MICROEMULSION, ITS PREPARATION PROCESS, CARE AND CLEANING FORMULATIONS, AND PAINTS AND DYES

专利摘要:
microemulsion of polysiloxanes containing quaternary ammonium groups, their preparation and use. the present invention relates to microemulsions comprising, as oil phase, a polysiloxane containing at least one quaternary ammonium group, to a process for their preparation, as well as to the use of such microemulsions.
公开号:BR112013033420B1
申请号:R112013033420-7
申请日:2012-03-19
公开日:2021-07-27
发明作者:Verena Dahl；Sascha Herrwerth；Christian Hartung；Joachim Venzmer Venzmer；Dirk Kuppert；Berend-Jan De Gans
申请人:Evonik Operations Gmbh；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] Object of the invention are microemulsions, which comprise, as oil phase, polysiloxanes containing at least one quaternary ammonium group, a process for their preparation, as well as the use of such microemulsions. TECHNICAL STATUS
[002] Polysiloxanes with quaternary ammonium groups and their use as hair care additives or textile softener are known from patent literature.
[003] In EP 1887024, with filing date 4.7.2007, terminal cationic polysiloxanes are described with a structure called the T structure and its use as a conditioner in cosmetic formulations. These cationic polysiloxanes show a pronounced conditioning and shine producing effect. However, high molecular weight cationic polysiloxanes with this T structure, which potentially perform better, have the problem of being highly viscous and therefore not manageable and not processable in cosmetic formulations.
[004] The same statement can be made for polysiloxanes that have multimer T structures, disclosed in PCT/EP2010/070071, with filing date 12.17.2010.
[005] One possibility of processing polysiloxanes in cosmetic formulations is represented by the dosage form of polyorganosiloxanes in the form of emulsions or microemulsions. Microemulsions are thermodynamically stable mixtures in water (aqueous phase), oil (immiscible phase with water) and surfactant (solubilizer). Microemulsions are known, in which the oil phases are significantly formed by polysiloxanes.
[006] US 4,620,878 describes the general preparation of emulsions and microemulsions, which contain linear aminofunctional polyorganosiloxanes. First, a concentrate consisting of a surface-active agent, polyorganosiloxane, and small amounts of water is prepared, which is then rapidly dispersed in the remaining water needed to form the microemulsion.
[007] EP 0459500 describes how microemulsions containing polysiloxanes can be prepared by emulsion polymerization.
[008] US 6,607,717 describes the preparation and use of emulsions and other formulations with quaternary polyorganosiloxanes, in comb form, under the use of nonionic ethoxylated emulsifiers.
[009] US 4,749,732 describes the use of aminoalkyl substituted polyorganosiloxanes and their administration as an emulsion or microemulsion in light hair care uses.
[0010] US 6,153,569 describes the use of microemulsions with aminofunctional polyorganosiloxanes to obtain clear shampoo formulations.
[0011] Softener compositions are known which are used in the rinsing step after cleaning or washing fabrics and/or textile products. In addition, it is known that softening compositions can contain one or more silicones or organically modified siloxanes, which reduce the wrinkling of fabrics after the rinsing and drying step, facilitate ironing, and cause a high softness or a improved rewetting ability. This is disclosed, for example, in WO 9524460, FR7621830, GB 1596792, US 4,426,299, US 4,806,255, GB 0239910 and US 4,855,072.
[0012] The use of microemulsions for introducing silicones in softener formulations is described for example in WO 92/01776.
[0013] The use of macroemulsions for introducing silicones in softener formulations is described for example in WO A 97/31997 and WO A 97/31998.
[0014] Aqueous lacquers, which contain polyurethane dispersions as a binder, are also known. Such dispersions are called single-component systems or 1K systems and are used for coating substrates of all types, preferably textile, metal, leather, plastic, paper, cardboard and wood. These are polymer chains, which are linked by urethane or urea bonds and also contain acidic groups, such as carboxylates or sulphonates, or alkaline groups, such as amines. By subsequent neutralization it is possible to convert such polyurethanes into stable aqueous dispersions. Often such 1-K systems are post-crosslinked by the addition of a water-soluble crosslinker, such as water-soluble melamine resins. Furthermore, additional groups can be installed on the molecule, which cause crosslinking after drying. A complete description of polyurethane dispersions, their chemical and technological bases and areas of application can be found, for example, in the book "Polyurethanes for Lacquers and Coatings" (Manfred Bock, Vincentz publisher, Hannover 1999).
[0015] It is known that lacquers based on such polyurethane dispersions may contain one or more organically modified silicones, which reduce the tendency to dirt and slip friction, eliminate grip-slip or stick-slip friction, make it hydrophobic the surface and perfect the sensory touch. This is disclosed for example in DE 3839937 and WO 03/106575.
[0016] The disadvantage of all microemulsions described in the prior art is that all nonionic surfactants designated as appropriate, without exception, have alkoxylated compounds.
[0017] In addition, all microemulsions described in the prior art contain exclusively siloxanes, which do not have any pronounced silicone character, and which do not have a good effectiveness as a conditioner, for example, for hair or textile products, or have comparatively a small affinity with certain surfaces.
[0018] It was the task of the present invention to find a possibility of presenting polysiloxanes, in particular those that at room temperature have a high viscosity, to make application uses manageable. Description of the Invention
[0019] Surprisingly, it was found that the microemulsions described below are capable of solving the object of the invention.
[0020] Object of the present invention are, therefore, microemulsions, which as a significant component forming the oil phase contain certain quaternary polysiloxanes with a (multi-)structure in T.
[0021] Another object of the invention is a process for preparing the microemulsions according to the invention, the use of the microemulsions according to the invention for the preparation of formulations, as well as formulations containing the microemulsions according to the invention.
[0022] An advantage of the microemulsions according to the invention is that the highly viscous quaternary polysiloxanes with (multi-)T structure can be converted to a low viscosity state, without losing their functionality or activity, but, on the contrary, increasing activity in your applications.
[0023] Another advantage of the present invention is that the quaternary polysiloxanes with (multi-)T structure in the formulations achieve better performance. The microemulsions of the present invention enhance the conditioning properties of the quaternary polysiloxanes with the (multi-) T structure such as combability, softness, volume, moldability, handleability, the detangling of damaged and undamaged hair, and the shine effect, as well as the effectiveness in care and cleaning effectiveness of formulations for domestic and industrial use. Furthermore, through the use of microemulsions, a more improved softness is produced, particularly in textile products, of cotton fabrics, for example than in the use of macroemulsions.
[0024] Another advantage of the present invention is that quaternary polysiloxanes with (multi-)T structure can be processed to form cosmetic formulations, which for example in pure form or diluted in appropriate solvents, due to high viscosity or due to poor compatibility, cannot be incorporated into cosmetic formulations.
[0025] A further advantage is that the microemulsions according to the invention are capable of being prepared for cosmetic uses essentially free of alkoxylated constituents. A further advantage of the microemulsions according to the invention containing Siliconquats with (multi-)T structure is that they have a particularly good conditioning effect in cosmetic, dermatological and pharmaceutical formulations. A further advantage of the invention is that quaternary polysiloxanes with (multi-)T structure, otherwise non-water-dilutable, can be converted to a water-dilutable form.
[0026] Object of the present invention is a microemulsion containing significantly oil phase forming components comprising:
[0027] A) a polysiloxane containing at least one quaternary ammonium group of the General Formula (I) Ma M'a1 M''a2M'''a3 Db D'b1D''b2 D'''b3 Tc T'c1 Qd Formula (I),
[0028] in which
[0029] M = (R13Si O1/2)
[0030] M' = (R2R12 Si O1/2)
[0031] M'' = (R3R12 Si O1/2)
[0032] M''' = (R4R12 Si O1/2)
[0033] D = (R12 Si O2/2)
[0034] D' = (R2R1 Si O2/2)
[0035] D'' = (R3R1 Si O2/2)
[0036] D''' = (R4R1 Si O2/2)
[0037] T = (R5 Si O3/2)
[0038] T' = (R2 Si O3/2)
[0039] Q = (Si O4/2)
[0040] a = 0 to 32; preferably 0 to 22, in particular 0 to 12;
[0041] a1 = 0 to 10, preferably 0 to 5, in particular 0;
[0042] a2 = 0 to 32; preferably up to 22, in particular 1 to 12;
[0043] a3 = 0 to 10; preferably 0 to 5, in particular 0;
[0044] with the proviso that
a + al + a2 + a3 > 3, in particular 3 to 22, preferably > 3, in particular 4 to 17;
[0046] b = 1 to 600, preferably 10 to 500, in particular 20 to 400;
[0047] b1 = 0 to 10, preferably 0 to 5, in particular 0;
[0048] b2 = 0 to 80, preferably 0 to 50, in particular 0 to 10;
[0049] b3 = 0 to 20, preferably 0 to 10, in particular 0;
[0050] c = 0 to 30, preferably 1 to 20, in particular 2 to 15;
[0051] c1 = 0 to 10, preferably 0 to 5, in particular 0;
[0052] d = 0 to 15, preferably 1 to 12, in particular 2 to 10;
[0053] with the proviso that
[0054] a2 + b2 > 1, preferably > 3, in particular > 3 and
c + cl + d > 1, preferably 1 to 20, preferably > 1, in particular 2 to 15, in particular > 3;
[0056] R1 = aromatic hydrocarbon radicals, independent of one another, the same or different, linear or branched, with 1 to 30 carbon atoms, preferably methyl or phenyl, in particular methyl;
[0057] R2 = alkoxy or acyloxy radicals, independent of one another, the same or different, such as for example methoxy, ethoxy, n-propoxy, or iso-propoxy, acetoxy radicals, in particular ethoxy radicals or iso-propoxy radicals;
[0058] R3 = organic radicals, independent of each other, equal or different, which carry the quaternary ammonium functions;
[0059] R4 = organic epoxy radicals, independent of each other, the same or different;
[0060] R5 = radicals R1, R3 or R4, preferably R1, independently of one another, the same or different, in particular methyl, phenyl, do-decyl or hexadecyl.
Under the term "decidedly oil phase forming component" it is understood in the context of the present invention that the polysiloxane contains at least 50% by weight of the oil phase; the remaining fraction of the oil phase may consist, for example, of the components designated below as G components.
[0062] The polysiloxanes described in the framework of the invention may have several units, which can be statistically distributed (static oligomer) or be arranged in an orderly manner (block oligomers) in these compounds. It is usual for the expert that the compounds are present in the form of a mixture with a distribution essentially regulated by the laws of statistics. Data for the number of units in such compounds should be understood as an average value, calculated over all these chemicals. All percentages indicated (%) are, when nothing different is mentioned, percentage by mass. All conditions, such as pressure and temperature, when nothing different is indicated, are standard conditions.
[0063] The polysiloxanes used in the microemulsions according to the invention preferably contain as epoxy radicals R4, preferably identical or different radicals selected from the group

