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    • 专利摘要:
    compounds and compositions of low viscosity polyorganosiloxanes comprising quaternary ammonium groups, methods for their production and use. the present invention relates to low viscosity polyorganosiloxanes comprising a) at least one polyorganosiloxane group, b) at least one quaternary ammonium group, c) at least one terminal ester group, methods of manufacturing these and their use for the modification of surfaces of substrates.
    公开号:BR112014024182B1
    申请号:R112014024182-1
    申请日:2013-03-26
    公开日:2021-06-29
    发明作者:Karl-Heinz Stachulla；Karl-Heinz Sockel；Sigfredo Gonzales；Roland Wagner；Anne Dussaud
    申请人:Momentive Performance Materials Gmbh；
    IPC主号:
    专利说明:

    Reference to Related Requests
    [001] This Application claims priority to United States Provisional Patent Application Serial Number 61/617,180, filed March 29, 2012. Field of Invention
    [002] The present invention provides a polyorganosiloxane having a low viscosity and comprising quaternary ammonium groups and terminal ester groups, methods for the production and use thereof. Background of the Invention
    [003] Silicone quats (silicones containing quaternary ammonium groups optionally containing polyorganosiloxane substituents) are known to be highly substantial. DE 3719086 describes the reaction of α,(^-diepoxides with tertiary amines in the presence of acids, producing α,o-diquaternary siloxanes. They can be used for hair care purposes. DE 3719086 describes tetraalkyl derivatives as well as aromatic imidazolinium derivatives.
    [004] The reaction of α,(^-diepoxides with di-tertiary amines in the presence of acids provides polyquaternary polyorganosiloxanes in polyloop (document EP-A-282720).The advantage of these materials is an improved resistance to hair washing.
    [005] The reaction of α,(^-diepoxides with dimethylamine in the presence of acids that produces polyquaternary polyorganosiloxanes in polyloop having a quat group between the siloxane blocks is described in US 6,730,766.
    [006] Polyquaternary imidazolinium derivatives are described in US 6,240,929. These cationic compounds have improved compatibility with anionic surfactants in cosmetic formulations.
    [007]The incorporation of alkylene oxide moieties in silicone quats further increases the hydrophilicity.
    [008] Silicone quats containing quat groups as well as polyethylene oxide moieties in side chains are described in US 5,098,979, US 5,153,294 and US 5,166,297. The substantivity of materials is relatively low.
    [009] Silicone-based block copolymers containing quat functions which also include polyether moieties are described in WO 02/10257, WO 02/10259 and US 2002/0103094 A. The alkylene oxide structures are incorporated in the copolymer in blocks as α,<B-difunctional portions.
    [010] The document US 6,242,554 describes α,<B-difunctional siloxane derivatives containing a polyether function and a quat function separated from each other. The substantivity of these monoquats is insufficient.
    [011] The document US 4,921,895 describes mixtures of polyether siloxanes and quaternary ammonium groups containing siloxane block copolymers for textile finishing purposes. Here, the use of polyether siloxane improves the finished products and hydrophilicity.
    [012] US 2007/0286837, US 2007/0041929, US 2008/0292575 and CN 101198311 describe combinations between silicone quats having a siloxane chain length of more than 200 D units and a second silicone for conditioning purposes of hair. A possible choice of the second silicone is the choice of silicone polyethers derived from ethylene oxide or propylene oxide or mixtures thereof. Specific structures are not provided.
    [013] None of the prior art descriptions above describe a direct methodology for the preparation of low viscosity polyorganosiloxanes comprising quaternary ammonium groups. Low viscosity materials would make the incorporation of substituents that enhance hydrophilicity, such as polyethers, superfluous or redundant, thus reducing system complexity. Invention Summary
    [014] The present invention provides a low viscosity silicone (oligomeric or polymeric siloxane which is a homopolymer, copolymer or terpolymer) functionalized with quaternary ammonium groups and comprising one or more terminal ester groups as follows: a polyorganosiloxane compound comprising: at least one polyorganosiloxane group, at least one quaternary ammonium group, at least one terminal ester group.
    [015] The present invention further provides a method of preparing the compounds of the present invention comprising reacting: at least one ditertiary diamine and/or secondary monoamine, at least one amino alkylating compound comprising at least one diepoxide, and at least at least one monofunctional organic acid, wherein at least one compound among compounds (i) and (ii) comprises polyorganosiloxane structural units. Detailed Description of the Invention
    [016] The present invention provides low viscosity polyorganosiloxanes comprising quaternary ammonium groups, their manufacture and the use of materials.
    [017] Surprisingly, polyorganosiloxanes comprising quaternary ammonium groups having a low viscosity are obtained by preparing polyorganosiloxane compounds comprising quaternary ammonium groups and terminal ester groups. That is, according to the present invention, polyorganosiloxane compounds are provided comprising: polyorganosiloxane groups, quaternary ammonium groups terminal ester groups wherein preferably, in one embodiment, the molar ratio of the quaternary ammonium groups b) and the terminal ester groups c) is less than 100:20.
    [018] The polyorganosiloxane compounds according to the invention are preferably linear copolymer compounds comprising the functional groups a), b) above, with at least part of the end groups being end ester groups resulting from the use of acids monofunctional organics as chain terminators (formally a [(AB)xA] type product (where x > 1). However, depending on the stoichiometry of the reactants, the polyorganosiloxane compounds according to the invention may also comprise compounds that result from the reaction of a difunctional monomer, with only one compound at each end of it ([(AB)xA] type product (where x = 1).
    [019] In a preferred embodiment, the polyorganosiloxane compounds of the invention do not contain polyalkylene oxide groups, except for the polyalkylene oxide groups in the terminal ester groups such as, in particular, those of the general formulas:
    with q = 0 to 200, r = 0 to 200, s = 0 to 200 and q + r + s = 1 to 600.
    [020] In a preferred embodiment of the polyorganosiloxane compounds according to the invention, at least one of the polyorganosiloxane groups are of the general formula:
    where R1 = C1-C22 alkyl, C1-C22 fluoroalkyl or aryl, n = 0 to 1000, and these may be identical or different if several S groups are present in the polyorganosiloxane compound, preferably, for example, n is, for example example, in the range 0-200 or >200 to 1000; K = is a bivalent or trivalent straight-chain, cyclic and/or branched C2-C40 hydrocarbon residue which is optionally interrupted by —O—, —NH—, trivalent N, —NR1—, —C(O) — , -C(S) - and optionally substituted by -OH, where R 1 is defined as above, so that the K residues may be identical or different from each other. In such a group —K—S—K—, the K residue is attached to the silicon atom of the S residue through a C-Si bond.
