Large particle size polyorganosiloxane emulsion and method for preparing same

Abstract

The present invention provides a method for preparing a storage-stable aqueous polyorganosiloxane emulsion comprising (A) at least one polyorganosiloxane, (B) at least one alkyl polyglycoside, (C) water, optionally (D) a further emulsifier different from (B), optionally (E) a thickener, and optionally (F) further additives typically present in polyorganosiloxane emulsions, wherein (i) per 100 parts of (A), there is present a total of 1.5 to 4.5 parts of (B); (ii) per 100 parts of (A), there is present a total of 0 to 3 parts of (D); (iii) per 100 parts of (A), the sum of (B) and (D) is 4.5 parts or less; and (iv) the method is (1) preparing an emulsifier-water mixture comprising at least one of (B), water (C), optionally (D), optionally (E), and optionally (F); (2) preparing a pre-emulsion by adding at least one of (A) to the emulsifier-water mixture, with the proviso that the pre-emulsion is prepared under low shear with a stirring device having a maximum peripheral speed of 4.5 m / sec; and optionally, (3) diluting the pre-emulsion by adding additional water (C); and optionally, (4) adding (F), wherein the method produces a polyorganosiloxane emulsion having a particle size D(50) of 1 μm to 50 μm.

Description

[Technical Field]

[0001] The present invention relates to a storage-stable aqueous polyorganosiloxane emulsion containing an alkyl polyglycoside as an emulsifier and having a relatively high viscosity and large particle size, and a method for preparing the emulsion. [Background technology]

[0002] Polyorganosiloxanes have a variety of uses. The terms "polyorganosiloxane" and "silicone" are used interchangeably in the present invention. In many applications, it is desirable for organosilicon compounds to be in diluted form, for ease of application and metering, especially in the case of viscous products. While organic solvents such as benzene or chlorinated hydrocarbons can be used for this purpose, this is disadvantageous from the standpoint of ecology and occupational hygiene. Therefore, they are most effectively used in the form of aqueous emulsions or dispersions, usually as water-dilutable oil-in-water emulsions. In this context, oil phase is understood to mean water-immiscible organosilicon compounds, optionally dissolved in an organic solvent.

[0003] Emulsions containing polyorganosiloxanes and other organosilicon compounds and methods for their preparation have long been known from the prior art and are described, for example, in the textbook W. Noll, Chemistry and Technology of Silicones, 1968, pp. 428-431, Verlag Chemie Weinheim.

[0004] Emulsifiers used in polyorganosiloxane emulsions are typically ethoxylated synthetic alcohols, ethoxylated fatty alcohols, ethoxylated triglycerides, ethoxylated fatty acids, and mixtures thereof (e.g., EP 200916, EP 0 463 431, and DE 19620405).

[0005] Emulsifiers based on polyethylene glycol ethers and esters are undesirable, particularly in cosmetic applications, due to potential skin irritation (e.g., U.S. Patent Application Publication No. 2007 / 178144 (corresponding to European Patent Application Publication No. 1813251)). In addition, there is a growing demand for products containing emulsifiers based on renewable raw materials.

[0006] Alkyl polyglycosides are emulsifiers that are prepared from renewable raw materials and do not contain polyethylene glycol groups.

[0007] It is known that silicone oils, such as polydimethylsiloxanes, can be emulsified with alkyl polyglycosides (see, for example, U.S. Pat. No. 5,133,897 (corresponding to European Patent Application Publication No. 0,418,479)). These emulsions can be prepared at low shear. The emulsifier is used in an amount of 2 to 40 parts, preferably 5 to 30 parts, based on the oil phase. For example, silicone oils with a viscosity of up to 2,000 mPa·s can be emulsified, and at least 11 parts of emulsifier per 100 parts of polyorganosiloxane are used to prepare a stable emulsion.

[0008] When a silicone antifoaming agent, i.e., a mixture of silicone oil and finely divided silica, is emulsified, a relatively high surfactant content is required, and the emulsion must be further stabilized with a thickener or alcohol (see EP-A-0769548 and EP-A-0774503). EP-A-0769548 uses at least 5 parts of emulsifier per silicone oil, preferably at least 28 parts. Similarly, EP-A-0774503 uses at least 5 parts of emulsifier per polyorganosiloxane, preferably at least 10 parts. In the examples of these patents, 25 and 50 parts of emulsifier are used per 100 parts of silicone oil / SiO2, respectively.

[0009] However, a high proportion of emulsifier is economically disadvantageous, especially for cost reasons.

[0010] German Patent Application Publication No. 102014212725 describes a method for preparing particularly finely divided emulsions based on high viscosity silicone oil and alkyl polyglycoside.By using high shear force, particle size of less than 300 nm is achieved.Therefore, these emulsions are stable even at a relatively low emulsifier concentration of only about 12 parts emulsifier per 100 parts silicone oil.However, this method has the disadvantage that it requires a suitable device that can generate high shear force in a high viscosity phase, which also means high energy consumption, which is ecologically and economically disadvantageous.

