Silicone (meth)acrylate particles, processes for their preparation and use thereof

Abstract

Particles obtainable by polymerization of a siloxane which has at least one (meth)acrylate group of the formula (I)
—O—C(O)—CR═CH.sub.2  (I)
where R=—H or —CH.sub.3, which are characterized in that the siloxane has an average molar ratio of groups of the formula (I) to Si atoms of less than 0.1 are provided.

Claims

1. A process for producing silicone (meth)acrylate particles, said process comprising: a) producing an emulsion of an aqueous phase and an organic phase, wherein the organic phase has at least one radical initiator and at least one siloxane having at least one (meth)acrylate group of formula (I)
—O—C(O)—CR═CH.sub.2  (I) where R=—H or —CH.sub.3, with the addition of at least one solid-body emulsifier and mixing of the two phases, where the organic phase forms an inner phase of the emulsion, and b) fully polymerizing the inner phase of the emulsion in the presence of a radical initiator which is more soluble in the organic phase than in the aqueous phase, wherein the at least one siloxane has an average molar ratio of groups of formula (I) to Si atoms of less than 0.1; wherein the at least one siloxane is a compound of formula (II): ##STR00004## wherein R.sup.1 is a methyl radical; R.sup.2 is independently selected, for each occurrence in Formula (II), from radicals having the formula —(CH.sub.2).sub.3—O—CH.sub.2—CH(OH)—CH.sub.2—O—C(O)—CH.sub.3; R.sup.3 is independently selected, for each occurrence in Formula (II), from a methyl radical or radicals that have a group according to formula (I); R′ is independently selected from groups according to formula (I); a=9 to 250; b=0 to 20; c=0 to 20; and with the proviso that, per siloxane of formula (II), if c=0, at least one radical R.sup.3 is present which has a group according to formula (I).

2. The process according to claim 1, wherein the radical initiator is added in a concentration of 0.05 to 2% by weight, based on the inner phase of the emulsion.

3. The process according to claim 1, wherein the solid-body emulsifier has an average particle size d.sub.50 of >100 nm to 200 nm.

4. The process according to claim 1, wherein the solid-body emulsifiers are selected from metal oxides, mixed oxides, nitrides, hydroxides, carbonates and silicates which are at least (partially)hydrophobicized with at least one compound selected from the group consisting of silanes, siloxanes, quaternary ammonium compounds, cationic polymers and fatty acids or anions thereof.

5. The process according to claim 1, wherein the at least siloxane having at least one (meth)acrylate group of formula (I) contains said group in the form of a radical selected from at least one of ##STR00005## ##STR00006## where R.sup.4 is hydrogen or a methyl group.

6. The process according to claim 5, wherein the radical is selected formulae (Ib) and (Ie).

7. The process according to claim 1, wherein the variable a is from 50 to 220.

8. The process according to claim 1, wherein the variable c is a value from 4 to 12, or c=0 and all of the radicals R.sup.3 are those radicals which have a group according to formula (I).

9. The process according to claim 1, wherein the organic phase contains substances which can be released from the silicone (methacrylate) particles, wherein said substances which can be released are selected from cosmetic oils, fragrances, silver and silver-containing compounds, dyes, and preservatives.

10. A composition of matter comprising the particles according to claim 1.

11. The composition of matter according to claim 10, wherein the particles are dispersed in an aqueous or an organic media.

12. The process according to claim 1, wherein the at least one siloxane has an average molar ratio of groups of formula (I) to Si atoms of 0.02 to 0.08.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) The particles according to the invention, and their preparation and uses are described below by way of example without any intention of limiting the invention to these exemplary embodiments.

(2) When ranges, general formulae or compound classes are specified hereinafter, these shall include not just the corresponding ranges or groups of compounds that are explicitly mentioned but also all sub-ranges and sub-groups of compounds which can be obtained by removing individual values (ranges) or compounds. Where documents are cited in the context of the present description, it is intended that their content fully form part of the disclosure content of the present invention. Where, in the context of the present invention, compounds, such as e.g., organomodified polysiloxanes, are described which can have different units multiple times, then these can occur in random distribution (random oligomer or polymer) or arranged (block oligomer or block polymer) in these compounds. Percentages are by weight, unless otherwise stated. Average values referred to hereinbelow are number averages, unless otherwise stated. Where material properties are given below, such as e.g., viscosities or the like, then, unless stated otherwise, these are the material properties at 25° C. If parameters are given below which have been determined by measurement, then, unless stated otherwise, the measurements have been carried out at a temperature of 25° C. and a pressure of 101.325 Pa. When chemical (empirical) formulae are used in the present invention, the reported indices can be not only absolute numbers but also average values. Indices relating to polymeric compounds are preferably average values.

(3) The process according to the invention comprises the steps: a) Producing an emulsion of an aqueous phase and of an organic phase, wherein the organic phase has at least one radical initiator and a siloxane which has at least one (meth)acrylate group of formula (I)
—O—C(O)—CR═CH.sub.2  (I)
where R=—H or —CH.sub.3, preferably —CH.sub.3,
with the addition of at least one solid-body emulsifier and mixing the two phases, where the organic phase forms the inner phase of the emulsion, and b) fully polymerizing the inner phase in the presence of a radical initiator which is more soluble in the organic phase than in the aqueous phase, characterized in that the siloxane has an average molar ratio of groups of formula (I) to Si atoms of less than 0.1, preferably from 0.02 to 0.08.

(4) Preference is given to using a siloxane which satisfies formula (II)

(5) ##STR00001##
where
R.sup.1=identical or different alkyl radicals, preferably methyl radicals,
R.sup.2=identical or different radicals not the same as R′, R.sup.1 and R.sup.3 which have carbon atoms,
R.sup.3=identical or different radicals R.sup.1 or radicals which have at least one group according to formula (I),
R′=identical or different radicals which have at least one group according to formula (I),
a=9 to 250,
b=0 to 20, preferably 0 or 1, preferably 0,
c=0 to 20,
and with the proviso that per siloxane of formula (II), if c=0 at least one radical R.sup.3 is present which has at least one group according to formula (I). The numerical values for a, b and c are preferably statistical average values.

(6) Besides carbon atoms, the radicals R.sup.2 can also have one or more hydrogen, oxygen and silicone atoms. Preferably, the radicals R.sup.2 have no silicon atoms. Preferred radicals R.sup.2 are those which have an acetate group. Particularly preferred radicals R.sup.2 are those which satisfy the formula —(CH.sub.2).sub.3—O—CH.sub.2—CH(OH)—CH.sub.2—O—C(O)—CH.sub.3.

(7) Preferably, at least one siloxane of formula (II) in which variable ‘a’ assumes a value from 50 to 220, preferably from 75 to 180, is used in the process according to the invention.

(8) The siloxane used in the process according to the invention is preferably a siloxane of formula (II) in which variable ‘c’ assumes a value of 0 or 4 to 12, and all radicals R.sup.3 are those radicals which have a group according to formula (I).

(9) Siloxanes preferably used in the process according to the invention are those of formula (II) in which variable ‘a’ assumes a value of 75 to 180 and variable ‘c’ assumes a value of 4 to 12 or variable ‘a’ assumes a value of 50 to 130 and variable ‘c’=0 and at the same time all radicals R.sup.3 are those radicals which have a group according to formula (I). The value for variable ‘b’ in these preferred embodiments is preferably 0.

(10) Silicone (meth)acrylates which can be used are, for example, the product TEGO® RC 711,726, 902 and their methacrylate variants available from Evonik Industries AG.

(11) Siloxanes which have at least one (meth)acrylate group of formula (I) that are used preferably in the process according to the invention are those which have this in the form of a radical from the group of the radicals

(12) ##STR00002## ##STR00003##
where R.sup.4 is hydrogen or a methyl group, preferably a methyl group. More preferably, siloxanes which have at least one (meth)acrylate group of formula (I) are those which have this in the form of a radical selected from the group comprising the radicals with the formulae (Ib) and (Ie), where R.sup.4 is a methyl group.

(13) In the process according to the invention, the siloxanes containing at least one (meth)acrylate group of formula (I), in particular those of formula (II), can be used individually or as mixtures, in particular as statistical mixtures. In the process according to the invention, preference is given to using mixtures of siloxanes, in particular those of formula (II) in which the siloxanes differ as regards their structure and/or their molecular weight.

(14) By virtue of using (particulate) solid-body emulsifiers, the process according to the invention can be used to produce particles, in particular those of the core/shell type. Such particles have the polymerized siloxane in the core and the particulate emulsifiers as shell.