    [021] In a preferred embodiment, the polyorganosiloxane compounds according to the invention comprise at least one repeating unit comprising at least one quaternary ammonium group selected from the general formulas:
    a mono or diquaternary, saturated or unsaturated heterocycle of the formulas:
    an aromatic ammonium heterocycle of the formula:
    wherein R is selected from monovalent organic groups having up to 22 carbon atoms and optionally one or more heteroatoms and where the free valences on the nitrogen atoms are attached to carbon atoms and T is selected from a bivalent organic group having up to 20 atoms of carbon and one or more heteroatoms. More specifically, T is selected from the group of bivalent hydrocarbon radicals comprising from one to twenty carbon atoms and, as used herein for the definition of T, the word comprising includes the group of heteroatoms selected from the group of oxygen, sulfur, nitrogen and phosphorus . In the present invention, the term quaternary ammonium group refers to a positively charged nitrogen atom that binds to 4 carbon atoms (formerly known as NR4+ groups).
    [022] In a preferred embodiment of the invention, the terminal ester groups are selected from the group of:

    wherein Z is selected from monovalent organic residues having up to 40 carbon atoms, optionally comprising one or more heteroatoms. As will be explained in detail below, these terminal ester groups result from the use of monofunctional organic acids, such as carboxylic acids (-OC(O)-Z), sulfonic acids (-OS(O)2-Z), acid half ester sulfuric acid -OS(O2)OZ), phosphoric acid monoester (-OP(O)(OZ)OH, phosphoric acid diester (-OP(O)(OZ)2) in reaction with diepoxides.
    [023] In a preferred embodiment, the polyorganosiloxane compounds according to the invention have the general formula (I):
    where: m is an average value from 1 to 100, preferably from 1 to 50, more preferably 1 to 20, even more preferably 1 to 10, k is 0 or an average value of > 0 to 50, preferably 1 to 20, more preferably 1 to 10, M represents a terminal group comprising terminal ester groups selected from:
    wherein Z is as defined above, R2 is selected from hydrogen or R, Y is T or a group of the formula:
    each as defined above, provided that at least one Y is a group of the formula
    , and T is as defined above.
    [024]If amine groups are present in the polyorganosiloxane compounds according to the invention, they can be protonated, for example, with organic or inorganic acids. Such compounds are sometimes referred to as acid addition salts of the polyorganosiloxane compounds according to the invention.
    [025] In a preferred embodiment, in the polyorganosiloxane compounds, the molar ratio of the quaternary ammonium groups b) and the terminal ester groups c) is less than 100:30 and is more preferably less than 100:50. The ratio can be determined by 13C-NMR.
    [026] The polyorganosiloxane compounds according to the invention are preferably manufactured by a process comprising the reaction of: at least one ditertiary diamine and/or secondary monoamine, at least one amino-alkylation compound comprising at least at least one diepoxide, and at least one monofunctional organic acid, wherein at least one compound among compounds (i) and (ii) comprises polyorganosiloxane structural units.
    [027] The present invention further relates to polyorganosiloxane compounds which are obtainable by means of the process according to the invention, as described above.
    [028] Another embodiment of the present invention relates to polyorganosiloxane compositions comprising: at least one polyorganosiloxane compound according to the invention, at least one polyorganosiloxane compound comprising at least one terminal ester group different from compound A).
    [029] In the definition of component A), reference can be made to the description of the polyorganosiloxane compounds of the invention. Polyorganosiloxane compound B) differs from polyorganosiloxane compound A) preferably in that it does not comprise quaternary ammonium groups. Preferred polyorganosiloxane compounds B) result from the reaction of monofunctional organic acids, in particular carboxylic acids, and polyorganosiloxane containing bisepoxides.
    [030] In the polyorganosiloxane compositions according to the invention, the weight ratio of compound A) to compound B) is preferably less than 90:10 or, in other words, the content of component B) is max. minus 10 percent by weight. In another preferred embodiment of the polyorganosiloxane compositions according to the invention, in compound A), the molar ratio of the quaternary ammonium groups b) and the terminal ester groups c) is less than 100:20.
    [031] Both the polysiloxane/polyorganosiloxane compounds and the polysiloxane/polyorganosiloxane compositions according to the invention preferably have a viscosity at 20°C and a shear rate of 0.1 s-1 (plate-plate system , 40 mm plate diameter, 0.5 mm spacing) of less than 100,000 mPas (100 Pas).
    [032] The present invention also relates to aqueous emulsions comprising at least one polyorganosiloxane compound and/or at least one polyorganosiloxane composition, as defined above or below. Such aqueous emulsions preferably comprise at least 30 percent by weight, preferably at least 50 percent by weight, even more preferably at least 80 percent by weight based on water relative to the total weight of the emulsion.
    [033] The present invention further relates to a surface treatment method comprising the step of applying polyorganosiloxane compounds, polyorganosiloxane compositions or aqueous emulsions, as defined in any one of the preceding claims, to the surface of a substrate . Any method of application is conceivable, for example simple wetting, contacting, washing, dipping, spraying, brushing, dispersing operations conventionally known in the art can be cited.
    [034] In such a method, preferably, one of the following compositions or formulations, respectively, are applied: cosmetic formulations for skin and hair care selected from Rinse-off and Leave-on conditioners, shampoos, styling gels, sprays and sprays; polishing formulations for treating and coating hard surfaces; formulations for drying automobiles and other hard surfaces; formulations for initial coating of textile fabrics and fibers; softener formulations additionally comprising non-ionogenic or anionic/non-ionogenic or cationic surfactants or betaine for application during or after washing fabrics; laundry formulations for washing fabrics based on nonionic or anionic/nonionic or cationic surfactants or betaine or formulations to prevent or reverse wrinkles in fabrics. Other preferred embodiments of the invention:
    [035] In the polyorganosiloxane structural unit with the general formula S:
    where R1 = C1-C22 alkyl, C1-C22 fluoroalkyl or aryl, n = 0 to 1000, preferably 0 to 500, more preferably 0 to 300, even more preferably 0 to 200, specifically 0 to 100 or in some cases , > 200 to 1000. K (in the group —K—S—K—) is preferably a bivalent or trivalent straight-chain, cyclic and/or branched C2-C40 hydrocarbon residue, which is optionally interrupted by — O—, —NH—, N trivalent, —NR1—, —C(O) —, —C(S) — and optionally substituted by —OH.
    [036] In the polyorganosiloxanes of the invention, the positive charges resulting from the ammonium group(s) are neutralized with inorganic anions, such as chloride, bromide, hydrogen sulfate, sulfate, or organic anions, such as carboxylates derived from carboxylic acids C1-C30, for example, acetate, propionate, octanoate, especially of C10-C18 carboxylic acids, for example, decanoate, dodecanoate, tetradecanoate, hexadecanoate, octadecanoate and oleate, alkyl polyether carboxylate, alkyl sulfonate, aryl sulfonate, alkylaryl sulfonate, alkyl sulfate, alkyl polyether sulfate, phosphates derived from mono alkyl/aryl ester of phosphoric acid and dialkyl/aryl ester of phosphoric acid. The properties of polyorganosiloxane compounds can be modified, inter alia, based on the selection of acids used.