[0064] Suitable radicals R3 are for example groups with the structure
[0065] -R6-R7,
[0066] in which
[0067] R6 preferably are radicals, the same or different, bivalent, selected from the group


[0068] R6 is particularly preferred:

[0069] R7 is selected from the group consisting of

[0070] R8 are the same or different radicals from the hydrogen or alkyl group having from 1 to 6 carbon atoms, preferably methyl;
[0071] R9 are hydrocarbon radicals, bivalent, the same or different, which if appropriate contain ether functions, preferably methylene;
[0072] Ri0, Rii, Ri2are, respectively independent of each other, hydrogen or alkyl radicals with i up to 30 C atoms or radicals of the formula:

[0073] R13 are the same or different radicals from the group -O-, -NRi6-;
[0074] R14 are divalent hydrocarbon radicals, the same or different, if appropriate branched, preferably ethylene or propylene;
[0075] R15 are alkyl, aryl or alkaryl radicals, the same or different, with 1 to 30 carbon atoms, which if appropriate contain ether functions, preferably methyl, ethyl or phenyl, in particular methyl;
[0076] R16 are radicals the same or different from the hydrogen or alkyl group having 1 to 6 carbon atoms;
[0077] m = 2 to 18;
[0078] n = 2 to 18, preferably 3;
[0079] o = 0 to 30, preferably 0 to 10, in particular 1 to 3;
[0080] p = 0 to 30, preferably 0 to 10;
[0081] are counterions, equal or different, positively charged on quaternary nitrogen groups, selected from inorganic or organic anions of HA acids, as well as their derivatives.
[0082] In another preferred embodiment of the present invention the counterion A- consists of positive charges on the quaternary nitrogen groups of the anion of a physiologically compatible HA acid, which particularly preferably is selected from acetic acid, acids L- hydroxycarboxylic acids, in particular lactic acid, or aromatic carboxylic acids.
[0083] Other preferred counterions come from usual quaternizing agents. These are in particular ethyl sulphate, methyl sulphate, toluene sulphonate, chloride and bromide.
[0084] An embodiment of the present invention comprises microemulsions according to the invention with at least one polysiloxane, which presents a simple T structure with terminal modification, characterized in that the microemulsion contains a polysiloxane with c = 1 and c + c1 + d = 1 (hereinafter c1 = d = 0) as well as a2 > 1 with a2 + a3 = 3 and a = a1 = b1 = b2 = b3 = 0.
[0085] The polysiloxanes comprised in the microemulsions according to the invention are prepared according to processes, as just described above in the publications EP 1887024 and PCT/EP2010/070071, being used for the preparation of polysiloxanes with simple structure T, preferably the process mentioned in EP 1887024. With reference to the preparation process, explicit mention is made of the disclosure of these documents, which replace the description in this document.
[0086] In the microemulsions of the present invention, polysiloxanes are advantageously used with an average molecular weight greater than 4000 g/mol, preferably greater than 7000 g/mol, in particular greater than 10000 g/mol, the average molecular weight being determined by means of 29Si-NMR.
[0087] Preferred microemulsions according to the invention have a domain size of the dispersed phases of less than 1000 nm, in particular less than 500 nm, and the determination of the size of the domains is carried out with the aid of the scattering methods known by the experts such as P. Lindner and Th. Zemb, "Neutrons, X-Rays and Light: Scattering Methods Applied to Soft Condensed Matter", Elsevier Science & Technology, November 2002 or O. Glatter and O. Kratky, "Small -angle X-ray Scattering" Academic Press Inc, December 1982.
[0088] In the microemulsions of the present invention, polysiloxanes are advantageously used with a viscosity > 1 Pas, in particular from 10 Pas to 100,000 Pas, (measured with a plate-plate geometry of a rheometer at T = 25°C, width of 1 mm slot at a shear rate of 1 s-1).
[0089] Preferred microemulsions according to the invention are characterized by the fact that they additionally contain at least one of the components
[0090] B) at least one nonionic surfactant;
[0091] C) a cotenso-active agent selected from the group containing anionic, cationic and amphoteric surfactants; and
[0092] D) water.
[0093] Preferred microemulsions according to the invention are characterized by the fact that they additionally contain at least one of the components B) and C) or B) and D) or C) and D) or B) and C) and D) .
[0094] Preferred nonionic surfactants are selected from the group containing, preferably consisting of,
[0095] Addition products of ethylene oxide and/or propylene oxide in linear fatty alcohols, fatty acids, fatty acid amides, fatty amines, and an alkyl phenol,
[0096] Glycerin monoesters and glycerin diesters, and sorbitan monoesters and diesters of saturated and unsaturated fatty acids and their ethylene oxide addition products,
[0097] Alkylmonoglycosides and alkyloligoglycosides and their products of addition of ethylene oxide in castor oil and/or hardened castor oil,
[0098] Partial esters based on linear, branched, saturated or unsaturated fatty acids, ricinoleic acid, 12-hydroxystearic acid, glycerin, polyglycerin, pentaerythritol, dipentaerythritol and sugar alcohols (for example sorbitol), plo alkylglycosides (for example, ,methylaglycoside, butylglycoside, laurylglycoside) as well as polyglycosides (eg cellulose), monoalkyl phosphate, dialkyl phosphate and trialkyl phosphate, as well as mono-PEG-alkyl phosphate, di-PEG-alkyl phosphate and /or tri-PEG-alkyl phosphate and its salts, citric acid esters, such as glyceryl stearate citrate, glyceryl oleate citrate and dilauryl citrate, as well as glyceryl caprylate, polyglyceryl caprylate, polyglyceryl caprate , other alkoxylated triglycerides, mixed or formal mixed ethers, if appropriate partially oxidized alkyl oligoglycosides, or alkenyl oligoglycosides or glucuronic acid derivatives, fatty acid-N-alky ilglucamides, protein hydrolyzate (in particular wheat-based vegetable products), polyol fatty acid ester, sugar esters, polysorbates and aminooxides, and mixtures of these surfactants.
[0099] Since the nonionic surfactants contain polyglycol ether chains, these can present a conventional homologous distribution, preferably, however a concentrated homologous distribution.
[00100] In the context of the present invention, under the term "fatty acids" can be understood in particular formic acid, acetic acid, propionic acid, butyric acid, valeric acid, capronic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecanic acid, palmitic acid, margaric acid, stearic acid, nondecanic acid, arachidonic acid, behenic acid, lignocerinic acid, cerotinic acid, montanic acid, melissin acid, undecylenic acid, acid myristoleic, palmitoleic acid, petroselinic acid, oleic acid, elaidinic acid, vacenic acid, gadoleic acid, icosenic acid, ketoleic acid, erucic acid, nervonic acid, linoleic acid, alpha-linolenic acid, gamma-linolenic acid, calenduleic acid, calendulic acid, punic acid, alpha-elaeostearic acid, beta-elaeostearic acid, arachidonic acid, thymnodonic acid, clupanodonic acid, cervonic acid, vernolic acid, ricin acid leico, those with a chain length of 6 to 22, in particular 8 to 18 C atoms, are particularly preferred; the analog is valid for the carbon backbone for the term "fatty alcohols" used in the context of the invention.
[00101] Preferred anionic surfactants are those having a carboxylate group, sulfate group, sulfonate group or phosphate group and a lipophilic radical. Typical examples of anionic surfactants are soaps, alkylbenzene sulphonates, alkane sulphonates, olefin sulphonates, alkyl ether sulphonates, glycerin ether sulphonates, alpha-methyl ester sulphonates, sulphofatty acids, alkyl sulphates, alkyl ether sulphates, alcohol ether sulphates , glycerin ether sulfates, fatty acid ether sulfates, mixed hydroxy ether sulfates, monoglyceride (ether) sulfates, fatty acid amide ether sulfates, monoalkyl and dialkyl sulfosuccinates, monoalkyl and diglyceride soap sulfosuccinates, sulfotris amide, alkyl ether carboxylates, ether carboxylic acids and their salts, acyl sarcosinates, fatty acid isethionate, fatty acid sarcosinate, fatty acid tauride, acyl amino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglycosides sulfate, fatty protein acid condensates (in particular pro. wheat-based vegetable ducts) and alkyl(ether)phosphates and mixtures of these surfactants.
[00102] Since the anionic surfactants contain polyglycol ether chains, these may present a conventional distribution of homologs, preferably, however concentrated.
[00103] As cationic active agents, quaternary ammonium compounds can be used in particular, in particular those equipped with at least one straight and/or branched, saturated or unsaturated alkyl chain, as well as alkyltrimethylammonium halides, as well as by for example cetyltrimethylammonium chloride or cetyltrimethylammonium bromide or behenyltrimethylammonium chloride, but also dialkyl dimethyl ammonium halides, as well as for example distearyl dimethyl ammonium chloride. Furthermore, as cationic surfactants, monoalkylamidoquats can be used, such as for example palmitamido propyltrimethyl ammonium chloride or the corresponding dialkylamidoquats.
[00104] In addition, as cationic active agents can be used compounds of quaternary esters, which can be quaternary fatty acid esters based on monoethanolamine, diethanolamine, or triethanolamine. Cationic surface active agents, in addition, can be alkylguanidinium salts.
[00105] Typical examples of amphoteric surfactants are amphoacetates, amphopropionates, alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates and imidazoliniumobetaines and sulfobetaines, as well as for example the N-alkyl-N,N-dimethylammonio-glycinate cocoalkyl-dimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinate, and for example coconut acylamino propyl-dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazoline respectively with 8 to 18 C atoms in the alkyl group or acyl group, as well as coconut acylamino ethyl hydroxyethyl carboxymethyl glycinate. A preferred bipolar ionic surfactant is the fatty acid amide derivative known below as INCI cocamidopropyl betaine.
