Shampoo composition comprising low viscosity emulsified silicone polymers and method to provide enha

专利摘要:
1/1 summary "shampoo composition comprising low viscosity emulsified silicone polymers" the present disclosure relates to a shampoo composition including (a) a silicone polymer including (i) one or more quaternary groups; (ii) at least one block of silicone comprising more than 200 units of siloxane; (iii) at least one polyalkylene oxide structural unit and (iv) at least one terminal ester group and (b) a detersive surfactant. the silicone polymer has a viscosity of up to 100,000 mpa.s. the silicone polymer is a pre-emulsified dispersion with a particle size less than about 1 micron.
公开号:BR112015009782B1
申请号:R112015009782-0
申请日:2014-06-26
公开日:2020-03-24
发明作者:Michael Albert Snyder；Joseph Harry Jansen；Roland Wagner；Martha Jane WEAVER
申请人:The Procter & Gamble Company；
IPC主号:

专利说明:

Invention Patent Descriptive Report: SHAMPOO COMPOSITION UNDERSTANDING EMULSIONED SILICON POLYMERS OF LOW VISCOSITY AND METHOD TO PROVIDE ENHANCED SKIN AND / OR HAIR BENEFITS.
FIELD OF THE INVENTION [0001] The present application provides for a shampoo composition comprising (1) a silicone polymer containing quaternary groups and silicone blocks bonded to alkylene oxides (eg, ethylene oxide and / or oxide of propylene), in which the silicone polymer has a viscosity of up to 100,000 mPa.s, and in which the silicone polymer is a pre-emulsified dispersion with a particle size of less than 1 micron; and (2) a detersive surfactant.
BACKGROUND OF THE INVENTION [0002] Silicone polymers are strategically important materials in hair treatment, specifically to provide conditioning benefits for hair. Human hair is damaged, for example, by combing, permanent curls and / or dyeing. Such damaged hair is often hydrophilic and / or in a rough condition especially when the hair dries, compared to undamaged or less damaged hair. Silicone polymers consisting of blocks of silicones and alkylene oxide (for example, ethylene oxide and propylene oxide (EO / PO) groups) bonded with functional groups of quaternary amines have been used to neutralize the hydrophilic nature of damaged hair . The silicone blocks are responsible for the conditioning and lubrication performance while the functional groups of the quaternary amines included in the polymer chain also help in deposition during the
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2/57 rinse. In particular, the ideal conditioning performance was observed in silicone blocks of more than 200 units D. However, these materials, when pure, generally have high viscosity. To obtain the desired conditioning benefits, these silicone polymers are traditionally used in mixtures with silicone copolyols or other diluents or solvents. [0003] Based on the arguments mentioned above, there is a need for shampoo compositions that provide even more optimized conditioning benefits, such as soft touch and reduced friction on wet hair and dry hair. In addition, there is a need for a shampoo composition that provides optimized conditioning benefits for damaged hair.
SUMMARY OF THE INVENTION [0004] In accordance with an embodiment of the invention, there is presented a shampoo composition comprising (a) a silicone polymer comprising: (i) one or more quaternary groups; (ii) at least one block of silicone comprising more than 200 units of siloxane; (iii) at least one polyalkylene oxide structural unit and (iv) at least one terminal ester group, in which said silicone polymer has a viscosity of up to 100,000 mPa.s, and in which said silicone polymer is a pre-emulsified dispersion with a particle size of less than about 1 micron; and (b) a detersive surfactant.
[0005] In accordance with another embodiment of the invention, a method is presented to provide improved cleaning and conditioning benefits for the hair and / or skin, a method which comprises the step of washing said hair and / or skin with a shampoo composition comprising (a) a silicone polymer comprising: (i) one or more quaternary groups; (ii) at least one block of silicone comprising more than 200 units of siloxane; (iii)
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3/57 at least one polyalkylene oxide structural unit; and (iv) at least one terminal ester group, wherein said silicone polymer has a viscosity of up to 100,000 mPa.s; and (b) a detersive surfactant. These and other features, aspects and advantages of the present invention will become evident to those skilled in the art from reading the description below.
DETAILED DESCRIPTION OF THE INVENTION [0006] Although the specification concludes with claims that particularly point and distinctly claim the invention, it is believed that it will be better understood from the description below.
[0007] In all the modalities of the presented invention, all percentages are by weight of the total composition, except in the case of specific statement to the contrary. All reasons are by weight, unless specifically stated otherwise. The number of significant figures is not representative of either the limitation of the quantities indicated or the accuracy of the measurements. All numerical quantities are understood to be modified by the word about, except where specifically indicated otherwise. Unless otherwise stated, all measurements are understood to be made at 25 ° C and under ambient conditions, with the term ambient conditions meaning conditions with less than 1 pressure atmosphere and about 50% relative humidity. All of these weights, referring to the ingredients in the list, are based on the active content and do not include vehicles or by-products that may be included in the commercially available materials, except where indicated otherwise.
[0008] The term which comprises, as used here, means that other steps and other ingredients that do not affect the final result can be added. This term covers the terms that consists of
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4/57 in and consisting essentially of. The processes of the presented invention may comprise, consist of and consist essentially of elements and limitations of the invention described herein, as well as any of the additional or optional ingredients, components, steps or limitations described herein.
A. Silicone polymer containing quaternary groups [0009] The compositions of the present invention comprise a low viscosity silicone polymer having a viscosity of up to 100,000 mPa.s. Without sticking to the theory, this low viscosity silicone polymer provides optimized conditioning benefits when compared to conventional silicones, because of the addition of hydrophobic functionalities - quaternary amines, ethylene oxides / prolylene oxides. Compared to the silicones with quaternary functionality previously disclosed, these new structures have significantly lower viscosity, so they do not need to be mixed with other lower viscosity dispersants and diluents in order to be able to formulate them as products. Low-viscosity silicone thinners and solvents often cause viscosity and stability losses in shampoo products. The present invention eliminates the need for these materials, since the silicone polymer has a viscosity low enough to be added directly or in emulsion form. The optimized conditioning benefits include soft touch, reduced friction and the prevention of hair damage, while eliminating the need to mix silicone in some modalities.
[00010] Structurally, the silicone polymer is a polyorganosiloxane compound comprising one or more groups of quaternary ammonium, at least one block of silicone comprising more than 200 units of siloxane, at least one structural unit of oxide
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5/57 polyalkylene and at least one terminal ester group. In one or more embodiments, the silicone block can comprise between 300 to 500 units of siloxane.
[00011] The silicone polymer is present in an amount of about 0.05% to about 15%, preferably about 0.1% to about 10%, more preferably about 0.15% about 5%, and most preferably about 0.2% to about 4%, by weight of the composition.
[00012] In a preferred embodiment, the polyorganosiloxane compounds, according to the invention, have the general formulas (Ia) and (Ib):
M — Y - [- (N + R2 — T — N + R2) —Y—] m - [- (NR ² —A — E — A'— NR ² ) —Y—] k — M (Ia)
M — Y - [- (N ⁺ R2 — T — N ⁺ R2) —Y—] m - [- (N ⁺ R ² 2 — A — E—
A'— N + R22) —Y—] k — M (Ib) where:
m is> 0, preferably 0.01 to 100, more preferably 0.1 to 100, even more preferably 1 to 100, specifically 1 to 50, more specifically 1 to 20, more specifically still 1 to 10, k is 0 or one average value of> 0 to 50, or preferably from 1 to 20, or even more preferably from 1 to 10,
M represents a terminal group, comprising terminal ester groups selected from among
-OC (O) -Z
-OS (O) 2-Z
-OS (O2) O-Z
-OP (O) (O-Z) OH
-OP (O) (O-Z) 2 where Z is selected from organic waste
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6/57 monovalent, having up to 40 carbon atoms, optionally comprising one or more;
A and A 'are each independently selected from a single bond or a divalent organic group having up to 10 carbon atoms and one or more hetero atoms, and
E is a group of polyalkylene oxide with the following general formula:
- [CH2CH2O] q— [CH2CH (CH3) O] r— [CH2CH (C2H5) O] s— where q = 0 to 200, r = 0 to 200, s = 0 to 200 and q + r + s = 1 to 600.
R ² is selected from hydrogen or R,
R is selected from monovalent organic groups having up to 22 carbon atoms and optionally one or more hetero atoms, and in which the free valences in the nitrogen atoms are linked to carbon atoms,
Y is a group with the formula:
—K — S — K— and —A — E — A'— or — A'— E — A—, with S =
wherein R1 = C1-C22-alkyl, C1-C22-fluoralkyl or aryl; n = 200 to 1,000, and these can be identical or different if several S groups are present in the polyorganosiloxane compound;
K is a bivalent or trivalent, cyclic and / or branched C2-C40 straight chain hydrocarbon residue that is optionally interrupted by —O -, - NH—, trivalent N, —NR ¹ -, - C (O) -, - C (S) - and optionally replaced by —OH, where R ¹ is defined as above,
T is selected from a divalent organic group having
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7/57 up to 20 carbon atoms and one or more hetero atoms.