    [037] Quaternary ammonium groups, as contained in the polyorganosiloxanes of the present invention, are usually generated through the reaction of ditertiary diamines with selected alkylating agents, in particular, from diepoxides (sometimes also referred to as bisepoxides) in the presence of difunctional monocarboxylic acids and alkyl dihalogen compounds.
    [038]R1 is more preferably C1-C18 alkyl, C1-C18 fluoroalkyl and aryl. Furthermore, R1 is preferably C1-C18 alkyl, C1-C6 fluoroalkyl and aryl. Furthermore, R1 is preferably C1-C6 alkyl, C1-C6 fluoroalkyl, more preferably C1-C4 fluoroalkyl and phenyl. Even more preferably, R1 is methyl, ethyl, trifluoropropyl and phenyl.
    [039] Within the scope of the present invention, the term "C1-C22 alkyl" means that the aliphatic hydrocarbon groups have from 1 to 22 carbon atoms, which can be straight-chain or branched. Methyl, ethyl, propyl, n-butyl, pentyl, hexyl, heptyl, nonyl, decyl, undecyl, isopropyl, neopentyl and 1,2,3-trimethyl hexyl serve as examples.
    [040] Within the scope of the present invention, the term "C1-C22 fluoroalkyl" means aliphatic hydrocarbon compounds with 1 to 22 carbon atoms, which can be straight-chain or branched and are substituted by at least one fluorine atom. Monofluoromethyl, monofluoroethyl, 1,1,1-trifluoroethyl, 1,1,1-trifluoropropyl, 1,2,2-trifluorobutyl are given as examples.
    [041] Within the scope of the present invention, "aryl" means phenyl unsubstituted or substituted one or more times by OH, F, Cl, CF3, C1-C6 alkyl, C1-C6 alkoxy, C3-C7 cycloalkyl, C2-C6 alkenyl or phenyl. The expression can also mean naphthyl if necessary.
    [042] In a preferred embodiment, the polyorganosiloxane compounds are of general formula (I):
    where each of the groups is as defined above. Z in M groups:
    is preferably a C1-C20, preferably C2 to C18, straight-chain, cyclic or branched, saturated or unsaturated hydrocarbon radical which may be interrupted by one or more -O- or -C(O)- and substituted by —OH.
    [043] Preferred M groups are -OC(O)-Z resulting from normal carboxylic acids, in particular with more than 10 carbon atoms such as, for example, dodecanoic acid.
    [044] In a preferred embodiment of the invention, the molar ratio of the polyorganosiloxane-containing repeating group —K—S—K— and the repeating group Y is between 100:0. As the case may require, it can also be between 100:1 and 1:100, preferably between 20:1 and 1:20, even more preferably between 10:1 and 1:10.
    [045] In the group
    , the R groups preferably represent a straight-chain, cyclic or branched monovalent C1-C20 hydrocarbon radical which may be interrupted by one or more -O-, -C(O) - and may be replaced by -OH , T preferably represents a straight-chain, cyclic or branched bivalent C1-C20 hydrocarbon radical which may be interrupted by -O-, -C(O) - and may be substituted by hydroxyl.
    [046] Viscosities of pure polymers according to this embodiment of the invention are preferably < 100,000 mPa.s, preferably < 70,000 mPa.s, more preferably < 50,000 mPa.s and even more preferably < 20,000 mPa.s. s specifically < 10,000 mPa.s, more specifically < 5,000 mPa.s but preferably does not fall much below 500 mPa.s, determined at 20°C and a shear rate of 0.1 s-1 . The molecular weight is between 10,000 and 100,000 g/mol, measured as the weight average Mw using gel permeation chromatography (GPC) and polystyrene as a standard.
    [047] In a preferred embodiment of the invention, K is a bivalent hydrocarbon radical having at least 4 carbon atoms, which contains a hydroxyl group and can be interrupted by an oxygen atom. Such groups include, for example:


    [048] The polyorganosiloxane compounds of the invention are preferably produced in a first modality, by means of a method in which, first, α,® functionalized Si-H siloxanes of the general structure:
    are converted, in the presence of a hydrosilylation catalyst and at temperatures of 50°C to 150°C, with 1.0 to 1.5 mol, based on SiH groups, of an alkenyl epoxide, which has an olefinic bond terminal, wherein the alkenyl epoxide contains at least four carbon atoms and may additionally contain a non-cyclic ether group. Cyclohexene vinyl oxide and allyl glycide ether are preferably used as epoxy-functional precursors for the production of functionalized epoxy siloxanes. Excess olefinic epoxide is then removed if necessary.
    [049] The bisepoxide is preferably reacted with a mixture of a diamine, for example, the preferred diamine of the formula:
    with R and T as defined above, or a secondary monoamine (which reacts twice to be quaternized).
    [050]Optionally, in addition, an alkyl ester of α,® halocarboxylic acid can act as an alkylating agent.
    [051] The reaction is preferably carried out in the presence of an organic acid at 40 °C to 150 °C, wherein the molar ratio of tertiary amino groups: ∑ (epoxy groups + optional halocarboxylic acid ester groups) is, for example, < 1:1, preferably < 0.98:1, more preferably < 0.9:1, even more preferably < 0.7:1, specifically < 0.5:1, the molar ratio of organic acid : epoxy groups ranges from 3:1 to 1:1, preferably from 2:1 to 1:1, more preferably from 1.5:1 to 1:1, even more preferably from 1.2:1 to 1:1 , specifically 1:1.
    [052] This means that, for example, by reducing the molar amount of tertiary amine and/or increasing the molar amount of organic acids, low viscosity polyorganosiloxane compounds of the present invention can be synthesized.
    [053] In a preferred variation of embodiment, species containing the various amino groups can be added to the batch, optionally together with the halocarboxylic acid ester derivatives, if necessary with the simultaneous addition of equimolar amounts of acid. It is also within the scope of the invention, however, to first cause the epoxy derivatives, the halocarboxylic acid ester derivatives and the di-tertiary amines to react in the presence of an amount of acid that is equivalent to that of the epoxy groups.
    [054] Likewise, it is possible to make the halocarboxylic acid ester derivatives and the di-tertiary amines to react, forming hydrophilic blocks and, after adding the epoxy derivatives, if necessary in the presence of an amount of acid that is equivalent to that of the epoxy groups in the reaction mixture.
    [055]During the time in which the individual components are being added, the sequential distribution in the polymers being formed can be influenced.
    [056] It is further within the scope of the present invention to cause various siloxane components of various chain lengths to react while maintaining the desired overall stoichiometry. From this it follows, for example, the possibility of creating a desired siloxane chain length using a single siloxane component or by the intentional mixing of several siloxane components.
    [057]Alkylation and quaternization reactions are preferably carried out in polar organic solvents.