[00106] In particular for cosmetic or topical uses, microemulsions, which are essentially free of alkoxylated compounds, are preferred. Under the term "essentially free of alkoxylated compounds" in the context of the present invention it can be understood that the microemulsion does not present any mentionable amount of alkoxylated compounds which exerts a surface-active influence. In particular it is to be understood here that alkoxylated compounds in amounts less than 1% by weight, preferably less than 0.1% by weight, particularly preferred less than 0.01% by weight relative to the total microemulsion are contained. in particularly undetectable amounts.
[00107] Among such microemulsions essentially free of alkoxylated compounds are, in particular, nonionic surfactants of component B) selected from the group consisting of:
[00108] glycerin monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids,
[00109] alkylmonoglycosides and alkyloligoglycosides, partial esters based on linear, branched, unsaturated or saturated fatty acids,
[00110] ricinoleic acid, as well as 12-hydroxystearic acid and glycerin, polyglycerin, pentaerythritol, dipentaerythritol, sugar alcohols (for example, sorbitol), alkylglycosides (for example, methylaglycoside, butylglycoside, laurylglycoside) as well as polyglycosides (for example, cellulose),
[00111] alkyl monophosphate, alkyl diphosphate and alkyl triphosphate and their salts,
[00112] citric acid esters, as well as for example glyceryl stearate citrate, glyceryl oleate citrate and dilauryl citrate, as well as glyceryl caprylate, polyglyceryl caprylate, polyglyceryl caprate and mixtures of these surfactants.
[00113] Since in the process of preparing microemulsions the presence of a solvent can facilitate the preparation of the emulsion, the preferred microemulsions of the present invention are characterized by the fact that they additionally contain a solvent E) selected from the group that preferably comprises it consists of hydrotropes, for example from the group of aliphatic alcohols such as ethanol, propanol or 1,3-propanediol, cyclic carbonates such as ethylene carbonate, propylene carbonate, glycerine carbonate, monocarboxylic or polycarboxylic acid esters such as acetate. ethyl, ethyl lactate, glycerin, isopropyl alcohol, dipropylene glycol, glycolether (eg obtainable under the names DOWANOL® from Dow Chemicals) or polyols. Polyols, of interest here, can have from 2 to 15 carbon atoms and at least two hydroxyl groups. Typical examples are: glycerin, alkylene glycols, such as for example ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, 1,2-propanediol, 1,2-butanediol, 1,2-pentandiol, 1,2- hexanediol, as well as polyethylene glycol or polypropylene glycol, polyhydroxycarboxylic acids, butyldiglycol and mixtures of these solvents.
[00114] To microbiologically stabilize the microemulsions according to the invention, it is advantageous when they contain a component F), preservative. These can be for example mixtures of one or more alkylparaben esters with phenoxyethanol alone. Alkylparaben esters can be methylparaben, ethylparaben, propylparaben and/or butylparaben. Instead of phenoxyethanol, other alcohols, such as benzyl alcohol or ethanol, can also be used. In addition, other preservatives can also be used, alone or mixed, such as phenoxyethanol, sorbic acid or benzoic acid, salicylic acid, 2-bromo-2-nitropropan-1,3-diol, chloroacetamide, diazolidinyl urea, DMDM hydantoin , iodopropynyl butylcarbamate, sodium hydroxymethylglycinate, and methylisothiazoline, chloromethyl-isothiazoline, ethylhexylglycerin or caprylyl glycol.
[00115] The oily phase of the microemulsion according to the invention may additionally contain a component G), an oil or mixture of oils, selected preferably consisting of monocaprylates of propylene glycol, monoesters or diesters of monocarboxylic and/or dicarboxylic acids , linear and/or branched, with 2 to 44 carbon atoms, with linear and/or branched, saturated or unsaturated, with 1 to 22 carbon atoms; as well as esterification products of aliphatic difunctional alcohols with 2 to 36 C atoms with monofunctional aliphatic carboxylic acids with 1 to 22 C atoms, long chain aryl acid esters of linear or branched, saturated or unsaturated alcohols with 1 to 22 C atoms, or also benzoic acid isostearylester, or benzoic acid octyldodecylester, monoesters (such as, for example, methylesters and isopropyl esters of fatty acids with 12 to 22 C atoms, such as, for example, methyl laurate, methyl stearate, methyl oleate, methyl erucate, isopropyl palmitate, isopropyl myristate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, decyl stearate isooctyl, isononyl palmitate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyl decylstearate, 2-octyldodecyl palmitate, oleyl oleate, oleyl erucate, oleate erucila) as well as esters, which are obtainable from aliphatic alcohol cuts and technical mixtures of aliphatic carboxylic acids; as well as mixtures of naturally occurring waxy monoesters or esters, as they are present, for example, in jojoba oil or spermaceti oil. Suitable dicarboxylic acid esters are, for example, di-n-butyl adipate, di-n-butyl sebacate, di-(2-ethylhexyl) adipate, di-(2-hexyldecyl) succinate, D-isotridecyl acetate. Suitable diolesters are, for example, ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di-(2-ethylhexanoate), butanediol diisostearate, dicaprylate/butanediol caprate and neopentylglycol dicaprylate. Other fatty acid esters which may be employed are for example C12-15 alkyl benzoate, dicaprylyl carbonate, diethylhexyl carbonate. Also as oil components, longer-chain triglycerides can be used, i.e. trivalent glycerin esters with three acid molecules, at least one of which is long-chain; in addition hydrocarbons also contain, in particular, liquid paraffins and isoparaffins, such as paraffin oil, isohexadecane, polydecene, petroleum jelly, Paraffinum perliquidum, squalan, ceresin; as well as linear or branched fatty alcohols such as oleic alcohol or octyldodecanol, and fatty alcohol ethers such as dicaprilyl ether; silicone oils and silicone waxes, such as polydimethylasiloxanes, cyclomethylasiloxanes, as well as aryl substituted polymethylsiloxanes or cyclomethylsiloxanes, or substituted alkyl or substituted alkoxy, Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, linear C6-C22 fatty acid esters with linear C6C22 fatty alcohols, branched C6-C13 carboxylic acid esters with linear C6-C22 fatty alcohols, linear C6-C22 fatty acid esters with branched C8-C18 alcohols in particular 2-ethylhexanol or isononanol, esters of C6-C13 carboxylic acids with branched alcohols, in particular 2-ethylhexanol or isononanol, esters of linear and/or branched fatty acids with polyvalent alcohols (such as e.g. propylene glycol, dimerdiol or trimertriol) and/or Guerbet alcohols, triglycerides based on C6-C10 fatty acids, mixtures of liquid monoglycerides/ diglycerides/ triglycerides based on C6 acids -C18- fatty, esters of C6-C22 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear C6-C22 fatty alcohol carbonates, Guerbet carbonates , benzoic acid esters with linear and/or branched C6-C22 alcohols (p. ex. FinsolvTM TN), dialkyl ether, ring-opening products of fatty acid esters epoxidized with polyols, silicone oils and/or aliphatic or naphthenic hydrocarbons.
[00116] In this context, the condition that the component G) makes up a maximum of 50% by weight of the entire oil phase applies.
[00117] In the preferred microemulsions according to the invention, component A) is contained in an amount of 10% by weight to 60% by weight, preferably in an amount of 15% by weight to 50% by weight, particularly preferred in an amount of 20% by weight to 45% by weight, the % by weight referring to the total microemulsion.
[00118] Particularly preferred microemulsions of the present invention are characterized by the fact that
[00119] component A) is contained in an amount of 10% by weight to 60% by weight, preferably in an amount of 15% by weight to 50% by weight, particularly preferred in an amount of 20% by weight to 45% by weight,
[00120] component B) is contained in an amount of 3% by weight to 30% by weight, preferably in an amount of 4% by weight to 20% by weight, particularly preferred in an amount of 5% by weight to 15% by weight,
[00121] component C) is contained in an amount of 0% by weight to 30% by weight, preferably in an amount of 3% by weight to 25% by weight, particularly preferred in an amount of 5% by weight to 20 % by weight,
[00122] component D) is contained in an amount of 10% by weight to 75% by weight, preferably in an amount of 15% by weight to 65% by weight, particularly preferred in an amount of 20% by weight to 55% by weight,
[00123] component E) is contained is contained in an amount of 0% by weight to 35% by weight, preferably in an amount of 3% by weight to 30% by weight, particularly preferred in an amount of 5% by weight up to 25% by weight,
[00124] component F) is contained in an amount of 0% by weight to 1% by weight, preferably in an amount of 0.0001% by weight to 0.5% by weight, and
[00125] component G) is contained in an amount of 0% by weight to 50% by weight, preferably in an amount of 1% by weight to 40% by weight, particularly preferred in an amount of 5% by weight to 20 % by weight of the total oil phase consisting of A) and G)
[00126] where the % by weight, with the exception of component G), refers to the total microemulsion.
[00127] Another object of the present invention is a process for preparing a microemulsion according to the invention comprising the process steps
[00128] I) Preparation of at least one polysiloxane as described above,
[00129] II) if appropriate, dissolution of the polysiloxane with at least one solvent E) and/or a nonionic surfactant of component B) and/or oil G)
[00130] III) addition of the remaining components that form the microemulsion, with the components water and preservatives being added last.
