Method for producing finely divided emulsions

Abstract

The invention relates to a robust, scalable method for producing finely divided aqueous emulsions from preparations containing polyorganosiloxanes and one or more organic monomers by homogenization using a high-pressure homogenizer equipped with a homogenizing valve, comprising a flat valve seat (1) having an opening (A), a valve plunger (2) and an impact ring (3), wherein the impact ring (3) is arranged on the valve seat (1) and rotationally symmetrically about the opening (A) thereof, and a valve housing surrounding the valve seat (1), valve plunger (2) and impact ring (3), wherein the valve plunger has a conical taper (2') which protrudes into the opening (A) of the valve seat, and the valve plunger (2) and valve seat (1) are arranged rotationally symmetrically and in such a way that a radial constriction is developed between them and forms a homogenizing gap (B), where the homogenization takes place under pressure, followed by ageing of the preparation by storage at a temperature of 15-28°C for a period of at least 6 weeks, and homogenization again.

Description

[0001] WA12411S / WI

[0002] 1

[0003] Methods for producing finely divided emulsions

[0004] The invention relates to a production-scale process for the production of fine aqueous emulsions suitable for the production of silicone organopolymer dispersions by homogenization.

[0005] Polyorganosiloxanes are used for the chemical modification of organic polymers or as binders, for example to achieve better resistance to weathering, chemical attack and thermal stress in the target applications, or to achieve a higher degree of hydrophobicity and to improve the organic polymers with which the polyorganosiloxanes are combined in this respect.

[0006] A prerequisite for polyorganosiloxanes or silanes to fulfill their function in the respective preparations is their good and homogeneous distribution within those preparations. This is a particular challenge in aqueous preparations, in which polyorganosiloxanes are generally insoluble.

[0007] Homogenization is the process of separating and mixing components in a fluid. A well-known example is milk homogenization, in which milk fat globules are broken down and dispersed throughout the bulk of the milk. See, for example, EP 1195190 and US 6305836. Homogenization is also used to process other emulsions, such as those containing silicone oils, and dispersions.

[0008] Purpose of the invention:

[0009] The problem to which the present invention is dedicated is to provide a method that makes it possible to produce finely divided preparations in the form of finely divided emulsions on a production scale. WA12411S / WI

[0010] 2

[0011] The inventive method ensures that the desired droplet size of the mixture of the organic and the organosilicon components is obtained in the aqueous preparation on a production scale and that at the same time a homogeneous distribution of the polyorganosiloxane components in the organic components is obtained or vice versa, depending on how the relative amounts of the organic to the polyorganosiloxane components are chosen.

[0012] Surprisingly, the problem was solved by an invention that contradicts the existing state of the art and not only corrects and clarifies it, but also improves it and creates a new teaching for action.

[0013] State of the art :

[0014] High-pressure homogenizers are a well-established technology for producing finely divided emulsions. They are widely used, for example, in the dairy and pharmaceutical industries.

[0015] There are also examples where high-pressure homogenizers are used to produce emulsions and dispersions containing polyorganosiloxane.

[0016] US2019241749 and US2019375938, for example, describe polyorganosiloxane-containing emulsions, for the preparation of which various methods based on physical convection are used. These include, for example, high-pressure methods using microfluidic devices or high-pressure homogenizers, and stirring methods using rapidly rotating stirring tools. Limiting parameters for the use of high-pressure homogenizers are not specified; only the pressures used are mentioned.

[0017] In US2019241749, an organic solvent is used as the organic component, which is also a disadvantage of this WA12411S / WI.

[0018] 3

[0019] The process is . The organic solvent may promote the uniform distribution of the polyorganosiloxane in the aqueous phase, however, it must be laboriously removed in the process after emulsion preparation because it represents an undesirable Volatile Organic Content (VOC ).

[0020] US5091002 teaches aqueous polyorganosiloxane-containing impregnating agents for hydrophobic building protection applications, which are produced using a high-pressure homogenizer. In this case, too, the homogenization parameters are specified solely by the pressure used. To achieve the required distribution of the siloxane component, several passes through the high-pressure homogenizer, referred to in this case as a gap homogenizer, are necessary, which costs time and therefore money, thus hindering the economic viability of the invention.

[0021] Combinations of polyorganosiloxanes or silanes with organic polymers in an aqueous environment and methods for their production are taught, for example, in EP 1256611 A2, where a microfluidic technology is used for the homogeneous distribution of the components in the aqueous phase, which is not further limited. The homogeneous distribution of the silicone and organic components is not considered, and in particular, it is not demonstrated. Only the average particle size is assumed as an indicator of the success of the homogeneous distribution in the aqueous phase, without specifying which exact average particle size is being referred to, i.e., a D50, a D90, or a similar verifiable value, or a weight- or number-averaged value. Apparently, neither the particle size nor the exact distribution of the silicone phase is relevant to the subject matter of the invention and teaching according to EP 1256611 A2.

[0022] Both US 2018 / 0305576 and US 7674868 teach the

[0023] Use of miniemulsion polymerization technology for the production of aqueous silicon copolymer dispersions WA12411S / WI

[0024] 4 containing components such as polyorganosiloxanes and organic components, such as polyacrylates.

[0025] US 7674868 is essentially silent on the production of the miniemulsions. Only once is a commercially available rotor stator system for homogenization mentioned.

[0026] US 2018 / 0305576 mentions possible methods for producing miniemulsions that involve the application of a high degree of shear force, such as rotor-stator systems with speeds of 4000-12000 rpm, and high-pressure homogenizers with pressures of 300-1000 bar, particularly 400-800 bar. Apart from speed or pressure, no further restrictions are specified regarding the shear or pressure units to be used, so it is within the scope of the teaching according to US 2018 / 0305576 that, if these parameters are observed, a finely divided miniemulsion with a uniform distribution of the polyorganosiloxane can be produced, particularly with any high-pressure homogenizer.The method for homogeneous distribution of the polyorganosiloxane is also not part of the scope of claim in US 2018 / 0305576, although US 2018 / 0305576 points out that the homogeneous distribution of the polyorganosiloxane is crucial for the successful implementation of the teaching according to US 2018 / 0305576.

[0027] A homogeneous distribution of the silicon-containing and silicon-free components in a reactive, finely divided emulsion, which is subsequently radically emulsion-polymerized to form a dispersion, leads, according to US 2018 / 0305576, to a synergistic enhancement of the properties of the organic polymer and the silicon-based component. This means that, with such dispersions, one typically finds not only high binding capacity and high-quality mechanical properties of the polymer, but also the resistance properties of the silicon component. In US 2018 / 0305576, these synergistic enhancement effects are used for the production of building coatings. Significantly improved properties are found, such as reduced blocking behavior and thus reduced WA12411S / WI.

[0028] 5

[0029] Susceptibility to soiling, as well as the possibility of targeted adjustment and tuning of surface hydrophobicity and hydrophilicity, coupled with good water-blocking properties. In particular, such synergistically acting hybrids can serve as binders for the production of coating systems that, in a single layer application, provide both good barrier properties against water penetration and possess a sufficiently hydrophilic surface that allows water to spread into a film, whereby thin films of water evaporate faster than the water droplets that form on hydrophobic surfaces. Therefore, such coatings are on average drier than purely hydrophobic or purely hydrophilic coatings.Since the corresponding coatings are achieved through a single application process and do not require first a hydrophobic, water-blocking coating and then a hydrophilic, water-spreading coating, such hybrid systems with uniformly distributed silicon-containing and silicon-free components are characterized by particular cost-effectiveness in application.

[0030] Furthermore, the building coatings according to US 2018 / 0305576 are always characterized by high storage and weathering stability and durability.

[0031] The copolymer dispersions according to US 2018 / 0305576 can be used to create both film-forming and porous coatings. By polymerizing silanes containing hydrolyzable and condensable groups into the copolymer, binders can be produced that are moisture-curing after application, allowing for adjustment of film hardness, thermoplasticity, and susceptibility to soiling.

[0032] US 2018 / 0305576 thus teaches the advantages that can be obtained with finely divided preparations with homogeneous distribution of silicon-containing and silicon-free components in building coatings.

[0033] As will be shown further below in the example part of the present invention, surprisingly and in contrast to WA12411S / WI

[0034] 6

[0035] The prior art reveals that not just any high-pressure homogenizer, even when operating within a specific pressure range, will produce a homogeneous emulsion or miniemulsion, especially not on a production scale, which is not explicitly mentioned or described anywhere in the prior art. Rather, it requires a combination of a special homogenizing valve, the correct pressure range, a suitable emulsifier system, and a specific process to produce an emulsion or miniemulsion.The aim is to obtain a miniemulsion at every production scale, i.e., the laboratory scale with a throughput of up to 4 l / h through a high-pressure homogenizer, the pilot scale with a throughput of up to 50 l / h through the high-pressure homogenizer, and the production scale with a throughput of up to 5000 l / h through the high-pressure homogenizer, which is not only equally finely divided at every scale, but also contains the polyorganosiloxane homogeneously mixed with the organic components. Particularly at the production scale with a throughput of more than 100 l / h, adherence to the parameters according to the invention is a prerequisite for the successful implementation of the homogenization process. At scales below 100 l / h, precise adherence to the determined parameters according to the invention, and thus to the process according to the invention, is less critical. It is possible that a transfer to the production scale has not yet been necessary, which is why this fact has not been recognized.This may explain the contradiction between the present invention and the state of the art, which until now may have only referred to the scale below 100 1 / h, so that the problem solved here had not yet arisen.

[0036] Based on the process parameters up to a scale of 100 1 / h, scaling up to production scale, which inevitably requires the use of different high-pressure homogenizers, is not feasible, so that a laboratory result cannot be further developed and is not commercially usable.

[0037] A homogenization device of a high-pressure homogenizer essentially consists of a large piston pump, which WA12411S / WI

[0038] 7. generates a high pressure, and a counter-pressure device in which the actual homogenization takes place. The counter-pressure device, the homogenizing valve, comprises a pressurized, elastic valve plunger, a valve seat, an impact ring, and a valve body that encloses the valve plunger and the valve seat. The valve plunger and the seat are normally rotationally symmetrical and arranged such that a radial throttle is formed between these two parts, creating a homogenizing gap.