[0011] For specific cosmetic applications, larger particle sizes are preferred (as per WO 03 / 092639), however, according to Stokes' law, the tendency to segregate increases with particle size (see in this respect H. Schubert et al., Chem. Ing. Techn. 61, 1989, pp. 701-711). Summary of the Invention

[0012] It was therefore an object of the present invention to provide a method for preparing a high-viscosity silicone oil-based emulsion containing an emulsifier based on renewable raw materials and having excellent stability even at very low emulsifier levels and large particle sizes, as well as a method for preparing such polyorganosiloxane emulsions.

[0013] This object is achieved by the present invention.

[0014] The present invention provides a method for preparing a storage-stable aqueous polyorganosiloxane emulsion, comprising the steps of: (A) at least one polyorganosiloxane of the following general formula: [ka] (In the formula, R 1 are the same or different and are a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, R 2 are the same or different and are a monovalent substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom; a is 0, 1, 2, or 3; b is 0, 1, 2, or 3, However, the total of a+b must be 3 or less. (B) at least one alkyl polyglycoside of the following general formula: [ka] (In the formula, A is a linear or branched, saturated or unsaturated alkyl group having 8 to 24 carbon atoms; G is a glycosidic group, m is the degree of glycosidation and is an integer ranging from 1 to 5 on average; (C) water, If desired, (D) a further emulsifier different from the alkyl polyglycoside (B); If desired, (E) a thickener; If desired, (F) further additives normally present in polyorganosiloxane emulsions; Including, (i) a total of 1.5 to 4.5 parts of alkyl polyglycosides (B) are present per 100 parts of polyorganosiloxane (A); (ii) the presence of a total of 0 to 3 parts of additional emulsifier (D) per 100 parts of polyorganosiloxane (A); (iii) the total of the alkyl polyglycoside (B) and the additional emulsifier (D) is 4.5 parts or less per 100 parts of the polyorganosiloxane (A); and (iv) The method further comprises 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) Preparation of a pre-emulsion by adding at least one polyorganosiloxane (A) to an emulsifier-water mixture, provided that the pre-emulsion is prepared under low shear using a stirring device with a maximum peripheral speed of 4.5 m / s; If desired, (3) diluting the pre-emulsion by adding additional water (C); If desired, (4) Addition of a further additive (F); Contains It is characterized by wherein the method produces a polyorganosiloxane emulsion having a particle size D(50) of 1 μm to 50 μm; A method is provided.

[0015] The present invention provides a storage stable aqueous polyorganosiloxane emulsion comprising: (A) at least one polyorganosiloxane of the following general formula: [ka] (In the formula, R 1 are the same or different and are a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, R 2 are the same or different and are a monovalent substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom; a is 0, 1, 2, or 3; b is 0, 1, 2, or 3, However, the total of a+b must be 3 or less. (B) at least one alkyl polyglycoside of the following general formula: [ka] (In the formula, A is a linear or branched, saturated or unsaturated alkyl group having 8 to 24 carbon atoms; G is a glycosidic group, m is the degree of glycosidation and is an integer ranging from 1 to 5 on average; (C) water, If desired, (D) a further emulsifier different from the alkyl polyglycoside (B); If desired, (E) a thickener; If desired, (F) further additives normally present in polyorganosiloxane emulsions; Including, (i) a total of 1.5 to 4.5 parts of alkyl polyglycosides (B) are present per 100 parts of polyorganosiloxane (A); (ii) a total of 0 to 3 parts of additional emulsifier (D) per 100 parts of polyorganosiloxane (A); (iii) the total of alkyl polyglycosides (B) and additional emulsifiers (D) is 4.5 parts or less per 100 parts of polyorganosiloxane (A); and (iv) The emulsion is subjected to the following process: (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) Preparation of a pre-emulsion by adding at least one polyorganosiloxane (A) to an emulsifier-water mixture, provided that the pre-emulsion is prepared under low shear using a stirring device with a maximum peripheral speed of 4.5 m / s; If desired, (3) diluting the pre-emulsion by adding additional water (C); If desired, (4) Addition of a further additive (F); Produced by a method comprising: It is characterized by However, the polyorganosiloxane emulsion has a particle size D(50) of more than 1 μm to a maximum of 50 μm. Further provided is an aqueous polyorganosiloxane emulsion.

[0016] In order to avoid excessive page count in the description of the invention, only preferred embodiments of individual features are specified below.

[0017] However, the expert reader should explicitly understand the format of this disclosure such that all combinations of different levels of priority are also explicitly disclosed and explicitly desired.

[0018] Preferably, polydimethylsiloxanes having a viscosity of 10,000 mPa·s to 3,000,000 mPa·s (measured at 25° C. according to DIN 53019) are used as polyorganosiloxane (A).

[0019] Preferably, alkyl polyglycosides (B) are used which have saturated alkyl groups with an average of 8 to 14 carbon atoms and an average degree of glycosidation m of 1.1 to 3.0.

[0020] In a preferred embodiment, no further emulsifier (D) is present.