[00131] The components A) to G), described in the processes according to the invention, correspond to the components described above in connection with the microemulsions according to the invention, and the respective preferred components of the microemulsions, of course, are preferably employed in the process according to the invention; in favor of completeness, it is mentioned that this statement is naturally valid for the quantities used of the individual components.
[00132] In the process according to the invention, no mechanical force should be employed to form an emulsion, since microemulsions are emulsions that form spontaneously; however, according to the invention, during all the process steps of I) - III) it is preferred to mix with a simple stirrer, for example with a pendulum stirrer.
[00133] The polysiloxanes described above as preferred, in the context of microemulsions according to the invention, are employed in the preferred process according to the invention.
[00134] During the preparation of the microemulsion, to avoid high viscose states that eventually occur, it may be advantageous when the process according to the present invention is characterized by the fact that the process steps of I) - III) are carried out at a slightly elevated temperature, for example at a temperature range from 21°C to 90°C, in particular from 30°C to 50°C.
[00135] The microemulsions of the present invention can be advantageously employed for preparing formulations for care and cleansing, in particular for skin and skin appendages, such as hair conditioners, as well as formulations for care and cleaning for home use and industrial, and these are selected, preferably, from the group of cosmetics, purifiers and for care formulations. Thus, these types of uses are also the object of the present invention.
[00136] The term "care formulation" can be understood here as a formulation that satisfies the purpose of keeping an object in its original shape, of minimizing or avoiding the effects of external influences (eg time, light, temperature, pressure , dirt, chemical reaction with other reactive compounds that come into contact with the object) such as aging, dirt, material fatigue, bleaching, or even enhancing the desired positive properties of the object. As a last point, an improved hair shine or a greater elasticity of the considered object can be mentioned.
[00137] In this context, care and cleaning formulations are not limited to cosmetic, pharmaceutical, or dermatological formulations, such as for the treatment of hair in the form of shampoos, 2-in-1 shampoos, liquid soaps, hair conditioners, fixative solutions for perms, coloring shampoos, hair fixatives, hair cures, products for laying the hair or for hair adjustment, preparations for hair styling (styling), hair lotions for hair dryers, foam fixatives, hair cures, leave-in conditioners, hair straightening products, shine enhancers and hair dye products, as well as other hair care and cleaning formulations, but they can also be those formulations, such as those used in homes and industry, for care and cleaning surfaces of inanimate objects such as tiles, wood, glass, ceramics, linoleum, plastic, lacquered surfaces, leather , fabrics, fibers. Examples of such objects are glass and window sills, separating glass for shower stalls, flooring such as rugs, tiles, laminates, parquet, cork, marble, stone and porcelain floors, ceramics for WCs, sinks, bidets, drains shower, bathtubs, doorknobs, fittings/hardware, appliances such as washing machines, dryers, dishwashers, ceramic or stainless steel sinks, furniture such as tables, chairs, shelves, shelves, windows, pots, dishes and cutlery, clothing, in particular underwear ("underwear"), boats, vehicles and aircraft such as automobiles, buses, motor boats and sailing boats, tools such as surgical instruments, vacuum cleaners, machines, plumbing , tanks and devices for transport, processing and storage in food processing. In this context, we are talking about the use in cleaning products and for household care, in industrial and institutional sectors.
[00138] In this context, the surfaces to be treated and cleaned are preferably a fiber or a textile product, in particular the surface of textile products, fabrics, clothing, upholstery or carpets.
[00139] Another object of this invention is the use of microemulsions according to the invention as conditioners for hair care products and hair post-treatment products, as products to improve the hair structure.
[00140] Still an object of the present invention are also formulations for care and cleaning, in particular for the skin and skin appendages, as well as formulations for domestic and industrial care and cleaning, in particular cosmetic formulations, and these they are preferably selected from the group of hair care agents and hair after-treatment agents for rinsing or remaining on the hair, for example shampoos with or without a pronounced conditioning effect, 2 in 1 shampoos, rinses, hair cures, hair masks, styling aids, styling products, hair dryer protective lotions, hair fixatives, perming products, hair straightening products and hair dye products, in particular conditioners and shampoos containing at least one microemulsion according to the invention.
Particularly preferred cosmetic formulations according to the invention are also essentially free of alkoxylated compounds.
[00142] Cleaning formulations and preferred care formulations according to the invention for domestic, industrial and institutional uses containing at least one of the microemulsions according to the invention are disinfectant, disinfectant cleaner, foam cleaner, floor cleaner, cleaner carpet cleaner, upholstery cleaner, floor care products, marble cleaner, parquet cleaner, stone cleaner and ceramic floor cleaner, cleaner, stainless steel cleaner, glass cleaner, dishwasher, cleaner plastics, toilet cleaner, wood cleaner, leather cleaner, detergent, clothing care products, disinfectant detergent, laundry product, fine laundry product, wool cleaner, fabric softener and impregnating agent, in particular softeners are particularly preferred.
Particularly preferred cleaning and care formulations according to the invention for domestic, industrial and institutional use containing at least one of the microemulsions according to the invention are textile care formulations for repeated cleaning and care of textile products and fabrics. In this context, a formulation for textile care is understood to mean any formulation with which flat textile fabrics treated with it receive an advantageous effect, such as a softening effect on textiles, resistance to creases or reduction of effects. harmful or negative effects that can occur in cleaning and/or conditioning and/or bearing, such as fading, graying, etc. Particularly preferred is that the formulation for textile care is a fabric softener formulation (softener).
[00144] Textile softening formulations (softeners) are in particular aqueous (i.e. they have a content by weight of at least 5% by weight of water relative to the formulation as a whole, which formulations contain as main effect constituent one or most cationic textile softener compounds, which have one or more long-chain alkyl groups in a molecule Widely disseminated cationic textile softener compositions include eg methyl-N-(2-hydroxyethyl)-N,N-di(seboacyloxyethyl) compounds ammonium or N,N-dimethyl-N,N-di(sebogacyloxyethyl)ammonium Other suitable ammonium compounds are disclosed in US 2010/0184634 in paragraphs [0027] through [0068], the express disclosure content of which is referenced in this regard. for that part of the disclosure. Textile softener formulations may in addition contain other additives and adjuvants, in particular perfumes, dyes, viscosity regulators, defoamers, preservatives, organic solvents, polymers not containing siloxane and other siloxane-containing polymers. In particular, textile softener formulations may contain from 0.001 to 25, particularly preferred from 0.01 to 15% by weight of one or more different additives or adjuvants, the % by weight referring to the total formulation.
[00145] As perfume, all formulations for textile softeners of the state of the art can be used, such as suitable known flavors or flavor mixtures, preferably in the form of a perfume oil. Examples of flavorings or perfumes are disclosed inter alia in DE 197 51 151 A1, page 4, lines 11 - 17. In particular the disclosed textile softening formulations may contain between 0.01 and 10, particularly preferred 0.1 to 5% by weight of one or more flavorings or flavor mixtures, the % by weight referring to the formulation as a whole.
[00146] As dyes, all textile softener formulations of the state of the art can be used, with water-soluble dyes being preferred. Examples of suitable water-soluble dyes are SANDOLAN® Walkblau NBL 150 (manufacturer Clariant) and Sicovit® Azorubin 85 E122 (manufacturer BASF). In particular the textile softener formulations may contain between 0.001 and 0.1% by weight, particularly preferred 0.002 to 0.05% by weight of one or more dyes or dye mixtures, where the % by weight refers to the formulation as a whole.
[00147] As a viscosity regulator for reducing viscosity, the textile softener formulation may contain an alkali metal salt or alkaline earth metal salt, preferably calcium chloride, in an amount of 0.05 - 2% by weight, being that % by weight refers to the formulation as a whole. As a viscosity regulator for increasing viscosity, the textile softener formulation may contain a suitable prior art thickener, the polyurethane thickeners known from WO 2007/125005 being preferred. Examples of suitable thickeners are TEGO® Visco Plus 3030 (manufacturer Evonik Tego Chemie), Acusol® 880 and 882 (manufacturer Rohm & Haas), Rheovis® CDE (manufacturer BASF), Rohagit® KF 720 F (manufacturer Evonik Rohm GmbH) and Poligel ® K100 from Neochem GmbH.
[00148] As defoamers, all textile softener formulations of the state of the art can be used, as suitable known defoamers. Examples of suitable commercially available defoamers are Dow Corning® DB-110A and TE-GO® Antifoam® 7001 XP. In particular suitable textile softener formulations may contain between 0.0001 and 0.05, particularly preferred 0.001 to 0.01% by weight of one or more different defoamers, the % by weight referring to the formulation as a whole.