[0039] An emulsion or dispersion is forced under high pressure into the valve, which acts as a flow restrictor. This creates an intense flow. The high-pressure fluid is forced through a typically narrow valve gap into a low-pressure environment. Homogenization occurs in the area surrounding the valve gap (homogenizing gap). The fluid experiences significant acceleration coupled with a sharp pressure drop as it passes through the valve gap. According to current scientific understanding, both the flow and cavitation contribute to the homogenization result. In the interest of maximum efficiency, homogenizing valves are optimized to allow the highest possible flow rates and to enable homogenization with the lowest possible energy (see US 6305836). Low energy in this context means low homogenization pressure.In addition, in the interest of better storage stability of the homogenized emulsions, it is necessary to produce a particle size distribution that is as homogeneous as possible in order to counteract both particle fusion (Ostwald ripening) and creaming or settling of the emulsified particles.

[0040] Subject of the invention:

[0041] Throughout the text of the invention, references to aggregate states, unless explicitly stated otherwise, always refer to the aggregate state at 25 °C and 1013 mbar. WA12411S / WI

[0042] 8

[0043] The invention relates to a scale-independent, in particular suitable for production scale, continuous and economical process for homogenizing an aqueous preparation containing at least one polyorganosiloxane and at least one organic monomer, resulting in a finely divided emulsion or dispersion characterized by a homogeneous particle size distribution and simultaneously a homogeneous distribution of the silicon-containing and organic components into one another.

[0044] In order for the process to be suitable for production scale, a throughput of more than 100 units of preparation to be homogenized per hour is necessary.

[0045] A first object of the invention is thus a scale-independent method for homogenizing an aqueous preparation with an acidic pH value, i.e. a pH value < 7, preferably < 6, particularly preferably < 5.5, in particular < 5, comprising the following components:

[0046] A) at least one organic monomer which is emulsifiable or self-emulsifying in water,

[0047] B) at least one liquid or water-soluble or dispersible polyorganosiloxane in the at least one organic monomer A), composed of repeating units of the general formula (II) ,

[0048] [R-'-b (OR 2 ) cS 10 ( 4 -bc ) / 2 ] (II) where R 1 is the same or different and means hydrogen or a Si-C-bonded Cl-C18 hydrocarbon residue in which C atoms not sitting next to each other in the chain are substituted by heteroatoms WA12411S / WI

[0049] 9 can, so that organofunctional residues are present which may also be ethylene unsaturated,

[0050] R 2is the same or different and hydrogen or Cl to C12 hydrocarbon residues can be residues and b and c each represent an integer, where b can take the values ​​0, 1, 2 and 3 and c can take the values ​​0, 1 and 2 and the sum b + c = 0, 1, 2 or 3, where preferably b + c = 0 only holds in at most 80% of all repetition units of formula (II),

[0051] C) at least one emulsifier preparation (C) comprising at least one ionic component selected from an anionic surfactant and a cationic surfactant, and at least one non-ionic component which may be a non-ionic surfactant or a monohydric aliphatic, cycloaliphatic or aromatic alcohol of formula (III) ,

[0052] R 3 -0H Formula (III) , where R 3a monovalent aliphatic, linear branched or cyclic hydrocarbon residue with 2 to 8 carbon atoms or an aromatic hydrocarbon residue with 6 to 8 carbon atoms, wherein there is an excess of ionic component over the non-ionic component, wherein the emulsifier preparation preferably consists of an anionic surfactant and the non-ionic component, which is preferably an alcohol of formula (III), in particular ethanol, WA12411S / WI

[0053] 10

[0054] D) optionally at least one partially or completely soluble organic monomer in water in an amount not exceeding 5% by weight, based on the total mass of all components A) to F), where partially or completely soluble means that a solubility of more than 10% by weight in water is given.

[0055] E) optionally at least one liquid excipient, such as stabilizers against microbial attack, antifoaming agents, viscosity modifiers, organic solvents, reactive diluents, film-forming agents, wherein preferably no single component E) constitutes more than 10% by weight of the total amount of all components A) - E) and the total amount of component E) does not constitute more than 30% by weight of the total mass of all components A) - E) and

[0056] F) Water, wherein the procedure comprises the following steps in the specified order:

[0057] 1) Mix all components A) to F) ,

[0058] 2) Production of a preemulsion by stirring, in particular using low shear energy, e.g. by stirring with a stirring device such as an anchor stirrer or paddle stirrer, at a stirring device speed of 30-500 revolutions per minute for a period of 10 to 60 min,

[0059] 3) Homogenizing the preemulsion using a

[0060] High-pressure homogenizer equipped with a WA12411S / WI

[0061] 11

[0062] Homogenizing valve comprising a flat valve seat

[0063] (1) with an opening (A) , in particular a central opening (A) , a valve plunger (2) and an impact ring (3) , wherein the impact ring (3) is on the valve seat (1) and rotationally symmetric about its opening

[0064] (A) is arranged, as well as a valve housing which encloses the valve seat (1), valve plunger (2) and impact ring (3), wherein the valve plunger (2) has a conical taper (2') which projects into the opening (A) of the valve seat and the valve plunger (2) and valve seat (1) are rotationally symmetric and arranged such that a radial throttle is formed between them, which forms a homogenizing gap (B), wherein the homogenizing takes place under pressure, preferably a pressure of 200 bar to 1000 bar,

[0065] 4) Maturation of the preparation obtained from step 3) by storage at a temperature of 15 - 28 °C, preferably 17 - 26 °C, particularly 18 - 25 °C for a period of at least 6 weeks, preferably at least 8 weeks, particularly preferably at least 10 weeks, and especially at least 12 weeks.

[0066] 5) Homogenizing the matured preparation from step 4) using the high-pressure homogenizer from step 3) under pressure, preferably a pressure of 200 bar to 1000 bar.

[0067] “Monomers” within the meaning of the invention are low-molecular-weight, reactive molecules that can combine to form unbranched or branched polymers.

[0068] The pH value to be adjusted according to the invention is achieved, for example, by using suitable acidic components from the group WA12411S / WI.

[0069] 12 of the preparation ingredients A) to E) are selected and used in sufficient quantities.

[0070] In a particular formulation, the aqueous preparation to be homogenized consists of the components defined above A), B), C), D), E), and F).

[0071] With regard to the emulsifier preparation C), there is advantageously an excess of anionic surfactant compared to the non-ionic component, such that preferably 2 to 20 times as much anionic surfactant as non-ionic component, particularly preferably 4 to 20 times as much anionic surfactant as non-ionic component, and in particular 6 to 20 times as much anionic surfactant as non-ionic component are contained in the emulsifier preparation, and the preferred combinations of anionic surfactant and non-ionic component are sodium dodecyl sulfate and ethanol, sodium dodecyl sulfate and n-propanol, sodium dodecyl sulfate and n-butanol, sodium dodecyl sulfate and iso-propanol, sodium dodecyl sulfate and tert- -Butanol, in particular sodium dodecyl sulfate and ethanol, and sodium dodecyl sulfate and tert.-Butanol, particularly preferably from sodium dodecyl sulfate and ethanol, wherein the preparation of sodium dodecyl sulfate and ethanol in a ratio of 13.6:1 by weight is preferably the most preferred combination.

[0072] Preferably the conical taper of the valve plunger ( 2 ' ) has a taper in the range of a = 10-25°, preferably a = 15-20° .

[0073] Preferably, the throughput of the preparation to be homogenized is more than 100 units / hour, in particular more than 500 units / hour, and especially more than 1000 units / hour. This allows the required production scales to be achieved.

[0074] The ripening process in step 4) is preferably carried out in a closed container that is at least 50% filled with WA12411S / WI

[0075] 13 of the preparation obtained from step 3) is filled, preferably to at least 60%, particularly preferably to at least 70%, especially to 80%, with the remainder being air space.

[0076] In a preferred embodiment, the proportion of component (A) is 5-45 percent by weight of the total aqueous preparation as 100%.

[0077] In a preferred embodiment, the proportion of component (B) is 3-20 percent by weight of the total aqueous preparation as 100%.

[0078] Preferably, the preparation according to the invention contains 0.5 to 8.0 wt%, preferably 0.6 to 7.0, particularly preferably 0.7 to 6.0, in particular 0.8 to 5.0 wt% based on the total aqueous preparation as 100% of the emulsifier preparation (C).

[0079] Homogenization takes place in the high-pressure homogenizer using a high-pressure homogenizing valve according to Figure 1 with valve seat (1), valve plunger (2) and impact ring (3) with axial flow guidance.

[0080] Examples of valves preferably installed in commercial high-pressure homogenizers that are not suitable for carrying out the process according to the invention are flat valves. After being deflected by 90°, the preemulsion passes through a radial gap between the valve seat (4, 7) and the valve plunger (5, 8). In this context, two types of flat valves can be distinguished: valves with a flat valve seat and plunger, and valves with a conical valve seat. Among the conical valve seats, a further distinction can be made between an external cone according to Figure 2 (NE 2, NE = not according to the invention) and an internal cone according to Figure 1 (NE 1). WA12411S / WI

[0081] 14

[0082] The examples show that, unlike the valve according to the invention, valves NE1 and NE2 cannot meet the requirements of a homogeneous particle size distribution combined with a uniform distribution of the silicon-containing and non-silicon-containing components of the preparation, particularly on a production scale, even when an emulsifier preparation according to the invention is used. In fact, it was found that the requirement of a homogeneous distribution of all components of a preparation according to the invention in the form of a fine dispersion or emulsion on a production scale is only achieved by combining a valve geometry according to the invention with the suitable emulsifier preparation using the method according to the invention.

[0083] Self-emulsifying and emulsifiable mean that the components are not soluble in water. Self-emulsifying components form clear to milky-turbid preparations when added to water. In particle size measurements, for example by dynamic light scattering, particles are always visible in the water, indicating that there is no molecularly dispersed solution, but rather two separate, distinguishable phases. Emulsifiable components are essentially immiscible with water, but form two macroscopically separate phases with water. Essentially means that the water solubility is below 100 g / L at 25 °C. Partially soluble, in contrast, means that the solubility is at or above 100 g / L, but not above 200 g / L. Solubility is present within the meaning of the present invention from a solubility of 200 g / L.The term solubility includes the term miscibility, whereby the specified limits apply equally, i.e., with the same limits, to immiscible, partially miscible, and miscible components.