[00013] K residues can be identical or different from each other. In the —K — S — K— portion, residue K is attached to the silicon atom of residue S via a C-Si bond.
[00014] Due to the possible presence of amine groups (- (NR ² —A— E — A'— NR ² ) -) in polyorganosiloxane compounds, they may have protonated ammonium groups, resulting from the protonation of such amine groups with organic acids or inorganic. Such compounds are sometimes called acid addition salts of the polyorganosiloxane compounds according to the invention.
[00015] In a preferred embodiment, a molar ratio between the quaternary ammonium groups b) and the terminal ester groups c) is less than 100: 20, even more preferably, is less than 100: 30 and is of maximum preference less than 100: 50. The ratio can be determined by ¹³ C-NMR.
[00016] In another embodiment, the polyorganosiloxane composition can comprise: (A) at least one polyorganosiloxane compound, comprising (i) at least one polyorganosiloxane group, (ii) at least one quaternary ammonium group, (iii) at at least one terminal ester group and (iv) at least one polyalkylene oxide group (as defined above); and (B) at least one polyorganosiloxane compound, comprising at least one terminal ester group other than compound (A).
[00017] In the definition of component (A), it can be linked to the description of the polyorganosiloxane compounds of the invention. The polyorganosiloxane compound (B) differs from the 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 polyorganosiloxanes containing
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8/57 bisepoxides.
[00018] In polyorganosiloxane compositions according to the invention, the ratio of the weight of compound (A) to the weight of compound (B) is preferably less than 90: 10. Or, in other words, the content of component (B) is at least 10% 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 (ii) to the terminal ester groups (iii) is less than 100: 10, even more preferably , is less than 100: 15 and is most preferably less than 100: 20.
[00019] The silicone polymer has a viscosity at 20 ° C and a shear rate of 0.1 s ^-1 (plate-to-plate system, plate diameter 40 mm, span width 0.5 mm) less than 100,000 mPa .s (100 Pa.s). In additional embodiments, the viscosities of pure silicone polymers can be in the range of 500 to 100,000 mPa.s, or, preferably, from 500 to 70,000 mPa.s, or, more preferably, from 500 to 50,000 mPa.s, or, more preferably, from 500 to 20,000 mPa.s. In other embodiments, the viscosities of pure polymers can be in the range of 500 to 10,000 mPa.s, or, preferably, from 500 to 5,000 mPa.s, determined at 20 ° C and a shear rate of 0.1 s ^{- 1} .
In addition to the silicone polymers mentioned above, preferred embodiments are shown below. For example, in the polyalkylene oxide group E of the general formula:
- [CH2CH2O] q— [CH2CH (CH3) O] r— [CH2CH (C2H5) O] s— where the q, r and s indices can be defined as follows:
q = 0 to 200, or preferably from 0 to 100, or more preferably from 0 to 50, or even more preferably from 0 to 20, r = 0 to 200, or preferably from 0 to 100, or more preferably 0 to 50, or even more preferably 0 to 20,
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9/57 s = 0 to 200, or preferably from 0 to 100, or more preferably from 0 to 50, or more preferably from 0 to 20, and q + r + s = 1 to 600, or preferably from 1 to 100, or more preferably from 1 to 50, or even more preferably from 1 to 40. [00020] For polyorganosiloxane structural units with the general formula S:
R1 = C1-C22-alkyl, C1-C22-fluoralkyl or aryl; n = 200 to 1000, or preferably 300 to 500, K (in the group —K — S — K—) is preferably a divalent or trivalent straight-chain, cyclic or branched C2-C20 hydrocarbon residue that is optionally interrupted by —O -, - NH—, trivalent N, —NR ¹ -, - C (O) -, - C (S) - and optionally replaced by —OH.
[00021] In specific embodiments, R ¹ is C1-C18 alkyl, C1-C18 fluoroalkyl and aryl. Furthermore, R ¹ is preferably C1-C18 alkyl, C1-C6 fluoroalkyl and aryl. Furthermore, R ¹ is more preferably C1-C6 alkyl, C1-C6 fluoroalkyl, more preferably C1-C4 fluoroalkyl and phenyl. Most preferably, R ¹ is methyl, ethyl, trifluoropropyl and phenyl.
[00022] As used here, the term C1-C22 alkyl means that the aliphatic hydrocarbon groups have from 1 to 22 carbon atoms which can be straight or branched chain. Portions of methyl, ethyl, propyl, n-butyl, pentyl, hexyl, heptyl, nonyl, decyl, undecyl, isopropyl, neopentyl and 1,2,3-trimethylhexyl serve as examples.
[00023] As also used here, the term fluoroalkyl C1-C22 means aliphatic hydrocarbon compounds with 1 to 22 atoms of
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10/57 carbon which can be straight or branched and are replaced with at least one fluorine atom. Monofluoromethyl, monofluoroethyl, 1,1,1-trifluorethyl, perfluoroethyl, 1,1,1-trifluoropropyl, 1,2,2-trifluorobutyl are suitable examples.
[00024] In addition, the term aryl means phenyl unsubstituted or substituted once or several times with OH, F, Cl, CF3, C1-C6 alkyl, C1-C6 alkoxy, C3-C7 cycloalkyl, C2-C6 alkenyl or phenyl . Arila can also mean naphthyl.
[00025] For the polyorganosiloxanes modalities, 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 that are derived from C1-C30 carboxylic acids, for example, acetate, propionate, octanoate, specifically C10-C18 carboxylic acids, for example, decanoate, dodecanoate, tetradecanoate, hexadecanoate, octadecanoate and oleate, alkyl polyether carboxylate, alkyl sulfonate, aryl sulfonate, aryl sulfonate, aryl sulfonate , alkyl sulfate, alkyl polyether sulfate, phosphates derived from phosphoric acid monoalkyl ester and aryl phosphonic acid dialkyl / aryl ester The properties of polyorganosiloxane compounds can be modified, among others, based on the selection of acids used.
[00026] Quaternary ammonium groups are usually generated by the reaction of tertiary diamines with alkylating agents, selected from among particular diepoxides (sometimes also called bisepoxides) in the presence of difunctional mono carboxylic acids and dihalogen alkyl compounds.
[00027] In a preferred embodiment, the polyorganosiloxane compounds are of the general formulas (Ia) and (Ib):
M — Y - [- (N + R2 — T — N + R2) —Y—] m - [- (NR ² —A — E — A'— NR ² ) —Y—] k — M (Ia)
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11/57
M — Y - [- (N ⁺ R2 — T — N ⁺ R2) —Y—] m - [- (N ⁺ R ² 2 — A — E— A'— N ⁺ R ² 2) —Y—] k —M (Ib) where each group is as defined above; however, the repetition units are in a statistical arrangement (that is, a non-block arrangement).
[00028] In another preferred embodiment, the polyorganosiloxane compounds can also have the general formulas (IIa) or (IIb):
M — Y - [- N ⁺ R2 — Y—] m - [- (NR ² —A— E — A'— NR ² ) - Y—] k — M (IIa)
M — Y - [- N ⁺ R2 — Y—] m - [- (N ⁺ R ² 2 — A — E — A'— N ⁺ R ² 2) - Y—] k — M (IIb) where each group is as defined above. Also in this formula, the repetition units are usually in a statistical arrangement (ie, a non-arrangement of blocks).
where, as defined above, M is
-OC (O) -Z,
-OS (O) 2-Z
-OS (O2) O-Z
-OP (O) (O-Z) OH
-OP (O) (O-Z) 2
Z is a linear, cyclic or branched, saturated or unsaturated C1-C20, or preferably C2 to 18, or more preferably a hydrocarbon radical, which can be interrupted by one or more —O—, or —C ( O) - and replaced with —OH. In a specific embodiment, M is -OC (O) -Z resulting from normal carboxylic acids, in particular with more than 10 carbon atoms, such as dodecanoic acid.
[00029] In another embodiment, a molar ratio between the repeat group —K — S — K— containing polyorganosiloxane and the polyalkylene repeat group —A — E — A'— or —A' — E — A— is in between
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12/57
100: 1 and 1: 100, or preferably between 20: 1 and 1:20, or more preferably between 10: 1 and 1:10.
[00030] In the group - (N + R2 — T — N + R2) -, R may represent a monovalent, cyclic or branched C1-C20 straight chain hydrocarbon radical, which may be interrupted by one or more —O—, - C (O) - and can be replaced by —OH, T can represent a divalent straight-chain, cyclic or branched C1C20 hydrocarbon radical, which can be interrupted by —O—, —C (O) - and can be replaced by hydroxyl.