[00149] As preservatives, the prior art textile softener formulation may contain suitable known bactericidal and/or fungicidal active substances, with water-soluble active substances being preferred. Examples of suitable commercially available bactericides are methylaparaben, 2-bromo-2-nitro-1,3-propanediol, 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one. Likewise, the textile softener formulation may contain an oxidation inhibitor as a preservative. Examples of suitable commercially customary oxidation inhibitors are ascorbic acid, 2,6-di-tert-butyl-4-methylphenol (BHT), butylhydroxyanisole (BHA), tocopherol and propylgallate. In particular textile softening compositions may contain between 0.0001 and 0.5, particularly preferred 0.001 to 0.2% by weight of one or more different preservatives. In particular, the textile softener formulation may contain between 0.001 and 0.1, particularly preferred 0.001 to 0.01% by weight of one or more different oxidation inhibitors, the % by weight referring to the total formulation.
[00150] As an organic solvent the textile softener formulation may contain short-chain alcohols, glycols and monoether glycol, with ethanol, 2-propanol, 1,2-propanediol and dipropylene glycol being preferred. In particular, textile softening compositions may contain between 0.1 and 10, particularly preferred from 0.2 to 5% by weight of one or more different organic solvents, the % by weight being based on the total formulation.
[00151] The textile softener formulation may contain one or more polymers not containing siloxane. Examples for this are carboxymethylcellulose, polyethylene glycol, polyvinyl alcohol, poly(meth)acrylate, polyethyleneimine or polysaccharides. In particular textile softener formulations may contain between 0.01 and 25, particularly preferred 0.1 to 10% by weight of one or more different polymers not containing siloxane, the % by weight referring to the total formulation.
[00152] The textile softener formulation can furthermore contain other additives not listed here that are obvious to the expert or state of the art.
[00153] Another object of the invention is the use of microemulsions according to the invention in washing products or cleaning products for textile care. By introducing it into a washing product or cleaning product, the consumer has at his disposal a washing product or cleaning product for textile care ("washing product or cleaning product 2 in 1") and he no longer needs to dose two products (the washing product or the cleaning product and the fabric softener), as well as no need to carry out any separate rinsing step. In addition to the formulation for textile care and surfactants, the washing product or cleaning product for textile care may contain other ingredients, which further improve the technical use and/or aesthetic properties of the washing product or product cleaning. Preferably the cleaning products and washing products additionally contain one or more materials from the group of surface active agents, builders, bleaches, bleach activators, enzymes, perfumes, perfume carriers, fluorescent agents, dyes, foam inhibitors, oils silicones, anti-redeposition agents, optical brighteners, graying inhibitors, shrinkage preventers, anti-crease, color transfer inhibitors, antimicrobial active substances, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, agents bitters, ironing aids, fobizing agents and impregnating agents, swelling agents and slip agents, neutral filler salts as well as UV absorbers. In particular the washing or cleaning agents for textile care according to the invention can be between 0.001 and 90, particularly preferred 0.01 to 45% by weight of one or more of the other contents mentioned herein, wherein the % in weight refers to the total weight of the formulation.
[00154] Examples of employable surface active agents are described in WO 2007/115872, page 17, lines 28 to line 21, line 24. Examples of builders, bleaches, bleach activators, bleach catalysts and enzymes are described in WO 2007/115872 , page 22, line 7 to line 25, line 26. Anti-redeposition agents, optical brighteners, graying inhibitors, color transition inhibitors are, for example, described in WO 2007/115872 at page 26, line 15 to page 28, lines 2. Examples of mesh protection agents, antimicrobial active substances, germicides, fungicides, antioxidants, preservatives, antistatics, ironing aids, UV absorbers which are described in WO 2007/115872 on pages 28, lines 14 to page 30, line 22. The content of the explicit disclosure in this regard is part of this disclosure.
[00155] A preferred formulation according to the invention contains the microemulsion according to the invention in an amount of 0.1% by weight to 99% by weight, preferably in an amount of 0.5% by weight to 20% by weight, particularly preferred in an amount of 1.0% by weight to 10% by weight, the % by weight referring to the total formulation.
[00156] The formulation according to the invention, in particular the cosmetic formulation, may for example contain at least one additional component, selected from the group of
[00157] emollients,
[00158] emulsifiers,
[00159] thickeners/viscosity regulators/stabilizers,
[00160] antioxidants,
[00161] hydrotropes (or polyols),
[00162] solid materials and fillers,
[00163] pearlescent shine additives,
[00164] deodorants and antiperspirants,
[00165] insect repellents,
[00166] self tanning,
[00167] preservatives,
[00168] conditioners,
[00169] perfumes,
[00170] dyes,
[00171] cosmetic active substances,
[00172] additives for care,
[00173] superfatting agents,
[00174] solvents.
[00175] Substances, which for example can be used as substituents of individual groups are known to experts and can be extracted for example from EP2273966A1. This patent application is introduced here by reference and is valid as part of the disclosure.
[00176] With reference to other optional components, as well as to the amounts employed of these components, express reference is made to relevant manuals known to those skilled in the art, for example K. Schrader, "Grundlagen und Rezepturen der Kosmetika", 2nd. edition, pages 329 to 341, publisher Huthig Buch Heidelberg.
[00177] Another object of the invention is the use of microemulsions according to the invention as additives for paints and colors, in particular for water-based paints and colors, preferably those in which polyurethane dispersions are employed as binders. Through the addition of microemulsion, the user obtains paints and colors that are distinguished, after application, by a small friction (adhesion) sliding and a modified handling, for example haptics.
[00178] Paints and colors, in particular for coating textile, metal, leather, plastic, paper and wood products, containing at least one microemulsion according to the invention or at least one microemulsion obtainable according to the process according to the invention, where these paints and colors preferably contain an aqueous polyurethane dispersion as a binder, are also object of the present invention.
[00179] In addition to the binder and microemulsion according to the invention, the lacquer or paint may contain other ingredients that further improve the application and/or aesthetic properties of the coating. Preferably the paint systems additionally contain one or more raw materials from the group of primary binder, co-binder, cross-linker, curing agents, surface-active agents, substrate cross-linkers, dispersion additives, rheology additives, defoamers, deaerators, thus such as inorganic or organic pigments, colorants, slip additives and leveling additives, fillers, matting agents, pearlizing polymers, natural and synthetic waxes, touch improvers, antimicrobial active substances, germicides, fungicides, antioxidants, preservatives, UV stabilizers and polar solvents.
[00180] According to the invention, inks or colors preferably contain the microemulsion according to the invention in an amount of 0.1% by weight to 99% by weight, preferably in an amount of 0.5% by weight up to 20% by weight, particularly preferred in an amount of 1.0% by weight to 10% by weight, the % by weight referring to the formulation as a whole.
[00181] The amounts of the respective additives are directed to the intended use. Typical formulations for the respective uses are known from the state of the art and are contained, for example, in the manufacturer's brochures of the corresponding basic materials and active substances. These existing formulations can as a rule be adopted unchanged. In case of need, the desired modifications for tuning and optimization can also be carried out by simple and uncomplicated experiments.
[00182] In the examples below, the present invention will be described by way of examples, without the invention, whose field of application is evident from the full specification and claims, being limited to the embodiments mentioned in the examples.
[00183] Figure 1 is a component part of the examples and shows the reduction of friction by the use of conditioners. Examples Siloxane 1: Polysiloxane T-Quat with N=121:
According to example 4 of EP 1887024 a quaternary polysiloxane was prepared, however with a total siloxane chain length of N=121. A highly viscous, slightly yellowish product with the following statistical structure was obtained here.
Siloxane 2: Polysiloxane T-Quat with N=151:
[00185] According to Example 4 of EP 1887024 a quaternary polysiloxane was prepared, however with a total polysiloxane chain length of N=151 and with lactic acid in place of acetic acid. A highly viscous, slightly yellowish product with the following statistical structure was obtained here.
Siloxane 3: Polysiloxane T-Quat with N=211:
According to Example 4 of EP 1887024 a quaternary polysiloxane was prepared, however with a total siloxane chain length of N=211. A highly viscous, slightly yellowish product with the following statistical structure was obtained here.
Siloxane 4: Multi-T-Quat polysiloxane with N=250:
[00187] According to Example 2 of PCT/EP2010/070071 a quaternary polysiloxane with 5 T units was prepared, however with a total polysiloxane chain length of N=250. A very viscous, slightly yellowish product was obtained here with the following statistical formula.