(15) It may be advantageous if, before step b), comonomers, in particular comonomers having ethylenically or vinylically unsaturated groups, are added to the organic phase. Such comonomers can be, e.g., mono- or poly-(meth) acrylated, organic mono- or oligomers, as are commercially available for example also under the group names LAROMER® (BASF AG), EBECRYL® (Cytec Surface Specialties) or DESMOLUX® (Bayer Material Science). Preference is given to using (meth)acrylates of long-chain fatty alcohols, such as, e.g., lauryl methacrylate, myristyl methacrylate, cetyl methyacrylate or stearyl methacrylate. Ethylenically mono- or polyunsaturated organic mono- or oligomers are to be understood as meaning organopolysiloxanes carrying ethylenically unsaturated, preferably vinylic groups. Preferably, the addition of the further comonomers takes place before step a).

(16) After the polymerization in step b) is complete, the organic comonomers can either be incorporated by covalent reaction into the polysiloxane (meth)acrylate network, or alternatively the organic comonomers can be present as an independent network. Mixed forms of these described limiting cases are likewise possible and form part of this invention.

(17) The solid-body emulsifiers used in the process according to the invention are preferably those which are selected from the group of (semi-)metal oxides, mixed oxides, nitrides, hydroxides, carbonates or silicates. Preferred solid-body emulsifiers have metal oxide and/or a semimetal oxide. Particularly preferred solid-body emulsifiers are based on silicon dioxide.

(18) In order to support the formation of an emulsion in which the inner phase is the organic phase, it may be advantageous to use those solid-body emulsifiers which have a contact angle of less than 90° at the water/organic phase interface in the process according to the invention. The contact angle can be determined as described by Bernard Paul Binks, Lucio Isa and Andrew Terhemen Tyowua in “Direct Measurement of Contact Angles of Silica Particles in Relation to Double Inversion of Pickering Emulsions” in document dx.doi.org/10.1021/la4006899 Langmuir 2013, 29, 4923-4927.

(19) It may be advantageous if solid-body emulsifiers are used which are hydrophobicized or partially hydrophobicized. Suitable hydrophobicizing agents are, e.g., compounds selected from the group of silanes, siloxanes, quaternary ammonium compounds, cationic polymers and fatty acids or anions thereof. If partially hydrophobicized solid-body emulsifiers are used, preference is given to using those which are not Janus particles (but have a uniform distribution of the hydrophobicized and non-hydrophobicized regions on the surface of the solid-body emulsifiers). Particularly preferred solid-body emulsifiers have silicon dioxide and are at least partially hydrophobicized, with preference being given to partially hydrophobicized particles which are not Janus particles.

(20) The solid-body emulsifiers used in the process according to the invention preferably have an average (volume-average) particle size (primary particle size) of >100 nm to <200 nm. The particle size of the solid-body emulsifiers can be determined in the known manner. The average primary particle size is preferably determined by dynamic light scattering. For this, for example, the ZetaSizer Nano ZSP from Malvern can be used. Alternatively, the particle size can be determined by the visual evaluation of an image created by transmission electron microscopy.

(21) The particulate emulsifiers (solid-body emulsifiers) can be used in the process according to the invention as they are or in the form of dispersions or sols, in particular aqueous dispersions or sols.

(22) The amount of particulate emulsifiers used is preferably 2 to 30% by weight, preferably 5 to 25% by weight, particularly preferably 7.5 to 20% by weight, based on the siloxanes used containing at least one (meth)acrylate group of formula (I).

(23) It may be advantageous if, in step a) of the process according to the invention, the preparation of the emulsion is carried out with the addition of one or more coemulsifiers. Coemulsifiers which can be used in the process according to the invention are in particular those compounds which interact with the solid-body emulsifier particles, preferably which, as a result of electrostatic interaction, attach evenly to the surface of the solid-body emulsifier particles and in so doing lead to a (partial) hydrophobicization of the emulsifier particles. In the process according to the invention, coemulsifiers which can be used are in particular compounds selected from the group of cationic surfactants. Cationic coemulsifiers which can be used are in particular cationic ammonium compounds. Such compounds are available, e.g., under the trade names VARISOFT® 470 P, VARISOFT® TC-90, VARISOFT® 110, VARISOFT® TA-100, ADOGEN® 442-100 P, ADOGEN® 432, ADOGEN® 470, ADOGEN® 471, ADOGEN® 464, VARIQUAT® K 300, VARIQUAT® B 343, VARIQUAT® 80 ME, REWOQUAT® 3690, REWOQUAT® WE 15, REWOQUAT® WE18, REWOQUAT® WE 28 or REWOQUAT® CR 3099 from Evonik Industries AG. In the process according to the invention, preference is given to using VARISOFT® TA-100 or VARISOFT® PATC (both available from Evonik Industries AG), particularly preferably VARISOFT® PATC as cationic coemulsifier. In the process according to the invention, even more preference is given to producing no silicone (meth)acrylate particles in whose preparation no cetyltrimethylammonium bromide or chloride is/has been used.

(24) Optionally, further components can be added to the organic phase in step a). The further components can be dissolved or dispersed in the organic phase or the mixture in step a). Based on the organic phase, the further components can preferably be present in a concentration of 0.01 to 99% by weight, preferably 0.1 to 80% by weight and particularly preferably from 1 to 50% by weight. Such further components can be functional components or non-functional components. Further components which can be used are in particular dispersible solids, such as, e.g., inorganic particles and/or fibres, such as, e.g., those of metal oxides, mixed oxides, nitrides, hydroxides, carbonates, silicates, pigments, carbon blacks, elements or alloys, and/or organic particles and/or fibres, such as, e.g., those of silicone resins, silicones or organic polymers or biopolymers, preferably with the proviso that the fillers are different from the emulsifiers used. Dispersible solids can for example be precipitated silica, diatomaceous earth (kieselgur), fumed silica, quartz flour, titanium dioxide, zinc oxide, cerium oxide, iron oxide, carbon black, graphite, carbon nanotubes or -fibres, alumosilicates, alkaline earth metal carbonates, aluminium trihydroxide, magnesium dihydroxide or other solids that are customary and known from the prior art, as well as each of the specified substances following surface modification with organosilicon compounds such as trimethyl chlorosilane, hexamethyl disilazane, (meth)acryloxypropyltrialkoxysilanes, aminopropyltrialkoxysilanes, polydimethylsiloxanes, polysiloxanes which carry Si—H groups, or pure carboxylic acids, chelating agents or fluoropolymers. These solids can serve, for example, as fillers for achieving certain mechanical properties, as UV stabilizers, as pigments, as antistatic additives or for achieving ferromagnetic properties.

(25) In the process according to the invention, the organic phase can also contain substances which can optionally be released from the particles, preferably over a prolonged period. Such substances may be, e.g., cosmetic oils and active ingredients, fragrances, pharmaceutical active ingredients, cosmetic active substances, antimicrobial active ingredients, also, for example, silver and silver-containing compounds, as well as dyes and preservatives.

(26) In some embodiments, it may be advantageous if in step a) of the process according to the invention the emulsion produced in step a) comprises 10 to 40% by weight of organic phase, particularly preferably 15 to 35% by weight, based on the emulsion.

(27) In other embodiments, it may be advantageous if in step a) of the process according to the invention an emulsion is generated whose average droplet size is adjusted from 0.01 to 1000 μm, preferably 0.1 to 500 μm and particularly preferably from 1 to 100 μm.

(28) In yet other embodiments, it may be particularly advantageous if in step a) of the process according to the invention the emulsion produced in step a) comprises 10-40% by weight of organic phase, particularly preferably 15-35% by weight, based on the emulsion, and the emulsion has an average droplet size of 0.01 to 1000 μm, preferably 0.1 to 500 μm and particularly preferably from 1 to 100 μm.

(29) The droplet size can be estimated with the assistance of a light microscope (up to about 1 μm as lower limit) by measuring the smallest and largest droplet diameter in each case in the field of vision; in this connection there should be at least 10×10 drops in the field of vision. Furthermore, it is possible to determine the droplet size distributions by means of the methods of statistical and dynamic light scattering familiar to the person skilled in the art. The MasterSizer 3000 from Malvern, for example, can be used for this purpose. This is also the case for dispersions of fully polymerized particles; moreover, the particle size can be determined by electron micrographs via SEM or TEM and is familiar to the person skilled in the art.

(30) Preferably, the emulsion in step a) is prepared by passing through the mixture comprising organic and aqueous phase and dispersing the mixture in at least one interaction chamber, preferably with a capillary thickness (internal diameter) of 50 to 500 μm, and preferably at a pressure of 50 to 1000 bar, preferably 100 to 800 bar, particularly preferably 200 to 600 bar and subsequent decompression of the mixture to ambient pressure, e.g., into a discharge reservoir. In this connection, preferably one of the aforementioned preferred droplet sizes is set. It may be advantageous if two or more serially connected interaction chambers are used. In this way, the desired droplet size can be adjusted more easily. The preparation of emulsions in interaction chambers is described in detail in U.S. Publication no. 2004-0063818 and DE 100 11 564, to which reference is expressly made. A suitable instrument for preparing the emulsions is supplied for example under the name Mikrofluidizer by Microfluidics.