[00031] The polyorganosiloxane compounds described above comprising quaternary ammonium functions and ester functions may also contain: 1) individual molecules that contain quaternary ammonium functions and no ester functions; 2) molecules that contain quaternary ammonium and ester functions; and 3) molecules that contain ester functions and no quaternary ammonium functions. Without limiting itself to the structure, the polyorganosiloxane compounds described above comprising quaternary ammonium functions and ester functions should be understood as mixtures of molecules comprising a certain average amount and ratio of both portions.
[00032] Various monofunctional organic acids can be used to produce the esters. Examples of embodiments include C1-C30 carboxylic acids, for example C2, C3, C8, C10-C18 carboxylic acids, for example, C12, C14, C16, saturated, unsaturated and functionalized C18 hydroxyl acids, polyether alkyl carboxylic acids, alkylsulfonic acids, arylsulfonic acids, alkylarylsulfonic acids, alkylsulfuric acids, alkyl polyethersulfuric acids, monoalkyl / aryl esters of phosphoric acid and dialkyl / aryl esters of phosphoric acid.
[00033] Other performance improvements can be achieved by pre-dispersing the silicone polymer in an emulsion of
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13/57 small particles (less than 1 micron) before being added to the base of the shampoo.
[00034] The term emulsion in this patent application describes any dispersion or stable emulsion of the silicone polymer prepared separately and used as one of the components of a shampoo composition.
[00035] Stable means that the viscosity, particle size and other important characteristics of the emulsion do not change significantly over a reasonable period of time when exposed to temperature, humidity, pressure, shear, light and other normal environmental conditions to which the pre- emulsion is exposed during packaging, storage and transport.
[00036] The preparation of the small particle emulsion may require pre-emulsification of the silicone polymer before it is added to the shampoo composition. A non-limiting example of a preparation method is shown below. All oil-soluble components are mixed in a container. Heat can be applied to allow the mixture to liquefy. All water-soluble components are mixed in a separate container and heated to approximately the same temperature as the oil phase. The oil phase and the aqueous phase are mixed in a high shear mixer (example, Turrax mixer, from IKA). The particle size of the conditioning conditioner is in the range of 0.01 to 5 pm, more preferably 0.05 to 1 pm, more preferably 0.1 to 0.5 pm. High energy mixing devices can be used to obtain the desired particle size. High-energy mixing devices include, but are not limited to, Microfluidizer from Microfluidics Corp., Sonolator from Sonic Corp., colloid mill from Sonic Corp.
[00037] Emulsifiers that can be selected for each
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14/57 silicon can be determined by its hydrophilic lipophilic balance value (BHL value). The appropriate range of the BHL value can be from 6 to 16, alternatively from 8 to 14. Emulsifiers with BHL greater than 10 are soluble in water. Emulsifiers with low BHL are soluble in lipids. To obtain an adequate BHL value, a mixture of two or more emulsifiers can be used. Suitable emulsifiers include non-ionic, cationic, anionic and amphoteric emulsifiers.
[00038] The concentration of the emulsifier in the emulsion should be sufficient to provide the emulsification of the conditioning conditioner necessary to obtain the desired particle size and emulsion stability and generally ranges from about 0.1% by weight to about from 50% by weight, from about 1% by weight to about 30% by weight, from about 2% by weight to about 20% by weight, for example. [00039] The use of pre-emulsified silicone dispersion can have multiple advantages, including: (i) silicones with small particle size in the emulsion results in more homogeneous deposition and reduces heterogeneous isolated deposits; and (ii) more homogeneous deposition is more favorable to provide softer hair / skin, facilitate combing and give more volume to the hair.
B. Detersive surfactant [00040] The shampoo composition of the present invention includes a detersive surfactant, which provides cleaning performance to the composition. The detersive surfactant, in turn, comprises an anionic surfactant, amphoteric or zwitterionic surfactants, or mixtures thereof. Various examples and descriptions of detersive surfactants are presented in US Patent No. 6,649,155; US Patent Application Publication No. 2008/0317698 and US Patent Application Publication No. 2008/0206355, which are hereby incorporated by reference in their entirety.
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15/57 [00041] The concentration of the detersive surfactant component in the shampoo composition should be sufficient to provide the desired performance in terms of cleaning and foaming and, in general, varies from about 2% by weight to about 50%, by weight, from about 5%, by weight, to about 30%, by weight, from about 8%, by weight, to about 25%, by weight, or from about 10%, by about 20% by weight. Consequently, the shampoo composition may comprise a detersive surfactant in an amount of about 5%, by weight, about 10%, by weight, about 12%, by weight, about 15%, by weight, of about 17% by weight, about 18% by weight, or about 20% by weight, for example.
[00042] Anionic surfactants suitable for use in the compositions are alkyl sulfates and alkyl ether. Other suitable anionic surfactants are the water-soluble salts of organic products of the sulfuric acid reaction. Other additional suitable anionic surfactants are the fatty acid reaction products esterified with isethionic acid and neutralized with sodium hydroxide. Other similar anionic surfactants are described in US patents No. 2,486,921; 2,486,922; and 2,396,278, which are incorporated herein by reference in their entirety.
[00043] Exemplary anionic surfactants for use in shampoo composition include ammonium lauryl sulfate, ammonium lauryl sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, lauryl sulfate monoethanolamine, diethanolamine lauryl sulfate, diethanolamine lauret sulfate, sodium sulfate lauryl monoglyceride, sodium lauryl sulfate, sodium lauret sulfate, potassium lauryl sulfate, potassium lauret sulfate, sodium lauryl sarcosinate, sodium lauryl sarcosinate, sodium lauryl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate,
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16/57 sodium cocoyl sulphate, sodium lauroyl sulphate, potassium cocoyl sulphate, potassium lauryl sulphate, triethanolamine lauryl sulphate, triethanolamine lauryl sulphate, monoethanolamine cocoyl sulphate, monoethanolamine lauryl sulphate, sodium tridecyl benzene sulphonate, dodec sodium benzene sulfonate, sodium cocoyl isethionate and combinations thereof. In another embodiment of the present invention, the anionic surfactant is sodium lauryl sulfate or sodium laureth sulfate.
[00044] Amphoteric or zwitterionic surfactants suitable for use in the shampoo compositions of the present invention include those known for their use in shampoos or other products for cleaning and personal care. The concentrations of these amphoteric surfactants range from about 0.5% by weight to about 20% by weight and from about 1% by weight to about 10% by weight. Non-limiting examples of suitable zwitterionic or amphoteric surfactants are described in US Patent Nos. 5,104,646 and 5,106,609, which are hereby incorporated by reference in their entirety.
[00045] Amphoteric detersive surfactants suitable for use in the shampoo composition include the widely described surfactants, as derivatives of secondary and tertiary aliphatic amines in which the aliphatic radical can be a straight or branched chain and in which one of the aliphatic substituents contains about 8 to about 18 carbon atoms, and the other contains an anionic group, such as carboxyl, sulfonate, sulfate, phosphate or phosphonate. Exemplary amphoteric detersive surfactants for use in the present shampoo composition include cocoanfoacetate, cocoanphodiacetate, lauroanfoacetate, lauroanphodiacetate and mixtures thereof.
[00046] Zwiterionic detersive surfactants suitable for use in the shampoo composition include those widely described as derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds, in which aliphatic radicals may be branched-chain
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17/57 or linear and in which one of the aliphatic substituents contains from about 8 to about 18 carbon atoms, and the other contains an anionic group, such as carboxyl, sulfonate, sulfate phosphate or phosphonate. In another modality, zwiterionics, such as betaine, are selected.
[00047] Non-limiting examples of other anionic, zwitterionic, amphoteric or optional additional surfactants suitable for use in compositions are described in McCutcheon's article, Emulsifiers and Detergents, 1989 yearbook, published by MC Publishing Co., and in US patents no. . 3,929,678, 2,658,072; 2,438,091; 2,528,378, which are incorporated herein by reference in their entirety.
[00048] In one embodiment, the composition comprises an anionic surfactant and a nonionic co-surfactant. In another embodiment, the surfactant system is free or substantially free of sulfate materials. Suitable sulfate-free surfactants are presented in publication WO 2011/120780 and in publication WO 2011/049932.