[00188] with R2 =
Siloxane 5: Multi-T-Quat polysiloxane with N=350:
[00189] According to Example 2 of PCT/EP2010/070071 a quaternary polysiloxane with 5 T units was prepared, however with a total polysiloxane chain length of N=350. Here a very viscous, clear, yellowish product was obtained having the following statistical formula.

[00190] with R2 =
Siloxane 6: Polysiloxane T-Quat with N=61:
According to Example 4 of EP 1887024 a quaternary polysiloxane was prepared, however with a total polysiloxane chain length of N=61. A highly viscous, slightly yellowish product with the following statistical structure was obtained here.
Examples of microemulsion formulation















Cosmetic application technology:
[00192] Next, 4 different products were tested in cosmetic formulations:
[00193] The ME18 microemulsion according to the invention is composed as follows (see above):

[00194] The microemulsion has a silicone active ingredient content of 30%. Comparative example product 2 (not according to the invention):
[00195] Here siloxane 2 was dissolved in 15% dipropylene glycol (ie active content of 85% silicone active ingredient). Comparative example 3 (not according to the invention):
[00196] Siloxane DC 2-8566 containing amino groups (commercially available from Dow Corning, INCI: Amodimethicone). The product consists of 100% silicone active ingredient. Comparative example 4 (not according to the invention):
[00197] Quaternary siloxane microemulsion DC 5-7113 (commercially available from Dow Corning, INCI: Silicone quaternium-16 (and) undeceth-11 (and) Butyloctanol (and) Undeceth-5). The microemulsion has a silicone active ingredient content of 22%. Application Technology Properties
[00198] The formulation constituents are designated, in the com-positions, in the form of the INCI momenclature generally known using English terms. All concentrations in the application examples are given in percent by weight.
[00199] 1) Test of skin conditioning (ability to care for the skin) and foam properties by means of a hand washing test:
[00200] For evaluation of skin conditioning (ability to care for the skin) and foam properties of the ME18 microemulsion according to the invention in aqueous, surfactant formulations, hand washing sensory tests were performed in comparison with comparative examples 2 and 3 according to the state of the art.
[00201] Comparative example 3 is widely disseminated in the industry as a care agent and holds as a highly active care agent in aqueous, surfactant formulations.
[00202] Comparative example 2 contains the same silicone active ingredient as the ME18 microemulsion.
[00203] A group consisting of 10 trained test persons washed their hands here in a definite way and evaluated foam and skin touch properties using a grading scale from 1 (poor) to 5 (very good).
[00204] The products used were tested respectively in a standardized surfactant formulation (Table 1).
[00205] As a 0b control formulation, a formulation without the addition of an organomodified siloxane is used. Table 1: Test Formulations for Hand Wash Testing.

[00206] A test with formulation example V2b cannot be performed, as a strong separation occurred. The silicone active ingredient cannot be stably processed into the formulation.
[00207] The sensory test results are summarized in table 2. Table 2: Hand washing test results


[00208] Table 2 shows the results of the hand washing test. Based on the measurement results, it is visible that the formulation 1b according to the invention, using the ME18 microemulsion according to the invention, is superior in all application properties, compared to the prior art comparative formulation V2b .
In this context, the results of formulation 1b according to the invention are designated as very good.
[00210] Based on the measured values it is visible that the microemulsion ME18 according to the invention in formulation 1b leads to an improvement of the skin properties and foam properties compared to comparative example 3 in formulation V3b.
[00211] Furthermore, it can be extracted from the measurement values, that the control formulation 0b without a silicone compound presents measurement values worse than formulations 1b and V3b.
[00212] Furthermore, the fact that comparative example 2 cannot be elaborated in comparative formulation V2b, despite comparative example 2 containing the same silicone active substance as the microemulsion ME18 according to the invention, is clear evidence that the microemulsions according to the invention represent a visible improvement over the state of the art, since the microemulsions according to the invention make it possible to use silicone active substances, which according to the state of the art cannot be used in surfactant formulations.
[00213] 2.) Capillary conditioning test through sensory tests:
[00214] For the technical evaluation of hair conditioning, the Microemulsion ME18 according to the invention and comparative example 3 were used in simple cosmetic formulations (shampoo and conditioner).
[00215] The use properties in use in a shampoo were verified in the following recipes: Table 3: Shampoo formulations for testing hair conditioning properties

[00216] To evaluate the properties of the formulation of shampoos, no post-treatment with a conditioner was performed during the test.
[00217] The properties of use in use in hair conditioners were verified in the following recipes: Table 4: Hair conditioner formulations for testing the conditioning properties of hair.

[00218] The pre-treatment of hair occurs, in the case of checking the properties of hair conditioners, by a shampoo that does not contain any conditioner.
[00219] For technical evaluation, hair tresses, used for sensory testing, are previously damaged by a perm treatment and a standard bleach treatment. For this, common products are used in hairdressers. During the test, the basic materials used, as well as the details of the evaluation criteria, are described in DE 103 27 871.
[00220] Standardized treatment of pre-damaged hair tresses, with samples of conditioners:
[00221] The pre-damaged hair tresses, as described above, are then treated with the shampoo described above or rinsed with the conditioner described above:
[00222] The locks of hair are moistened under warm running water. Excess water is lightly pressed by hand, then shampoo is applied and gently incorporated into the hair (1 mL/hair lock (2 g)). After a residence time of 1 min the hair is rinsed for 1 min.
[00223] If appropriate, it is immediately rinsed and gently incorporated into the hair (1 mL/hair lock (2 g)). After a residence time of 1 min the hair is rinsed for 1 min.
[00224] Before sensory evaluation the hair is air-dried at 50% air humidity and dried at 25oC for at least 12 h.
[00225] Evaluation criteria:
[00226] Sensory assessments occur according to observations (grades), which are awarded on a scale from 1 to 5, with 1 being the worst and 5 the best assessment. The individual test criteria obtain their own assessment respectively.
[00227] The test criteria are: wet combability, wet feel, dry combability, dry feel, appearance/gloss.
[00228] The following tables compare the results of the sensory evaluation of the treatment carried out, as described above, of hair tresses with formulation 1c according to the invention, with the comparative formulation V2c and with the control formulation 0c ( Placebo without substance test). Table 5:
[00229] Hair conditioning results from shampoo formulation

[00230] The results surprisingly show that formulation 1c according to the invention with microemulsion ME18 according to the invention has significantly better ratings than comparative formulation V2c with comparative example 3 according to the state of the art. It is particularly visible and it is worth noting the good evaluation of the gloss properties of all the formulations according to the invention. Table 6: Hair conditioning results from hair conditioner formulations


[00231] Also in the use of hair conditioners the 1d formulation according to the invention shows very good sensory evaluations with the microemulsion ME18 according to the invention. Thus, the already very good properties of the comparative formulation V2d with the comparative example 3 are further enhanced by the formulation 1d according to the invention with the microemulsion according to the invention.
[00232] A significantly better gloss assessment is also obtained by using the 1d formulation according to the invention.
[00233] 3.) Test of friction value on dry hair by friction test:
[00234] The conditioning effectiveness of the products on dry hair was verified with the aid of a friction force measurement method (see also US 2009/0324530). An instrument from the firm Instron was used here (Instron 5942, Instron Deutschland GmbH, Pfungstadt, Germany).
[00235] The instrument measures the force that is needed to pull a piece through a lock of natural hair. The difference in the measuring force before and the measuring force after treatment with the conditioning agent produces a reduction in the friction value, and thus an objectively detected value for the quality of the conditioner used.
[00236] The 200 g piece in weight and measuring 6 x 7 cm x 0.5 cm was fitted with a solid rubber surface. This surface is renewed for each lock. Strands of natural hair pre-damaged by bleaching and prewashed (7 cm wide, 18 cm free hair length, about 8.5 g) were used.
[00237] Treatment of locks:
[00238] The products were applied from a hair conditioner. The microemulsion according to the invention was verified in comparison with Comparison Examples 2 and 4. The respective formulations are summarized in Table 7. Table 7: Conditioner formulation for friction test on hair.