[0021] Preferably, 0.1 to 1 part of xanthan gum per 100 parts of polyorganosiloxane (A) is used as the thickener (E).

[0022] Preferably, the instability index of the polyorganosiloxane emulsion after centrifugation at 2300 xg for 8 hours is less than 0.1.

[0023] In a preferred embodiment, the polyorganosiloxane emulsion has a particle size D(50) of 3 μm to 20 μm.

[0024] Preferably, the polyorganosiloxane emulsion has a content of less than 0.1% by weight of octamethylcyclotetrasiloxane (D4), relative to the total weight of the polyorganosiloxane emulsion.

[0025] The inventive polyorganosiloxane emulsion and the inventive process for preparing same are described in more detail below.

[0026] Components (A) to (F) used in the method of the present invention may each be one of such components, or may be a mixture of at least two of the respective components.

[0027] Polyorganosiloxane (A) The polyorganosiloxane (A) of general formula (I) used in the emulsion according to the present invention is preferably liquid at 25°C and preferably has a viscosity measured at 25°C in accordance with DIN ISO 53019 of 10 to 50,000,000 mPa·s, particularly preferably 10,000 to 3,000,000 mPa·s.

[0028] The polyorganosiloxane (A) preferably contains 5 to 10,000 units of formula (I), and particularly preferably consists of units of formula (I) in which the average value of a is 1.9 to 2.3 and the average value of b is 0 to 0.2.

[0029] R 1 may be the same or different and are a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, preferably a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom.

[0030] R 2 may be the same or different and are a monovalent substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a hydrogen atom.

[0031] Preferably, in the units of formula (I), there is at most one group R2 has the definition of a hydrogen atom.

[0032] base R 2 is preferably a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, and particularly preferably a hydrogen atom, or a methyl group or a phenyl group.

[0033] In a preferred embodiment, in particular, 80 mol % or more of the groups R in the polyorganosiloxane (A) 2 has the definition of a methyl group, and 20 mol % or less has the definition of an aminopropyl group or an aminoethylaminopropyl group.

[0034] Hydrocarbon group R 1 or R 2 Non-exhaustive examples of aryl groups include, for example, methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl (e.g., n-hexyl), heptyl (e.g., n-heptyl), octyl (e.g., n-octyl), and isooctyl (e.g., 2,2,4-trimethylpentyl), nonyl (e.g., n-nonyl), decyl (e.g., n-decyl), dodecyl (e.g., n-dodecyl), and octadecyl groups. (e.g., n-octadecyl group); cycloalkyl groups such as, for example, cyclopentyl, cyclohexyl, and cycloheptyl groups, and methylcyclohexyl groups; alkenyl groups such as, for example, vinyl, 1-propenyl, and 2-propenyl groups; aryl groups such as, for example, phenyl, naphthyl, anthryl, and phenanthryl groups; alkaryl groups such as, for example, o-, m-, p-tolyl, xylyl, and ethylphenyl groups; and aralkyl groups such as, for example, benzyl and α- and β-phenylethyl groups.

[0035] Substituted group R 1 or R 2Non-exhaustive examples of include hydrocarbon groups substituted with halogen groups, cyano groups, glycidoxy groups, polyalkylene glycol groups, or amino groups, such as trifluoropropyl groups, cyanoethyl groups, glycidoxypropyl groups, polyalkylene glycol propyl groups, and hydrocarbon groups bearing amino groups.

[0036] Amino-substituted group R 2 Non-exhaustive examples of: 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-CH 11 NH(CH2)3- and where: H2N(CH2)3- and H2N(CH2)2NH(CH2)3- is particularly preferred.

[0037] In formula (I), the sum of a+b is 3 or less, preferably an average value of 1.5 to 2.4, particularly preferably an average value of 1.9 to 2.3, and very particularly preferably an average value of 1.95 to 2.05.

[0038] Non-exhaustive examples of polyorganosiloxanes (A) for use in the emulsions of the present invention include aminopropyldimethylsiloxy-, aminoethylaminopropyldimethylsiloxy-, vinyldimethylsiloxy-, trimethylsiloxy-, dimethylalkoxysiloxy-, or dimethylhydroxy-terminated polydiorganosiloxanes (especially polydimethylsiloxanes) containing pendant aminopropyl, aminoethylaminopropyl, or carboxyalkyl groups.

[0039] Preferred polyorganosiloxanes (A) are polyorganosiloxanes of the formula: [ka] (In the formula, R 1 and R 2 is, according to the above definition, c is 0, 1, or 2, preferably 0 or 1; p is 1 to 100,000, preferably 5 to 10,000. is.

[0040] Non-exhaustive examples of preferred polyorganosiloxanes (A) for use 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)3 HO(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 (In the formula, n is 50 to 5,000; m is 1 to 100; R may be, for example, a group of the formula -C3H6NH2, -C3H6NH-C2H4NH2, or -C 10 H 20 COOH group).