(31) In order to obtain an emulsion with droplet sizes in the preferred range, the droplets of which preferably have a spherical morphology, in the event of the addition of coemulsifiers, it may be advantageous to only add the coemulsifier or the coemulsifiers after a preemulsion V1 has been prepared in a part step a1). This preemulsion V1, e.g., can be obtained by emulsifying a mixture of siloxanes comprising (meth)acrylate groups of formula (I), water and emulsifier, preferably particulate emulsifier and particularly preferably nanoparticulate SiO.sub.2 and even more preferably IDISIL Si5530 from Evonik Industries AG while applying strong shear forces, as is possible, e.g., with a rotor-rotor system. A suitable rotor-rotor system is supplied, e.g., as Co-Twister Homogenizer by Symex.

(32) It may be particularly advantageous if, before the preparation of the preemulsion V1 in a part step a0), the radical initiator required for the subsequent reaction is dissolved in the siloxane used containing (meth)acrylate groups of formula (I). Suitable solubility promoters can optionally be used for this purpose.

(33) To stabilize the preemulsion V1, the coemulsifier is added to this in a further part step a2). The coemulsifiers can be added as pure substance or in the form of a solution, e.g., an aqueous solution. By adding the coemulsifier to the preemulsion V1, the droplet size of the drops present in the preemulsion V1 can be quasi frozen. Droplet size distribution can thus be adjusted by the time of the addition of the cosurfactant. Inter alia, the droplet size distribution of the emulsion can be preadjusted by the addition amount of emulsifier and coemulsifier. Preferably, the weight ratio of particulate emulsifier to coemulsifiers is from 100:1 to 1:1, preferably from 50:1 to 3:1.

(34) The stabilized preemulsion V2 obtained in step a2) is then dispersed in step a3) in a homogenizer with interaction chamber. Preferably, the emulsion in step a) is produced by passing through the mixture comprising organic and aqueous phase and dispersing the mixture in at least one interaction chamber, preferably with a capillary thickness (internal diameter) of 50 to 500 μm, and preferably at a pressure of 50 to 1.000 bar, preferably 100 to 800 bar, particularly preferably 200 to 600 bar and subsequent decompression of the mixture to ambient pressure, e.g., into a discharge reservoir. In this regard, preferably one of the aforementioned preferred droplet sizes is set. It may be advantageous if two or more serially connected interaction chambers are used. In this way, the desired droplet size can be adjusted particularly easily. A suitable homogenizer is supplied, for example, under the name Mikrofluidizer by Microfluidics.

(35) Preferably, in step a3) of the process according to the invention, interaction chambers are used, of which at least one has a capillary thickness of 100 to 300 μm. In step a) of the process according to the invention, particular preference is given to using interaction chambers, of which at least one, preferably all, have at least one diverting bend.

(36) By virtue of carrying out part steps a1) to a3) and using a homogenizer with interaction chamber in part step a3), it is particularly easy to produce spherical droplets with a desired droplet size distribution.

(37) The polymerization of the emulsion prepared in process step a) is initiated in step b) by one of the radical initiators added to the emulsion which is characterized in that it is more soluble in the organic phase than in the aqueous phase. The radical initiator is preferably added in a concentration of 0.05 to 2% by weight, preferably 0.1 to 1% by weight and particularly preferably >0.15 to 0.6% by weight, based on the inner (organic) phase. As described above, it may be advantageous if the radical initiator used in process step b) is added to the organic phase before or during process step a). The full polymerization preferably takes place in the form of a suspension polymerization.

(38) Radical initiators which can be used are customary compounds suitable as radical initiators, preferably organic radical initiators. Preferably used radical initiators are those which form radicals by supplying thermal energy. Particularly preferably used radical initiators are those which, after the radical start, become compounds which are tolerable in cosmetic products, such as, e.g., hydrocarbons, alcohols or acids having 8 to 30 carbon atoms. Radical initiators which can be used are in particular peroxides which are derived from organic acids, in particular fatty acids. Among these compounds, which are also known as diacyl peroxides, preference is given to lauroyl peroxide (dilauroyl peroxide), decanoyl peroxide and isononanoyl peroxide. Particular preference is given to using dilauroyl peroxide as radical initiator. The initiation preferably takes place by increasing the temperature. The radical initiators used are preferably not redox systems. Optionally, it may be advantageous if the radical initiators are used in combination with radical transfer agents. Preferred radical transfer agents can be, e.g., acetylacetone, acetone or the like. Such systems are well known as radical initiators and are prior art in the field of emulsion polymerization.

(39) Process step b) is preferably carried out at elevated temperature. Preferably, process step b) is carried out with stirring and preferably under protective gas/inertization. Alternatively, the polymerization in step b) can be carried out in a conventional manner as described in the prior art.

(40) After carrying out polymerization step b), it may be advantageous to separate off the resulting particles from the suspension. For this, e.g., the water can be removed by customary methods, for example, by filtration or centrifugation. In order to increase the rate of the drying operation, it may be advantageous to wash the particles in one of the wash cycles, e.g., with ethanol.

(41) It may be advantageous if the particles are surface-modified after the synthesis. The surface modification can take place by customary methods. The surface modification can be carried out with organic and/or inorganic as well as with charged and/or uncharged substances.

(42) It may be particularly advantageous if the modifying agent has at least one functional group which can enter into a covalent, ionic or coordinate bond or hydrogen bridge bonds with the surface to be modified.

(43) Besides the at least one functional group which can enter into a bond with the surface of the core/shell silicone particle, the modifying agent can additionally have further radicals which modify the properties of the particles. Such radicals, or else parts thereof, can, for example, be hydrophobic or hydrophilic or carry one or more functional groups in order, in this way, to make the silicone particles compatible with the surrounding medium.

(44) The particles according to the invention obtainable by polymerization of a siloxane which has at least one (meth)acrylate group of formula (I)
—O—C(O)—CR═CH.sub.2  (I)
where R=—H or —CH.sub.3, are characterized in that the siloxane (used) has an average molar ratio of groups of formula (I) to Si atoms of less than 0.1. Preferably, the particles according to the invention are obtainable by a process as described above.

(45) Preferably, the particles according to the invention are obtainable by a process comprising the steps:

(46) Producing an emulsion from an aqueous phase and an organic phase, wherein the organic phase has at least one siloxane which has at least one (meth)acrylate group of formula (I)
—O—C(O)—CR═CH.sub.2  (I)
where R=—H or —CH.sub.3,
with the addition of at least one solid-body emulsifier and mixing of the two phases, where the organic phase forms the inner phase of the emulsion, and fully polymerizing the inner phase in the presence of a radical initiator which is more soluble in the organic phase than in the aqueous phase, which is characterized in that the siloxane has an average molar ratio of groups of formula (I) to Si atoms of less than 0.1, in particular by the process according to the invention described above.

(47) The particles according to the invention preferably have a polymer which has been obtained by polymerization of siloxanes containing at least one (meth)acrylate group of the formula (I) and optionally other monomers optionally in the presence of further components such as, for example, fillers, auxiliaries or active substances etc. in the presence of a radical initiator, in particular an organic radical initiator.

(48) The particles according to the invention preferably have an average particle size d.sub.50 from 1 to 40 μm, preferably from 3 to 20 μm, particularly preferably 5 to 15. Preferred particles have a particle size d.sub.90 of 10 to 100 μm, preferably of 15 to 80 μm, particularly preferably 40 to 70 μm. The particle size d.sub.10 of the particles according to the invention is preferably from 0.5 to 15 μm, preferably from 1 to 10 μm, particularly preferably 2 to 7.5 μm. More preferably, the particles according to the invention are those which satisfy all of the aforementioned values for d.sub.10, d.sub.50 and d.sub.90, in particular the values given as being most preferred. The determination of the values d.sub.10, d.sub.50 and d.sub.90 takes place preferably by statistical laser diffraction methods familiar to the person skilled in the art. For this, the MasterSizer 3000 with attached Aero S dry dispersing unit from Malvern can for example be used.

(49) The particles according to the invention can have (meth)acrylate compounds that have not fully reacted but are covalently bonded to the polymer (compounds which have a free group of the formula (I)), preferably in a concentration of less than 5000 ppm by mass (wppm), preferably less than 3000 ppm by mass, particularly preferably less than 1500 ppm by mass, based on the particle. The fraction of non-fully reacted (meth)acrylate compounds can be determined, for example, by hydrolysis of the particles in ethanolic potassium hydroxide solution and subsequent determination of the released (meth)acrylic acid by means of HPLC.