C. Deposition polymer [00049] The shampoo composition may also comprise a cationic deposition polymer. Such cationic deposition polymers may include at least one of (a) a cationic guar gum polymer, (b) a non-cationic galactomannan polymer, (c) a cationic tapioca polymer, (d) a cationic copolymer of monomers of acrylamide and cationic monomers and / or (e) a non-crosslinked and synthetic cationic polymer, which may or may not form liotropic liquid crystals by combining with the detersive surfactant, (f) a cationic cellulose polymer. In addition, the cationic deposition polymer can be a mixture of deposition polymers. (1) Cationic guar gum polymers [00050] According to one embodiment of the present invention, the shampoo composition comprises a cationic guar gum polymer, which is a derivative of galactomannan gum (guar gum)
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18/57 cationically replaced. Guar gum for use in the preparation of these guar gum derivatives is typically obtained as a naturally occurring material from the seeds of the guar plant. The guar gum molecule itself is a straight-chain mannan, which is branched at regular intervals with single-membered galactose units into alternative mannose units. The mannose units are linked to each other by β (1-4) glycosidic bonds. Galactose branching occurs through an α (1-6) bond. The cationic derivatives of guar gums are obtained through the reaction between the hydroxyl groups of polygalactomannan and reactive reactive compounds of quaternary ammonium. The degree of substitution of the cationic groups on the guar gum structure needs to be sufficient to provide the cationic charge density described above.
[00051] According to one embodiment, the cationic guar gum polymer has an average weight MW less than about 2.5 million g / mol and has a charge density of about 0.05 meq / g about 2 , 5 meq / g. In one embodiment, the cationic guar gum polymer has an average weight MW less than 1.5 million g / mol, or from about 150 thousand to about 1.5 million g / mol, or from about 200 thousand to about 1.5 million g / mol, or from about 300,000 to about 1.5 million g / mol, or from about 700,000 to about 1.5 million g / mol. In one embodiment, the cationic guar gum polymer has a charge density of about 0.2 to about 2.2 meq / g, or about 0.3 to about 2.0 meq / g, or about 0.4 to about 1.8 meq / g; or from about 0.5 meq / g to about 1.7 meq / g.
[00052] According to one embodiment, the cationic guar gum polymer has an average weight MW less than about 1 million g / mol and has a charge density of about 0.1 meq / g to about
2.5 meq / g. In one embodiment, the cationic guar gum polymer has an average weight of PM less than 900 thousand g / mol or about 150 thousand
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19/57 to about 800,000 g / mol or from about 200,000 to about 700,000 g / mol or from about 300,000 to about 700,000 g / mol or from about 400,000 to about 600,000 g / mol, from about 150,000 to about 800,000 g / mol, or from about 200,000 to about 700,000 g / mol, or from about 300,000 to about 700,000 g / mol, or about 400 thousand to about 600 thousand g / mol. In one embodiment, the cationic guar gum polymer has a charge density of about 0.2 to about 2.2 meq / g, or about 0.3 to about 2.0 meq / g, or about 0.4 to about 1.8 meq / g; or from about 0.5 meq / g to about 1.5 meq / g.
[00053] In one embodiment, the composition comprises from about 0.01% to less than about 0.7%, or from about 0.04% to about 0.55%, or about 0.08 % to about 0.5%, or from about 0.16% to about 0.5%, or from about 0.2% to about 0.5%, or from about 0.3% to about 0.5%, or about 0.4% to about 0.5% of cationic guar gum polymer (a), by total weight of the composition.
[00054] The cationic guar gum polymer can be formed from quaternary ammonium compounds. In one embodiment, the quaternary ammonium compounds that form the cationic guar gum polymer adapt to general formula 1:
R5
I
R ⁴ N — R ⁶ z
R3 where R ³ , R ⁴ and R ⁵ are methyl or ethyl groups; or R ⁶ is an epoxy alkyl group with the general formula 2:
IH ₂ C --- CH-R7O or R ⁶ is a halohydrin group with the general formula 3: X-CH ₂ -CH-R7—
OH where R ⁷ is a C 1 to C 3 alkylene; X is chlorine or bromine and Z is
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20/57 an anion such as Cl-, Br-, I- or HSO4-.
[00055] In one embodiment, the cationic guar gum polymer adapts to general formula 4:
R4
R ⁸ - CH CH R7- N ⁺ - R5 _ -
II ^z
OH R3 where R ⁸ is guar gum; and where R ⁴ , R ⁵ , R6 and R ⁷ are as defined above; and where Z is a halogen. In one embodiment, the cationic guar gum polymer adapts to formula 5:
IR ⁸ - O ~ CH ₂ CH CH ₂ NV3H ₃ ) ₃ Cr
OH [00056] Suitable cationic guar gum polymers include derivatives of cationic guar gum, such as hydroxypropyltrimony guar chloride. In one embodiment, the cationic guar gum polymer is a hydroxypropyltrimony guar gum chloride. Specific examples of types of guar hydroxypropyltrimony chloride include the Jaguar® series commercially available from Rhone-Poulenc Incorporated, for example, Jaguar® C-500, commercially available from Rhodia. Jaguar® C-500 has a charge density of 0.8 meq / g and a PM of 500,000 g / mol. Jaguar® C-17, which has a cationic charge density of about 0.6 meq / g and a PM of about 2.2 million g / mol and is available from the Rhodia Company. Jaguar® C 13S, which has a PM of 2.2 million g / mol and a cationic charge density of about 0.8 meq / g (available from the Rhodia Company). Other guar-hydroxypropyltrimony chlorides are: guarhydroxypropyltrimony chloride with a charge density of about 1.1 meq / g and PM of about 500,000 g / mol, available from ASI, with a charge density of about 1.5 meq / g and PM of about 500,000 g / mol, available from ASI. Other guar-hydroxypropyltrimony chlorides are: Hi-Care 1000, which has a charge density of about 0.7 meq / g
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21/57 and a PM of around 600,000 g / mol and is available from Rhodia; N-Hance 3269 and N-Hance 3270, which have a charge density of about 0.7 meq / g and PM of about 425,000 g / mol and are available from ASI; N-Hance 3196, which has a charge density of about 0.8 and a PM of about 1,100,000 g / mol and is available from ASI. AquaCat CG518 has a charge density of about 0.9 meq / g and a PM of around 50,000 g / mol and is available from ASI. BF-13, which is a borate-free boron (boron) gum with a charge density of about 1.1 meq / g and PM of about 800,000, and BF-17, which is a borate-free boron (boron) gum. with a load density of about
1.7 meq / g and PM of around 800,000, both available from ASI. (2) Cationic non-guar galactomannan polymers [00057] The shampoo compositions of the present invention may comprise a galactomannan polymer derivative with a ratio between mannose and galactose greater than 2: 1 on a monomer to monomer basis, the derivative of galactomannan polymer, selected from the group consisting of a cationic galactomannan polymer derivative and an amphoteric galactomannan polymer derivative with a net positive charge. When used in the present invention, the term cationic galactomannan refers to a polymer of galactomannan to which a cationic group is added. The term amphoteric galactomannan refers to a galactomannan polymer to which a cationic group and an anionic group are added, so that the polymer has a net positive charge.
[00058] Galactomannan polymers are present in the seed endosperm of the Legume family. Galactomannan polymers are created from a combination of mannose monomers and galactose monomers. The galactomannan molecule is a straight chain branched mannan at intervals
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22/57 regular with single member galactose units in specific mannose units. The mannose units are linked to each other by β (1-4) glycosidic bonds. Galactose branching occurs through an α (1-6) link. The ratio between mannose monomers and galactose monomers varies according to the species of the plant, and is also affected by the climate. Derivatives of the non-guar galactomannan polymer of the present invention have a ratio of mannose to galactose greater than 2: 1 on a monomer to monomer basis. The appropriate ratio of mannose to galactose can be greater than about 3: 1, and the ratio of mannose to galactose can be greater than about 4: 1. Analysis of the ratios between mannose and galactose is well known in the art, and is typically based on the measurement of galactose content.
[00059] Gum for use in preparing non-guar galactomannan polymer derivatives is typically obtained in the form of a naturally occurring material, such as seeds or grains from plants. Examples of various non-guar galactomannan polymers include, but are not limited to, Tara gum (3 parts mannose / 1 part galactose), locust bean or locust bean (4 parts mannose / 1 part galactose) and cassia gum (5 parts mannose / 1 part galactose) .
[00060] In one embodiment of the invention, galactomannan polymer derivatives do not have MW of about 1,000 to about 10,000,000 and / or about 5,000 to about 3,000,000.
[00061] The shampoo compositions of the present invention can include galactomannan polymer derivatives with a cationic charge density of about 0.5 meq / g to about 7 meq / g. In one embodiment of the present invention, galactomannan polymer derivatives have a cationic charge density of about 1 meq / g to about 5 meq / g. The degree of substitution of the cationic groups on the structure of the galactomannan needs to be sufficient to
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23/57 provide the cationic charge density described above.