[00239] The hair conditioners formulations were applied at a concentration of 0.5 g/2 g of hair in a lock, evenly distributed for 1 min and further, left to act for 1 min and rinsed with water at 38oC for 3 min. The locks were allowed to dry overnight at 22°C and 50% relative humidity, before being measured using the methods described above on the Instron force measuring instrument.
[00240] The friction value reductions obtained by using the conditioner are shown in figure 1.
[00241] Through the measurement values it can be observed that, with the formulation 2e according to the invention and with the microemulsion 1 according to the invention, a clear reduction of friction can be obtained, in relation to the comparison formulations V1e and V3e to comparative examples 4 and 2.
[00242] Furthermore, it is visible that a more pronounced friction reduction with formulation 2e according to the invention can be aimed for with microemulsion ME18 than with comparative formulation V1e with comparative example 4 according to the state of the art. Consequently comparative example 4 not according to the invention (microemulsion according to the state of the art) is less effective than formulation 2e according to the invention with microemulsion M18 according to the invention.
[00243] Formulation V 3e with comparative example 2 contains the same quaternary siloxane structure as formulation 2e according to the invention with microemulsion ME18 according to the invention. Surprisingly, with formulation 2e a noticeably more widespread reduction in friction was found. Consequently, the ME18 microemulsion represents a visible improvement over the state of the art. Other formulation examples:
[00244] The formulation examples indicated in the table below show exemplary substituents of a series of possible compositions according to the invention.
[00245] If the preparation of the formulation requires the preparation or mixing of separate formulation components, this is called a multi-phase preparation.
[00246] If a two-phase preparation is required, both phases A and B are characterized by A and B in the tables given. In three-phase processes the three phases are called A, B and C. When nothing different is indicated in the following tables, the data is given in % by weight. Formulation Example 1) Clear Shampoo
Formulation Example 2) Shampoo, PEG- & sulfate free

Formulation example 3) Clear Conditioning Shampoo
Formulation example 4) Clear Conditioning Shampoo

Formulation Example 5) Clear Conditioning Shampoo

Formulation example 6) Clear Conditioning Shampoo
Formulation Example 7) Clear Conditioning Shampoo
Formulation example 8) Pearl Shampoo

Formulation example 9) Shampoo, PEG- & sulfate free
Formulation example 10) Conditioner without Rinse

Formulation example 11) No Rinse Conditioner
Formulation example 12) No Rinse Conditioner
Formulation example 13) No Rinse Conditioner

Formulation example 14) Conditioner without Rinse
Formulation example 15) Conditioning Spray for Moisturizing (Leave-In Conditioner Spray)

Formulation example 16) Moisturizing Conditioning Spray
Formulation example 17) Moisturizing Conditioning Foam (Leave-In Conditioner Foam)
Formulation example 18) Strong Hold Styling Gel

Formulation example 19) foam product for body care
Formulation example 20) body care product

Formulation example 21) foam product for body care

Formulation example 22) Mild Foam Bath
Formulation example 23) Conditioner without Rinse

Formulation example 24) Conditioner without Rinse
Formulation example 25) Conditioner without Rinse

Formulation example 26) moisturizing skin cleanser
Formulation example 27) Shower gel

Formulation example 28) body cleanser

Formulation example 29) Body cleansing foam
Formulation example 30) Cloudy Conditioning Shampoo

Formulation example 31) Light & Body Wash, PEG- and Sulphate Free
Formulation example 32) Sprayable Hairmilk, PEG-free
Application technology for textile care
[00247] To determine the softening effectiveness of the microemulsion according to the invention on textile fabrics, cotton cloths were treated with it.
[00248] Preparation of a siloxane macroemulsion (not according to the invention - Comparative example) (Formulation example T1)
[00249] 20 parts of siloxane 5 heated at 40°C to 80°C are introduced under stirring in a glass beaker with a stirrer. Then, under stirring, 10 parts by weight of dipropylene glycol, 10 parts by weight of a fatty alcohol ethoxylate with a degree of ethoxylation of 6. are added sequentially with water to 100 parts by weight and stirred. until the mixture has cooled to room temperature, however for at least 15 min.
[00250] Preparation of a siloxane microemulsion (according to the invention) example formulation T2:
[00251] Corresponds to the example of ME 33 microemulsion formulation Preparation of softener formulations:
[00252] Example of formulation T3: ca. 5% by weight of siloxane-free softener formulation (not according to the invention - reference)
[00253] 33.3 g of a REWOQUAT® WE 18 (trade name of Evonik Goldschmidt GmbH, esterquat based on triethanolamine with an active content of 90%) heated at 40 to 80°C under stirring were added under stirring at 556 g of tap water, liquid heated to 45 - 65°C, stirred for 20 min with a propeller stirrer at 45 - 65°C and cooled for about an hour at room temperature.
[00254] Example of formulation T4: softener formulation containing siloxane (comparative example - not according to the invention)
[00255] 33.3 g of a liquid REWOQUAT® WE 18, heated to 40 to 80°C, were weighed together into a 50 ml polypropylene centrifuge tube together with 0.28 g of siloxane 5 and mixed intensively by stirring with a Vortex mixer. This turbid mixture was completely added, under stirring, to 556 g of tap water heated to 45 - 65°C, stirred for 20 min with a propeller stirrer at 45 - 65°C and cooled in about a time. hour at room temperature.
[00256] Example of formulation T5: Softener formulation containing siloxane (comparative example - not according to the invention)
[00257] 33.3 g of a REWOQUAT® WE 18 (trade name of Evonik Goldschmidt GmbH, triethanolamine based on esterquat with an active content of 90%) liquid, heated to 40 to 80°C were introduced under stirring at 556 g tap water heated to 45 - 65°C, stirred for 20 min with a propeller stirrer at 45 - 65°C, then 1.40 g of the siloxane macroemulsion of formulation example T2 was added and cooled in a time span of about an hour at room temperature.
[00258] Example of formulation T6: Softener formulation containing siloxane (according to the invention):
[00259] 33.3 g of a REWOQUAT® WE 18 (trade name of Evonik Goldschmidt GmbH, triethanolamine based on esterquat with an active content of 90%) liquid heated at 40 to 80°C were introduced under stirring to 556 g of tap water heated to 45 - 65°C, stirred for 20 minutes with a propeller stirrer at 45 - 65°C, then 1.37 g of the siloxane microemulsion of formulation example T3 was added and cooled in a time span of about one hour at room temperature. Pre-treatment of a cotton fabric:
[00260] Toweled cotton fabrics of 80 cm x 50 cm with a weight per unit area of about 350 g/m2 were washed twice with a washing powder, rinsed twice, centrifuged and hung without folds on a clothesline and air-dried. Treatment of cotton fabrics:
[00261] The above-described formulations T3 to T6 were diluted with cold tap water forming rinsing solutions, whose total active concentration, ie the sum of REWOQUAT® WE 18 and Siloxane 5, is 0.025% by weight.
[00262] The cotton towels were immersed for 10 minutes in two liters of the rinsing solution. It should be noted that towels are evenly moistened by the rinse solution. Then, the towels were centrifuged and dried at room temperature, and hung on the clothesline without folds. The treated cotton towels were cut into 10 equal pieces of 16 cm by 25 cm.
[00263] For the evaluation of the touch, an experienced team of 9 testers was assembled, who anonymously evaluated the touch of the sample of the cotton fabric treated with the rinsing solutions, with the aid of a sensory test with the hands. This gave each tester their own cotton towel. The assessment is carried out on a scale from 0 (hard and unpleasant to the touch) to 5 (soft and pleasant to the touch) with the possibility of integer values.
[00264] For the evaluation of the touch the individual values are added, so that from the 9 testers a maximum soft touch of 45 can be produced.
[00265] In the touch samples, an untreated sample not openly labeled (blind value) was also added in addition. Summary of Soft Touch Results

[00266] From the data in the table it can be seen that the softness of the cotton fabric can be greatly improved with the use of a siloxane 5 microemulsion. Direct mixing of REWOQUAT® WE 18 and siloxane 5, as well as the use of a macroemulsion, in contrast, lead to a reduction in softness to the touch. Coating application technology: Formulation example 1) 1K PUR lacquer

Preparation of coatings:
[00267] 100 grams of 1K PUR lacquer, together with either 0.0, 1.5 or 3.0 grams of ME35 or ME36 microemulsion, were weighed in a 180 mL polyethylene beaker (06 cm) and then homogenized with a Dispermaten homogenized with a notched disc (0 3 cm) for 3 minutes of stirring at 2000 rpm (Sample 1-5). After 24 hours of residence time, the paint is applied to a black, PVC phospho laminate (System Leneta ®, 43 x 28 cm) with the aid of a Kasten spatula of a 60 μm system. The coating is then dried for 72 hours at room temperature. Alternatively, the paint is applied with the aid of a 75 μm spiral spatula to a beige leather and likewise dried. Checking of slip (adherence) friction (slip value):
[00268] Slip values were measured on a PVC laminate with an Instron 3300 apparatus (Instron Deutschland GmbH, Pfungstadt, Germany). The appliance measures the force that is required to pull a piece over the coated laminate. The cylinder-shaped part weighing 500 grams and a contact surface of 12.6 cm2 was thus equipped with a felt surface, where this surface is renewed for each measurement. Then the piece was pulled so far (with increasing force) until it moved with a speed of 6 mm/s. The pulling force (load), which is required for the part to move, is also measured. A high adhesion/slip friction or Stick-Slip behavior becomes noticeable through the strong oscillations of the measurement of the tensile force (load) in the measurement.
[00269] Figure 2 shows a representative measurement curve. With the increasing concentration of the microemulsion, the sliding friction is reduced. The strong oscillations of the load in unadditivated samples indicate a high friction friction and adhesion. By adding ME35, the load oscillations in the measurement are reduced, ie the adhesion/slip friction is reduced. Touch Verification:
[00270] For the evaluation of the haptics, an experienced tester qualitatively evaluated the coverings made from calfskin leather. The tester named sample 1 as rubbery. Samples 2 through 5, in contrast, were considered soft. test composition