[0041] When reactive polyorganosiloxanes (e.g., those with vinyl or OH end groups) are preferably used as polyorganosiloxane (A), chain extension, polycondensation, or, in the presence of suitable reactants, crosslinking, for example, may be carried out in the emulsion. This type of reaction is known to those skilled in the art, and emulsions prepared according to the invention contain polyorganosiloxanes or crosslinked polyorganosiloxane elastomers with viscosities above 1,000,000 mPa·s (measured at 25°C according to DIN 53019).

[0042] The polyorganosiloxanes (A) used in the emulsions according to the invention are preferably prepared by relevant processes in the literature.

[0043] Alkyl polyglycoside (B) In a preferred embodiment, the alkyl polyglycoside (B) is a compound of the general formula (II) (In the formula, A is, according to the above definition, G is a hexose or pentose unit or a mixture thereof; m is as defined above) is.

[0044] Compounds of this type are described, for example, in US Pat. No. 5,133,897 (corresponding to EP-A-0 418 479).

[0045] Alkyl polyglycoside (B) is 1 H NMR spectroscopy (e.g., Bruker Avance 500 MHz NMR spectrometer), where the average chain length of the alkyl group A or the average degree of glycosidation m is 1It can be determined by integrating the areas under the H NMR signals (this is known to the person skilled in the art and is described, for example, in the text by H. Friebolin, Ein- und zweidimensionale NMR-Spektroskopie [One- and Two-Dimensional NMR Spectroscopy], 5th Edition, 2013, p. 35, Wiley-VCH-Verlag, and processed, for example, according to the operating instructions of the Bruker Topspin 3.2 NMR data analysis software).

[0046] Preferably, the alkyl polyglycoside (B) has a saturated alkyl group with an average of 8 to 14 carbon atoms and an average degree of glycosidation of 1.1 to 3.0.

[0047] Particularly preferred are alkylpolyglycosides (B) based on fatty alcohols with 8 to 10 carbon atoms and with an average degree of glycosidation of 1.4 to 2.0.

[0048] Non-exhaustive examples of alkyl polyglycosides (B) include D-glucopyranose, oligomeric, decyl octyl glycoside available under the trade name Disponil® APG 215 (BASF SE) or TRITON® CG 110 (Stockmeier GmbH), D-glucopyranose, oligomeric, C10-16 alkyl glycoside available under the trade name Glucopon® 650 EC and Glucopon® GD 70 (BASF SE).

[0049] Water (C) The water (C) used may be any type of water that has also been used to prepare polyorganosiloxane emulsions.

[0050] The water (C) used is preferably partially or completely deionized water, distilled water or (repeatedly) double-distilled water, water for medical or pharmaceutical purposes, such as purified water (Aqua purificata according to the European Pharmacopoeia).

[0051] 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.

[0052] The water (C) is used in an amount of preferably 10 to 1,000 parts by weight, particularly preferably 40 to 500 parts by weight, per 100 parts by weight of the polyorganosiloxane (A).

[0053] Further emulsifiers (D) The polyorganosiloxane emulsion according to the present invention may optionally contain a further emulsifier (D). In this case, any nonionic, anionic or cationic emulsifier known to those skilled in the art may be used. Here, emulsifiers based on renewable raw materials are preferred.

[0054] The further emulsifier (D) is preferably a commercially available emulsifier.

[0055] Non-exhaustive examples of chemical types of additional emulsifiers (D) include sorbitan esters, glycerol esters, polyglycerol esters, alkyl sulfates, and alkyl phosphates.

[0056] Preferably, the further emulsifiers (D) optionally used according to the invention may be used in pure form or as a solution of one or more emulsifiers in water or an organic solvent.

[0057] Thickener (E) As component (E), the emulsions according to the invention may optionally contain thickeners, preferably cellulose ethers and polysaccharides (e.g. xanthan gum), particularly preferably xanthan gum.

[0058] When the thickener (E) is used, the amount thereof is preferably 0.01 to 2 parts per 100 parts of the polyorganosiloxane (A).

[0059] Further Additives (F) In addition to components (A) to (E), a further additive (F) that is usually added to silicone emulsions may be used if desired.

[0060] Non-exhaustive examples of further additives (F) include further siloxanes different from the polyorganosiloxane (A) (e.g., polyether siloxanes or silanes, especially alkoxysilanes), fillers, additives (e.g., preservatives, bactericides, wetting agents, corrosion inhibitors, dyes, and fragrances), and mixtures thereof.

[0061] If further siloxanes different from the polyorganosiloxane (A) are used, they are preferably used in an amount of 0.1 to 1 part per 100 parts of the polyorganosiloxane (A).

[0062] When silanes are used, they are preferably used in an amount of 0.1 to 50 parts per 100 parts of the polyorganosiloxane (A).

[0063] Non-exhaustive examples of additives that may be used in accordance with the present invention include 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 metal benzoates, benzoic acid, alkali metal sorbates, sorbic acid, iodopropynyl butylcarbamate, benzyl alcohol, and 2-bromo-2-nitropropane-1,3-diol.

[0064] When an additive is used, the amount thereof is preferably 0.0005 to 2 parts per 100 parts of the polyorganosiloxane (A).Additives (F), particularly preservatives, are preferably used in the method according to the present invention.