(50) Preferred particles according to the invention are those which have a core/shell structure (so-called silicone (meth)acrylate composite particles). In these, a shell, where the shell is preferably formed by particulate emulsifiers, surrounds the inner core which has the polymerized silicone (meth)acrylate. Particularly preferred silicone (meth)acrylate particles are those in which the shell is formed from the aforementioned inorganic particles whose surface is preferably modified.

(51) Preferred particles can be those in which the shell is modified. Such a modification can be carried out, e.g., with cationic substances, such as organic ammonium ions or cationic polymers, cationic siloxanes, organic polymers such as, for example, polyacrylates, carboxylic acids or carboxylic acid anions, chelating agents, diketones, siloxanes or condensed silanes as described above. The surface modification can be bonded physically or chemically to the polymer particle. Furthermore, the surface modifiers can carry functional groups such as, for example, in the case of the use of functional silanes. The surface modifiers can consist of discrete molecules, but can also be crosslinked.

(52) Besides the silicone (meth)acrylate, the particles can possibly comprise comonomers used during the polymerization. These comonomers can be completely or partially incorporated by reaction into the polysiloxane (meth)acrylate network or else be in the form of an independent network. Mixed forms of these described limiting cases are likewise possible and form part of this invention.

(53) It may be advantageous if the particles have further components which are not constituents which have originated from the emulsifiers, monomers or comonomers. Based on the polysiloxane (meth)acrylate polymers, the particles have these further components preferably in a concentration of 0.01 to 99% by weight, preferably from 0.1 to 80% by weight and particularly preferably from 1 to 50% by weight. Such further components can be functional components or non-functional components. Further components which may be present in the particles are in particular solids, such as, e.g., inorganic particles and/or fibres, such as, e.g., those of metal oxides, mixed oxides, nitrides, hydroxides, carbonates, silicates, pigments, carbon blacks, elements or alloys, and/or organic particles and/or fibres, such as, e.g., those of silicone resins, silicones or organic polymers or biopolymers, preferably with the proviso that the fillers of the emulsifiers used are different. Further components can be selected in particular from precipitated silica, diatomeous earth (kieselgur), fumed silica, quartz flour, titanium dioxide, zinc oxide, cerium oxide, iron oxide, carbon black, graphite, carbon nanotubes or -fibres, alumosilicates, alkaline earth metal carbonates, aluminium trihydroxide, magnesium dihydroxide and other solids that are customary and known from the prior art, as well as each of the specified substances following surface modification with organosilicon compounds such as trimethylchlorosilane, hexamethyl disilazane, (meth)acryloxypropyltrialkoxysilanes, aminopropyltrialkoxysilanes, polydimethylsiloxanes, polysiloxanes which carry Si—H groups, or pure carboxylic acids, chelating agents or fluoropolymers. These solids can serve for example as fillers for achieving certain mechanical properties, as UV stabilizers, as pigments, as antistatic additives or for achieving ferromagnetic properties.

(54) The further components can be added subsequently to the already polymerized particles by means of swelling and diffusion. This can also take place with the assistance of a solvent, which is removed again afterwards. However, it is also possible to add the further components during the preparation process (see above). In particular, the further components in step a) of the process according to the invention can be added to the organic phase. The further components can be dissolved in the polymer matrix or else bonded to the matrix by an optionally labile covalent bond.

(55) The silicone (meth)acrylate particles according to the invention can include one or more substances, in particular selected from the aforementioned further components, which can be released from the particles. The release can take place in the corresponding applications over a prolonged period. The release can take place, e.g., by means of diffusion or hydrolysis reactions and subsequent diffusion.

(56) Substances that are to be released that can be present in the particles are, for example, cosmetic oils and active ingredients, fragrances, pharmaceutical active ingredients, antimicrobial active ingredients, also for example silver and silver-containing compounds, as well as dyes and preservatives. These substances can be present either in dissolved form or else embedded in the silicone (meth)acrylate matrix or else bonded to the silicone (meth)acrylate matrix by means of a labile chemical bond.

(57) The particles according to the invention or produced according to the invention can be used alone or in a mixture with further particles, pigments and/or further customary additives, e.g., in the form of powders or dispersions, in cosmetic or pharmaceutical preparations or in care compositions.

(58) The preparation of the dispersions with the particles according to the invention can take place by means of the customary methods corresponding to the prior art, although it is advantageous to further process the particles resulting after the polymerization according to step b) of the process according to the invention and washing with alcohol(s) or water without prior drying to give, for example, aqueous dispersions. This is also possible if, for example, a desired surface modification can take place directly from aqueous or alcoholic phase, which has a favorable effect on the process economics.

(59) The silicone (meth)acrylate particles according to the invention and/or dispersions comprising these can be used as additives in cosmetics and toiletries, e.g., as matting agents, as absorbers for skin sebums or for producing a pleasant, velvety-silky skin feel, as mild abrasive in washing and care formulations, and as formulation constituents or carrier materials that release active ingredients or auxiliaries over a prolonged period.

(60) The composition according to the invention is preferably a cosmetic or pharmaceutical preparation or a care composition, in particular a care composition for skin and/or hair, preferably human skin and/or hair.

(61) The present invention thus also provides care and cleaning formulations, in particular for skin and skin appendages, and also for the home and industry, in particular cosmetic formulations, with these preferably being selected from the group of skin and hair treatment compositions, for example formulations for skin care or decorative cosmetics, shampoos with or without pronounced conditioner effect, liquid soaps and shower gels, comprising particles according to the invention.

(62) A formulation preferred according to the invention comprises the particles according to the invention in an amount from 0.1% by weight to 99% by weight, preferably in an amount of 0.5% by weight to 50% by weight, particularly preferably in an amount of 1.0% by weight to 20% by weight, where the % by weight are based on the total formulation.

(63) Cosmetic care and cleaning formulations according to the invention can for example comprise at least one additional component selected from the group of:

(64) surfactants,

(65) emollients,

(66) emulsifiers,

(67) coemulsifiers,

(68) thickeners/viscosity regulators/stabilizers,

(69) antioxidants,

(70) hydrotropes (or polyols),

(71) solids and fillers,

(72) pearlescence additives,

(73) deodorant and antiperspirant active ingredients,

(74) insect repellents,

(75) self-tanning agents,

(76) preservatives,

(77) conditioners,

(78) perfumes,

(79) dyes,

(80) cosmetic active ingredients,

(81) care additives,

(82) superfatting agents,

(83) solvents,

(84) UV filters,

(85) electrolytes,

(86) multifunctional additives,

(87) moisturizing substances.

(88) Substances which can be used as exemplary representatives of the individual groups are known to the person skilled in the art and can be found for example in EP2273966A1. This patent application is herewith incorporated as reference and thus forms part of the disclosure.

(89) As regards further optional components and the amounts of these components used, reference is made expressly to the relevant handbooks known to the person skilled in the art, e.g., K. Schrader, “Grundlagen and Rezepturen der Kosmetika [Fundamentals and Formulations of Cosmetics]”, 2nd edition, pages 329 to 341, Hüthig Buch Verlag Heidelberg.

(90) The amounts of the particular additives are governed by the intended use.

(91) Typical guide formulations for the respective applications are known prior art and are contained for example in the brochures of the manufacturers of the particular basic materials and active ingredients. These existing formulations can usually be adopted unchanged. If necessary, the desired modifications can, however, be undertaken without complication by means of simple experiments for the purposes of adaptation and optimization.

(92) Preferred formulations according to the invention are aqueous, surface-active formulations; these comprise preferably at least 50% by weight, preferably 70% by weight of water and at least one surfactant.

(93) Besides the particles according to the invention, in particular nonionic surfactants of the component selected from the group consisting of glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids, alkyl mono- and oligoglycosides, partial esters based on linear, branched, unsaturated or saturated fatty acids, ricinoleic acid, and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (e.g., sorbitol), alkyl glucoside (e.g., methyl glucoside, butyl glucoside, lauryl glucoside, cocoglucoside), and polyglucosides (e.g., cellulose), mono-, di- and trialkylphosphates and salts thereof, citric acid esters such as, e.g., glyceryl stearate citrate, glyceryl oleate citrate and dilauryl citrate, and glyceryl caprylate, polyglyceryl caprylate, polyglyceryl caprate and mixtures of these surfactants are present in the formulations according to the invention.

