingredients The raw materials listed in Table 4 are available under the following trade names:1) Citric Acid, Sigma 2) Gnawing ® CAB 81830%, Clariant WA12245-S / We 27 3) Genapol ® LRO 26, 5%, Clariant 4) N-Hance ® BF 13, Ashland 5) Texapon ® K 12 G, BASF 6) Carbopol ® 980, Lubrizol 7) L-(+)lactic acid, 90%, Bernd Kraft GmbH 8) Phenoxyethanol, Ethylhexylglycerin: Euxyl ® PE 9010, Schülke & Mayr 9) Ceraphyl TM 41 Ester, Ashland 10) Sodium hydroxide, Sigma-Aldrich 11) Purest sodium chloride, Bernd Kraft GmbH. Compared to a shampoo without silicone emulsion, the wet combing force on Caucasian hair is reduced by 30%. If the non-inventive emulsion from Example C2 is used instead of the inventive emulsion from Example 2, the wet combing force is reduced by only 10%.

Claims

WA12245-S / We 28 claims 1. Process for the preparation of storage-stable, aqueous polyorganosiloxane emulsions comprising (A) at least one polyorganosiloxane of the general formula R 2 a(R 1 O)bSiO(4-ab) / 2 (I), where R 1 may be the same or different and represents a hydrogen atom or a monovalent, substituted or unsubstituted hydrocarbon radical, R 2 may be the same or different and represents a monovalent, substituted or unsubstituted hydrocarbon radical having 1 to 30 carbon atoms or a hydrogen atom, a is 0, 1, 2 or 3, b is 0, 1, 2 or 3, with the proviso that the sum a+b is ≤ 3, (B) at least one alkyl polyglycoside of the general formula (II), where A is a linear or branched, saturated or unsaturated alkyl radical having 8 to 24 C atoms, G is a glycoside radical and m is the degree of glycosidation and is an integer from 1 to 5 on average, (C) water, optionally (D) further emulsifiers which are different from the alkyl polyglycosides (B), optionally (E) thickeners and optionally WA12245-S / We 29 (F) further additives which are usually contained in polyorganosiloxane emulsions, characterized in that (i) a total of 1.5 to 4.5 parts of alkyl polyglycoside (B) per 100 parts of polyorganosiloxane (A) are contained, (ii) a total of 0 to 3 parts of further emulsifiers (D) per 100 parts of polyorganosiloxane (A) are contained, (iii) the sum of the parts of alkyl polyglycoside (B) and further emulsifiers (D) is ≤ 4.5 per 100 parts of polyorganosiloxane (A) and (iv) the process comprises the following steps (1) preparation of an emulsifier-water mixture comprising at least one alkyl polyglycoside (B) and water (C) and optionally further emulsifiers (D), optionally thickeners (E) and optionally further additives (F) (2) preparation of a Pre-emulsion by adding at least one polyorganosiloxane (A) to the emulsifier-water mixture, with the proviso thatthat the preparation of the pre-emulsion takes place under the influence of low shear forces using stirring devices with maximum peripheral speeds of 4.5 m / s, optionally (3) diluting the pre-emulsion by adding further water (C) and optionally (4) adding further additives (F), whereby the process produces polyorganosiloxane emulsions having a particle size D(50) of 1 μm to 50 μm.

2. The process according to claim 1, characterized in that polydimethylsiloxanes with a viscosity of 10,000 mPa·s to 3,000,000 mPa·s (determined at 25°C according to DIN 53019) are used as polyorganosiloxanes (A). WA12245-S / We 30 3. Process according to claim 1 or 2, characterized in that alkyl polyglycosides (B) having a saturated alkyl radical with an average of 8 to 14 carbon atoms and an average degree of glycosidation m of 1.1 to 3.0 are used.

4. Process according to claim 1, 2 or 3, characterized in that further emulsifiers (D) are not present.

5. Process according to one of claims 1 to 4, characterized in that 0.1 to 1 part(s) of xanthan gum per 100 parts of polyorganosiloxane (A) are used as thickener (E).

6. Process according to one of claims 1 to 5, characterized in that the instability index of the polyorganosiloxane emulsions, after centrifugation for 8 hours at 2,300xg, is < 0.

1.