[0084] Organic monomers according to the invention can be liquid, solid, or gaseous. Solid and gaseous organic monomers can be used according to the invention when they are dissolved or dispersed in liquid monomers, which may also be solvents WA12411S / WI.

[0085] The monomers can be converted into a liquid form or injected into the medium to be polymerized under appropriate pressure. In this way, it is possible to use gaseous or solid monomers within the limits of their solubility in other monomers. There are no restrictions on the combination of organic monomers. That is, it is permissible to combine organic monomers of group A). ​​The same applies analogously to the combination of organic monomers with polyorganosiloxanes, or the combination of polyorganosiloxanes with polyorganosiloxanes. Here, too, any mixtures are permitted as long as the dosage and handling form remains liquid for the combination.

[0086] Examples of self-emulsifying or emulsifiable organic monomers are unreactive solvents such as aromatic, cycloaliphatic, or aliphatic solvents like toluene, xylene, ethylbenzene, aromatic-free hydrocarbons (possibly as mixtures with defined boiling ranges), cyclohexane, cycloheptane, reactive monomers such as vinyl esters, (meth)acrylic esters, vinyl aromatics, olefins, 1,3-dienes, vinyl ethers, and vinyl halides, and other monomers, especially those that can be copolymerized with the aforementioned reactive monomers. Furthermore, Group A) includes mono-, di-, or polycarboxylic acids, provided they do not meet the criteria of partial solubility or solubility, in particular aromatic, aliphatic, or cycloaliphatic di- or polycarboxylic acids and their derivatives, such as...Phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, maleic anhydride, fumaric acid, succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, dimethyl terephthalate, naphtha, 1-indicarboxylic acid, cyclohexanedicarboxylic acid, hexahydrophthalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, 1,12-dodecanedicarboxylic acid and 1,14-tetradecanedicarboxylic acid, as well as their diesters and anhydrides or aliphatic, cycloaliphatic or aromatic mono-, di- or polyols, also provided that they meet the criteria of WA12411S / WI.

[0087] 16

[0088] Partial solubility and solubility are not met, such as phenol, bisphenol A, perhydrobisphenol A, selected isomers of dimethylolcyclohexane, 3 ( 4 ) , 8 ( 9 ) -dihydroxymethyltricyclo [ 5 . 2 . 1 . 02 .6] decane, ethylene-unsaturated carboxylic acid amides and nitriles, preferably acrylamide such as diacetone acrylamide (DAAM) and acrylonitrile, mono- and diesters of fumaric acid and maleic acid such as the diethyl and diisopropyl esters as well as maleic anhydride, polyethylene-unsaturated comonomers, for example divinyl adipate, diallyl maleate, allyl methacrylate or triallyl cyanurate, or post-crosslinking comonomers, for example acrylamidoglycolic acid (AGA), methyl acrylamidoglycolic acid methyl ester (MAGME), N-methylolacrylamide (NMA), N-methylolmethacrylamide, N-methylolallylcarbamate, alkyl ethers such as isobutoxy ether or esters of N-methylolacrylamide, N-methylolmethacrylamide and N-methylolallylcarbamate, epoxide-functional monomers such as glycidyl methacrylate and glycidyl acrylate.

[0089] Suitable vinyl esters are those of carboxylic acids with 1 to 15 carbon atoms. Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methyl vinyl acetate, vinyl pivalate, and vinyl esters of α-branched monocarboxylic acids with 9 to 11 carbon atoms, for example VeoVa9, are preferred. R or VeoVal O R (Trade names of the company Resolution). Vinyl acetate is particularly preferred.

[0090] Suitable monomers from the group of acrylic or methacrylic esters are esters of unbranched or branched alcohols with 1 to 15 carbon atoms. Preferred methacrylic or acrylic esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, and norbornyl acrylate. Particularly preferred are methyl acrylate, methyl methacrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and norbornyl acrylate. WA12411S / WI

[0091] 17

[0092] Other examples of monomers A) are vinyl aromatics such as styrene, alpha-methylstyrene, the isomeric vinyltoluenes and vinylxylenes, as well as divinylbenzenes.

[0093] Among the vinyl halogen compounds are vinyl chloride, vinylidene chloride, tetrafluoroethylene, difluoroethylene, hexyl perfluoroethylene, 3,3,3-trifluoropropene,

[0094] Perfluoropropyl vinyl ether, hexafluoropropylene, chlorotrifluoroethylene and vinyl fluoride are typical examples.

[0095] Examples of monomeric olefins of group A) are ethene, propene, 1-alkylethenes, and polyunsaturated alkenes such as dienes, e.g., 1,3-butadiene and isoprene. Ethene and 1,3-butadiene are particularly favored.

[0096] Further examples of monomers A) are those of formula (IV)

[0097] In formula (IV) R means 4 , R 5 , R 6 , R 7 and R 8 independently of each other a hydrogen radical, a hydrocarbon group or a hydrocarbon group substituted with foreign atoms.

[0098] Examples of residues R 4 , R 5 , R 6, R 7 and R 8 are the hydrogen residue, saturated hydrocarbon residues such as methyl, ethyl, n-propyl, iso-propyl, the primary, secondary and tertiary butyl residue, the hydroxyethyl residue, aromatic WA12411S / WI

[0099] 18

[0100] Residues such as the phenylethyl group, the phenyl group, the benzyl group, the methylphenyl group, the dimethylphenyl group, the ethylphenyl group, heteroatom-containing residues such as the hydroxymethyl group, the carboxyethyl group, the methoxycarbonylethyl group and the cyanoethyl group, and acrylate and methacrylate residues, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate and norbornyl acrylate, olefinically or acetylenically unsaturated hydrocarbon residues e.

[0101] If necessary, the adjacent residues R8 and R 5 as well as the adjacent remnants R 4 and R 6 They can also be linked together to form the same cyclic saturated or unsaturated residue, resulting in annelated polycyclic structures.

[0102] Examples of phenolic compounds of formula (IV) are phenol, ortho-, meta- or para-cresol, 2, 6-, 2,5-, 2,4- or 3,5-dimethylphenol, 2-methyl-6-phenylphenol, 2, 6-diphenylphenol, 2, 6-diethylphenol, 2-methyl-6-ethylphenol, 2,3, 5-, 2,3, 6- or 2, 4, 6-trimethylphenol, 3-methyl-6-tertiary-butylphenol, thymol and 2-methyl-6-allylphenol.

[0103] All the information listed is for illustrative purposes only and should not be understood as limiting.

[0104] Examples of polyorganosiloxanes (B) are silicone oils, silicone polymers, and silicone resins, which may or may not be liquid. To obtain a liquid emulsifiable preparation, it is sufficient if the silicone oils, silicone polymers, or silicone resins can be dispersed or dissolved in organic monomers (A), provided that the polyorganosiloxanes from units of formula (II) are solids. WA124HS / WI

[0105] 19

[0106] Typical repetition units according to formula (II) are those of formulas R 1 3-c (OR 2 ) c SiOi / 2(Ha) , R 2 2-c (OR 2 ) c SiO2 / 2(Hb) , R 2 SiO3 / 2(IIc) and SiO4 / 2(Hd) , where c has the meanings given above and the difference 3-c can take the values ​​3, 2, 1 and 0 and the difference 2-c the values ​​2, 1 and 0. Preferred values ​​for 3-c are 3 and 2, preferred values ​​for 2-c are 2 and 1. R 1 and R2 have the meanings given above, with several remainders R 1 or R 2 in the same repetition unit of formula (II) or (Ha) to (Hd) may differ from each other.

[0107] The remains R 1 These residues can be either functional or non-functional. When selecting the residues, compliance with the solubility criterion must be ensured.

[0108] Functional residues R 1 Examples include linear, branched or cyclic ethylene unsaturated residues such as monounsaturated C2 to Cio residues such as the vinyl, acrylate and methacrylate residues.

[0109] In the remains R 1 They may contain one or more identical or different heteroatoms selected from O, S, Si, O1, F, Br, P or N atoms.

[0110] In addition to the double bond, functional residues R can thus be formed. 1Other functional groups may also be present, such as halogen, carboxy, anhydride, carbinol, sulfinato, sulfonato, amino, azido, nitro, epoxy, alcohol, ether, glycol, ester, thioether and thioester groups, as well as aromatic isocyclic and heterocyclic groups.

[0111] Examples of preferred non-functional residues R 1 are alkyl radicals, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. -Butyl-, n-Pentyl-, iso-Pentyl-, neo-Pentyl-, tert. -Pentyl group, hexyl groups, such as n-hexyl group, heptyl groups, such as n-heptyl group, octyl groups, such as n-octyl group and iso-octyl groups, such as 2,2,4-trimethylpentyl group, nonyl groups, such as n-nonyl group, decyl groups, such as n-decyl group, dodecyl groups, such as n-dodecyl group, and octadecyl groups, such as n-octadecyl group, hexadecyl group, cycloalkyl groups, such as cyclopentyl, cyclohexyl, WA12411S / WI

[0112] 20

[0113] Cycloheptyl and methylcyclohexyl groups, aryl groups such as phenyl, naphthyl, anthryl, and phenanthryl groups, alkaryl groups such as tolyl, xylyl, and ethylphenyl groups, and aralkyl groups such as benzyl and β-phenylethyl groups. Particularly preferred hydrocarbon groups R 1 These are the methyl, isooctyl, propyl and phenyl residues, although this list is only illustrative and not exhaustive.

[0114] Silicone oils are preferably composed of repeating units of formula (Hb) as chain-forming units, where c is preferably 0. The silicone oils are preferably terminated with units of formula (Ila), where c is also preferably 0. In addition, small amounts of network-forming building blocks according to formula (IIc) or (Ild) may be present. Their proportion is typically no higher than 20 mol% of the total silicone oil structure.