[00062] In one embodiment of the present invention, the galactomannan polymer derivative is a cationic derivative of the non-guar galactomannan polymer, which is obtained by reacting the hydroxyl groups of the polygalactomannan polymer and reactive quaternary ammonium compounds. Quaternary ammonium compounds suitable for use in forming suitable cationic galactomannan polymer derivatives include those that conform to general formulas 1 to 5, as defined above.
[0001] Non-cationic galactomannan polymer derivatives formed from the reagents described above are represented by the general formula 6:
R ¹
R — O — CH ₂ —CH — R ^s —Ν' — R Z '
I I
OH R ³ where R is the gum. The cationic galactomannan derivative can be a gum-hydroxypropyl trimethyl ammonium chloride, which can be more specifically represented by the general formula 7:
R — O — CH ₂ —CH — CH ₂ N ⁺ (CH ₃ ) 3Cr
OH [00063] In another embodiment of the invention, the galactomannan polymer derivative is an amphoteric galactomannan polymer derivative with a net positive charge, obtained when the cationic galactomannan polymer derivative further comprises an anionic group.
[00064] In one embodiment of the invention, the non-cationic galactomannan has a ratio of mannose to galactose greater than about 4: 1, a MW of about 100,000 to about 500,000 and / or about 150,000 to about 400,000 and a cationic charge density of
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24/57 about 1 meq / g to about 5 meq / g and / or 2 meq / g to about 4 meq / g, in addition to being derived from cassias.
[00065] The shampoo compositions of the present invention can comprise at least about 0.05%, by weight of the composition, of a galactomannan polymer derivative. In one embodiment of the present invention, shampoo compositions comprise from about 0.05% to about 2%, by weight of the composition, of a galactomannan polymer derivative.
(3) Cationically modified starch polymer [00066] The shampoo compositions of the present invention can comprise water-soluble cationically modified starch polymers. When used in the present invention, the term cationically modified starch refers to a starch to which a cationic group is added prior to the degradation of that starch to a lower molecular weight, or to a starch to which a cationic group is added after modification of the starch to obtain a desired molecular weight. The definition of the term cationically modified starch also covers amphoterically modified starches. The term amphoterically modified starch refers to a starch hydrolyzate to which a cationic group and an anionic group are added. [00067] The shampoo compositions of the present invention can comprise cationically modified starch polymers in a range of about 0.01% to about 10% and / or about 0.05% to about 5% by weight composition.
[00068] The cationically modified starch polymers shown in the present invention have a percentage of nitrogen bound from about 0.5% to about 4%.
[00069] Cationically modified starch polymers for use in the shampoo compositions of the present invention can have a molecular weight of about 850,000 to about 15,000,000 and about
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25/57
900,000 to about 5,000,000. For use in the present invention, the term molecular weight refers to the weight average molecular weight. Weight average molecular weight can be measured by gel permeation chromatography (GPC) using a Waters 600E HPLC pump and a Waters 717 autosampler equipped with a GPC Gel MIXED-A column from Polymer Laboratories PL (part number 1110-6200 , 600.times.7,5 mm, 20 µm), with a column temperature of 55 ° C. C. and a flow rate of 1.0 mL / min (mobile phase consisting of dimethyl sulfoxide with 0.1% lithium bromide), and using Wyatt DAWN EOS MALLS detectors (multiangular laser light scattering detector) and Optilab DSP from Wyatt (interferometric refractometer) arranged in series (using 0.066 dn / dc), all detectors at a temperature of 50 ° C, with a method created using a polysaccharide standard of narrow distribution (PM = 47,300) from Polymer Laboratories and an injection volume of 200 pL.
[00070] The shampoo compositions of the present invention can include cationically modified starch polymers that have a charge density of about 0.2 meq / g to about 5 meq / g / or about 0.2 meq / g to 2 meq / g. The chemical modification to obtain such a charge density includes, but is not limited to, the addition of amino groups and / or ammonium groups to the starch molecules. Some non-limiting examples of these ammonium groups may include substituents such as hydroxypropyl trimethyl chloride, hydroxypropyl trimethyl ammonium chloride, hydroxypropyl stearyl dimethyl ammonium chloride and hydroxylpropyl dodecyl dimethyl ammonium chloride See Solarek, DB, Cationic Starches in Modified Starches: Properties and Uses, Properties and Uses, Wurzburg, OB, Ed., CRC Press, Inc., Boca Raton, Fla. 1986, pp 113-125. The cationic groups can be added to the starch before degradation at a lower molecular weight or can be added after such modification.
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26/57 [00071] Cationically modified starch polymers can have a degree of cationic group substitution of about 0.2 to about 2.5. When used in the present invention, the term degree of substitution of cationically modified starch polymers means the average number of hydroxyl groups in each anhydroglycosis unit derivatized by substituent groups. Since each anhydroglycosis unit has three hydroxyl groups potentially available for substitution, the maximum possible degree of substitution is
3. The degree of substitution is expressed as the number of moles of substituting groups per mole of anhydroglycosis units, on a molar average basis. The degree of substitution can be determined using proton nuclear magnetic resonance spectroscopy (.sup.1H NMR) methods, well known in the art. Suitable NMR.sup.1H techniques include those described in Observation on NMR Spectra of Starches in Dimethyl Sulfoxide, Iodine-Complexing, and Solvating in Water-Dimethyl Sulfoxide, by Qin-Ji Peng and Arthur S. Perlin, Carbohydrate Research, 160 (1987), 57-72; and in An Approach to the Structural Analysis of Oligosaccharides by NMR Spectroscopy, by J. Howard Bradbury and J. Grant Collins, Carbohydrate Research, 71, (1979), 15-25.
[00072] The source of starch before chemical modification can be chosen from a variety, such as tubers, vegetables, cereals and grains. Non-limiting examples of these sources may include corn starch, wheat starch, rice starch, waxy corn starch, oat starch, cassava starch, waxy barley, waxy rice starch, gluten-free rice starch, sweet rice starch, amioca, potato starch, tapioca starch, oat starch, sago starch, rice pudding or mixtures thereof.
[00073] In one embodiment of the present invention, cationically modified starch polymers are selected from corn starch
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27/57 degraded cationic, cationic tapioca, cationic potato starch and combinations of these items. In another embodiment, the cationically modified starch polymers are cationic corn starch and cationic tapioca.
[00074] Starch, before degradation or after modification to a lower molecular weight, may comprise one or more additional modifications. For example, these modifications can include crosslinking, stabilization reactions, phosphorylations and hydrolysations. Stabilization reactions can include alkylation and esterification.
[00075] Cationically modified starch polymers can be incorporated into the composition in the form of hydrolyzed starch (for example, acid, enzyme, or alkaline degradation), oxidized starch (for example, peroxide, peracid, hypochlorite, alkaline, or any other oxidizing agent), physically or mechanically degraded starch (for example, through the input of thermomechanical energy from the processing equipment), or combinations thereof.
[00076] An ideal form of starch can be that which is readily soluble in water and forms a substantially clear solution (percent transmittance.gtoreq.80 at 600 nm) in water. The transparency of the composition is measured by ultraviolet / visible spectrophotometry (UV / VIS), which determines the absorption or transmission of UV / VIS light by a sample, using a Gretag Macbeth Color i 5 colorimeter, according to the related instructions. A wavelength of light of 600 nm proved to be adequate to characterize the degree of clarity of cosmetic compositions.
[00077] Suitable cationically modified starches may be available from known starch suppliers. Also suitable for use in the present invention is modified nonionic starch which can be further derivatized into a starch
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Cationically modified as is known in the art. Other suitable modified starch-based starting materials can be quaternized, as is known in the art, to produce the cationically modified starch polymer suitable for use in the invention.
(4) Cationic copolymer of an acrylamide monomer and a cationic monomer [00078] According to one embodiment of the present invention, the shampoo composition can comprise a cationic copolymer of an acrylamide monomer and a cationic monomer, having the copolymer, a charge density of about 1.0 meq / g to about 3.0 meq / g. In one embodiment, the cationic copolymer is a synthetic cationic copolymer of acrylamide monomers and cationic monomers.
[00079] In one embodiment, the cationic copolymer comprises:
(i) an acrylamide monomer of the following formula AM:
R ⁹
Formula AM where R ⁹ is H or C1-4 alkyl; and R ¹⁰ and R ¹¹ are independently selected from the group consisting of H, C1-4 alkyl, CH2OCH3, CH2OCH2CH (CH ₃ ) 2 and phenyl, or together they are C ₃ -6cycloalkyl; and (ii) a cationic monomer according to Formula CM:
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29/57
CM formula where k = 1, each between v, v 'and v' 'is, independently, an integer from 1 to 6, w is zero or an integer from 1 to 10, and X- is an anion.