[0065] The emulsions according to the invention have a particle size (median of the volume distribution) between 1 μm and 50 μm, in particular between 3 μm and 20 μm, based on the D(50) value of the volume distribution measured according to the Fraunhofer principle of diffraction (according to ISO 13320). The parameters estimated in this measurement are a spherical model with a refractive index of 1.33 for the continuous phase, a refractive index of 1.39 for the dispersed phase, and an absorption of 0.01.

[0066] The emulsions prepared according to the invention preferably have a non-volatile content, determined in accordance with DIN EN ISO 3251, of preferably 1% to 80% by weight, particularly preferably 50% to 70% by weight.

[0067] The pH of the emulsion prepared according to the present invention is preferably 3-10, particularly preferably 3-8.

[0068] A storage-stable emulsion is one which does not undergo visible separation into two phases after storage at 50°C for 30 days, preferably in a drying cabinet.

[0069] Preferably, the polyorganosiloxane emulsion according to the present invention may be prepared batchwise or continuously, for example according to US Patent Application Publication No. 2018 / 193808 (equivalent to EP 3349888).

[0070] The peripheral speed v (speed at the edge of the rotor or disc) (meters per second) is calculated by the following formula:

number

[0071] The higher the peripheral speed v, the stronger the shear force acting on the dispersed product.

[0072] According to the invention, a peripheral speed v of at most 4.5 m / s, preferably at most 3 m / s, particularly preferably at most 2 m / s, very particularly preferably at most 1 m / s should be selected.

[0073] Preferably, the method according to the invention is carried out at ambient atmospheric pressure (ie, about 1,010 hPa).

[0074] The method according to the present invention is preferably carried out at a temperature of 0°C to 80°C, preferably at a temperature of 2°C to 50°C, particularly preferably at a temperature of 5°C to 30°C.

[0075] Preferably, the process of the present invention is carried out at room temperature (ie, about 25° C.) or at a temperature established by combining the ingredients at room temperature without further heating or cooling.

[0076] The present invention further provides the use of a polyorganosiloxane emulsion prepared by the method of the present invention in a cosmetic composition, such as a body care or hair care product.

[0077] The emulsions prepared according to the invention can in principle be used for all other purposes for which emulsions containing polyorganosiloxanes have been used up to now (for example as release agents, lubricants, hydrophobizing agents, as well as for impregnating fibers, in the processing of rubber and plastics or in metal processing, and as hydrophobizing agents for glass and mineral building materials).

[0078] The method according to the present invention has the advantage that, despite the extremely low emulsifier content and the action of low shear force, it is possible to obtain an emulsion that is highly stable on storage and has a mean particle size of 1 μm to 50 μm, particularly 3 μm to 20 μm (volume distribution D(50) value). This advantage makes the method according to the present invention energy-efficient and therefore economically and ecologically advantageous.

[0079] The large particle size of the polyorganosiloxane emulsions according to the invention, obtainable by the process according to the invention, further offers performance advantages, especially in cosmetic hair care products.

[0080] The use of alkyl polyglycosides (B) as emulsifiers based on renewable raw materials is resource-friendly. Furthermore, the use of polysaccharide-based emulsifiers in cosmetic applications can minimize potential skin irritation and intolerance caused by conventional emulsifiers based on polyethylene glycol ethers and esters.

[0081] In addition, the polyorganosiloxane emulsions of the present invention have excellent performance properties, such as good conditioning effects in hair care products, i.e., a significant reduction in combing force in both wet and dry states, as well as good effects as release agents and lubricants, and good wetting ability on various substrates. [Example]

[0082] The subject matter of the present invention is illustrated by the following examples, without however limiting the invention to the disclosure therein.

[0083] In the following examples, unless otherwise specified, all parts and percentages are by weight. Unless otherwise specified, the following examples are carried out at ambient atmospheric pressure (i.e., about 1,010 hPa) and room temperature (i.e., about 25°C), or at a temperature established by combining the components at room temperature without further heating or cooling. All viscosity values ​​described in the examples are based on a temperature of 25°C.

[0084] 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; measurement principle: Fraunhofer diffraction according to ISO 13320). The parameters assumed in the measurement are a refractive index of 1.33 for the continuous phase, a refractive index of 1.39 for the dispersed phase, and a spherical model with an absorption of 0.01. The reported measurement is the median D(50) of the volume distribution.

[0085] To determine the oil viscosity, 20g of polyorganosiloxane emulsion is mixed with 30g of acetone, and the emulsion is separated. The acetone-water phase is removed, and this procedure is repeated once more. The polymer is then washed three times with water, and dried at 110°C with stirring until no water droplets are visible, and then post-treated in a drying cabinet at 110°C for another 8 hours.

[0086] The viscosity of the polyorganosiloxane emulsions and, for the determination of oil viscosity, the viscosity of the removed oil is measured at 25°C according to DIN 53019 using an MCR 302 rheometer (manufactured by Anton Paar GmbH, Graz). A CP50-2 cone-plate system is used to determine the flow curves over a shear rate range of 0.1 to 100 / s. In the examples, the viscosity is reported at 10 / s.