    [058] Suitable solvents are, for example, organic solvents and water including, in particular, mixtures of organic solvents and water, preferably polar organic solvents and water. Polar organic solvents generally include those comprising at least one heteroatom such as, in particular, oxygen, for example alcohols, especially methanol, ethanol, i-propanol and n-butanol; glycols, such as ethylene glycol, diethylene glycol, triethylene glycol, its methyl-, ethyl- and butyl ethers, 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, its methyl-, ethyl- and butyl ethers and 1,3- propylene glycol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate, butyl acetate, methoxypropyl acetate and 2-ethylhexyl acetate; ethers such as tetrahydrofuran; and nitro compounds such as nitromethane.
    [059] It is preferred to carry out the reactions with a weight ratio of ∑ polymeric components: ∑ (organic solvents + water) in a weight range of 100:0 to 20:80, preferably 99.999:0.001 to 20:80, more preferably 95:5 to 20:80, even more preferably 95:5 and 50:50, more preferably 95:5 and 60:40.
    [060] The amount of water in the reaction composition varies, in one embodiment, from 0.1-0.5% by weight, in another embodiment, preferably from 0.01-0.1% by weight; in another embodiment, the amount is in the range of 2-10% by weight and preferably between 0.5-2% by weight. In a preferred embodiment of the invention, the desired amount of water is added separately. It is also possible to add the desired amount of water, for example, in the form of solvent azeotropes or by the amount that is present in commercial grades.
    [061] The polyorganosiloxane compounds described above comprising quaternary ammonium functions and ester functions may contain individual molecules which contain quaternary ammonium functions and no ester functions, molecules which contain quaternary ammonium functions and ester functions, as well as molecules which contain ester functions and no quaternary ammonium function.
    [062] The polyorganosiloxane compounds described above comprising quaternary ammonium functions and ester functions should be understood as mixtures of molecules comprising a certain amount and average proportion of both portions.
    [063] Another less preferred embodiment of the invention relates to polyorganosiloxane compositions comprising: at least one polyorganosiloxane compound as defined above, at least one polyorganosiloxane compound comprising at least one terminal ester group different from compound A).
    [064] Such polyorganosiloxane compositions comprising quaternary ammonium functions and polyorganosiloxane compounds comprising ester functions are physically mixed in order to adjust the desired ratio of quat(N+):ester and the desired viscosity according to the invention.
    [065] Both compounds are mixed in a ratio which fulfills the viscosity requirement described above according to the invention. The blends have a viscosity at 20°C and a shear rate of 0.1 s-1 from 500 to 100,000 mPas, preferably from 500 to 70,000 mPas, more preferably 500 to 50,000 mPas, even more preferably 500 to 20,000 mPas, specifically 500 to 10000 mPas, more specifically 500 to 5000 mPa.s. The molecular weight is between 10,000 and 100,000 g/mol, measured as weight average Mw by gel permeation chromatography (GPC) and polystyrene as a standard.
    [066] Polyorganosiloxane compounds A) comprising quaternary ammonium functions are, for example, known from WO 02/10257. The synthesis of polyorganosiloxane compounds comprising ester functions is known from WO 2011/064255. They can, for example, be synthesized from the corresponding epoxy siloxanes by means of esterification with acids in the presence of a tertiary amine catalyst. Preferred polyorganosiloxane compounds B) comprising an ester function are modified α,o-ester derivatives of the structure M-(K-Sn-K)-M having siloxane chain length in the range of n = 0 to 1000, preferably 0 to 500, more preferably 0 to 300, even more preferably 0 to 200, specifically 0 to 100 Alternatively, comb-type derivatives comprising ester function as side groups in a difunctional siloxane unit (OSiMeR* with R* = ester group carbon bonded) and optionally terminal ester moieties (O1/2SiMe2R* with R* = carbon bonded ester group) of the same chain length range of n are also preferred. The number of siloxy units containing ester group is preferably from 1 to 500, more preferably 1 to 250, more preferably 1 to 150, even more preferably 1 to 100, specifically 1 to 50, more specifically 1 to 25.
    [067] Preferred monofunctional organic acids that provide the esters are those that form the counterions mentioned above. Preferred examples are C1-C30 carboxylic acids, eg C2, C3, C8 carboxylic acids, C10-C18, eg C12, C14, C16, C18 saturated, unsaturated and hydroxyl functionalized acids, alkyl polyether carboxylic acids, alkyl sulfonic acids, aryl sulfonic acids, alkyl aryl sulfonic acids, alkyl sulfuric acids, alkyl polyether sulfuric acids, mono alkyl/aryl phosphoric acid esters and dialkyl/aryl phosphoric acid esters.
    [068] The invention also relates to the use of the polyorganosiloxane compounds described above in cosmetic formulations for skin and hair care, in polishing agents for treatment and coating of hard surfaces, in formulations for drying cars and other hard surfaces, for example, after automatic washing, for finishing fabrics and textile fibers, as separate softeners for use after fabrics have been washed with non-ionogenic or anionic/non-ionogenic detergent formulations, as softeners in fabric washing formulations that are based on non-ionic or anionic/non-ionic surfactants and as a means of preventing or removing wrinkles in tissues.
    [069] The invention further relates to the use of the polyorganosiloxane compounds described above as hydrophilic wash-resistant softeners for use in original fabric finishing.
    [070] The invention further relates to compositions containing at least one of the polyorganosiloxane compounds together with at least one additional component that is commonly used in such a composition.
    [071] Below, a number of typical examples of these types of compositions are provided, in which the polyorganosiloxane compounds of the invention can be advantageously used:
    [072] Typical adjuvants in these types of compositions are, for example, the materials described in A. Domsch: Die Kosmetischen Praeparate [Cosmetic Preparations] Vol. I and II, 4th Edition, Verl. fuer chem. Industrie [Publishers for the Chemical Industry], U. Ziolkowsky KG, Augsburg and the International Cosmetic Ingredient Dictionary and Handbook, 7th Ed. 1997 by JA Wenninger, GN McEwen, Vol. 1-4 by The Cosmetic, Toiletry and Fragrance Association, Washington A.D Anionic Shampoo
    [073]This formulation example is provided as a basic formulation. Anionic shampoos commonly contain, but are not limited to, the following components: • Alkyl sulfates, alkyl ether sulfates, sodium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl sulfate, ammonium lauryl ether sulfate, TEA-lauryl sulfate, TEA- lauryl ether sulphates, alkylbenzene sulphonates, α-olefin sulphonates, paraffin sulphonates, sulfosuccinates, N-acyltauredes, sulphate-glycerides, sulphated alkanolamines, carboxylate salts, N-acyl amino acid salts, silicones, etc.
    non-ionic shampoo
    [074]This formulation example is provided as a basic formulation. Nonionic shampoos commonly contain, but are not limited to, the following components: •Monoalkanolamides, monoethanolamides, monoisopropanolamides, polyhydroxy derivatives, sucrose monolaurate, polyglycerin ether, amine oxides, polyethoxylated derivatives, sorbitol derivatives, silicones, etc.