(94) Preferred cleaning and care formulations according to the invention for the home and industry are textile-softening formulations and textile-care washing or cleaning compositions, dishwashing detergents, household cleaners, disinfectants, disinfectant cleaners, foam cleaners, floor cleaners, carpet cleaners, upholstery cleaners, floor care products, marble cleaners, parquet cleaners, stone and ceramic floor cleaners, wipe care compositions, stainless steel cleaners, glass cleaners, plastic cleaners, sanitary cleaners, wood cleaners, leather cleaners, detergents, laundry care compositions, disinfectant detergents, standard detergents, gentle detergents, wool detergents, fabric softeners and impregnating compositions, with dishwashing detergents and household cleaners, in particular hand dishwashing detergents, being particularly preferred.

(95) Particularly preferred cleaning and care formulations according to the invention for the home and industry additionally comprise one or more substances from the group of surfactants, builders, bleaches, bleach activators, enzymes, perfumes, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, greying inhibitors, shrink preventers, anticrease agents, colour transfer inhibitors, antimicrobial active ingredients, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistats, bittering agents, ironing aids, phobicization and impregnation agents, swelling and slip-resist agents, neutral filling salts, and UV absorbers.

(96) In particular, the cleaning and care formulations according to the invention for the home and industry can comprise between 0.001 and 90% by weight, particularly preferably 0.01 to 45% by weight, of one or more of the further ingredients mentioned here, where the % by weight refer to the total formulation.

(97) Examples of surfactants that can be used are described in WO 2007/115872, page 17, line 28 to page 21, line 24.

(98) Examples of builder substances, builders, bleaches, bleach activators, bleach catalysts and enzymes are described in WO 2007/115872, page 22, line 7 to page 25, line 26.

(99) Antiredeposition agents, optical brighteners, greying inhibitors, transfer inhibitors are described by way of example in WO 2007/115872 on page 26, line 15 to page 28, line 2.

(100) Examples of anticrease agents, antimicrobial active ingredients, germicides, fungicides, antioxidants, preservatives, antistats, ironing aids, UV absorbers are described in WO 2007/115872 on page 28, line 14 to page 30, line 22. Their explicit disclosure content in this regard forms part of this disclosure by virtue of this reference.

(101) The examples listed below illustrate the present invention by way of example, without any intention of restricting the invention, the scope of application of which is apparent from the entirety of the description and the claims, to the embodiments specified in the examples.

EXAMPLES

Comparative Example 1

(102) Particles of silicone methacrylate with an average molar ratio of methacrylate groups to Si atoms of 0.055; with redox radical initiator

(103) 163.25 g of demineralized water and 62.50 g of IDISIL SI-5530 were mixed and adjusted to pH 7 with hydrochloric acid. The mixture was introduced into a beaker and, with stirring, 125 g of a silicone methacrylate of the formula (I) where a=170, b=0, c=8, R.sup.1═CH.sub.3, R.sup.3═R′=—C.sub.6H.sub.12—O—C(O)—C(CH.sub.3)═CH.sub.2 were added. The mixture was sheared using a Dispermat at 5000 rpm for 30 minutes. Then, 2.25 g of 5% strength by weight VARISOFT® PATC solution were added dropwise and the mixture was sheared for a further 30 minutes at 5000 rpm. The stabilized preemulsion was admixed with 45 g of dipotassium hydrogen phosphate dissolved in 27.0 g of demineralized water and sheared again at 5000 rpm for 30 minutes. The resulting emulsion was homogenized by passing through a homogenizer (in the examples in each case a microfluidizer from Microfluidics was used) with an interaction chamber with 200 μm diameter at 800 bar pressure.

(104) For the polymerization, 325 g of the emulsion were placed into a 1 l round-bottomed flask and heated to 80° C. under a nitrogen atmosphere. With constant stiffing, a solution of 12.5 g of ammonium peroxodisulphate in 40 ml of demineralized water was slowly added dropwise to the heated solution. Then, 7.5 g of a 39% strength by weight sodium hydrogensulphite solution was added. The reaction mixture was stirred for a further 2 h at 80° C. After the polymerization, a considerable brown colouration of the reaction mixture was observed.

(105) For bleaching the cured dispersion, at 80° C. 15 g of a 30% strength hydrogen peroxide were added with continuous stiffing, during which a considerable lightening of the reaction mixture was established. Then, the particle dispersion was slowly cooled to room temperature and filtered. The resulting particles were washed five times with 150 ml of water in each case and dried to constant mass in a vacuum drying cabinet at 50° C. By means of electron microscopic viewing of the particles, it was possible to determine an average size of the particles of approximately 10 μm. It was noticeable here that the particles had indentations (“dimples”).

(106) To determine the fraction of methacrylate groups which have not reacted but are covalently bonded to the particles, these were hydrolyzed by alkaline ester cleavage and the methacrylic acid released during this was quantified by means of HPLC. For this, 0.5 g of the particles were boiled for 1 hour at reflux in 25 ml of 1 normal ethanolic potassium hydroxide solution, 5 ml of H.sub.2O and 1 ml of diethylene glycol monoethyl ether. The hydrolyzate was transferred with a small amount of ethanol to a 50 ml measuring flask and topped up. Then, the sample was diluted with water in the ratio 1:10 and at the same time adjusted to pH 2 with concentrated sulphuric acid. The subsequent chromatographic separation of the sample was carried out by means of RP HPLC with UV detection (HPLC system: Agilent 1100, column: Macchery & Nagel Pyramid C18). Here, a residual methacrylate content of 11 000 ppm was ascertained.

Example 1 According to the Invention

(107) Particles of silicone methacrylate with an average molar ratio of methacrylate groups to Si atoms of 0.055; with oil-soluble radical initiator

(108) 228.5 g of demineralized water and 50.0 g of IDISIL SI 5530 were mixed and adjusted to pH 7 with hydrochloric acid. The mixture was introduced into a beaker and, with stirring, 100 g of a silicone methacrylate of the formula (I) where a=170, b=0, c=8, R.sup.1=CH.sub.3, R.sup.3═R′=—C.sub.6H.sub.12—O—C(O)—C(CH.sub.3)═CH.sub.2, in which 0.3 g of lauryl peroxide have been dissolved beforehand, were added. Then, the mixture was sheared using a Dispermat at 5000 rpm for 30 minutes. Next, 5.5 g of a 1% strength by weight VARISOFT® PATC solution were slowly added dropwise and the mixture was sheared for a further 30 minutes at 5000 rpm. The resulting preemulsion was homogenized by passing through a homogenizer with an interaction chamber with 200 μm diameter at 800 bar pressure.

(109) For the polymerization, the emulsion was transferred to a 500 ml round-bottomed flask and then a stream of nitrogen was introduced for 45 min with stirring. The reaction mixture was then heated to 80° C. and kept at this temperature for 3 h with gentle stirring. After cooling, the thus cured particle dispersion was filtered. The resulting particles were washed twice with water and then dried to constant mass in a vacuum drying cabinet at 50° C. By means of electron microscopic viewing of the particles, an average size of the particles of approximately 10 μm could be ascertained. In contrast to the particles described in Comparative Example V1, the particles had a “more spherical” morphology and no indentations on the particles could be found.

(110) To determine the fraction of methacrylate groups that have not reacted but are bonded covalently to the particles, the analytical method described in Comparative Example V1 was used. Here, a residual methacrylate content of 1040 ppm was found. This is thus more than a factor of ten less than the ascertained residual methacrylate content of the particles described in Comparative Example 1.

Comparative Example V1

(111) Particles of silicone methacrylate with an average molar ratio of methacrylate groups to Si atoms of 0.25; with oil-soluble radical initiator

(112) 228.5 g of demineralized water and 50.0 g of IDISIL SI 5530 were mixed and adjusted to pH 7 with hydrochloric acid. The mixture was introduced into a beaker and, with stirring, 100 g of a silicone methacrylate of the formula (I) where a=15, b=0, c=5, R.sup.1═R.sup.3═CH.sub.3, R′═(CH.sub.2).sub.3—O—CH.sub.2—CH(OH)—CH.sub.2—O—C(O)—C(CH.sub.3)═CH.sub.2, in which 0.3 g of lauryl peroxide were dissolved beforehand, were added. Then, the mixture was sheared using a Dispermat at 5000 rpm for 30 minutes. Next, 5.5 g of a 1% strength by weight VARISOFT® PATC solution were slowly added dropwise and the mixture was sheared for a further 30 minutes at 5000 rpm. The resulting preemulsion was homogenized by passing through a homogenizer with an interaction chamber with 200 μm diameter at 800 bar pressure.

(113) For the polymerization, the emulsion was transferred to a 500 ml round-bottomed flask and then a stream of nitrogen was introduced for 45 min with stirring. The reaction mixture was then heated to 80° C. and kept at this temperature for 3 h with gentle stirring. After cooling, the thus cured particle dispersion was filtered. The resulting particles were washed twice with water and then dried to constant mass in a vacuum drying cabinet at 50° C.