[0115] Silicone polymers are composed of the same repeating units as silicone oils, but differ from silicone oils in the sense of the present inventions in that they have higher molecular weights and higher viscosities. Silicone oils have viscosities in the range of 2 mPas to 100,000 mPas. Silicone polymers, accordingly, have viscosities above 100,000 mPas. The group of silicone oils also includes, in particular, cyclic or linear oligoorganosiloxanes with a defined degree of polymerization, such as di-, tri-, tetra-, and pentasiloxanes comprising 2, 3, 4, or 5 repeating units, especially disiloxanes, which can be used as pure substances or in mixtures.

[0116] Other typical polyorganosiloxanes according to the invention are silicone resins which contain, as characteristic repeating units, those of formulas (IIc) and (Ild) in larger quantities, in particular more than 20 mol%. Silicone resins can also consist of 100 mol% repeating units of formula

[0117] (llc) be structured. The repetition units of the formula

[0118] (lld), however, are present at a maximum of 80 mol%. Otherwise WA12411S / WI

[0119] 21 The repetition units of formula (Ila) and (Ilb) may be present.

[0120] For all polyorganosiloxanes according to the invention, the sum of all repeating units (Ila) to (Ild) equals 100 mol-%.

[0121] Silicone resins can be liquids with viscosities typically ranging from 20 mPas to 500,000 mPas at 25°C, or they can be solids at 25°C with glass transition temperatures typically ranging from 25°C to 250°C. It should be noted that there are also silicone resins that are solid and do not exhibit a glass transition until they decompose. This is the case, for example, with MQ resins of certain compositions and degrees of crosslinking. These are also subject to the invention, provided that solutions or dispersions in monomers A) can be obtained with them.

[0122] The exclusion criterion and delimitation for polyorganosiloxanes (B) is their solubility in water. Polyorganosiloxanes (B) are soluble in water in amounts of less than 10% by weight, preferably less than 8% by weight, and particularly less than 6% by weight.

[0123] Typical examples of partially or completely soluble organic monomers in water are mono-, di- or polyols, especially aliphatic polyols such as ethylene glycol, propanediols [1,2 and 1,3], butanediol-1,4; hexanediol-1,6; neopentyl glycol and other neodiols; hydroxypivalic acid neopentyl glycol esters; trimethylpendanediol; polyether polyols, polyhydric alcohols such as trimethylolpropane; pentaerythritol; Di-trimethylolpropane, cycloaliphatic polyols such as certain isomers of dimethylolcyclohexane, alcohols such as ethanol, methanol, propanol, butanol, isopropanol, ketones such as methyl ethyl ketone, acetone, cyclohexanone, ethylene unsaturated mono- and dicarboxylic acids such as acrylic acid and methacrylic acid, monomers with hydroxyl groups, for example, methacrylic acid and acrylic acid hydroxyalkyl esters such as hydroxyethyl or hydroxypropyl acrylate or methacrylate. WA12411S / WI

[0124] 22

[0125] All lists are for illustrative purposes only and are not to be understood as limiting.

[0126] The aqueous emulsions or dispersions according to the invention, which contain emulsifiable or self-emulsifying components, also contain emulsifying and dispersing agents such as those listed, for example, in McCutcheon's Emulsifiers & Detergents, North American Edition, MC Publishing Co., Glen Rock, NJ (2006). The distinctive feature of the present invention, namely that it must include a combination of an anionic or cationic surfactant and a non-ionic component, which represents a differentiating feature from the prior art, has already been discussed above. Preferably, this is a combination of an anionic surfactant and a non-ionic component, wherein the former is in particular sodium dodecyl sulfate and the non-ionic component is preferably a monohydric aliphatic alcohol.

[0127] Suitable surfactants or emulsifiers also include anionic emulsifiers:

[0128] 1. Alkyl sulfates, especially those with a chain length of 8 to 18 C atoms, alkyl and alkaryl ether sulfates with 8 to 18 C atoms in the hydrophobic residue and 1 to 40 ethylene oxide (EO) or propylene oxide (PO) units.

[0129] 2. Sulfonates, especially alkylsulfonates with 8 to 18 carbon atoms, alkylarylsulfonates with 8 to 18 carbon atoms, taurides, esters and semi-esters of sulfosuccinic acid with monohydric alcohols or alkylphenols with 4 to 15 carbon atoms; optionally, these alcohols or alkylphenols may also be ethoxylated with 1 to 40 EO units.

[0130] 3. Alkali and ammonium salts of carboxylic acids with 8 to 20 carbon atoms in the alkyl, aryl, alkaryl, or aralkyl group. WA12411S / WI

[0131] 23

[0132] 4. Phosphoric acid esters and their alkali and ammonium salts, especially alkyl and alkaryl phosphates with 8 to 20 carbon atoms in the organic residue, alkyl ether or alkaryl ether phosphates with 8 to 20 carbon atoms in the alkyl or alkaryl residue and 1 to 40 EO units, as non-ionic emulsifiers:

[0133] 5. Polyvinyl alcohol, which still contains 5 to 50%, preferably 8 to 20%, vinyl acetate units, with a degree of polymerization of 500 to 3000.

[0134] 6. Alkyl polyglycol ethers, preferably those with 8 to 40 EO units and alkyl groups of 8 to 20 C atoms.

[0135] 7. Alkylaryl polyglycol ethers, preferably those with 8 to 40 EO units and 8 to 20 C atoms in the alkyl and aryl groups.

[0136] 8. Ethylene oxide / propylene oxide (EO / PO) block copolymers, preferably those with 8 to 40 EO or PO units.

[0137] 9. Addition products of alkylamines with alkyl groups of 8 to 22 C atoms with ethylene oxide or propylene oxide.

[0138] 10. Fatty acids with 6 to 24 carbon atoms.

[0139] 11. Alkyl polyglycosides of the general formula R*-O-Z o , wherein R* represents a linear or branched, saturated or unsaturated alkyl group with on average 8 - 24 C atoms and Zo represents an oligoglycoside group with on average o = 1 - 10 hexose or pentose units or mixtures thereof .

[0140] 12. Natural products and their derivatives, such as lecithin, lanolin, saponins, cellulose; cellulose alkyl ethers and WA12411S / WI

[0141] 24

[0142] Carboxyalkyl celluloses, whose alkyl groups each have up to 4 carbon atoms.

[0143] 13. Linear organo(poly)siloxanes containing polar groups, especially those with alkoxy groups with up to 24 carbon atoms and / or up to 40 EO and / or PO groups, as cationic emulsifiers:

[0144] 14. Salts of primary, secondary and tertiary fatty amines with 8 to 24 carbon atoms with acetic acid, sulfuric acid, hydrochloric acid and phosphoric acids.

[0145] 15. Quaternary alkyl and alkylbenzeneammonium salts, especially those whose alkyl group has 6 to 24 carbon atoms, in particular the halides, sulfates, phosphates and acetates.

[0146] 16. Alkylpyridinium, alkylimidazolinium, and alkyloxazolinium salts, especially those whose alkyl chain has up to 18 carbon atoms, specifically the halides, sulfates, phosphates, and acetates, as ampholytic emulsifiers:

[0147] 17. Long-chain substituted amino acids, such as N-alkyl-di-(aminoethyl-)glycine or N-alkyl-2-aminopropionic acid salts.

[0148] 18. Betaines, such as N-(3-acylamidopropyl)-N,N-dimethylammonium salts with a C8-C18 acyl group and alkyl-imidazolium betaines.

[0149] Preferred non-ionic dispersing aids are the addition products of alkylamines with ethylene oxide or propylene oxide listed above under 9, the alkyl polyglycosides listed above under 11, and WA12411S / WI above.

[0150] 25 under 5. on polyvinyl alcohol. Particularly preferred polyvinyl alcohols contain 5 to 20%, in particular 10 to 15%, vinyl acetate units and preferably have a degree of polymerization of 500 to 3000, in particular 1200 to 2000.

[0151] Other additives include biocides, thickeners, antifoaming agents, pH adjusters, preservatives, solubilizers, and hydrophobic additives such as linear, branched, or cyclic C12 cis alkanes, which seal the emulsified droplets against water and thus suppress the migration of water-soluble components from the droplets. A typical example of such a hydrophobic additive is hexadecane.

[0152] Organopolysiloxanes containing SiC-bound residues with basic nitrogen can be used as additional auxiliary substances, provided that the amine number of the organopolysiloxane is at least 0.01 but no more than 0.99.

[0153] The proportion of auxiliary materials is preferably 0.1 to 30 wt.%, in particular 0.1 to 25 wt.%, based on the total amount of components A) - E).

[0154] Furthermore, the preparations according to the invention contain water of preferably 10 to 90 wt.%, in particular 15 to 80 wt.%, based on the total amount of all components A) to F).

[0155] The procedure:

[0156] The steps of the procedure are carried out in the order listed, from 1 to 5:

[0157] 1. Mix all components A) to F) ,

[0158] 2. Preparation of a preemulsion by stirring, especially using low shear energy, e.g. by stirring WA12411S / WI

[0159] 26 with a stirring device, such as an anchor stirrer or paddle stirrer, at a stirring device speed of 30-500 revolutions per minute for a period of 10 to 60 min,

[0160] 3. Homogenizing by means of a high-pressure homogenizer equipped with a homogenizing valve according to the invention, under pressure, preferably under a pressure of 200 bar to 1000 bar,

[0161] 4. Maturation of the preparation obtained from step 3 after passage through the high-pressure homogenizer at a temperature of 15–28 °C, preferably 17–26 °C, particularly 18–25 °C, for a period of at least 6 weeks, preferably at least 8 weeks, particularly preferably at least 10 weeks, and especially at least 12 weeks.

[0162] 5. Homogenizing the preparation from step 4 by means of a high-pressure homogenizer using the same homogenizing valve according to the invention as already used in step 3, under pressure, preferably a pressure of 200 bar to 1000 bar.

[0163] The ripening is preferably carried out in a closed container which is filled to at least 50% with the preparation obtained from step 3, preferably to at least 60%, particularly preferably to at least 70%, especially to 80%, with the remainder being air space.

[0164] In the process according to the invention, the components to be homogenized can be mixed together in any order. This means that the order in which the components are mixed together is irrelevant to the success of the homogenization, and no special requirements are placed on the mechanics of the mixing process in step 1. In particular, this means that only low shear energies are required. Low shear energies here refer to shear energies such as those achieved by using WA12411S / WI.