[0087] To determine the content of octamethylcyclotetrasiloxane (D4), 0.5 g of sample is mixed with 10 mL of ultrapure acetone containing 120 ppm of n-dodecane as an internal standard. After 16 hours of shaking, two phases are formed. 10 μL of the supernatant is injected into a gas chromatograph. Measurements are performed in duplicate. The D4 content in the emulsion is determined based on a prerecorded calibration curve. The D4 content can then be calculated therefrom.

[0088] To determine the instability index, the emulsion is centrifuged at 4,000 rpm (corresponding to approximately 2300 × g) for 8 hours using a LUMiFuge® 110.2-69 (LUM GmbH, Berlin) and a cuvette with a path length of 2 mm. Stability is characterized by the instability index output by the device software. If this is 0, the emulsion is stable, and if it is 1, the emulsion is completely separated (see Dispersion Letters Technical, T4 (2013) 1-4, Update 2014 in this regard). In other words, the smaller this value, the more stable the emulsion.

[0089] The combing force of wet hair is determined using damaged Caucasian hair (braid damage level B, double draw) tresses (Kerling International Haarfabrik GmbH) weighing 2 g and 20 cm long. Combing force is measured by the double comb method using an Instron 3343 tensile tester according to Y.K. Kamath and Hans-Dietrich Weigmann, J. Soc. Cosmet. Chem., 37, 111-124, 1986. First, the combing force in the wet state is measured along a measurement section of an untreated tress. Then, the tress is treated with a cosmetic composition according to the present invention, and the force absorption during the combing procedure is measured. The reported measurement is the decrease in combing force along the measurement section (work) that occurs between the treated and untreated tresses. The average value is formed from five tresses. The decrease in combing force is reported as a percentage.

[0090] Raw materials used Polyorganosiloxane A1: Trimethylsiloxy-terminated polydimethylsiloxane with a viscosity of 60,000 mPa·s.

[0091] Polyorganosiloxane A2: A mixture of trimethylsiloxy-terminated polydimethylsiloxanes with viscosities of 300,000 mPa·s and 1,000 mPa·s; the viscosity of this mixture is 60,000 mPa·s.

[0092] Polyorganosiloxane A3: A hydroxyl-terminated polydimethylsiloxane with a viscosity of 80,000 mPa·s.

[0093] Polyorganosiloxane A4: Trimethylsiloxy-terminated polydimethylsiloxane with a viscosity of 20,000 mPa·s.

[0094] Polyorganosiloxane A5: Trimethylsiloxy-terminated polydimethylsiloxane with a viscosity of 330,000 mPa·s.

[0095] Alkyl polyglycoside B1: A 63% aqueous solution of caprylyl / decyl glycoside (available from BASF SE under the name DISPONIL® APG 215) with a surface tension (1 g / L) of 29 mN / m and a pour point below 0° C.

[0096] Alkyl polyglycoside B2: A 53% aqueous solution of alkyl polyglycoside C10-16 (available from BASF SE under the name Glucopon® 600 CSUP) with a surface tension (1 g / L) of 28 mN / m and a pour point of 5°C.

[0097] Alkyl polyglycoside B3: A 50% aqueous solution of decyl octyl polyglycoside (available under the name TRITON® CG-50 from Stockmeier Chemie GmbH Co KG, Bielefeld) with a surface tension (1 g / L) of 29 mN / m and a pour point of 0° C.

[0098] Further emulsifier D1: Sorbitan monolaurate (available under the name SPAN® 20 from Croda GmbH Nettetal).

[0099] Further emulsifier D2: Octyldecyl phosphate ester (acid value 330 mg KOH / g) (available under the name CRODAFOS® 810 A from Croda GmbH Nettetal)

[0100] Thickener E: Xanthan gum (available under the name Xanthan FN from Jungbunzlauer Ladenburg GmbH Ladenburg).

[0101] Further additives (preservatives) F1: Potassium sorbate, benzoic acid, and sodium benzoate (available from CSC JAKLECHEMIE GmbH & Co. KG Nuremberg).

[0102] Further additives (preservatives) F2: Phenoxyethanol (available from Thor GmbH Speyer).

[0103] Preparation of polyorganosiloxane emulsion The emulsions are prepared in an IKA® magic PLANT laboratory mixer equipped with an anchor stirrer with scraper, manufactured by IKA® Werke GmbH & Co. KG Staufen. The batch size in each case is 1,500 g at 25° C. The formulations of Examples 1 to 9 according to the invention and Comparative Examples C1 to C3 can be seen in Table 1 below.

[0104] 82.5 g of deionized water (C) is first charged, and then component (B), and optionally component (D) and component (E) are added. These are mixed for 10 minutes at a stirring speed of 75 / min (corresponding to a peripheral speed of 0.63 m / s). Component (A) is metered in over 60 minutes and mixed for another 60 minutes at 75 / min. The remaining water is added over 60 minutes and stirred at 75 / min. In all experiments, 1.5 g of potassium sorbate, 1.95 g of benzoic acid, and 4.5 g of sodium benzoate are finally added as component (F) (preservative F1) and stirred for 30 minutes.