In one embodiment, cationic monomer according to e X- is Cl- to form the [00080]
Formula CM and where k = 1, v = 3 and w = 0, z = 1 following structure:
[00081] The above structure can be called diquaternary. In another embodiment, the cationic monomer follows the formula CM and v and v '' are both 3, v '= 1, w = 1, y = 1 and X- is Cl-, as:
[00082] The above structure can be called a triquaternary.
[00083] In one embodiment, the acrylamide monomer is acrylamide or methacrylamide.
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30/57 [00084] In one embodiment, the cationic copolymer (b) is AM: TRIQUAT, which is a copolymer of acrylamide and 1,3propanediamine, N- [2 - [[[dimethyl [3 - [(2-methyl- 1-oxo-2propenyl) amino] propyl] ammonium] acetyl] amino] ethyl] 2-hydroxy-N, N, N ', N', N'-pentamethyl-, trichloride. AM: TRIQUAT is also known as polyquaternium 76 (PQ76). AM: TRIQUAT can have a charge density of 1.6 meq / g and a PM of 1.1 million g / mol.
[00085] In an alternative embodiment, the cationic copolymer is an acrylamide monomer and a cationic monomer, in which the cationic monomer is selected from the group consisting of: (methyl) amino ethyl dimethyl acrylate, (methyl) dimethylaminopropyl acrylate , ditherc-thiobutylaminoethyl (meth) acrylate, dimethylamino methyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide; ethylenimine, vinylamine, 2-vinylpyridine, 4-vinylpyridine; trimethyl ammonium chloride ethyl (meth) acrylate, trimethyl ammonium methyl sulfate (meth) acrylate, dimethyl ammonium benzyl chloride ethyl (meth) acrylate, 4-benzoyl benzyl dimethyl ammonium ethyl acrylate, trimethyl ammonium chloride ethyl (methyl ) acrylamide, trimethylammoniopropyl chloride (meth) acrylamide, vinylbenzyltrimethylammonium chloride, diallyldylmethylammonium chloride and mixtures thereof.
[00086] In one embodiment, the cationic copolymer comprises a cationic monomer selected from the group consisting of: cationic monomers include ethyl trimethyl ammonium (meth) acrylate, ethyl trimethyl ammonium methyl (meth) acrylate, dimethyl ammonium benzyl chloride ethyl (meth) acrylate, 4-benzoyl benzyl dimethyl ammonium ethyl acrylate, trimethyl ammonium ethyl (meth) acrylamide, trimethylammoniopropyl (meth) acrylamide chloride, vinylbenzyltrimethylammonium chloride, and mixtures thereof.
[00087] In one embodiment, the cationic copolymer is soluble in water. In one embodiment, the cationic copolymer is formed from
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31/57 (1) copolymers of (meth) acrylamide and cationic monomers based on (meth) acrylamide and / or cationic monomers stable to hydrolysis, (2) terpolymers of (meth) acrylamide, monomers based on acid esters (met ) cationic acrylic and monomers based on (meth) acrylamide, and / or cationic monomers stable to hydrolysis. Monomers based on cationic (meth) acrylic acid esters can be cationized esters of (meth) acrylic acid containing a quaternized N atom. In one embodiment, the cationized esters of (meth) acrylic acid containing a quaternized N atom are quaternized dialkylaminoalkyl (meth) acrylates with C1 to C3 in the alkyl and alkylene groups. In one embodiment, the cationized esters of (meth) acrylic acid containing a quaternized N atom are selected from the group consisting of: ammonium salts of dimethylamino methyl (meth) acrylate, dimethyl amino ethyl (meth) acrylate, (meth) dimethylaminopropyl acrylate, diethylamino methyl (meth) acrylate, diethylaminoethyl (meth) acrylate; and (meth) diethylaminopropyl acrylate quaternized with methyl chloride. In one embodiment, the cationized esters of (meth) acrylic acid containing a quaternized N atom is amino ethyl dimethyl acrylate, which is quaternized with an alkyl halide or with methyl chloride or benzyl chloride or dimethyl sulfate (ADAME-Quat ). In one embodiment, the cationic monomer when based on (meth) acrylamides is dialkyl amino alkyl (meth) acrylamides quaternized with C1 to C3 in the alkyl and alkylene or dimethylaminopropylacrylamide groups, which is quaternized with an alkyl halide or methyl chloride or chloride benzyl or dimethyl sulfate. [00088] In one embodiment, the cationic monomer based on a (meth) acrylamide is a dialkyl amino alkyl (meth) acrylamide quaternized with C1 to C3 in the alkyl and alkylene groups. In one embodiment, the cationic monomer based on a (meth) acrylamide is dimethylaminopropylacrylamide, which is quaternized with a halide of
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32/57 alkyl, specifically methyl chloride, benzyl chloride or dimethyl sulfate.
[00089] In one embodiment, the cationic monomer is a cationic monomer with stable hydrolysis. Cationic monomers stable to hydrolysis can be, in addition to a dialkyl amino alkyl (meth) acrylamide, all monomers that can be considered stable to the OECD hydrolysis test. In one embodiment, the cationic monomer is stable to hydrolysis and the cationic monomer stable to hydrolysis is selected from the group consisting of: diallyl dimethyl ammonium chloride and water soluble derivatives of cationic styrene.
[00090] In one embodiment, the cationic copolymer is an acrylamide terpolymer, quaternized 2-dimethylamoniomethyl (meth) acrylate with methyl chloride (ADAME-Q) and 3dimethylammoniopropyl (meth) quaternized acrylamide with methyl chloride (DIMAPA-Q) .
[00091] In one embodiment, the cationic copolymer is formed from acrylamide and acrylamidopropyltrimethylammonium chloride, in which acrylamidopropyltrimethylammonium chloride has a charge density of about 1.0 meq / g to about 3.0 meq / g.
[00092] In one embodiment, the cationic copolymer has a charge density of about 1.1 meq / g to about 2.5 meq / g or about 1.1 meq / g to about 2.3 meq / g or from about 1.2 meq / g to about 2.2 meq / g or from about 1.2 meq / g to about 2.1 meq / g or from about 1.3 meq / g to about 2, 0 meq / g or about 1.3 meq / g about 1.9 meq / g.
[00093] In one embodiment, the cationic copolymer has a PM of about 100,000 g / mol to about 2 million g / mol or about 300,000 g / mol to about 1.8 million g / mol or about 500 thousand g / mol to about 1.6 million g / mol or about 700 thousand g / mol to about 1.4
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33/57 million g / mol or from about 900 thousand g / mol to about 1.2 million g / mol.
[00094] In one embodiment, the cationic copolymer is a copolymer of trimethylammoniopropylmethacrylamide chloride-N-acrylamide, which is also known as AM: MAPTAC. AM: MAPTAC can have a charge density of about 1.3 meq / g and a PM of about 1.1 million g / mol. In one embodiment, the cationic copolymer is AM: ATPAC. AM: ATPAC can have a charge density of about
1.8 meq / g and a PM of about 1.1 million g / mol.
(5) Cationic synthetic polymer [00095] According to an embodiment of the present invention, the shampoo composition can comprise a cationic synthetic polymer that can be formed from
i) one or more cationic monomer units and, optionally ii) one or more monomer units carrying a negative charge and / or iii) a non-ionic monomer, the subsequent charge of the copolymer being positive. The ratio of the three types of monomers is given by m, p and q, where m is the number of cationic monomers, p is the number of negatively charged monomers, and q is the number of nonionic monomers.
[00096] In one embodiment, cationic polymers are synthetic cationic polymers soluble in water or dispersible, non-crosslinked, which have the following structure:
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34/57
plus be one or where A, can cationic:
of the following portions
starch, alkyl starch, ester, ether, alkyl or where "= alkylaryl;
where Y = C1C22 alkyl, alkoxy, alkylidene, alkyl or aryloxy;
where Ψ = C1-C22 alkyl, alkyloxy, alkylaryl or alkylaryloxy; where Z = C1-C22 alkyl, alkyloxy, aryl or aryloxy;
where R1 = H, straight or branched C1-C4 alkyl;
where s = 0 or 1, n = 0 or> 1;
where T and R7 = C1-C22 alkyl; and where X- = halogen, hydroxide, alkoxide, sulfate or alkyl sulfate.
Where the monomer having a negative charge is defined by R2 '= H, straight or branched C1-C4 and R3 alkyl as:
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35/57
D Q 0 N-CH3 (CH2) u (CH2) ₂ (CH2) ₂ | 11 (CH2) ₂ CH3 ^ N ~~ CH3 CH3 ^ N ΌΗ3 0 ^J t + (CH2) u CH2 HO-P = O O = S = O J Ç = O THE- THE- THE- THE-
where D = O, N or S;
where Q = NH2 or O;
where u = 1-6;
where t = 0-1; and where J = oxygenated functional group containing the following elements P, S, C.