[0165] 27 for example, can be achieved by commercially available reactor or laboratory stirrers and with commercially available drive units, such as with an anchor stirrer or a paddle stirrer at a low speed of, for example, 30 - 500 revolutions per minute, or on a laboratory scale simply by shaking all components, either with a commercially available laboratory shaker or simply manually by shaking a container containing the preparation.

[0166] The order in which components A) to F) are added to each other has no influence on the homogenization result according to the inventive process. This means that, for example, in step 2 of the inventive process it is permissible to first dissolve all water-soluble components in water, to dissolve all components soluble in organic monomers in monomers, and then to combine the aqueous and monomer solutions together to form a preemulsion by applying moderate shear energy according to the specifications of the mixing unit available and used.

[0167] Likewise, according to the inventive method, the preemulsion can be prepared by mixing all water-soluble components to form an aqueous solution and then adding the monomer-soluble components to this aqueous solution and preparing the preemulsion by mixing the preparation using low shear energy. This procedure can also be reversed, starting with the monomer-soluble components and then proceeding with the water-soluble components and water. In principle, it is also conceivable to mix the components together in a completely arbitrary order to obtain the preemulsion, without regard to whether they are monomer-soluble or water-soluble.

[0168] This procedure also yields the same homogenization result after passing through a high-pressure homogenizer equipped according to the invention and WA12411S / WI

[0169] 28. Complete application of the process according to the invention. The latter approach is therefore also according to the invention, but not preferred, because the complete dissolution of the water-soluble components in the water or the complete dissolution of the monomer- or solvent-soluble components in the water or in the monomer or solvent can take longer than with the aforementioned approaches. Thus, this variant is technically possible, but with slight compromises regarding the speed of implementation and therefore the economic efficiency of the entire process. It is particularly preferred to first dissolve all water-soluble components in the water and then add all monomer-soluble components to the aqueous solution. This requires only a minimum number of stirred tanks and thus obtains a homogeneous mixture most quickly.

[0170] The preemulsion has a pH value < 7 as specified according to the invention. It can be stable for a limited time. However, this is not a prerequisite for the successful implementation of the process according to the invention. Limited time stability means from 30 minutes to several weeks without macroscopically detectable separation. The preemulsion is accordingly described as unstable in this text if it begins to separate macroscopically detectably within less than 30 minutes. In the process according to the invention, the stability or instability of the preemulsion is not a criterion for the success of the process, as long as it is ensured that the preemulsion reaches the high-pressure homogenizer according to the invention homogeneously. This can be achieved by continuously stirring an unstable preemulsion before it is conveyed through the high-pressure homogenizer according to the invention.A stable preemulsion as defined in this document can, depending on its stability, also be stored at rest beforehand, i.e., without stirring, and then transferred to the high-pressure homogenizer according to the invention, provided that it is still homogeneous at the moment it is transferred to the high-pressure homogenizer according to the invention. WA12411S / WI.

[0171] 29

[0172] In the third step of the process, the preemulsion is sheared by a high-pressure homogenizer containing a homogenizing valve according to the invention under a suitable pressure. The optimal pressure depends on the specific preparation and the desired homogenization result and must be determined for each preparation. The pressure range to be used extends from 200 bar to 1000 bar, with 400–1000 bar being particularly preferred, especially 400–900 bar. High pressures have proven particularly advantageous when using the homogenizing valve according to the invention because they are especially effective, particularly high pressures of 600–900 bar. In this pressure range, the process according to the invention is most robust, i.e., the effects of process changes are least decisive for a consistent homogenization result, and thus operational implementation is easiest to achieve.

[0173] The use of the previously described homogenizing valve in the high-pressure homogenizer in combination with the described emulsifier composition is essential.

[0174] The method according to the invention can only be implemented with such a valve.

[0175] In the third step, a particularly thorough mixing of all preparation components is achieved and ensured. The preparation obtained after the third step is not storage-stable in that it separates into two phases, one of which is predominantly aqueous and the other predominantly organic. The organopolysiloxane of formula (II) is located in the predominantly organic phase. "Predominantly" means that components of the other species are also present in both phases. These two species refer, on the one hand, to the organic components of the preparation ingredients and the organopolysiloxane of formula (II), and on the other hand, to water and the water-soluble or predominantly water-soluble preparation components. WA12411S / WI

[0176] 30

[0177] This means that the predominantly aqueous phase also contains organic monomers, provided these are water-soluble, partially soluble, or self-emulsifying. The organic phase also contains aqueous components, possibly coarsely emulsified and stabilized by the emulsifier mixture. This stabilization of the aqueous components in the predominantly organic phase is not stable, so the proportion of aqueous components in the predominantly organic phase changes during step 4, the maturation period, for example, through droplet coalescence and the separation of aqueous components into the predominantly aqueous phase. During the maturation period according to step 4, a gradual further separation of the predominantly organic phase into its aqueous and organic components is observed.

[0178] In step 4, the preparation preferably rests for 6–12 weeks. The optimal time for step 4 is temperature-dependent. The lower the temperature of the preparation during this step, the longer it takes, with a temperature window of 22°C ± 3°C proving optimal. If this temperature window is maintained, the process takes an average of 8 weeks ± 2 weeks, depending on the exact composition of the preparation. A higher temperature does not noticeably shorten step 4 and may be disadvantageous with volatile components and when using reactive monomers. In step 5, the preparation obtained from step 4 is first homogenized by applying moderate shear energy, analogous to step 2, and then, analogous to step 3, passed under pressure through a high-pressure homogenizer, which is again equipped with a homogenizing valve according to the invention.The execution of the low shear energy pre-emulsification and high-pressure homogenization corresponds to the detailed description of steps 2 and 3.

[0179] The inventive method has the particular advantage that a stable emulsion with a WA12411S / WI can be produced on a production scale.

[0180] 31 homogeneous distribution of silicon-containing and silicon-free components is obtained in each other. The resulting emulsions have homogeneous particle size distributions. A homogeneous particle size distribution is characterized by the fact that only one peak is obtained in the particle size distribution diagram by scattered light measurement.

[0181] The homogeneous distribution of silicon-containing and silicon-free components can be demonstrated by electron microscopy. Due to their different electron densities, silicon-containing and silicon-free materials can be readily distinguished from one another, for example, using transmission electron microscopy (TEM).

[0182] The preparations according to the invention can be used in various ways. Reactive preparations can, in principle, be subjected to reaction, for example, for the purpose of polymerization, copolymerization, oligomerization, or for hardening or crosslinking during an application process. The reaction can optionally take place in steps, as is the case, for example, for the production of molded parts via intermediates such as prepregs. Intermediate stages of a reaction cascade can be obtained either by the evaporation of sufficient quantities of volatile components followed by coalescence, by partial reaction in the case of controllable reactions, or, if several possible reaction mechanisms are present, by exploiting the more reactive mechanism in the first stage. The subsequent stage or stages then utilize the remaining reactivity accordingly.following the same or different reaction mechanisms. In principle, the preparations obtained can therefore either be further refined in subsequent stages of a manufacturing chain by utilizing a reactivity, or they can be directly applied to achieve a specific application goal. Depending on the application goal, the preparation itself can be used as a ready-to-use dosage form WA12411S / WI.

[0183] 32 serve or it is further formulated or broken in order to release the ingredients and utilize their effect.

[0184] Due to the large number of conceivable ingredients of the preparation usable according to the invention, the selection of potential fields of application is not fundamentally limited. Accordingly, only typical fields of application in which the preparations according to the invention can be used will be mentioned below as examples.

[0185] They can be used, for example, as additives to preparations for coatings or without further additives as a pure material forming a film over substrates or curing into blocks or other shapes, whereby the preparations can be used both in the form obtained after homogenization and in a form obtained by subsequent polymerization or copolymerization, for example by radical emulsion polymerization or miniemulsion polymerization.

[0186] They can be used as a preparation according to the invention or in form obtained by subsequent reactive refinement for the production of coating materials and impregnations and coatings and coverings obtained therefrom on substrates such as metal, glass, wood, mineral substrates, synthetic and natural fibers for the production of textiles, carpets, floor coverings, or other goods that can be produced from fibers, leather, plastics such as films, molded parts; they can be incorporated into elastomer masses in liquid or reacted form and can serve for the purpose of reinforcement or for improving other performance properties such as controlling transparency, heat resistance, yellowing tendency, and weathering resistance.

[0187] Depending on the application, the preparations according to the invention or the WA12411S / WI obtained therefrom by further reaction can be used.

[0188] 33

[0189] Preparations may contain further additives. Examples of such substances include solvents or film-forming aids, mixtures of at least two organic solvents, pigment wetting and dispersing agents, surface-effect additives, such as those used to achieve textures like hammered or orange peel textures, antifoaming agents, substrate wetting agents, surface leveling agents, adhesion promoters, release agents, further organic polymers, which may be identical to, but do not necessarily have to be identical to, polymers already contained in the preparation, surfactants, hydrophobic additives, and further polyorganosiloxanes.

[0190] Examples:

[0191] The process according to the invention and the compositions are described below using examples. All percentages refer to weight. Unless otherwise specified, all manipulations are carried out at room temperature (25°C) and under normal pressure (1.013 bar).

[0192] Unless otherwise stated, all data describing product properties apply at room temperature of 25°C and under normal pressure (1.013 bar).

[0193] The equipment in question is standard laboratory equipment, such as that offered for sale by numerous equipment manufacturers.

[0194] Ph means a phenyl group = CeHs-

[0195] Me means one methyl group = CH3- . Me2 accordingly means two methyl groups.

[0196] HCl means hydrogen chloride.

[0197] In this text, substances are characterized by providing data obtained through instrumental analysis. The underlying measurements are performed either according to publicly available standards or according to WA12411S / WI.

[0198] 34 specially developed procedures were determined. To ensure the clarity of the communicated teaching, the methods used are listed below.

[0199] In all examples, all references to parts and percentages refer to weight, unless otherwise stated.

[0200] Viscosity:

[0201] Unless otherwise specified, viscosities are determined by rotational viscometric measurement according to DIN EN ISO 3219. Unless otherwise specified, all viscosity values ​​apply at 25°C and a standard pressure of 1013 mbar.