    Amphoteric shampoo
    [075]This formulation example is provided as a basic formulation. Product formulations in this category commonly contain, but are not limited to, the following components: •N-alkyl-iminodipropionates, N-alkyl-iminopropionates, amino acids, amino acid derivatives, starch betaine, imidazolinium derivatives, sulphobetaines, sultains, betaine , silicones, etc.

    cationic shampoo
    [076]This formulation example is provided as a basic formulation only. Product formulations in this category commonly contain, but are not limited to, the following components: •Bis-quaternary ammonium compounds, bis(trialkyl ammonium acetyl) diamines, starch amines, alkyl ammonium esters, silicones, etc.
    fasteners
    [077]This formulation example is provided as a basic formulation only. Formulations in this category commonly contain, but are not limited to, the following components: •Fatty acids, fatty acid esters, ethoxylated fatty acids, ethoxylated fatty acid esters, fatty alcohols, ethoxylated fatty alcohols, glycols, glycol esters, glycerine, esters glycerin, lanolin, lanolin derivatives, mineral oil, petroleum jelly, lecithin, lecithin derivatives, waxes, wax derivatives, cationic polymers, proteins, protein derivatives, amino acids, amino acid derivatives, humectants, thickeners, silicones, etc.
    "Clear Rinse-Off" Fasteners
    [078]This formulation example is provided as a basic formulation. Product formulations in this category commonly contain, but are not limited to, the following components: • Fatty acids, fatty acid esters, ethoxylated fatty acids, ethoxylated fatty acid esters, fatty alcohols, ethoxylated fatty alcohols, glycols, glycol esters, glycerin , glycerin esters, lanolin, lanolin derivatives, mineral oil, petroleum jelly, lecithin, lecithin derivatives, waxes, wax derivatives, cationic polymers, proteins, protein derivatives, amino acids, amino acid derivatives, humectants, thickeners, silicones , etc.

    Hair Foam Fixers
    [079]This formulation example is provided as a basic formulation. Product formulations in this category contain, but are not limited to, the following components: • Fatty acids, fatty acid esters, ethoxylated fatty acids, ethoxylated fatty acid esters, fatty alcohols, ethoxylated fatty alcohols, glycols, glycol esters, glycerin, glycerin esters, lanolin, lanolin derivatives, mineral oil, petroleum jelly, lecithin, lecithin derivatives, waxes, wax derivatives, cationic polymers, proteins, protein derivatives, amino acids, amino acid derivatives, humectants, thickeners, silicones, solvents, ethanol, isopropanol, isoparaffinic solvents, butane, propane, isobutane, CFC's fluorinated aerosol propellants, dimethyl ether, compressed gases, etc.
    Hair Spray (Fixers)
    [080]This formulation example is provided as a basic formulation only. Formulations in this category commonly contain, but are not limited to, the following components: •Fatty acids, fatty acid esters, ethoxylated fatty acids, ethoxylated fatty acid esters, fatty alcohols, ethoxylated fatty alcohols, glycols, glycol esters, glycerine, esters glycerin, lanolin, lanolin derivatives, mineral oil, petroleum jelly, lecithin, lecithin derivatives, waxes, wax derivatives, cationic polymers, proteins, protein derivatives, amino acids, amino acid derivatives, humectants, thickeners, silicones, solvents, ethanol, isopropanol, isoparaffinic solvents, etc.
    Hair Spray Fixers
    [081]This formulation example is provided as a basic formulation. Product formulations in this category commonly contain, but are not limited to, the following components: • Fatty acids, fatty acid esters, ethoxylated fatty acids, ethoxylated fatty acid esters, fatty alcohols, ethoxylated fatty alcohols, glycols, glycol esters, glycerin , glycerin esters, lanolin, lanolin derivatives, mineral oil, petroleum jelly, lecithin, lecithin derivatives, waxes, wax derivatives, cationic polymers, proteins, protein derivatives, amino acids, amino acid derivatives, humectants, thickeners, silicones , solvents, ethanol, isopropanol, isoparaffinic solvents, butane, propane, isobutane, CFC's fluorinated aerosol propellants, dimethyl ether, compressed gases, etc.
    Hair Gel Fixers
    [082]This formulation example is provided as a basic formulation. Product formulations in this category commonly contain, but are not limited to, the following components: • Thickeners, cellulose derivatives, acrylic acid derivatives, fixative polymers, conditioning chemicals, glycols, glycol esters, glycerin, glycerin esters, lanolin , lanolin derivatives, mineral oil, petroleum jelly, lecithin, lecithin derivatives, waxes, wax derivatives, cationic polymers, proteins, protein derivatives, amino acids, amino acid derivatives, humectants, silicones, solvents, ethanol, isopropanol, isoparaffin solvents , etc.
    Rinse off conditioner
    [083]This formulation example is provided as a basic formulation. Formulations in this category commonly contain, but are not limited to, the following components: • Cationic hydrocarbon based conditioners, cationic silicone based conditioners, high melting point fatty compounds, low melting oil type ester compounds, thickeners, cellulose derivatives, fixative polymers, ethylene glycols, propylene glycols, glycol esters, glycerin, glycerin esters, monohydric alcohols, polyhydric alcohols, cationic polymers, nonionic co-emulsifiers and betaine, silicones, forming agents complex, solvents, fragrances, vitamins, etc.
    Hair styling gel
    [084]This formulation example is provided as a basic formulation. Product formulations in this category commonly contain, but are not limited to, the following components: • Fixative polymers, lacquers, acrylic acid derivatives, cellulose derivatives, vinyl derivatives, conditioning chemicals, glycols, glycol esters, glycerin, esters of glycerin, lanolin, lanolin derivatives, mineral oil, petroleum jelly, lecithin, lecithin derivatives, waxes, wax derivatives, cationic polymers, proteins, protein derivatives, amino acids, amino acid derivatives, humectants, thickeners, silicones, solvents, ethanol , isopropanol, isoparaffinic solvents, etc.

    [085]This formulation example is provided as a basic formulation. Product formulations in this category commonly contain, but are not limited to, the following components: • Fixative polymers, lacquers, acrylic acid derivatives, cellulose derivatives, vinyl derivatives, conditioning chemicals, glycols, glycol esters, glycerin, esters of glycerin, lanolin, lanolin derivatives, mineral oil, petroleum jelly, lecithin, lecithin derivatives, waxes, wax derivatives, cationic polymers, proteins, protein derivatives, amino acids, amino acid derivatives, humectants, thickeners, silicones, solvents , ethanol, isopropanol, isoparaffinic solvents, butane, propane, isobutane, CFC's fluorinated aerosol propellants, dimethyl ether, compressed gases, etc.