[0105] [Table 1]

[0106] In Table 2 below, inventive Examples 1 to 9 show only slight signs of the onset of separation (instability index less than 0.1) when measuring the instability index at 2300×g after 8 hours, while non-inventive Examples C1 to C3, which have a higher emulsifier content, exhibit similar viscosities but show significant signs of separation with instability indexes above 0.3, otherwise above 0.5.

[0107] [Table 2]

[0108] Example 10: Emulsion Polymerization with Polyorganosiloxane Emulsion of the Present Invention 82.5 g of deionized water (C) is initially charged, followed by 60 g of B1 (corresponding to an active content of 37.8 g) and 5.25 g of E, and mixing is continued for 10 minutes at a stirring speed of 75 min / min (corresponding to a peripheral speed of 0.63 m / s). 895.65 g of component A3 is metered in over 60 minutes and mixed for another 60 minutes at 75 min / min. 4.22 parts of (B) are used per 100 parts of (A). The remaining water is added over 60 minutes and stirred at 75 min / min. 1.79 g of component D2 is then added and stirred for 30 minutes. The emulsion is stored at 4°C for 48 hours and then neutralized with 31.5 g of triethanolamine. 13.5 g of phenoxyethanol is then added as component (F) (preservative F2).

[0109] Comparative Example C4: Emulsion Polymerization with a Non-Invention Polyorganosiloxane Emulsion 82.5 g of deionized water (C) is initially charged, followed by 375 g of B1 (corresponding to an active content of 236.2 g) and mixing for 10 minutes at a stirring speed of 75 min / min (corresponding to a peripheral speed of 0.63 m / s). 895.65 g of component A3 is metered in over 60 minutes and mixed for another 60 minutes at 75 min / min. 26.37 parts of (B) are used per 100 parts of (A). The remaining water is added over 60 minutes and stirred at 75 min / min. 35 g of component D2 is then added and stirred for 30 minutes. The emulsion is stored at 4°C for 48 hours and then neutralized with 31.5 g of triethanolamine. 13.5 g of phenoxyethanol is then added as component (F) (preservative F2).

[0110] [Table 3]

[0111] As Table 3 shows, the polyorganosiloxane emulsion of the present invention of Example 10 allows for the formation of very high viscosity oils without compromising emulsion stability and without forming significant amounts of octamethylcyclotetrasiloxane (D4).

[0112] In the non-invention polyorganosiloxane emulsion of Comparative Example C4, the viscosity of the oil increased only slightly. Therefore, there was no test for D4 content. Despite its much smaller particle size and slightly higher viscosity, the instability index was significantly worse.

[0113] Example 11: Application as a hair care product A shampoo is formulated from the ingredients shown in Table 4.

[0114] [Table 4]

[0115] The ingredients identified in Table 4 are available under the following trade names: 1) Citric acid (Sigma) 2) Genagen® CAB 818 30% (Clariant) 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 (SchUlke & Mayr) 9)Ceraphyl(TM)41 Ester(Ashland) 10) Sodium hydroxide (Sigma-Aldrich) 11) Ultra-pure sodium chloride (Bernd Kraft GmbH)

[0116] When compared to a shampoo without silicone emulsion, wet combing force on Caucasian hair is reduced by 30%.

[0117] When the non-invention emulsion of Example C2 is used in place of the inventive emulsion of Example 2, the wet combing force is reduced by only 10%.

Claims

1. 1. A method for preparing a storage-stable aqueous polyorganosiloxane emulsion, comprising: (A) at least one polyorganosiloxane of the following general formula: 【Chemical 1】 (In the formula, R １ are the same or different and are a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, R ２ are the same or different and are a monovalent substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom; a is 0, 1, 2, or 3; b is 0, 1, 2, or 3; provided that the sum of a + b is 3 or less) (B) at least one alkyl polyglycoside of the following general formula: 【Chemistry 2】 (In the formula, A is a linear or branched, saturated or unsaturated alkyl group having 8 to 24 carbon atoms; G is a glycoside group, m is the degree of glycosidation, an integer ranging from 1 to 5 on average; (C) water; If desired, (D) a further emulsifier different from the alkyl polyglycoside (B); If desired, (E) a thickener; If desired, (F) further additives normally present in polyorganosiloxane emulsions; Including, (i) a total of 1.5 to 4.5 parts of alkyl polyglycosides (B) are present per 100 parts of polyorganosiloxane (A); (ii) a total of 0 to 3 parts of additional emulsifier (D) is present per 100 parts of polyorganosiloxane (A); (iii) the total amount of alkyl polyglycoside (B) and additional emulsifier (D) is 4.5 parts or less per 100 parts of polyorganosiloxane (A); and (iv) the method comprises 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 low shear using a stirring device with a maximum peripheral speed of 4.5 m / s; If desired, (3) diluting the pre-emulsion by adding additional water (C); and If desired, (4) adding a further additive (F); Contains It is characterized by wherein the method produces a polyorganosiloxane emulsion having a particle size D(50) of 1 μm to 50 μm. method.