[0202] Refraction index:

[0203] The refractive indices are determined in the wavelength range of visible light, unless otherwise specified, at 589 nm at 25°C and normal pressure of 1013 mbar according to the standard DIN 51423.

[0204] Transmission:

[0205] The transmission is determined by UV-VIS spectroscopy. A suitable instrument is, for example, the Analytik Jena Specord 200.

[0206] The measurement parameters used are: Range: 190–1100 nm, Step size: 0.2 nm, Integration time: 0.04 s, Measurement mode: Step operation. The first step is the reference measurement (background). A quartz plate attached to a sample holder (dimensions of the quartz plate: approx. 6 x 7 cm, thickness approx. 2.3 mm) is placed in the sample beam path and measured against air.

[0207] The sample measurement then takes place. A quartz plate attached to the sample holder, bearing a sample layer approximately 1 mm thick, is placed in the sample beam path and measured against air. Internal billing against WA12411S / WI

[0208] 35

[0209] The background spectrum provides the transmission spectrum of the sample.

[0210] Molecule compositions:

[0211] The molecular compositions are determined by nuclear magnetic resonance spectroscopy (for terminology see ASTM E 386: High-resolution nuclear magnetic resonance spectroscopy (NMR) : Terms and symbols), whereby the 1 H-core and the 29 The silicon core is being measured.

[0212] Description ^-H-NMR measurement

[0213] Solvent: CDC13, 99, 8%d

[0214] Sample concentration: approx. 50 mg / 1 ml CDC13 in 5 mm NMR-

[0215] tube

[0216] Measurement without the addition of TMS, spectral reference of residual CHC13 to CDC13 at 7.24 ppm

[0217] Spectrometer: Bruker Avance I 500 or Bruker Avance HD 500 Sample head: 5 mm BBO sample head or SMART sample head (Company:

[0218] Bruker)

[0219] Measurement parameters:

[0220] Pulprog = zg30

[0221] TD = 64k

[0222] NS = 64 or 128 (depending on the sensitivity of the probe head)

[0223] SW = 20.6 ppm

[0224] AQ = 3.17 s

[0225] dl = 5 s

[0226] SFO1 = 500.13 MHz

[0227] 01 = 6.175 ppm WA12411S / WI

[0228] 36

[0229] Processing parameters:

[0230] SI = 32k

[0231] WDW = EM

[0232] LB = 0.3 Hz

[0233] Depending on the type of spectrometer used, individual adjustments to the measurement parameters may be necessary.

[0234] Description 29 Si-NMR measurement

[0235] Solvent: C6D6 99.8%d / CC14 1:1 v / v with l% by weight

[0236] Cr(acac)a as a relaxation reagent

[0237] Sample concentration: approx. 2 g / 1.5 ml solvent in 10 mm NMR-

[0238] tube

[0239] Spectrometer: Bruker Avance 300

[0240] Sample head: 10 mm 1H / 13C / 15N / 29S1 glass-free QNP sample head

[0241] (Bruker company)

[0242] Measurement parameters:

[0243] Pulprog = zgig60

[0244] TD = 64k

[0245] NS = 1024 (depending on the sensitivity of the probe head)

[0246] SW = 200 ppm

[0247] AQ = 2.75 s

[0248] dl = 4 s

[0249] SFO1 = 300.13 MHz

[0250] 01 = -50 ppm

[0251] Processing parameters:

[0252] SI = 64k

[0253] WDW = EM

[0254] LB = 0.3 Hz

[0255] Depending on the type of spectrometer used, individual adjustments to the measurement parameters may be necessary. WA12411S / WI

[0256] 37

[0257] Molecular weight distributions:

[0258] Molecular weight distributions are determined as weight mean Mw and number mean Mn using gel permeation chromatography (GPC or size exclusion chromatography (SEC)) with a polystyrene standard and refractive index detector (RI detector). Unless otherwise specified, THE is used as the eluent and DIN 55672-1 is applied. The polydispersity is the quotient Mw / Mn.

[0259] Glass transition temperatures:

[0260] The glass transition temperature is determined by differential scanning calorimetry (DSC) according to DIN 53765, perforated crucible, heating rate 10 K / min.

[0261] Determination of particle size:

[0262] Particle sizes were measured using the Dynamic Light Scattering (DLS) method, with determination of the zeta potential. The following equipment and reagents were used for the analysis: 10 x 10 x 45 mm polystyrene cuvettes, single-use Pasteur pipettes, and ultrapure water.

[0263] The sample to be measured is homogenized and filled into the measuring cuvette without bubbles.

[0264] The measurement is performed at 25°C after an equilibration time of 300s with high resolution and automatic measurement time setting.

[0265] The values ​​given always refer to the value D(50). D(50) is to be understood as the volume-averaged particle diameter, where 50% of all measured particles have a volume-averaged diameter smaller than the stated value D(50).

[0266] D(90) is to be understood as the volume-averaged particle diameter at which 90% of all measured particles have a WA12411S / WI

[0267] 38 volume-averaged diameters smaller than the stated value D(90).

[0268] D(99) is to be understood as the volume-averaged particle diameter, where 99% of all measured particles have a volume-averaged diameter smaller than the stated value D(99).

[0269] Determination of dielectric properties: Df, Dk

[0270] The dielectric properties are determined according to IPC TM 650 2.5.5.13 using a network analyzer.

[0271] Keysight / Agilent E8361A using the split-cylinder resonator method at 10 GHz.

[0272] Microscopy procedure: the micro- / nanostructure was characterized using light microscopy or transmission electron microscopy.

[0273] Light microscopy:

[0274] Sample preparation: Place 1 drop of undiluted sample onto a microscope slide; cover with a coverslip.

[0275] Device: LEICA DMRXA2 with CCD camera LEICA DFC420 (2592x1944 pixels)

[0276] Image: Transmitted light - interference contrast, various magnification levels

[0277] Transmission electron microscopy: Sample preparation: 1 drop of sample (dilution 1:20, adjustment necessary if required) onto coated TEM grid; addition of a contrast agent if required; drying at room temperature

[0278] Device: ZEISS LIBRA 120 with Sharp Eye CCD camera (1024x1024 pixels)

[0279] Figure: Excitation voltage 120 kV; TEM bright field; various magnification levels WA12411S / WI

[0280] 39

[0281] High-pressure homogenizer:

[0282] The high-pressure homogenizers used were those from HST, a company belonging to the Krones Group. The HST HL1 homogenizer, equipped with three different homogenizing valves, was used as a pilot unit with a throughput of up to 50 liters per hour. These included a homogenizing valve according to the invention as described in the text, and the two homogenizing valves NE1 and NE2, which are not according to the invention. As a further modification, only polytetrafluoroethylene (PTFE) seals were used on the unit. Otherwise, the unit was used as offered by HST in its standard configuration.

[0283] HST used the HL 3 high-pressure homogenizer for production scale, which was equipped with homogenizing valves identical in design to those used in the experiments for the HL 1 high-pressure homogenizer, although these were adapted in their dimensions for operation with a throughput of up to 1500 1 / h.

[0284] In all examples, water is always fully demineralized water, unless explicitly stated otherwise.

[0285] Example 1:

[0286] Comparison of the inventive preparation of a preparation using three different methods for producing the preemulsion with a non-inventive method.

[0287] In both cases, the HST high-pressure homogenizer HL1 is used, in the case according to the invention with the homogenizing valve according to the invention, and in the case not according to the invention with the homogenizing valve NE1.

[0288] The homogenizing valve according to the invention uses a valve piston with the geometry and dimensions shown in Figure 4, combined with the WA12411S / WI shown in Figure 5.

[0289] The valve seat described in section 40 is described. The numerical specifications describing the dimensions of the two components are in mm.

[0290] The following preparation components were used for the preemulsion in the specified quantities, the result of which

[0291] The composition corresponds quite closely to the miniemulsion composition according to Example 4 of US 2018 / 0305576 according to the invention, with the difference that in the present case

[0292] In this case, instead of using sodium dodecyl sulfate alone as an emulsifier, a preparation of sodium dodecyl sulfate and ethanol was used. According to Example 4 of the invention in US 2018 / 0305576, a rotor-stator system is used for homogenization. WA12411S / WI

[0293] 41

[0294] The components are used to produce preemulsions in three different ways:

[0295] 1. Mix all water-soluble components. Mix all monomer-soluble or monomer-dispersible components. Combine the aqueous solution and the monomer solution.

[0296] 2. Mix all water-soluble components. Add the organic components to the aqueous solution.

[0297] 3. Any mixture of components without regard to solubilities

[0298] In detail, the procedure in point 1, using an example with specific mass specifications for the components, looked like this: In a 1 m 3453.15 kg of water are placed in a stirred tank at 23°C and 1013 mbar. To this are added 168.58 kg of aqueous sodium dodecyl sulfate ethanol solution, containing 15% sodium dodecyl sulfate (25.29 kg) and 1.1% ethanol (1.85 kg), 141.44 kg of water, 4.89 kg of 2% hydroquinone monomethyl ether solution, and 13.49 kg of methacrylic acid. The components are stirred with an anchor stirrer for 30 minutes at 30 revolutions per minute until a clear solution is obtained.

[0299] Into a second 1 m 3 Stirred at 23°C and 1013 mbar, 402.58 kg of polyorganosiloxane solution in butyl methacrylate, 396.84 kg butyl acrylate, 191.68 kg methyl methacrylate, 49.56 kg styrene, and 5.06 kg hexadecane are added. This WA12411S / WI is also stirred.

[0300] 42

[0301] Mix for 30 minutes with an anchor stirrer at 30 revolutions per minute and obtains a slightly cloudy mixture.