    Hair Spray (Styling)
    [086]This formulation example is provided as a basic formulation. Product formulations in this category commonly contain, but are not limited to, the following components: •Vinyl derivatives, fixative polymers, lacquers, fatty acids, fatty acid esters, ethoxylated fatty acids, ethoxylated fatty acid esters, fatty alcohols, fatty alcohols ethoxylates, glycols, glycol esters, glycerin, glycerin esters, lanolin, lanolin derivatives, mineral oil, petroleum jelly, lecithin, lecithin derivatives, waxes, wax derivatives, cationic polymers, proteins, protein derivatives, amino acids, derivatives of amino acids, humectants, thickeners, silicones, solvents, ethanol, isopropanol, isoparaffinic solvents, butane, propane, isobutane, CFC's fluorinated aerosol propellants, dimethyl ether, compressed gases, etc.

    [087] The use of the polyorganosiloxane derivatives specified in the invention for applications in the hair care field produces favorable results in relation to strengthening, shine, fixation, full-bodied appearance, volume, humidity regulation, color retention, protection against environmental factors (UV, salt water, etc.), maneuverability, antistatic properties, dyeability, etc. EXAMPLES
    [088]The following examples are intended to describe the present invention in greater detail without limiting its scope. Example 1 (Not Invention)
    [089] In a 500 ml three-necked flask equipped with a reflux condenser, thermometer and mechanical stirrer, 150 g (58.7 mmol of epoxy groups) of a silicone diepoxide of the structure:
    1.76 g (58.7 mmol) of lauric acid, 5.06 g of N,N,N',N'-tetramethyl-hexanediamine (58.7 mmol of tert.amine), 31.3 g of 2-propanol and 10.4 g of distilled water are mixed at room temperature. The mixture is heated to reflux for 6 hours. Then the solvents are removed and the material analyzed by means of NMR and viscometry (see Table 1). Water dispersibility as well as emulsion stability are poor. Example 2 (Invention)
    [090] In a 500 ml three-necked flask equipped with a reflux condenser, thermometer and mechanical stirrer, 150 g (58.7 mmol of epoxy groups) of a silicone diepoxide of the structure:
    11.76 g (58.7 mmol) of lauric acid, 2.53 g of N,N,N',N'-tetramethyl-hexanediamine (29.35 mmol of tert.amine), 30.8 g of 2-propanol and 10.3 g of distilled water are mixed at room temperature. The mixture is heated to reflux for 6 hours. Then the solvents are removed and the material analyzed by means of NMR and viscometry (see Table 1). Water dispersibility as well as emulsion stability are improved and at an acceptable level. Table 1
    *4 g of polyorganosiloxane material was added to 200 g of water and mixed with an Ultra Thurrax, ** 13C-NMR.
    [091]The data show that, in the case of Example 1, the reaction protocol that is not of the invention provides a material that contains some ester functions, but has a very high viscosity. As a consequence, a very poor, irregular, lumpy and sticky dispersion in water is formed. Example 2 shows that reaction protocols according to the invention provide low viscosity materials which can be easily dispersed in small droplets having sufficient stability. Example 3 (Invention)
    [092] The non-inventive product of Example 1 is mixed with a lauroyl ester-modified siloxane of the structure:
    which was synthesized from the corresponding epoxy siloxane, lauric acid and triethylamine (catalyst) in propylene glycol mono methyl ether according to WO 2011/064255.
    [093] Mixing experiments are summarized in Table 2. Table 2
    *4 g of polyorganosiloxane material was added to 200 g of water and mixed with an Ultra Thurrax.
    [094] The data for Examples 3.2 and 3.3 in Table 2 show that physical mixing of the non-inventive material of Example 1 with an ester-modified siloxane provides mixtures which fall within the scope of the invention. Example 4 (Invention)
    [095] In a 500 ml three-necked flask equipped with reflux condenser, thermometer and mechanical stirrer, 97.4 g (9 mmol epoxy groups) of a silicone diepoxide of the structure:
    0.36 g (6 mmol) of acetic acid, 0.52 g of N,N,N',N'-tetramethyl-hexanediamine (6 mmol of tert.amine), 96.5 g of methoxypropanol and 1 .97 g of distilled water are mixed at room temperature. The mixture is heated to reflux for 4 hours. Then 0.18 g (3 mmol) of acetic acid are added and the mixture is refluxed for a further 4 hours. Solvents are removed. A polymeric material is obtained having a solids content of 95.68% (120°C/30 min) and a viscosity of 4300 mPa.s (20°C, 0.1 s-1). Example 5 (Invention)
    [096] Conditioning performance was evaluated using a Diastron Pentear Force apparatus. Individual discolored braids (4 g) from International Hair Importers were washed with 10% sodium lauryl sulfate solution and dried. The tresses were placed in a humidity controlled chamber at 50% (relative humidity - RH) overnight before the baseline measurement of strength to comb, Fb.
    [097] The silicone polymer was dissolved in isopropanol to obtain solutions of 0.014% by weight and 0.07% by weight. About 2.8 g of isopropanol solution was evenly distributed over the hair braid with a pipette to obtain 100 ppm and 500 ppm silicone polymer on the hair, respectively. After drying overnight in an oven at 50 °C, the braids were placed in the humidity controlled chamber at 50% relative humidity before measuring the comb force of the treated braid, Ft. to the value of (Fb - Ft) x 100/Ft.
    [098]The results are summarized in Table 3. Table 3
    3 Polyaminopropylmethyl siloxane
    [099] Table 3 shows that the polyorganosiloxane of the invention allows a much better reduction of dry comb strength at low concentrations in the hair care composition.
    权利要求:
    Claims (16)
    [0001]
    1. A polyorganosiloxane compound comprising: a) at least one polyorganosiloxane group, b) at least one quaternary ammonium group, c) at least one terminal ester group, wherein the polyorganosiloxane compound is a linear copolymer compound which comprises the groups functional above a) and b), with at least part of the terminal groups being terminal ester groups c) resulting from the use of monofunctional organic acids as chain terminators, the copolymer being of the [(AB)xA] type, CHARACTERIZED by the fact that d) is greater than 1 and the molar ratio of quaternary ammonium groups b) and terminal ester groups c) is less than 100:20.
    [0002]
    2. A polyorganosiloxane compound, according to claim 1, CHARACTERIZED by the fact that it does not contain polyalkylene oxide groups, except for the terminal ester groups.
    [0003]
    3. Polyorganosiloxane compound, according to claim 1 or 2, CHARACTERIZED by the fact that the polyorganosiloxane group a) has the general formula:
    [0004]
    4. A polyorganosiloxane compound, according to any one of claims 1 to 3, CHARACTERIZED by the fact that the quaternary ammonium group b) is selected from the general formulas:
    [0005]
    5. A polyorganosiloxane compound, according to any one of claims 1 to 4, CHARACTERIZED by the fact that the terminal ester group is selected from the group of:
    [0006]
    6. Polyorganosiloxane compound, according to any one of claims 1 to 5, CHARACTERIZED by the fact that the polyorganosiloxane compound has the formula selected from the general formula (I) and (II):
    [0007]
    7. Polyorganosiloxane compound, according to claim 6, CHARACTERIZED by the fact that m is from 1 to 50. 8. Polyorganosiloxane compound, according to claim 6, CHARACTERIZED by the fact that m is from 1 to 20.