2. 2. The method according to claim 1, wherein polydimethylsiloxanes having a viscosity of from 10,000 mPa·s to 3,000,000 mPa·s (measured at 25° C. according to DIN 53019) are used as polyorganosiloxanes (A).

3. 3. The process according to claim 1, wherein alkyl polyglycosides (B) are used which have saturated alkyl groups with an average of 8 to 14 carbon atoms and an average degree of glycosidation m of 1.1 to 3.

0.

4. 4. The method according to claim 1, 2 or 3, characterized in that no further emulsifier (D) is present.

5. 5. The method according to claim 1, wherein 0.1 to 1 part of xanthan gum per 100 parts of polyorganosiloxane (A) is used as thickener (E).

6. The method according to any one of claims 1 to 5, characterized in that the instability index of the polyorganosiloxane emulsion after centrifugation at 2300 x g for 8 hours is less than 0.

1.

7. 7. The method according to claim 1, wherein the polyorganosiloxane emulsion has a particle size D(50) of 3 μm to 20 μm.

8. The polyorganosiloxane emulsion contains less than 0.1 wt % of octamethylcyclotetrasiloxane (D ４ 8. The method according to claim 1, wherein the first and second hydroxyl groups are hydrogen atoms.

9. 1. A storage-stable aqueous polyorganosiloxane emulsion comprising: (A) at least one polyorganosiloxane of the following general formula: 【Chemistry 3】 (In the formula, R １ are the same or different and are a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, R ２ are the same or different and are a monovalent substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom; a is 0, 1, 2, or 3; b is 0, 1, 2, or 3; provided that the sum of a + b is 3 or less) (B) at least one alkyl polyglycoside of the following general formula: 【Chemistry 4】 (In the formula, A is a linear or branched, saturated or unsaturated alkyl group having 8 to 24 carbon atoms; G is a glycoside group, m is the degree of glycosidation and is an integer on average from 1 to 5; (C) water; If desired, (D) a further emulsifier different from the alkyl polyglycoside (B); If desired, (E) a thickener; If desired, (F) further additives normally present in polyorganosiloxane emulsions; Including, (i) a total of 1.5 to 4.5 parts of alkyl polyglycosides (B) are present per 100 parts of polyorganosiloxane (A); (ii) a total of 0 to 3 parts of additional emulsifier (D) is present per 100 parts of polyorganosiloxane (A); (iii) the total amount of alkyl polyglycoside (B) and additional emulsifier (D) is 4.5 parts or less per 100 parts of polyorganosiloxane (A); and (iv) The emulsion is subjected to the following steps: (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 low shear using a stirring device with a maximum peripheral speed of 4.5 m / s; If desired, (3) diluting the pre-emulsion by adding additional water (C); and If desired, (4) adding a further additive (F); Produced by a method comprising: It is characterized by However, the polyorganosiloxane emulsion has a particle size D(50) of 1 μm to 50 μm. Aqueous polyorganosiloxane emulsion.

10. 10,000 mPa s to 3,000,000 mPa s (measured at 25 ° C. in accordance with DIN 53019) is used as polyorganosiloxane (A). The polyorganosiloxane emulsion according to claim 9, characterized in that a polydimethylsiloxane having a viscosity of from 10,000 mPa s to 3,000,000 mPa s (measured at 25 ° C. in accordance with DIN 53019) is used as polyorganosiloxane (A).

11. 11. The polyorganosiloxane emulsion according to claim 9, wherein an alkyl polyglycoside (B) is used having a saturated alkyl group with an average of 8 to 14 carbon atoms and an average degree of glycosidation m of 1.1 to 3.

0.

12. 12. Polyorganosiloxane emulsion according to claim 9, 10 or 11, characterized in that no further emulsifier (D) is present.

13. The polyorganosiloxane emulsion according to any one of claims 9 to 12, characterized in that 0.1 to 1 part of xanthan gum is used as a thickener (E) per 100 parts of polyorganosiloxane (A).

14. The polyorganosiloxane emulsion according to any one of claims 9 to 13, characterized in that the instability index of the polyorganosiloxane emulsion after centrifugation at 2,300 x g for 8 hours is less than 0.

1.

15. The polyorganosiloxane emulsion according to any one of claims 9 to 14, characterized in that the polyorganosiloxane emulsion has a particle size D(50) of 3 μm to 20 μm.

16. The polyorganosiloxane emulsion contains less than 0.1 wt % of octamethylcyclotetrasiloxane (D ４ The polyorganosiloxane emulsion according to any one of claims 9 to 15, characterized in that it has

17. Use of a polyorganosiloxane emulsion according to any one of claims 9 to 16 or a polyorganosiloxane emulsion prepared as claimed in any one of claims 1 to 8 in a cosmetic preparation.

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