[0302] The two preparations are cooked in 2 m 3A stirrer with an anchor stirrer is pumped, with the aqueous solution first being completely transferred into the stirrer. The stirrer is then started. The preparation of organic monomers and polyorganosiloxane is then pumped in. A milky white preparation is obtained, which is stirred for 30 minutes at 23 °C and 1013 mbar at 30 revolutions per minute. The stirrer is then switched off. The resulting milky preparation retains its appearance unchanged for 3 hours. After this time, a clear phase begins to separate from the milky phase. By stirring again, the two phases can be recombined and separate again within a few hours upon standing. => Preparation 1.1

[0303] The procedure for 2. corresponds to that described for 1., with the difference that the aqueous phase is in a 2 m 3The aqueous solution is prepared using an agitator with an anchor stirrer. The other components are then added to this aqueous solution in the order and quantities specified above, while stirring at 30 revolutions per minute. This also results in a milky preparation, which separates within a few hours of standing still, recognizable by the formation of a clear second phase alongside the milky phase. => Preparation 1.2

[0304] The procedure for step 3 corresponds to that described for step 2, with the difference that the individual components are added together in the quantities already specified for steps 1 and 2, while stirring, in the following order:

[0305] Water

[0306] Methacrylic acid Methyl methacrylate solution Polydimethylsiloxane in butyl methacrylate WA12411S / WI

[0307] 43

[0308] Sodium dodecyl sulfate solution with ethanol, butyl acrylate

[0309] Solution hydroquinone monomethyl ether styrene

[0310] Hexadecan

[0311] Methacrylic acid

[0312] This method also yields a milky preparation, which, upon standing undisturbed for a few hours, begins to separate into a second clear phase alongside the milky one. Preparation in this case takes no longer than in methods 1 and 2 because all solid components were already pre-dissolved. => Preparation 1.3

[0313] Of the quantities of preemulsion obtained, 50% were homogenized in the manner according to the invention, i.e. using a homogenizing valve according to the invention and applying the method according to the invention in all described steps, and 50% were homogenized in a non-inventive manner using a non-inventive homogenizing valve.

[0314] To demonstrate that pressure alone is not a sufficient criterion for the effectiveness of the homogenization process, all homogenization trials were conducted in the ideal pressure range between 600 and 900 bar, specifically at 700 bar. The high-pressure homogenizer was at room temperature (23°C) at the time of product entry. The heat input into the preparations during the homogenization process increased the product temperature to 36–42°C. The throughput through the homogenizer was 1500 units / hour, so that the approximately 800 kg of preparation for each of the inventive and non-inventive methods passed completely through the high-pressure homogenizer within 32–35 minutes.

[0315] The homogenizer was operated according to the manufacturer's instructions. Each preemulsion was tested once before and once after the storage period WA12411S / WI.

[0316] 44 samples, each lasting 6 weeks, were passed through the high-pressure homogenizer at 23°C, as per the inventive process. The viscosity of the preemulsions upon entering the homogenizer was: 1.1: 123 mPas, 1.2: 136 mPas, 1.3: 132 mPas. The following results were obtained:

[0317] The viscosities given in this example were all measured at a rotational speed of 0.89 1 / min.

[0318] Inventive procedure:

[0319] From preparation 1.1, an emulsion with the following properties was obtained:

[0320] Viscosity: 46,000 mPas

[0321] Particle size distribution:

[0322] A single peak is obtained at 177 nm. The peak's full width at half maximum (FWHM) is 57.55 nm. D50 = 157 nm, Dgo = 266 nm, Dgg = 358 nm

[0323] Distribution of the silicone resin according to transmission electron microscopy (TEM):

[0324] Figure 6 shows light gray areas attributable to organic monomers and dark gray to almost black areas attributable to polyorganosiloxane. A uniform distribution of the dark gray polyorganosiloxane components within the lighter gray organic components is evident. The particles appear as core-shell structures with a darker core of polyorganosiloxane around which the lighter gray organic components are grouped. Water is present between these components, but some of it evaporates due to the vacuum technology used in TEM imaging, resulting in WA12411S / WI.

[0325] 45 Partial coalescence is indicated, which, however, is a technology-related artifact known to experts and not a property of the preparation.

[0326] From preparation 1.2, an emulsion with the following properties was obtained:

[0327] Viscosity: 48,000 mPas

[0328] Particle size distribution:

[0329] A single peak is obtained at 159.9 nm. The peak's half-width is 49.09 nm.

[0330] D50 = 139 nm Dgo = 234 nm Dgg = 325 nm

[0331] Distribution of the silicone resin according to transmission electron microscopy (TEM):

[0332] By analogous interpretation of the TEM image in Figure 7 as for preparation 1.1 and according to the inventive procedure, a homogeneous distribution of the polyorganosiloxane and the organic components is recognizable.

[0333] From preparation 1.3, an emulsion with the following properties was obtained:

[0334] Viscosity: 45,000 mPas

[0335] Particle size distribution:

[0336] A single peak is obtained at 166.8 nm. The peak's half-width is 53.05 nm.

[0337] D50 = 168 nm Dgg = 268 nm Dgg = 356 nm WA12411S / WI

[0338] 46

[0339] Distribution of the silicone resin according to

[0340] Transmission electron microscopy (TEM):

[0341] By analogous interpretation of the TEM image in Figure 8 as for preparation 1.1 and the procedure according to the invention, a homogeneous distribution of the polyorganosiloxane and the organic components is recognizable.

[0342] Non-inventive procedure with homogenizing valve NE1 :

[0343] From preparation 1.1, an emulsion with the following properties was obtained:

[0344] Viscosity: 8,000 mPas

[0345] Particle size distribution:

[0346] Two overlapping peaks of comparable intensity are obtained at 158.5 nm and 361.1 nm. Due to the overlap, a full width at half maximum (FWHM) cannot be specified for each peak.

[0347] D50 = 316 nm

[0348] Dgo = 607 nm

[0349] Dgg = 822 nm

[0350] Distribution of the silicone resin according to transmission electron microscopy (TEM):

[0351] Figure 9 shows a significantly more inhomogeneous distribution of the light and dark grey areas, with a significantly stronger accumulation of the polyorganosiloxane in the overall larger particles.

[0352] From preparation 1.2, an emulsion with the following properties was obtained: WA12411S / WI

[0353] 47

[0354] Viscosity: 27,000 mPas

[0355] Particle size distribution:

[0356] A peak is obtained at 194.6 nm with a half-width of 51.55 nm.

[0357] D50 = 190 nm

[0358] Dgo = 286 nm

[0359] Dgg = 377 nm

[0360] The particle size distribution in this procedure corresponds to the particle size distribution in the procedure according to the invention. Therefore, one might conclude that the result is equivalent to the procedure according to the invention. However, electron microscopy, which shows the distribution of the polysiloxane and the organic components, reveals that this is not the case.

[0361] Furthermore, a difference from the inventive method is revealed here in that the inventive method is insensitive to the procedure used in the preparation of the preemulsion. The preparation of the preemulsion is the only difference between preparation 1.1 and preparation 1.2. Such susceptibility of the result to individual parameters is disadvantageous in everyday operation.

[0362] Distribution of the silicone resin according to transmission electron microscopy (TEM):

[0363] In accordance with the differences in particle size distribution between preparation 1.1 and preparation 1.2 observed in non-inventive procedures, preparation 1.2 also shows a better distribution of the polysiloxane with 1.2 than with 1.1 in the TEM image in Figure 10. However, the distribution of the polysiloxane does not reach the quality achieved with preparation 1.2 in WA12411S / WI.

[0364] 48 according to the inventive method. This also means that in preparation 1.2, after homogenization with the non-inventive valve NE1, larger polysiloxane enrichments are found than in the inventive method.

[0365] From preparation 1.3, an emulsion with the following properties was obtained: viscosity: 12,000 mPas

[0366] Particle size distribution:

[0367] Two separately resolved peaks are obtained: one at 76.22 nm with a full width at half maximum (FWHM) of 9.8 nm and the other at 264.0 nm with a FWHM of 71.12 nm. The peak intensities differ significantly, with the peak at 76.22 nm exhibiting an intensity of 6.7% and the peak at 264 nm having an intensity of 93.3%.

[0368] D50 = 250 nm

[0369] Dgo = 390 nm Dgg = 513 nm

[0370] Distribution of the silicone resin according to transmission electron microscopy (TEM):

[0371] Figure 11 again shows a more inhomogeneous distribution of the light and dark grey areas, with a significantly stronger accumulation of polyorganosiloxane.

[0372] In non-inventive procedures, three clearly distinguishable homogenization results are obtained using three different methods for producing the preemulsion. These differ particularly with regard to the particle size distribution. The differences in viscosity observed in non-inventive procedures are interpreted as a consequence of the differences in particle size and particle size distribution. The distribution of WA12411S / WI

[0373] 49

[0374] Polysiloxane is produced significantly less uniformly using methods other than those according to the invention. Using methods other than those according to the invention, the preemulsion produced according to methods 1 and 2 yields the best results. In contrast, the method according to the invention is robust and, regardless of the method used to prepare the preemulsion, provides a consistent result with respect to the uniformity of the polyorganosiloxane distribution, particle size distribution, and viscosity.

[0375] This example demonstrates that the production of a finely divided emulsion or miniemulsion with a homogeneous distribution of the polyorganosiloxane, as required for the successful implementation of the invention according to US 2018 / 0305576, is possible, but only by using the inventive method discovered here as a novel process.

[0376] All emulsions produced according to the invention are storage-stable, i.e., they do not separate into macroscopically recognizable phases even after more than 6 months of storage, and neither the particle size distributions nor the silicon distributions change during storage. Emulsions not produced according to the invention show the formation of a clear second phase alongside the milky-white emulsion phase after only 4 weeks. This formation progresses over time; that is, the clear phase increases in size while the milky phase decreases. After approximately 6 months, the clear phase comprises about 1 / 3 of the total preparation volume.

[0377] In US 2018 / 0305576, no example uses a high-pressure homogenizer to produce a miniemulsion.

[0378] Example 2:

[0379] Comparative example: Try preparations 1.1, 1.2 and

[0380] 1. 3 to homogenize with the homogenizing valve NE2. WA12411S / WI

[0381] 50

[0382] Preparations 1.1, 1.2, and 1.3 are produced as described in Example 1. In contrast to Example 1, the HST homogenizer HL1 is equipped with the homogenizing valve NE2, and different pressures are used. Furthermore, each preemulsion is passed through the high-pressure homogenizer once before and once after storage according to the inventive method, as described in Example 1. The table summarizes the homogenization results. WA12411S / WI

[0383] 51

[0384] As the experimental results show, a stable emulsion could not be obtained in any case. However, as Example 1 has already demonstrated, the composition of the preparations is suitable for producing a stable emulsion, regardless of the method used to prepare the preemulsion. In particular, Example 1 showed that this is possible with the high-pressure homogenizer used, so that a lack of suitability of the chosen device can be ruled out. This example also demonstrated that it is not sufficient to increase the homogenization pressure to improve the homogenization result, as the prior art suggests. Rather, in this case, better, albeit unsuitable because unstable, homogenization results are found at lower pressures.