    [0008]
    8. A polyorganosiloxane compound, according to claim 6, CHARACTERIZED by the fact that m is from 1 to 20.
    [0009]
    9. A polyorganosiloxane compound, according to claim 6, CHARACTERIZED by the fact that m is from 1 to 10.
    [0010]
    10. A polyorganosiloxane compound, according to any one of claims 1 to 9, CHARACTERIZED by the fact that it has protonated ammonium groups.
    [0011]
    11. Process for the manufacture of polyorganosiloxane compounds, as defined in any one of claims 1 to 10, CHARACTERIZED by the fact that it comprises the reaction of: (i) at least one ditertiary diamine and/or secondary monoamine, (ii) by at least one amino alkylating compound which comprises at least one diepoxide, and (iii) at least one monofunctional organic acid, wherein at least one compound from compounds (i) and (ii) comprises polyorganosiloxane structural units.
    [0012]
    12. Polyorganosiloxane composition CHARACTERIZED in that it comprises: A) at least one polyorganosiloxane compound as defined in any one of claims 1 to 10, and B) at least one polyorganosiloxane compound comprising at least one terminal ester group different from the compound THE).
    [0013]
    13. Polyorganosiloxane composition according to claim 12, CHARACTERIZED by the fact that the weight ratio of compound A) to compound B) is less than 90:10.
    [0014]
    14. Aqueous emulsion, CHARACTERIZED by the fact that it comprises at least one polyorganosiloxane compound as defined in any one of claims 1 to 10, or a polyorganosiloxane composition as defined in claim 12 or 13.
    [0015]
    15. Method for surface treatment CHARACTERIZED in that it comprises the step of applying the polyorganosiloxane compound, as defined in any one of claims 1 to 10, a polyorganosiloxane composition, as defined in claim 12 or 13, or an aqueous emulsion thereof on the surface of a substrate.
    [0016]
    16. Method according to claim 15, CHARACTERIZED by the fact that the polyorganosiloxane compositions or applied emulsions comprise one of the following: cosmetic formulations for skin and hair care selected from Rinse-off and Leave-on conditioners, shampoos, modeling gels, sprays and sprays; polishing formulations for treating and coating hard surfaces; formulations for drying automobiles and other hard surfaces; formulations for initial coating of textile fabrics and fibers; softener formulations additionally comprising betaine or cationic or anionic/non-ionogenic or non-ionogenic surfactants for application during or after washing fabrics; laundry formulations for fabric washing based on betaine or cationic or anionic/non-ionogenic or non-ionogenic surfactants or formulations to prevent or reverse wrinkles in fabrics.
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    同族专利:
    公开号 | 公开日
    CN104334646A|2015-02-04|
    EP2831178B1|2020-07-22|
    US20150056155A1|2015-02-26|
    EP3357973A1|2018-08-08|
    IN2014MN01906A|2015-07-10|
    US9512275B2|2016-12-06|
    WO2013148635A1|2013-10-03|
    EP2831177B1|2018-05-09|
    BR112014024182A2|2017-06-20|
    US20150299400A1|2015-10-22|
    CN104302705A|2015-01-21|
    WO2013148629A1|2013-10-03|
    JP2015514879A|2015-05-21|
    CN104302705B|2017-04-12|
    EP2831178A1|2015-02-04|
    JP2015519413A|2015-07-09|
    CN104334646B|2017-02-22|
    EP3357973B1|2019-07-31|
    IN2014MN01877A|2015-07-03|
    US9428616B2|2016-08-30|
    EP2831177A1|2015-02-04|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE3705121A1|1987-02-18|1988-09-01|Goldschmidt Ag Th|POLYQUATERIAL POLYSILOXANE POLYMERS, THEIR PRODUCTION AND USE IN COSMETIC PREPARATIONS|
    DE3719086C1|1987-06-06|1988-10-27|Goldschmidt Ag Th|Diquartere polysiloxanes, their production and use in cosmetic preparations|
    DE3802622C2|1988-01-29|1989-11-02|Th. Goldschmidt Ag, 4300 Essen, De|
    US5098979A|1991-03-25|1992-03-24|Siltech Inc.|Novel silicone quaternary compounds|
    US5153294A|1991-03-25|1992-10-06|Siltech Inc.|Silicone ester quaternary compounds|
    US5166297A|1991-03-25|1992-11-24|Siltech Inc.|Silicone ester quaternary compounds|
    FR2777010B1|1998-04-01|2000-06-16|Oreal|HETEROCYCLIC QUATERNARY POLYAMMONIUM SILICIATED POLYMERS AND THEIR USE IN COSMETIC COMPOSITIONS|
    EP1000959B1|1998-11-14|2003-04-16|Goldschmidt AG|Polyetherquat functional polysiloxanes|
    US7041767B2|2000-07-27|2006-05-09|Ge Bayer Silicones Gmbh & Co. Kg|Polysiloxane polymers, method for their production and the use thereof|
    AU9168701A|2000-07-27|2002-02-13|Ge Bayer Silicones Gmbh And Co|Polyammonium-polysiloxane compounds, methods for the production and use thereof|
    US6903061B2|2000-08-28|2005-06-07|The Procter & Gamble Company|Fabric care and perfume compositions and systems comprising cationic silicones and methods employing same|
    DE10139963A1|2001-08-14|2003-03-06|Wacker Chemie Gmbh|Organopolysiloxanes containing quaternary ammonium groups and process for their preparation|
    WO2003078504A1|2002-03-20|2003-09-25|Ge Bayer Silicones Gmbh & Co. Kg|Branched polyorganosiloxane polymers|
    US7585494B2|2002-11-04|2009-09-08|Momentive Performance Materials Gmbh|Formulations used for the treatment of substrate surfaces|
    DE10316662A1|2003-04-11|2004-11-11|Ge Bayer Silicones Gmbh & Co. Kg|Reactive amino and / or ammonium polysiloxane compounds|
    DE102005014311A1|2005-03-30|2006-10-12|Ge Bayer Silicones Gmbh & Co. Kg|Polyamino and / or polyammonium-polysiloxane-colpolymer compounds with comb-like arranged polyalkylenonide units|
    US20070041929A1|2005-06-16|2007-02-22|Torgerson Peter M|Hair conditioning composition comprising silicone polymers containing quaternary groups|
    DE102005036602A1|2005-08-01|2007-02-08|Ge Bayer Silicones Gmbh & Co. Kg|Polyammonium polysiloxane|
    US20070286837A1|2006-05-17|2007-12-13|Torgerson Peter M|Hair care composition comprising an aminosilicone and a high viscosity silicone copolymer emulsion|
    DE102006035512A1|2006-07-31|2008-02-07|Evonik Goldschmidt Gmbh|New polysiloxane compounds useful e.g. as a conditioning agent for hair treating agent, in hair follow-up treating agent, to prepare skin care formulations and to prepare formulations for the cleaning and caring of vehicles|
    US8728450B2|2007-05-23|2014-05-20|The Procter & Gamble Company|Hair conditioning composition comprising quaternized silicone polymer, grafted silicone copolyol, and dialkyl cationic surfactant|