Example 2 According to the Invention

(114) Particles of silicone methacrylate with an average molar ratio of methacrylate groups to Si atoms of 0.047; with oil-soluble radical initiator

(115) 228.5 g of demineralized water and 50.0 g of IDISIL SI 5530 were mixed and adjusted to pH 7 with hydrochloric acid. The mixture was introduced into a beaker and, with stirring, 100 g of a silicone methacrylate of the formula (I) where a=83, b=0, c=0, R.sup.1═CH.sub.3, R.sup.3═(CH.sub.2).sub.3—O—CH.sub.2—C(CH.sub.2—O—C(O)—C(CH.sub.3)═CH.sub.2).sub.2—CH.sub.2—CH.sub.3, in which 0.3 g of lauryl peroxide were dissolved beforehand, were added. Then, the mixture was sheared using a Dispermat at 5000 rpm for 30 minutes. Next, 5.5 g of a 1% strength by weight VARISOFT® PATC solution were slowly added dropwise and the mixture was sheared for a further 30 minutes at 5000 rpm. The resulting preemulsion was homogenized by passing through a homogenizer with an interaction chamber with 200 μm diameter at 800 bar pressure.

(116) For the polymerization, the emulsion was transferred to a 500 ml round-bottomed flask and then a stream of nitrogen was introduced for 45 min with stirring. The reaction mixture was then heated to 80° C. and kept at this temperature for 3 h with gentle stirring. After cooling, the thus cured particle dispersion was filtered. The resulting particles were washed twice with water and then dried to constant mass in a vacuum drying cabinet at 50° C.

(117) The majority of the formulation examples listed below are emulsions of the oil-in-water (O/W) type or water-in-oil (W/O) type. These can be produced by customary methods known to the person skilled in the art using typical stirring units. W/O emulsions are preferably produced by slowly stirring the water phase into the oil phase with subsequent homogenization. In the case of the described O/W emulsions, oil and water phase are preferably combined without stirring and then homogenized. This can be performed in a cold-cold process or in a hot-hot process in which the homogenization takes place at about 70° C. The silicone (meth)acrylate particles according to the invention can be processed in principle in any stage of the process. In most of the example formulations, either the incorporation into the finished emulsion was carried out at temperatures <60° C. or the silicone (meth)acrylate particles were introduced directly at the start of the emulsion preparation together with the oil phase.

(118) The nomenclature on the subject “incorporability” used for the assessment of the emulsion comparative examples is based on the following requirements. Under identical conditions as far as time of addition of the silicone (meth)acrylate particles and utilization of shearing units and rates is concerned, an easy incorporability describes no unusual effort for producing the formulation and the result is a uniform distribution of the silicone (meth)acrylate particles without troublesome agglomerates. If the incorporation is difficult, when using the same shearing unit and the same shearing rate, a longer shearing input has to be provided in order to arrive at an agglomerate-free formulation, or particle agglomerates cannot be incorporated without the agglomerates which affect the sensory properties.

(119) The nomenclature on the subject “stability” used for the assessment of the emulsion comparative examples is based on the following requirements. If the stability is assessed as “good”, this means that such an emulsion is stable for at least one month at room temperature, −5° C. and 40° C. “Stable” means here that no oil or water separation at all occurs, that the appearance of the emulsion remains homogeneous and that no significant changes in viscosity, colour or odour occur in the emulsion.

(120) The skin feel of the cosmetic formulations described in the following examples was determined by a panel. At least five people compared the sensory properties of the cosmetic formulations and of the respective comparison formulation without knowing the composition. The properties are listed which the majority of the people described as preferable.

Example 3 and Comparison Example V3

(121) The formulations given in Table 1a were prepared. The evaluation of the formulations was carried out with regard to their incorporability, stability, appearance and skin feel and is given in Table 1b.

(122) TABLE-US-00001 TABLE 1a Formulations re Example 3 and Comparative Example V3, oil-in-water care cream Example 3 V3 A TEGO ® Care 165 6.0% 6.0% (Evonik Industries AG) (Glyceryl stearate); PEG-100 stearate) Stearyl alcohol 3.0% 3.0% Mineral oil 4.0% 4.0% Ethylhexyl palmitate 4.0% 4.0% B Glycerol 3.0% 3.0% Water 75.0% 75.0% C Silicone methacrylate particles from 5.0% Ex. 1 according to the invention Silicone methacrylate particles from 5.0% Comparative Ex. V1 Z Methylparaben, ethylparaben, q.a. q.a. methylisothiazolinone, perfume

(123) TABLE-US-00002 TABLE 18b Results of Example 3 and Comparative Example V3, oil-in-water care cream Example 3 V3 Incorporability Easy, More difficult than agglomerates can for Example 3, be readily separation of the separated off by agglomerates shearing takes longer Stability Good Good Appearance White, White, homogeneous homogeneous Skin sensation During During application: application: velvety-silky, Velvety-silky, very smooth, smooth; 5 minutes not rough; 5 after application: minutes after somewhat rough, application: very dry smooth, powdery

Example 4 and Comparison Example V4:Water-in-Oil Foundation

(124) The formulations given in Table 2a were prepared. The evaluation of the formulations was carried out with regard to their stability, appearance and skin feel and is shown in Table 2b.

(125) TABLE-US-00003 TABLE 2a Water-in-oil foundation according to Example 4a, 4b and Comparative Example V4: Example 4a 4b V4 A ABIL ® EM 90 3.0% 3.0% 3.0% (Evonik Industries AG) (Cetyl PEG/PPG-10/1 Dimethicone) Diethylhexyl carbonate 10.0% 10.0% 10.0% Cyclopentasiloxane 7.6% 7.6% 7.6% Ethylhexyl palmitate 3.4% 3.4% 3.4% Iron oxide 1.8% 1.8% 1.8% Titanium dioxide 7.2% 7.2% 7.2% Talc 2.0% 2.0% 2.0% Silicone methacrylate 2.5% particles from Ex. 1 according to the invention Silicone methacrylate 2.5% particles from Ex. 2 according to the invention Silicone methacrylate 2.5% particles from comparative Ex. 2 B NaCl 1.0% 1.0% 1.0% Glycerol 2.0% 2.0% 2.0% Water 59.5% 59.5% 59.5% Z Phenoxyethanol; q.a. q.a. q.a. methylparaben; ethylparaben, butylparaben; propylparaben, isobutylparaben, perfume

(126) TABLE-US-00004 TABLE 2b Water-in-oil foundation according to Example 4a, 4b and Comparative Example V4: Example 4a 4b V4 Incorporability Easy, Easy, Easy, agglomerates agglomerates agglomerates can be readily can be readily can be readily separated by separated by separated by shearing shearing shearing Stability Good Good Good Appearance Brownish, Brownish, Brownish, homogeneous homogeneous homogeneous Skin sensation During During During application: application: application: velvety-silky, velvety-silky, powdery, powdery powdery rough; 5 very smooth, smooth, minutes after not rough; 5 not rough; 5 application: minutes after minutes after rough, dry application: application: very smooth, smooth, velvety-silky velvety-silky

Further Formulation Examples

Example 5: O/W Serum with Cosmetic Active Ingredients According to Table 3

(127) TABLE-US-00005 TABLE 3 O/W serum with cosmetic active ingredients according to Example 5 Polyglyceryl-6 Stearate (and) Polyglyceryl-6 Behenate* 2.5% Caprylic/Capric Triglyceride** 2.0% Oleyl Erucate*** 2.0% Persea Gratissima (Avocado) Oil 1.0% Aqua; Ethylhexyl Stearate; Sodium Hyaluronate 3.0% Crosspolymer; Polyglyceryl-4 Diisostearate/Polyhydroxystearate/Sebacate; Sodium Isostearate**** Water to 100% Butylene glycol 5.0% Tetrapeptide-21; Glycerin; Butylene Glycol; Aqua***** 2.0% Hydrolyzed hyaluronic Acid****** 0.1% Silicone methacrylate particles from Ex. 1 1.00%  Xanthan Gum 0.5% Sodium Hydroxide (10% aq.) 0.2% Benzyl Alcohol, Benzoic Add, Sorbic Acid 0.8% Polyglutamic acid; Sclerotium Glucan; Betaine; 3.0% Urea; Potassium Lactate******* *TEGO ® Care PBS 6 (Evonik Industries AG) **TEGOSOFT ® CT (Evonik Industries AG) ***TEGOSOFT ® OER (Evonik Industries AG) ****Hyacare ® Filler CL (Evonik Industries AG) *****TEGO ® PEP 4-17 (Evonik Industries AG) ******Hyacare ® 50 (Evonik Industries AG) *******TEGO ® Smooth Complex (Evonik Industries AG)