权利要求:
Claims (17)
[0001]
1. Microemulsion, characterized by the fact that it comprises, as a significant oil phase forming component: (A) at least one polysiloxane containing quaternary ammonium groups of General Formula (I) Ma M'a1 M''a2M'''a3 Db D'b1D''b2 D'''b3 Tc T'c1 Qd Formula (I), in which M = (R13Si O1/2) M' = (R2R12Si O1/2) M'' = (R3R12 Si O1/ 2) M''' = (R4R12Si O1/2) D = (R12 Si O2/2) D' = (R2R1 Si O2/2) D'' = (R3R1 Si O2/2) D''' = (R4R1 Si O2/2) T = (R5 Si O3/2) T' = (R2 Si O3/2) Q = (Si O4/2) a = 0 to 32; preferably 0 to 22, in particular 0 to 12; a1 = 0 to 10, preferably 0 to 5, in particular 0; a2 = 0 to 32; preferably 0 to 22, in particular 1 to 12; a3 = 0 to 10; preferably 0 to 5, in particular 0; with the proviso that a + al + a2 + a3 > 3, preferably > 3; b = 1 to 600, preferably 10 to 500, in particular 20 to 400; b1 = 0 to 10, preferably 0 to 5, in particular 0; b2 = 0 to 80, preferably 0 to 50, in particular 0 to 10; b3 = 0 to 20, preferably 0 to 10, in particular 0; c = 0 to 30, preferably 1 to 20, in particular 2 to 15; c1 = 0 to 10, preferably 0 to 5, in particular 0; d = 0 to 15, preferably 1 to 12, in particular 2 to 10; with the proviso that a2 + b2 > 1, preferably > 3, in particular > 3, and c + cl + d > 1, preferably > 1, in particular > 3; R1 = independently of one another are the same or different linear or branched hydrocarbon radicals, if appropriate, aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably methyl or phenyl, in particular methyl; R2 = independently of one another are the same or different alkoxy or acyloxy radicals, such as for example methoxy, ethoxy, n-propoxy, or iso-propoxy, acetoxy radicals, in particular ethoxy or iso-propoxy radicals; R3 = independently of each other are the same or different organic radicals, which carry quaternary ammonium functions; R4 = independently of each other are the same or different organic epoxy radicals; R5 = independently of one another are radicals, the same or different, R1, R3 or R4, preferably R1, in particular methyl, phenyl, dodecyl or hexadecyl.
[0002]
2. Microemulsion according to claim 1, characterized in that it contains a polysiloxane with: R4 identical or different radicals selected from the group
[0003]
3. Microemulsion according to claim 1, characterized in that it contains a polysiloxane with: R3 groups with the formation -R6-R7, where R6 are the same or different bivalent radicals selected from the group
[0004]
4. Microemulsion, according to any one of claims 1 to 3, characterized by the fact that it contains a polysiloxane with: c = 1, and c + c1 + d = 1.
[0005]
5. Microemulsion according to any one of claims 1 to 4, characterized in that the polysiloxane has an average molecular weight greater than 4000 g/mol, preferably greater than 7000 g/mol, in particular greater than 10000 g /mol.
[0006]
6. Microemulsion according to any one of claims 1 to 5, characterized in that it additionally contains at least one of the components: (B) a nonionic surfactant, (C) a cosurfactant selected from the group that contains, preferably consists of anionic, cationic and amphoteric surfactants, and (D) water.
[0007]
7. Microemulsion according to any one of claims 1 to 6, characterized in that it is essentially free of alkoxylated compounds.
[0008]
8. Microemulsion according to claim 7, characterized in that component (B) is selected from the group consisting of: glycerin monoester and glycerin diester, and sorbitan monoester and sorbitan diester of fatty acids saturated and unsaturated, alkyl monoglycoside and alkyl oligoglycoside, partial ester based on linear, branched, unsaturated or saturated fatty acids, ricinoleic acid, as well as 12-hydroxystearic acid and glycerin, polyglycerin, pentaerythritol, sugar dipentaerythritol, (eg sorbitan), alkyl glucosides (eg methyl glucoside, butyl glucoside, lauryl glucoside) as well as polyglucosides (eg cellulose), alkyl monophosphate, alkyl diphosphate and alkyl triphosphate and their salts, citric acid ester, such as glyceryl citrate stearate, glyceryl citrate oleate and dilauryl citrate, as well as glyceryl caprylate, polyglyceryl caprylate, caprate of polyglyceryl, and mixtures of these surfactants.
[0009]
9. Microemulsion according to any one of claims 1 to 8, characterized in that it additionally contains a component (E), solvent, selected from the group comprising hydrotropes, for example from the group of aliphatic alcohols, such as ethanol, propanol or 1,3-propanediol, cyclic carbonates such as ethylene carbonate, propylene carbonate, glycerin carbonate, monocarboxylic or polycarboxylic acid esters such as ethyl acetate, ethyl lactate, glycerin, isopropyl alcohol, dipropylene glycol, glycol ether and polyols.
[0010]
10. Microemulsion according to any one of claims 1 to 9, characterized in that it additionally contains a component (F), a preserving agent, and/or a component (G), an oil or a mixture of oils.
[0011]
11. Microemulsion according to any one of claims 1 to 10, characterized in that it contains: component (A) in an amount of 10% by weight to 60% by weight; component (B) in an amount of 3% by weight to 30% by weight; component (C) in an amount of 0% by weight to 30% by weight; component (D) in an amount of 10% by weight to 75% by weight; component (E) in an amount of 0% by weight to 35% by weight; component (F) in an amount of 0% by weight to 1% by weight and component (G) in an amount of 0% by weight to 50% by weight of the total oil phase, consisting of (A) and (G), wherein % by weight, except in the case of component (G), refer to the total microemulsion.
[0012]
12. Process for preparing a microemulsion as defined in any one of claims 1 to 11, characterized in that it covers the steps of the process (I) provision of at least one polysiloxane, as defined in claim 1, (II) if appropriate dissolution of the polysiloxane with at least one solvent (E) and/or a nonionic surfactant of component (B) and/or oil (G), and (III) addition of the remaining microemulsion forming components, where the water and preservative components are added last.
[0013]
13. Process according to claim 12, characterized in that mixing is conducted with a simple stirrer during process steps (I) to (III).
[0014]
14. Care and cleansing formulations, in particular for skin and skin appendages and for domestic and industrial use, in particular cosmetic formulation, fabric softener formulations and laundry products or fabric detergents, characterized by the fact that they contain at least one microemulsion as defined in any one of claims 1 to 11, or at least one microemulsion obtainable according to a process as defined in claim 12 or 13, these preferably being selected from the group of treatment agents. hair and hair after-treatment agents for rinsing or remaining on hair, care and cleaning formulations for boats, vehicles and aircraft, as well as conditioners.
[0015]
15. Formulation according to claim 14, characterized in that it contains the microemulsion in an amount of 0.1% by weight to 99% by weight, the % by weight referring to the total formulation.
[0016]
16. Paints and dyes, in particular for coating fabric, metal, leather, plastic, paper, cardboard and wood, characterized in that they preferably contain, as a binder, an aqueous polyurethane suspension, which contain at least one microemulsion as defined in any one of claims 1 to 11, or at least one microemulsion obtainable by a process as defined in claim 12 or 13.
[0017]
17. Paints and dyes, according to claim 16, characterized in that it contains the microemulsion in an amount of 0.1% by weight to 99% by weight, with the % by weight referring to the total formulation .

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同族专利:

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公开号 | 公开日

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DE102011078382A1|2013-01-03|

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JP2014528967A|2014-10-30|

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CN103648629A|2014-03-19|

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BR112013033420A2|2017-01-24|

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EP2726185A1|2014-05-07|

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WO2013000592A1|2013-01-03|

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US20140134125A1|2014-05-15|

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US9138385B2|2015-09-22|

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EP2726185B1|2018-10-03|

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KR20140056235A|2014-05-09|

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KR101970371B1|2019-04-18|

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JP6328048B2|2018-05-23|

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-05-12| B25D| Requested change of name of applicant approved|Owner name: EVONIK OPERATIONS GMBH (DE) |

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2020-07-07| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-02-02| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-06-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-07-27| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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DE102011078382.2|2011-06-30|

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DE102011078382A|DE102011078382A1|2011-06-30|2011-06-30|Microemulsion of quaternary ammonium group-containing polysiloxanes, their preparation and use|

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PCT/EP2012/054785|WO2013000592A1|2011-06-30|2012-03-19|Microemulsion of quaternary polysiloxanes containing ammonium groups, production and use thereof|

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