    DE102008014761A1|2008-03-18|2009-12-10|Momentive Performance Materials Gmbh|Use of polyamino and / or polyammonium-polysiloxane copolymer compounds|
    US9340650B2|2009-11-24|2016-05-17|Momentive Performance Materials Gmbh|Hydrophilic/lipophilic modified polysiloxanes as emsulsifiers|
    IN2014MN01906A|2012-03-29|2015-07-10|Momentive Performance Mat Inc|
    JP6250028B2|2012-03-29|2017-12-20|モメンティブ パフォーマンス マテリアルズ ゲーエムベーハー|Low viscosity polyorganosiloxane containing quaternary ammonium groups, process for producing the same and use thereof|CA2867315C|2012-03-29|2017-06-27|Michael Albert Snyder|Hair conditioning compositions comprising low viscosity silicone polymers|
    JP6250028B2|2012-03-29|2017-12-20|モメンティブ パフォーマンス マテリアルズ ゲーエムベーハー|Low viscosity polyorganosiloxane containing quaternary ammonium groups, process for producing the same and use thereof|
    IN2014MN01906A|2012-03-29|2015-07-10|Momentive Performance Mat Inc|
    US20150010487A1|2013-07-03|2015-01-08|The Procter & Gamble Company|Shampoo composition comprising low viscosity silicone polymers|
    US9198849B2|2013-07-03|2015-12-01|The Procter & Gamble Company|Shampoo composition comprising low viscosity emulsified silicone polymers|
    WO2015047786A1|2013-09-27|2015-04-02|The Procter & Gamble Company|Hair conditioning compositions comprising low viscosity emulsified silicone polymers|
    US20160100573A1|2014-10-10|2016-04-14|Momentive Performance Materials Inc.|Quaternary organosilicon surfactants, methods of making same and applications containing the same|
    CN105622945B|2016-03-30|2018-09-14|科凯精细化工（上海）有限公司|Deep finishing agent of a kind of increasing and preparation method thereof|
    US9988404B2|2016-04-07|2018-06-05|Momentive Performance Materials Inc.|Ester-modified organosilicon-based surfactants, methods of making same and applications containing the same|
    US10160834B2|2016-07-13|2018-12-25|Momentive Performance Materials Inc.|Low viscosity polyorganosiloxanes comprising quaternary ammonium groups, methods for the production and the use thereof|
    JP6952768B2|2016-10-21|2021-10-20|ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ|Stable compact shampoo product with low viscosity and containing viscosity reducing agent|
    WO2018075833A1|2016-10-21|2018-04-26|The Procter & Gamble Company|Low viscosity hair care composition|
    WO2018075846A1|2016-10-21|2018-04-26|The Procter & Gamble Company|Concentrated shampoo dosage of foam designating hair conditioning benefits|
    EP3528895A1|2016-10-21|2019-08-28|The Procter & Gamble Company|Concentrated shampoo dosage of foam for providing hair care benefits|
    CN109862944A|2016-10-21|2019-06-07|宝洁公司|For with the foam of dosage form volume and amount of surfactant needed for optimal formulation space delivery consumer|
    US20180110688A1|2016-10-21|2018-04-26|The Procter & Gamble Company|Concentrated Shampoo Dosage of Foam for Providing Hair Care Benefits|
    WO2018075855A1|2016-10-21|2018-04-26|The Procter & Gamble Company|Dosage of foam for delivering consumer desired dosage volume, surfactant amount, and scalp health agent amount in an optimal formulation space|
    EP3528774A1|2016-10-21|2019-08-28|The Procter and Gamble Company|Concentrated shampoo dosage of foam designating hair volume benefits|
    US10982051B2|2017-06-05|2021-04-20|Momentive Performance Materials Inc.|Aqueous compositions for hair treatment comprising polyorganosiloxanes with polyhydroxyaromatic moieties|
    US11179312B2|2017-06-05|2021-11-23|Momentive Performance Materials Inc.|Aqueous compositions for the treatment of hair|
    US11224567B2|2017-06-06|2022-01-18|The Procter And Gamble Company|Hair compositions comprising a cationic polymer/silicone mixture providing improved in-use wet feel|
    US11141370B2|2017-06-06|2021-10-12|The Procter And Gamble Company|Hair compositions comprising a cationic polymer mixture and providing improved in-use wet feel|
    JP2020536885A|2017-10-10|2020-12-17|ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ|Sulfate-free personal cleansing composition with low mineral salt content|
    EP3694480A1|2017-10-10|2020-08-19|The Procter and Gamble Company|Compact shampoo composition containing sulfate-free surfactants|
    EP3694481A1|2017-10-10|2020-08-19|The Procter and Gamble Company|Compact shampoo composition with amino acid based anionic surfactants and cationic polymers|
    US10426713B2|2017-10-10|2019-10-01|The Procter And Gamble Company|Method of treating hair or skin with a personal care composition in a foam form|
    EP3727324A1|2017-12-20|2020-10-28|The Procter & Gamble Company|Low viscosity conditioner composition containing silicone polymers|
    US10912732B2|2017-12-20|2021-02-09|The Procter And Gamble Company|Clear shampoo composition containing silicone polymers|
    EP3501488B1|2017-12-21|2021-04-14|Momentive Performance Materials GmbH|Aqueous silicone polymer compositions|
    US20200163850A1|2018-11-24|2020-05-28|Momentive Performance Materials Gmbh|Use of polyhydroxyaromatic compounds for the treatment of fibrous amino acid based substrates|
    US10617617B1|2018-12-04|2020-04-14|Momentive Performance Materials Inc.|Polycarboxylic acid compounds for the treatment of fibrious amino acid based substrates, especially hair|
    US11090255B2|2018-12-04|2021-08-17|Momentive Performance Materials Inc.|Use of polycarboxylic acid compounds for the treatment of fibrious amino acid based substrates, especially hair|
    WO2021123911A2|2019-12-17|2021-06-24|Momentive Performance Materials Gmbh|Nonionic polymeric fatty acid compounds for the treatment of fibrous amino acid-based substrates, especially hair|
    WO2021123904A1|2019-12-17|2021-06-24|Momentive Performance Materials Gmbh|Polymeric fatty acid compounds for the treatment of fibrous amino acid-based substrates, especially hair|
    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-02-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-11-24| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-05-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-29| 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 26/03/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261617180P| true| 2012-03-29|2012-03-29|
    US61/617,180|2012-03-29|
    PCT/US2013/033806|WO2013148629A1|2012-03-29|2013-03-26|LOW VISCOSITY POLYORGANOSILOXANES COMPRISING QUATERNARY AMMONIUM GROUPS, METHODS FOR THE PRODUCTION AND THE USE THEREOF |
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