Example 6: O/W Cream According to Table 4

(128) TABLE-US-00006 TABLE 4 O/W cream according to Example 6 Polyglyceryl-3 methylglucose distearate 3.00% Glyceryl stearate 2.00% Cetearyl alcohol 1.00% Ethylhexyl stearate 10.00% Decyl oleate 9.00% Silicone methacrylate particles from Ex. 1 1.50% Glycerol 3.00% Water to 100% Sodium benzoate, potassium sorbate, phenoxyethanol, q.s. perfume

Example 7: Impregnation Solution for Wet Wipes According to Table 5

(129) TABLE-US-00007 TABLE 5 Impregnation solution for wet wipes according to Example 7 Ethylhexyl stearate, phenoxyethanol, sorbitan laurate, 5.70% polyglyceryl-4 laurate, dilauryl citrate* Cyclomethicone 2.00% Silicone methacrylate particles from Ex. 1 2.00% Water to 100% Glycerol 3.00% Carbomer**  0.10%. Sodium hydroxide (10% in water) q.s. *TEGO ® Wipe Flex (Evonik Industries AG) **TEGO ® Carbomer 141 (Evonik Industries AG)

(130) The impregnation solution can be used with the help of customary impregnation or spraying processes for producing cosmetic wet wipes (e.g., for baby care, make-up removers, cleansing wipes). For this, typically nonwovens are used, which generally have fibres of polyolefins, polyesters, celluloses, rayon, polyamides, polyester amides or polyvinyl alcohols or consist of these or which are composed of mixed fibres of these components.

Example 8: Make-Up Powder Foundation According to Table 6

(131) TABLE-US-00008 TABLE 6 Make-up powder foundation according to Example 8: Zinc stearate 3.00% Mica 40.00% Talc 24.00% Iron oxide 5.00% Silicone methacrylate particles from Ex. 1 10.00% Titanium dioxide 8.00% Cetylethyl hexanoate 2.00% Squalane 3.00% Cetearylethyl hexanoate 2.00%. Mineral oil (30 mPas) 2.00% PEG/PPG-4/12 dimethicone 1.00% Aluminium starch octenylsuccinate q.s. Iron oxide q.s. Perfume q.s.

Example 9: Make-Up Foundation According to Table 7

(132) TABLE-US-00009 TABLE 7 Make-up foundation according to Example 9 Phenyltrimethicone 14.00% Ethylhexyl palmitate 14.60% Cetylethyl hexanoate 5.00% Carnauba wax 4.70% Stearoxydimethicone 4.00% PVP/eicosene copolymer 1.00% Cetylstearyl heptanoate 2.85% Covabead LH 85, polymethyl methacrylate particles 3.00% Silicon dioxide 0.25%. Zinc oxide 7.00% Nylon-12 2.00% Talc Covasil 4.05 9.50% Acrylate copolymer 2.00% Silicone methacrylate particles from Ex. 1 3.00% Aluminium starch octenylsuccinate 9.50% Iron oxide 3.10% Titanium dioxide (and) dimethicone 14.50%

Example 10: Eyeshadow Formulation According to Table 8

(133) TABLE-US-00010 TABLE 8 Eyeshadow formulation according to Example 10 Cyclomethicone to 100% PPG-3 myristyl ether 7.00% Polyglyceryl-4 isostearate; cetyl PEG/PPG-10/1 dimethicone; 1.00% hexyl laurate* Dimethicone (20 mPas) 2.50% Cera alba 4.50% Carnauba wax 2.00% A-C Copolymer 400 (ethylene/VA copolymer) 2.50% Ozocerite 5.80% C18-36-acid triglyceride 2.00% Liquipar oil (isobutylparaben (and) isopropylparaben (and) 0.20% butylparaben) Silicone methacrylate particles from Ex. 1 4.00% Titanium dioxide 5.00% Chromium oxide (green) 10.00% CI 77491 (and) aluminium powder (and) silicon dioxide 5.00% CI 77891 (and) CI 77288 (and) mica 10.00% *ABIL ® WE 09 (Evonik Industries AG)

Example 11: O/W Sunscreen Lotion According to Table 9

(134) TABLE-US-00011 TABLE 9 O/W sunscreen lotion according to Example 11 Glyceryl stearate citrate 3.00% Cetearyl alcohol 1.00% Cetyldimethicone 0.20% C.sub.12-C.sub.15 alkyl benzoate 4.80% Triisostearin 1.00% Diethylhexyl carbonate 6.00% Titanium dioxide; trimethoxycaprylylsilane* 3.00% Tocopheryl acetate 0.50% Ethylhexyl methoxycinnamate  5.00%. Butylmethoxydibenzoylmethane 2.50% Carbomer 0.20% Xanthan 0.40% Sodium carboxymethylbetaglucan 0.10% Glycerol 2.00% Water to 100% Silicone methacrylate particles from Ex. 1 1.50% Sodium hydroxide (10% in water) q.s. Perfume q.s. *Tego ® Sun T 805 (Evonik Industries AG)

Example 12: AP/Deo Roll-on According to Table 10

(135) TABLE-US-00012 TABLE 10 Formulation according to Example 12 Steareth-2 2.20% Steareth-20 1.00% Cetearylethyl hexanoate 2.00% PPG-11 stearyl ether 2.00% Dimethicone 0.50% Polyglyceryl-3 caprylate 0.50% Aluminium chlorohydrate 5.00% Water to 100% Glycerol 3.00% Silicone methacrylate particles from Ex. 1  0.30%. Perfume q.s. Citric acid (50% in water) q.s. Phenoxyethanol; ethylhexylglycerol q.s.

Example 13: Lipstick Formulation According to Table 11

(136) TABLE-US-00013 TABLE 11 Formulation according to Example 13 Cyclopentasiloxane 34.00% Behenoxydimethicone 3.00% Stearyldimethicone 10.00% Polyisobutene 5.00% Phenyltrimethicone 8.00% Isododecane 4.00% Bis-diglyceryl polyacyladipate-2 4.00% Ceresin 24.00% Titanium dioxide 1.00% Carmine red 1.00% D&C Red No. 7 3.00% Polyethylene 1.00% Silicone methacrylate particles from Ex. 1 1.00% Aluminium starch octenylsuccinate & lauroyllysine 1.00%

Example 14: Mascara Formulation According to Table 12

(137) TABLE-US-00014 TABLE 12 Formulation according to Example 14 Sucrose stearate 4.00% Polyglyceryl-3 methylglucose distearate 2.00% Stearyl alcohol 1.00% Candelilla wax 5.00% Carnauba wax 1.75% Beeswax 4.25% Hydrogenated rice bran wax 5.00% Adipic acid/diethylene glycol/glycerol crosspolymer 5.00% Ceramide NP 0.05% Iron oxide 10.00%  Silicone methacrylate particles from Ex. 1 0.50% Water to 100% 1,3-Butanediol 3.00% Triethanolamine 1.80% Acrylate/octylacrylamide copolymer 5.00% Phenoxyethanol; methylparaben; ethylparaben, butylparaben; 0.60% propylparaben, isobutylparaben Phenoxyethanol 0.50%

Example 15: Make-Up Foundation According to Table 13

(138) TABLE-US-00015 TABLE 13 Formulation according to Example 15 Bis(Glyceryl/Lauryl) Glyceryl/Lauryl Dimethicone* 4.00% Diethylhexyl carbonate** 3.10% Phenoxyethyl caprylate*** 3.10% Mineral oil 6.30% Titanium dioxide 4.00% Iron oxide 2.50% Talc 1.00% Boron nitride 1.00% Dicaprylyl carbonate (and) stearalkonium 2.00% hectorite (and) propylene carbonate Silicon methacrylate particles from Ex. 1 1.00% Nylon-10/10**** 1.00% Dimethicone; Dimethicone/Vinyl Dimethicone Crosspolymer 4.00% Glycerol 4.00% Magnesium sulphate heptahydrate 1.50% Water to 100% Methylparaben; Ethylparaben; Propylparaben; n-Propylparaben; 0.70% Phenoxtol *ABIL ® EM 120 (Evonik Industries AG) **TEGOSOFT ® DEC (Evonik Industries AG) ***TEGOSOFT ® XC (Evonik Industries AG) ****TEGOLON ® ECO 10-10 (Evonik Industries AG)