[00097] Where the nonionic monomer is defined by R2 = H, C1-C4 linear or branched alkyl, R6 = alkyl, alkylaryl, aryloxy, alkyloxy, β linear or branched alkylaryloxy is defined as
where G 'and G are, independently of each other, O, S or
N-H and L = 0 or 1.
[00098] Examples of cationic monomers include aminoalkyl (meth) acrylates, (meth) aminoalkyl (meth) acrylamides; monomers comprising at least one secondary, tertiary or quaternary amine function, or a heterocyclic group containing a nitrogen atom, vinyl amine or ethylenimine; dialkyl ammonium salts; their mixtures, their salts, and the macromonomers that derive from them.
[00099] Additional examples of cationic monomers include dimethyl amino ethyl (meth) acrylate, dimethyl amino propyl (meth) acrylate, dithertiobutylaminoethyl (meth) acrylate, dimethylamino methyl (meth) acrylamide, dimethyl amino propyl (methyl) acrylamide, ethylenimine vinyl
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36/57 amine, 2-vinylpyridine, 4-vinylpyridine, trimethyl ammonium ethyl (meth) acrylate, trimethyl ammonium methyl (meth) acrylate, dimethyl ammonium benzyl chloride ethyl (meth) acrylate, 4-benzoyl benzyl chloride dimethyl ammonium ethyl acrylate, trimethyl ammonium chloride ethyl (meth) acrylamide, trimethyl ammonium chloride propyl (meth) acrylamide, vinylbenzyl trimethyl ammonium chloride, dimethyl ammonium chloride.
[000100] Suitable cationic monomers include those comprising a quaternary ammonium group of the formula -NR3 ⁺ , where R, which is identical or different, represents a hydrogen atom, an alkyl group comprising from 1 to 10 carbon atoms, or a benzyl group, optionally carrying a hydroxyl group, and comprise an anion (counterion). Examples of anions are halides such as chlorides, bromides, sulphates, hydrosulphates, alkylsulphates (for example, comprising 1 to 6 carbon atoms), phosphates, citrates, formates and acetates.
[000101] Suitable cationic monomers include trimethylammonioethyl chloride (meth) acrylate, methylsulfate trimethylammonioethyl (meth) acrylate, benzyl chloride dimethylammonioethyl (methyl) acrylate, methylbutylamethylamethylamethylethylmethylamethylamethylamethylamethylamethylamethylamethylmethylamethylamethylamethylamethylamethylamethylamethylamethylamethylamethylammonium. [000102] Additional suitable cationic monomers include trimethylammoniopropyl (meth) acrylamide chloride.
[000103] Examples of negatively charged monomers include ethylenically unsaturated alpha monomers comprising a phosphate or phosphonate group, ethylenically unsaturated alpha monocarboxylic acids, monoalkyl esters of ethylenically unsaturated alpha dicarboxylic acids, monoalkylamides of ethylenically unsaturated alpha-methylenedylated acids, alpha-dicarboxylic acids
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37/57 unsaturated compounds that comprise a sulfonic acid group, and salts of ethylenically unsaturated alpha compounds that comprise a sulfonic acid group.
[000104] Suitable negatively charged monomers include acrylic acid, methacrylic acid, vinylsulfonic acid, vinylsulfonic acid salts, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid salts, alpha-acrylamidomethylpropanesulfonic acid, salts of alpha-acrylamidylmethylsulfonic methacrylsulfonic acid, 2-sulfonic acid. , acrylamido-2methylpropanesulfonic acid (AMPS), salts of acrylamido-2methylpropanesulfonic acid and styrenesulfonate (SS).
[000105] Examples of nonionic monomers include vinyl acetate, alpha-ethylenically unsaturated carboxylic acid amides, esters of alpha-ethylenically unsaturated monocarboxylic acids with a hydrogenated or fluorinated alcohol, poly (ethylene oxide) acrylate (this ie, polyethoxylated (meth) acrylic acid), monoalkyl esters of alpha-ethylenically unsaturated dicarboxylic acids, monoalkylamides of alpha-ethylenically unsaturated dicarboxylic acids, vinyl nitriles, vinylamine amides, vinyl alcohol, vinylpyrolidone and aromatic vinyl compounds.
[000106] Suitable nonionic monomers include styrene, acrylamide, methacrylamide, acrylonitrile, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
[000107] The anionic counterion (X-), in association with synthetic cationic polymers, can be any known counterion, as long as the polymers remain soluble or dispersible in water in the shampoo composition or in a coacervated phase of the composition of
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38/57 shampoo, and as long as the counterions are physically and chemically compatible with the essential components of the shampoo composition or do not unduly prejudice, in any other way, the performance, stability or aesthetics of the product. Some non-limiting examples of these counterions include halides (for example, chlorine, fluorine, bromine, iodine), sulfate and methyl sulfate.
[000108] In one embodiment, the cationic polymer described in the present invention helps to restore the hydrophobic epicuticle of damaged and chemically treated hair. The microscopically thin layer F provides natural resistance to climate action, while helping to retain moisture and prevent further damage. Chemical-based treatments damage the hair cuticle and remove its protective F layer. As the F layer is removed, the hair becomes more and more hydrophilic. It has been found that when lyotropic liquid crystals are applied to chemically treated hair, the hair becomes more hydrophobic and younger, both in terms of appearance and touch. Without sticking to any particular theory, it is believed that the complex of lyotrophic liquid crystals creates a hydrophobic layer or film that lines the hair fibers, protecting it, much like the natural epicuticle does. The hydrophobic layer restores hair to a generally new and healthier looking state. Lyotrophic liquid crystals are formed by combining the synthetic cationic polymers described here with the anionic detergent surfactant component of the aforementioned shampoo composition. The synthetic cationic polymer has a relatively high charge density. It should be noted that some synthetic polymers with a relatively high cationic charge density do not form lyotrophic liquid crystals, mainly due to their abnormal linear charge densities. These cationic synthetic polymers are described in WO
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94/06403 to Reich et al. The synthetic polymers described in the present invention can be formulated into a stable shampoo composition that provides optimized conditioning performance to damaged hair.
[000109] Cationic synthetic polymers that can form lyotropic liquid crystals have a cationic charge density of about 2 meq / gm to about 7 meq / gm, and / or about 3 meq / gm to about 7 meq / gm , and / or from about 4 meq / gm to about 7 meq / gm. In some embodiments, the cationic charge density is about 6.2 meq / gm. Polymers also have MW of about 1,000 to about 5,000,000, and / or about 10,000 to about 2,000,000, and / or about 100,000 to about 2,000,000.
[000110] In another embodiment of the invention, cationic synthetic polymers that provide enhanced conditioning and deposition of beneficial agents, but do not necessarily form lyotropic liquid crystals, have a cationic charge density of about 0.7 meq / gm to about 7 meq / gm, and / or from about 0.8 meq / gm to about 5 meq / gm, and / or from about 1.0 meq / gm to about 3 meq / gm. Polymers also have PMs from about 1,000 to about 5,000,000, from about 10,000 to about 2,000,000, and from about 100,000 to about 2,000,000.
[000111] The concentration of cationic polymers varies from about 0.025% to about 5%, from about 0.1% to about 3%, and / or from about 0.2% to about 1%, in weight of the shampoo composition.
(6) Cationic Cellulose Polymers [000112] Suitable cationic cellulose polymers can be hydroxyethylcellulose salts reacted with substituted trimethylammonium epoxide, called polyquaternium 10 in the industry (CTFA) and available from Dow / Amerchol Corp. (Edison, N.J., USA) in their Polymer LR, JR and KG series of polymers. Other suitable types of
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40/57 cationic cellulose includes polymeric quaternary ammonium salts of hydroxy ethyl cellulose reacted with epoxide substituted by lauryl dimethyl ammonium, cited in the industry (CTFA) as Polyquaternium 24. These materials are available from Dow / Amerchol Corp. under the trade name Polymer LM-200. Other suitable types of cationic cellulose include the polymeric quaternary ammonium salts of hydroxyethylcellulose reacted with substituted lauryldimethylammonium epoxide and substituted trimethylammonium epoxide, called in the industry (CTFA) polyquaternium 67. These materials are available from Dow / Amerchol Corp., under the name commercial SoftCAT Polymer SL-5, SoftCAT Polymer SL-30, Polymer SL-60, Polymer SL-100, Polymer SK-L, Polymer SK-M, Polymer SK-MH and Polymer SK-H.