7. Process according to one of claims 1 to 6, characterized in that the polyorganosiloxane emulsions have a particle size D(50) of 3 μm to 20 μm. 8.Process according to one of claims 1 to 7, characterized in that the polyorganosiloxane emulsions have an octamethylcyclotetrasiloxane (D4) content of less than 0.1 wt. %, based on the total weight of the polyorganosiloxane emulsion.

9. Storage-stable, aqueous polyorganosiloxane emulsions comprising (A) at least one polyorganosiloxane of the general formula R. 2 a(R 1 O)bSiO(4-ab) / 2 (I), where WA12245-S / We 31 R 1 may be the same or different and represents a hydrogen atom or a monovalent, substituted or unsubstituted hydrocarbon radical, R 2 may be the same or different and represents a monovalent, substituted or unsubstituted hydrocarbon radical having 1 to 30 carbon atoms or a hydrogen atom, a is 0, 1, 2 or 3, b is 0, 1, 2 or 3, with the proviso that the sum a+b is ≤ 3, (B) at least one alkyl polyglycoside of the general formula where A is a linear or branched, saturated or unsaturated alkyl radical having 8 to 24 C atoms, G is a glycoside radical and m is the degree of glycosidation and is an integer from 1 to 5 on average, (C) water, optionally (D) further emulsifiers which are different from the alkyl polyglycosides (B), optionally (E) thickeners and optionally (F) further additives which are usually contained in polyorganosiloxane emulsions, characterized in that (i) a total of 1.5 to 4.5 parts of alkyl polyglycoside (B) are present per 100 parts of polyorganosiloxane (A), (ii) a total of 0 to 3 parts of further emulsifiers (D) are present per 100 parts of polyorganosiloxane (A), (iii) the sum of the parts of alkyl polyglycoside (B) and further emulsifiers (D) ≤ 4.5 per 100 parts of polyorganosiloxane (A) is WA12245-S / We 32 and (iv) the emulsions are prepared by a process comprising the steps of (1) preparing an emulsifier-water mixture comprising at least one alkyl polyglycoside (B) and water (C) and optionally further emulsifiers (D), optionally thickeners (E) and optionally further additives (F), (2) preparing a pre-emulsion by adding at least one polyorganosiloxane (A) to the emulsifier-water mixture, with the proviso that the pre-emulsion is prepared under the action of low shear forces using stirring devices with maximum peripheral speeds of 4.5 m / s, optionally (3) diluting the pre-emulsion by adding further water (C) and optionally (4) adding further additives (F), with the proviso that the polyorganosiloxane emulsions have a particle size D(50) of 1 μm to 50 μm. 10.Polyorganosiloxane emulsions according to claim 9, characterized in that polydimethylsiloxanes having a viscosity of 10,000 mPa·s to 3,000,000 mPa·s (determined at 25°C according to DIN 53019) are used as polyorganosiloxanes (A).

11. Polyorganosiloxane emulsions according to claim 9 or 10, characterized in that alkyl polyglycosides (B) having a saturated alkyl radical with an average of 8 to 14 carbon atoms and an average degree of glycosidation m of 1.1 to 3.0 are used. WA12245-S / We 33 12. Polyorganosiloxane emulsions according to claim 9, 10 or 11, characterized in that further emulsifiers (D) are not present.

13. Polyorganosiloxane emulsions according to any one of claims 9 to 12, characterized in that 0.1 to 1 part(s) of xanthan gum per 100 parts of polyorganosiloxane (A) are used as thickener (E).

14. Polyorganosiloxane emulsions according to any one of claims 9 to 13, characterized in that the instability index of the polyorganosiloxane emulsions, after centrifugation for 8 hours at 2,300xg, is <0.

1.

15. Polyorganosiloxane emulsions according to one of claims 9 to 14, characterized in that the polyorganosiloxane emulsions have a particle size D(50) of 3 μm to 20 μm. 16.Polyorganosiloxane emulsions according to any one of claims 9 to 15, characterized in that the polyorganosiloxane emulsions have an octamethylcyclotetrasiloxane (D4) content of less than 0.1% by weight, based on the total weight of the polyorganosiloxane emulsion.

17. Use of the polyorganosiloxane emulsions according to any one of claims 9 to 16 or prepared according to any one of claims 1 to 8 in cosmetic compositions.

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