Example 16: Blemish Balm with SPF 15 Formulation According to Table 14

(139) TABLE-US-00016 TABLE 14 Blemish balm with SPF 15 formulation according to Example 16 Polyglyceryl-3 methylglucose distearate* 3.00% Glyceryl Stearate 2.50% Stearyl Alcohol 1.50% Diethylhexyl Carbonate** 6.90% Aqua; Ethylhexyl Stearate; Sodium 2.00% Hyaluronate Crosspolymer; Polyglyceryl-4 Diisostearate/Polyhydroxystearate/Sebacate; Sodium Isostearate*** Phytosphingosine 0.10% Ethylhexyl methoxycinnamate 5.00% Diethylamino Hydroxybenzoyl Hexyl 3.00% Benzoate Titanium Dioxide CI 77891 3.00% Talc 2.00% Yellow iron oxide**** 0.36% Red iron oxide***** 0.12% Black iron oxide****** 0.08% Isoamyl cocoate******* 4.44% Phenoxyethyl caprylate******** 4.00% Nylon-10/10********* 1.50% Silicone methacrylate particles from Ex. 1 1.50% Water to 100% Glycerol 3.00% Hydrolyzed Hyaluronic Acid********** 0.10% Tetrapeptide-21; Glycerol; Butylene Glycol; 2.00% Aqua*********** Ethanol 3.00% Methylparaben, Ethylparaben, 0.80% Methylisothiazolinone *TEGO ® Care 450 (Evonik Industries AG) **TEGOSOFT ® DEC (Evonik Industries AG) ***HyaCare ® Filler CL (Evonik Industries AG) ****Unipure Yellow LC 182 (Sensient) *****Unipure Red LC 381 (Sensient) ******Unipure Black LC 989 (Sensient) *******TEGOSOFT ® AC (Evonik Industries AG) ********TEGOSOFT ® XC (Evonik Industries AG) *********TEGOLON ® EC 10-10 (Evonik Industries AG) **********HyaCare ® 50 (Evonik Industries AG) ***********TEGO ® Pep 4-17 (Evonik Industries AG)

Example 17: Shower Gel Formulation According to Table 15

(140) TABLE-US-00017 TABLE 15 Formulation according to Example 17 Acrylates/C10-30 Alkyl Acrylate Crosspolymer* 1.60% Water to 100% Sodium lauryl sulphate 21.40%  Cocamidopropylbetaine** 5.30% Polyglyceryl-3 Caprate*** 0.50% Silicone methacrylate particles from Ex. 1 2.00% Sodium hydroxide (10% in water) q.s. Phenoxyethanol; Methylisothiazolinone q.s. Perfume q.s. *TEGO ® Carbomer 341 ER (Evonik Industries AG) **TEGO ® Betain F 50 (Evonik Industries AG) ***TEGOSOFT ® PC 31 (Evonik Industries AG)

Example 18: Conditioner Formulation According to Table 16

(141) TABLE-US-00018 TABLE 16 Formulation according to Example 18 Water to 100% Cetrimonium chloride* 2.00% Behentrimonium chloride** 2.00% Cyclopentasiloxane; Dimethiconol*** 1.00% Silicone methacrylate particles from Ex. 1 0.50% Cetearyl alcohol**** 5.00% Phenoxyethanol; methylisothiazolinone q.s. Perfume q.s. *VARISOFT ® 300 (Evonik Industries AG) **VARISOFT ® BT 85 (Evonik Industries AG) ***ABIL ® OSW 5 (Evonik Industries AG) ****TEGO ® Alkanol 1618 (Evonik Industries AG)

Example 19: 2-in-1-Shampoo Formulation According to Table 17

(142) TABLE-US-00019 TABLE 17 Formulation according to Example 19 Sodium lauryl sulphate 60.00%  Sodium cumene sulphonate 3.00% Water to 100% Cocamidopropylbetaine* 8.00% Cocamide MEA** 1.50% Glycol distearate*** 1.50% Cetyl alcohol**** 0.50% Dimethicone (1000 mPas) 1.50% Silicone methacrylate particles from Ex. 1 1.00% Nylon-10/10***** 0.50% Xanthan Gum 0.75% Phenoxyethanol; methylisothiazolinone q.s. Perfume q.s. *TEGO ® Betain F 50 (Evonik Industries AG) **REWOMID ® C 212 (Evonik Industries AG) ***TEGIN ® G 100 (Evonik Industries AG) ****TEGO ® Alkanol 16 (Evonik Industries AG) *****TEGOLON ® ECO 10-10 (Evonik Industries AG)

Example 20: Styling Wax Formulation According to Table 18

(143) TABLE-US-00020 TABLE 18 Formulation according to Example 20 Water to 100% Propylene glycol 2.00% Glycerol 11.00% Methoxy PEG/PPG-7/3 Aminopropyldimethicone* 0.50% Isosteareth-20** 14.50% Laureth-4*** 10.00% Paraffinum Perliquidum 6.00% C12-15 Alkyl Benzoate**** 6.00% Silicone methacrylate particles from Ex. 1 1.00% Phenoxyethanol; methylisothiazolinone q.s. Perfume q.s. *ABIL ® Soft AF 100 (Evonik Industries AG) **REWODERM ® 66 E 20 (Evonik Industries AG) ***TEGO ® Alkanol 4 (Evonik Industries AG) ****TEGOSOFT ® TN (Evonik Industries AG)

Example 21: Leave-in-Conditioner Formulation According to Table 19

(144) TABLE-US-00021 TABLE 19 Formulation according to Example 21 Ceteareth-25* 4.00% Cyclopentasiloxane; Dimethiconol** 16.00%  Methoxy PEG/PPG-7/3 Aminopropyldimethicone*** 1.00% Silicone methacrylate particles from Ex. 1 3.00% Laureth-4**** 0.50% Carbomer***** 0.50% Water to 100% Propylene glycol 5.00% Sodium hydroxide (10% in water) to pH 5-6 Perfume q.s. Phenoxyethanol; methylisothiazolinone q.s. *TEGIN ® ACID C (Evonik Industries AG) **ABIL ® OSW 5 (Evonik Industries AG) ***ABIL ® Soft AF 100 (Evonik Industries AG) ****TEGO ® Alkanol L 4 (Evonik Industries AG) *****TEGO ® Carbomer 140 (Evonik Industries AG)

Example 22: Light W/O Cream According to Table 20

(145) TABLE-US-00022 TABLE 20 Formulation according to Example 22 Bis-PEG/PPG-14/14 Dimethicone; Caprylic/Capric 3.00% Triglyceride* Hydrogenated Castor Oil 0.80% Microcrystalline Wax 1.20% Isopropyl Palmitate** 4.30% Isohexadecane 4.30% Dimethicone (5 mPas) 10.40%  Silicone methacrylate particles from Ex. 1 2.00% Glycerol 3.00% Sodium Chloride 2.00% Creatine*** 0.50% Water to 100.00% Phenoxyethanol; ethylhexylglycerol 0.70% Perfume q.s. *ABIL ® EM 97 S (Evonik Industries AG) **TEGOSOFT ® P (Evonik Industries AG) ***TEGO ® Cosmo C100 (Evonik Industries AG)

Example 23: W/O Moisturizing Cream According to Table 21

(146) TABLE-US-00023 TABLE 21 Formulation according to Example 23 Cetyl PEG/PPG/10/1 Dimethicone* 2.00% Mineral oil (30 mPas) 17.00%  Hydrogenated Castor Oil 0.40% Silicone methacrylate particles from Ex. 1 2.00% Microcrystalline wax 0.60% Sodium Chloride 0.50% Water to 100.00% Urea 10.00%  Phenoxyethanol; ethylhexylglycerol 0.70% Perfume q.s. *ABIL EM 90 (Evonik Industries AG)

Example 24: Cationic O/W Formulation According to Table 22

(147) TABLE-US-00024 TABLE 22 Formulation according to Example 24 Distearyldimonium chloride* 1.00% Polyglyceryl-3 Methylglucose Distearate** 2.00% Glyceryl Stearate*** 2.00% Stearyl Alcohol**** 1.00% Cetyl Ethylhexanoate***** 9.00% Caprylic/Capric Triglyceride***** 10.00%  Silicone methacrylate particles from Ex. 1 1.50% Glycerol 3.00% Water to 100.00% Methylparaben, Ethylparaben, Methylisothiazolinone 0.80% Perfume q.s. *VARISOFT ® TA 100 (Evonik Industries AG) **TEGO ® Care 450 (Evonik Industries AG) ***TEGIN ® M Pellets (Evonik Industries AG) ****TEGO ® Alkanol 18 (Evonik Industries AG) *****TEGOSOFT ® CO (Evonik Industries AG) ******TEGOSOFT ® CT (Evonik Industries AG)

(148) While the present invention has been particularly shown and described with respect to various embodiments thereof, it will be understood by those skilled in the art that the foregoing and other changes in forms and details may be made without departing from the spirit and scope of the present invention. It is therefore intended that the present invention not be limited to the exact forms and details described and illustrated, but fall within the scope of the appended claims.