[0385] In all cases where an emulsion was obtained after passage through the high-pressure homogenizer that was stable long enough to allow particle size measurement, multimodal particle size distributions were found, exhibiting several resolvable peaks in the range of 90 nm to 10,000 nm, indicating a recognizable coarse fraction in the pm range. This inhomogeneity is understood to be the cause of the low stability of the obtained emulsions. Due to particle fusion, macroscopically separated phases form after a relatively short storage time, as is also the case with the preemulsions. A distribution of WA12411S / WI

[0386] 52

[0387] Polyorganosiloxane could not be determined in the samples obtained due to their insufficient stability.

[0388] If only this variant of the high-pressure homogenizer had been available as a homogenizing unit to produce the miniemulsion according to Example 4 of the invention in US 2018 / 0305576, the invention described therein would not have been achieved.

[0389] Example 3:

[0390] Non-inventive comparative example: Attempt at homogenization without ethanol in preparations 1.1, 1.2 and 1.3.

[0391] Preparations 1.1, 1.2, and 1.3, which were prepared analogously to those in Example 1 with the exception that no ethanol was used and the same amount of water was used in the aqueous solution of sodium dodecyl sulfate instead of ethanol, were otherwise treated in the same way as described in Example 1. Since the condition that a non-ionic emulsifying agent must be present is not met, both procedures, with and without a homogenizing valve according to the invention, are not in accordance with the invention, even when all steps of the process according to the invention are applied.

[0392] In no case was a stable emulsion obtained. After the second pass through the high-pressure homogenizer, unstable emulsions were obtained, all of which began to separate within a few days, recognizable by the formation of a clear second phase.

[0393] For comparison, the preemulsions 1.1, 1.2, and 1.3 of this Example 3 were passed through a pilot-scale high-pressure homogenizer without ethanol in the preparation, with a maximum throughput of 50 1 / h instead of a production-scale high-pressure homogenizer with 1500 1 / h. In this case, a radial valve as shown in Figure 12 WA12411S / WI was used.

[0394] The geometries specified in sections 53 and 13 were used. In all cases, a stable miniemulsion was obtained after one pass through the high-pressure homogenizer, exhibiting a particle size distribution with only one peak and a particle size of D50 < 200 nm. This means that the storage steps followed by another pass through the high-pressure homogenizer are not necessary in this case. When preparations 1.1, 1.2, and 1.3 are used with ethanol, this result remains unchanged when the high-pressure homogenizer is used at a pilot scale with a throughput of 50 1 / h. This indicates that the pilot scale is significantly more robust and easier to implement than the production scale. Therefore, it is reasonable to assume that the prior art, which did not recognize this problem, was limited to the pilot scale and neglected the production scale.

Claims

WA12411S / WI 54 Claims Claim 1 Method for homogenizing an acidic aqueous preparation, comprising the following components: A) at least one organic monomer which is emulsifiable or self-emulsifying in water, B) at least one liquid or water-soluble or dispersible polyorganosiloxane in the at least one organic monomer A), composed of repeating units of the general formula (II) , [R-'-b (OR 2 ) cS 10 ( 4 -bc ) / 2 ] (II) where R 1 is the same or different, and means hydrogen or a Si-C-bonded Cl-C18 hydrocarbon residue in which C atoms not sitting next to each other in the chain can be substituted by heteroatoms, so that organofunctional residues are present which can also be ethylene unsaturated, R 2is the same or different and hydrogen or Cl to C12 hydrocarbon residues can be residues and b and c each represent an integer, where b can take the values ​​0, 1, 2 and 3 and c can take the values ​​0, 1 and 2 and the sum b + c = 0, 1, 2 or 3, C) at least one emulsifier preparation (C) comprising at least one ionic component selected from an anionic surfactant and a cationic surfactant, and at least one non-ionic component comprising a WA12411S / WI 55 may be a non-ionic surfactant or a monohydric aliphatic, cycloaliphatic or aromatic alcohol of formula (III) , R 3 -0H (III) , where R 3means a monovalent aliphatic, linear branched or cyclic hydrocarbon residue with 2 to 8 carbon atoms or an aromatic hydrocarbon residue with 6 to 8 carbon atoms, wherein there is an excess of ionic component over the non-ionic component, D) optionally at least one partially or completely soluble organic monomer in a quantity not exceeding 5% by weight of the total mass of all components A) to F), where partially or completely soluble means that a solubility of more than 10% by weight in water is given, E) optionally at least one liquid excipient, and F) Water, wherein the procedure comprises the following steps in the specified order: 1) Mix all components A) to F) , 2) Preparation of a preemulsion by stirring, 3) Homogenizing the preemulsion using a high-pressure homogenizer equipped with a WA12411S / WI 56 Homogenizing valve comprising a flat valve seat (1) comprising an opening (A), a valve plunger (2) and an impact ring (3), wherein the impact ring (3) is arranged on the valve seat (1) and rotationally symmetrical about its opening (A), and a valve housing which encloses the valve seat (1), valve plunger (2) and impact ring (3), wherein the valve plunger (2) has a conical taper (2') which projects into the opening (A) of the valve seat and the valve plunger (2) and valve seat (1) are rotationally symmetric and arranged such that a radial throttle is formed between them, which forms a homogenizing gap (B), with homogenization taking place under pressure, 4) Maturation of the preparation obtained from step 3) by storage at a temperature of 15 - 28 °C for a period of at least 6 weeks, and 5) Homogenize the matured preparation from step 4) using the high-pressure homogenizer from step 3) under pressure. Claim 2 Method according to claim 1, wherein the conical taper of the valve plunger (2 ') has a taper in the range of a=10-25° . Claim 3 Method according to claim 1 or 2, wherein the throughput of the preparation to be homogenized is more than 100 1 / h. Claim 4 WA12411S / WI 57 A method according to any of the preceding claims, wherein the at least one organic monomer (A) is selected from the group consisting of unreactive solvents, vinyl esters, (meth)acrylic acid esters, vinyl aromatics, olefins, 1,3-dienes, vinyl ethers, vinyl halides, mono-, di- or polycarboxylic acids and their diesters and anhydrides, aliphatic, cycloaliphatic or aromatic mono-, di- or polyols, ethylene unsaturated carboxylic acid amides and nitriles, mono- and diesters of fumaric acid and maleic acid and their anhydrides, polyethylene unsaturated comonomers, post-crosslinking comonomers, alkyl ethers or esters of N-methylolacrylamide, N-methylolmethacrylamide and N-methylolallylcarbamate and epoxide-functional monomers. Claim 5 A method according to any of the preceding claims, wherein the at least one organic monomer (A) is selected from the group consisting of vinyl esters, acrylic esters, methacrylic esters, vinyl aromatics, vinyl halogens, monomeric olefins and monomers A) of formula (IV) in which R 4 , R 5 , R 6 , R 7 and R 8 independently of each other, they mean a hydrogen radical, a hydrocarbon group, or a hydrocarbon group substituted with foreign atoms. WA12411S / WI 58 Claim 6 Method according to one of the preceding claims, wherein the at least one organic monomer (A) is selected from the group consisting of acrylic acid esters and methacrylic acid esters of unbranched or branched alcohols having 1 to 15 C atoms. Claim 7 The method of claim 6, wherein the at least one organic monomer (A) is selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate and norbornyl acrylate. Claim 8 A method according to any one of the preceding claims, wherein the anionic surfactant in component C) is selected from the group consisting of alkyl sulfonates, sulfonates, alkali and ammonium salts of carboxylic acids with 8 to 20 carbon atoms in the alkyl, aryl, alkaryl or aralkyl residue, phosphoric acid partial esters and their alkali and ammonium salts, and / or wherein the nonionic surfactant is selected from the group consisting of polyvinyl alcohol, which still has 5 to 50% vinyl acetate units with a degree of polymerization of 500 to 3000, alkyl polyglycol ethers, alkyl aryl polyglycol ethers, ethylene oxide / propylene oxide (EO / PO) block copolymers, addition products of alkylamines with alkyl residues of 8 to 22 carbon atoms with ethylene oxide or propylene oxide, fatty acids with 6 to 24 C atoms, alkyl polyglycosides of the general formula R*-O-Z o , wherein R* WA12411S / WI 59 a linear or branched, saturated or unsaturated alkyl group with on average 8 - 24 C atoms and Z o an oligoglycoside residue with on average o = 1 - 10 hexose or pentose units or mixtures thereof, natural substances and their derivatives, such as lecithin, lanolin, saponins, cellulose; cellulose alkyl ethers and carboxyalkyl celluloses, whose alkyl groups each possess up to 4 carbon atoms, linear organo(poly)siloxanes containing polar groups, and / or wherein the cationic surfactant is selected from the group consisting of salts of primary, secondary and tertiary fatty amines with 8 to 24 carbon atoms with acetic acid, sulfuric acid, hydrochloric acid and phosphoric acids, quaternary alkyl and alkylbenzeneammonium salts, alkylpyridinium, alkylimidazolinium and alkyloxazolinium salts. Claim 9 Method according to one of the preceding claims, wherein the ionic component in component C) is sodium dodecyl sulfate and the non-ionic component in component C) is a monohydric aliphatic alcohol. Claim 10 Method according to one of the preceding claims, wherein the pressure in step 3) or in step 5) is 400 bar to 1000 bar. Claim 11 Method according to one of the preceding claims, wherein the proportion of component (A) is 5-45 percent by weight of the total aqueous preparation as 100%. WA12411S / WI 60 Claim 12 Method according to any one of the preceding claims, wherein the The proportion of component (B) is 3-20% by weight of the total aqueous preparation, which is less than 100%. Claim 13 Method according to one of the preceding claims, wherein the proportion of component (C) is 0.5-8 percent by weight of the total aqueous preparation as 100%. Claim 14 Homogenized preparation obtainable by a method according to any of the preceding claims.

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