[000113] In one embodiment, the shampoo composition may comprise a plurality of cationic conditioning polymers. According to one embodiment, when two cationic conditioning polymers are present, the ratio of the weight of a first cationic conditioning polymer to a second cationic conditioning polymer is about 1,000: 1 to about 2: 1. In one embodiment, the weight ratio of the first cationic conditioning polymer to the second cationic conditioning polymer is about 1,000: 1 to about 4: 1. In one embodiment, the weight ratio of the first cationic conditioning polymer to the second cationic conditioning polymer is about 800: 1 to about 4: 1, or about 500: 1 to about 4: 1, or about from 100: 1 to about 5: 1, or from about 100: 1 to about 6: 1, or from about 50: 1 to about 6.5: 1, or from about 50: 1 to about from 7: 1, or from about 50: 1 to about 8.3: 1, or from about 50: 1 to about 16.7: 1.
D. Vehicle [000114] Shampoo compositions can take the form of spillable liquids (under ambient conditions). Such compositions can
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41/57 comprises a vehicle present with a content of about 20% by weight to about 95% by weight, or even about 60% by weight to about 85% by weight. The vehicle can contain water or a miscible mixture of water and organic solvent and, in one aspect, it can comprise water with little or no significant concentration of organic solvent, except when consequently incorporated into the composition, as secondary ingredients of other essential or optional components.
[000115] The vehicle useful in embodiments of the shampoo compositions of the present invention includes water and water and aqueous solutions of lower alkyl alcohols and polyhydric alcohols. The lower alkyl alcohols useful in the present invention are monohydric alcohols having 1 to 6 carbons, in one aspect, ethanol and isopropanol. Exemplary polyhydric alcohols usable in the present invention include propylene glycol, hexylene glycol, glycerin and propanediol.
E. Optional ingredients [000116] In accordance with embodiments of the present invention, the shampoo composition may further comprise one or more optional ingredients, including beneficial agents. Suitable beneficial agents include, but are not limited to, conditioning agents, silicone emulsions, anti-dandruff actives, gel nets, chelating agents and natural oils, such as sunflower oil or castor oil. Suitable additional optional ingredients include, but are not limited to, perfumes, perfume microcapsules, dyes, particles, antimicrobials, foam promoters, antistatic agents, rheology modifiers and thickeners, suspension and structuring materials, pH adjusting agents and buffers, preservatives, pearling agents, solvents, thinners, antioxidants, vitamins and combinations thereof.
[000117] These optional ingredients must be physically and chemically compatible with the components of the composition and not
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42/57 must in any event unduly impair the stability, aesthetics or performance of the product. The CTFA Cosmetic Ingredient Handbook, Tenth Edition (published by Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, DC, USA) (2004) (hereinafter CTFA), describes a wide variety of non-limiting materials that can be added to the composition of the present invention.
1. Silicones [000118] The shampoo composition may further comprise one or more silicone conditioning agents in addition to the silicone quaternary polymers disclosed in Section A. The additional silicone based conditioning agent may comprise volatile silicone, non-volatile silicone or combinations of them. The concentration of the silicone based conditioning agent typically ranges from about 0.01% to about 10% by weight of the composition, from about 0.1% to about 8%, from about 0, 1% to about 5% and / or from about 0.2% to about 3%. Some non-limiting examples of suitable silicone-based conditioning agents, and optional suspending agents for silicone, are described in US Patent No. 34,584 and US Patent No. 5,104,646 and US No. 5,106,609, whose descriptions are hereby incorporated by reference. Silicone-based conditioning agents for use in the compositions of the present invention can have viscosity, measured at 25 ° C, from about 20 to about
2,000,000 square millimeters per second (mm ² / s), from about 1,000 to about 1,800,000 mm ² / s, from about 50,000 to about 1,500,000 mm ² / s and / or from about 100,000 to about 1,500,000 mm ² / s (about 20 to about 2,000,000 centistokes (cSt), from about 1,000 to about 1,800,000 cSt, from about 50,000 to about 1,500,000 cSt and / or from about 100,000 to about 1,500,000 cSt).
[000119] The dispersed particles of silicone-based conditioning agent typically have an average diameter value in the range of about
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43/57 from 0.01 micrometer to about 50 micrometer. For the application of small particles to the hair, the average volumetric diameters of the particles are typically in the range of about 0.01 micrometer to about 4 micrometer, from about 0.01 micrometer to about 2 micrometer, from about 0.01 micrometer to about 0.5 micrometer. For the application of larger particles to the hair, the average volumetric diameters of the particles typically range from 5 micrometers to about 125 micrometers, from about 10 micrometers to about 90 micrometers, from about 15 micrometers to about 70 micrometers and / or from about 20 micrometers to about 50 micrometers.
[000120] Additional reference materials on silicones, including sections that discuss silicone fluids, gums and resins, as well as the manufacture of silicones, can be found in the Encyclopedia of Polymer Science and Engineering, vol. 15, 2d ed., Pp 204-308, John Wiley & Sons, Inc. (1989), incorporated herein by reference.
[000121] Silicone emulsions suitable for use in the embodiments of the present invention include, among others, emulsions of insoluble polysiloxanes prepared according to the descriptions provided in US patent No. 4,476,282 and in US patent application publication no. 2007/0276087. Consequently, suitable insoluble polysiloxanes include polysiloxanes such as hydroxiterminated alpha-polysiloxanes or omega-polysiloxanes, or alkoxiterminated alpha-polysiloxanes or omega-polysiloxanes with a molecular weight in the range of about 50,000 to about 500,000 g / mol. Insoluble polysiloxane can have an average molecular weight in the range of about 50,000 to about 500,000 g / mol. For example, insoluble polysiloxane can have an average molecular weight in the range of about 60,000 to about 400,000; from about 75,000 to about 300,000; from about 100,000 to about 200,000; or the average molecular weight can be about 150,000 g / mol. Insoluble polysiloxane can have an average particle size
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44/57 in the range of 30 nm to about 10 microns. The average particle size can be within the range of about 40 nm to about 5 microns, from about 50 nm to about 1 micron, from about 75 nm to about 500 nm or about 100 nm, for example .
[000122] The average molecular weight of the insoluble polysiloxane, the viscosity of the silicone emulsion and the particle size comprising the insoluble polysiloxane are determined by the methods commonly used by those skilled in the art, such as the methods presented in Smith, AL The Analytical Chemistry of Silicones , John Wiley & Sons, Inc .: New York, 1991. For example, the viscosity of the silicone emulsion can be measured at 30 ° C with a Brookfield viscometer with 6 spindle at 2.5 rpm. The silicone emulsion may also include an additional emulsifier along with the anionic surfactant.
[000123] Other classes of silicones suitable for use in the compositions of the present invention include, but are not limited to: i) silicone fluids, including, but not limited to, silicone oils which are dispersible materials and have a viscosity of less than about 1,000,000 mm ² / s (1,000,000 cSt), measured at 25 ° C; ii) aminosilicones that contain at least one primary, secondary or tertiary amine; iii) cationic silicones containing at least one quaternary ammonium functional group; iv) silicone gums that include materials with viscosity greater than or equal to 1,000,000 mm ² / s (1,000,000 cSt), measured at 25 ° C; v) silicone resins that include highly cross-linked polymeric siloxane systems; vi) silicones with a high refractive index, whose refractive index is at least 1.46 and vii) mixtures of them.
2. Organic conditioning materials [000124] The shampoo composition may also comprise at least one organic conditioning material, such as an oil or a wax, either alone or in combination with other agents
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45/57 conditioners, such as the silicones described above. The organic material can be non-polymeric, oligomeric or polymeric. It can be in the form of an oil or a wax and can be added to the formulation neat or in a pre-emulsified form. Some non-limiting examples of organic conditioning materials include, among others: i) hydrocarbon oils; ii) polyolefins, iii) fatty esters, iv) fluorinated conditioning compounds, v) fatty alcohols, vi) alkylglycosides and alkylglycoside derivatives; vii) quaternary ammonium compounds; polyethylene glycols and polypropylene glycols with a molecular weight of up to about 2,000,000, such as those with CTFA names PEG-200, PEG400, PEG-600, PEG-1000, PEG-2M, PEG-7M, PEG-14M, PEG-45M and mixtures of them.
3. Emulsifiers [000125] A variety of anionic and nonionic emulsifiers can be used in the shampoo composition of the present invention. Anionic and non-ionic emulsifiers can be monomeric or polymeric in nature. Monomeric examples include, illustratively and not restrictively, alkyl ethoxylates, alkyl sulfates, soaps and fatty esters and their derivatives. Polymeric examples include, illustratively and not restrictively, polyacrylates, polyethylene glycols and block copolymers, and derivatives thereof. Naturally occurring emulsifiers, such as lanolines, lecithin and lignin, and their derivatives, are also non-limiting examples of useful emulsifiers.
4. Chelating agents [000126] The shampoo composition can also comprise a chelator. Suitable chelators include those listed in AE Martell & RM Smith, Critical Stability Constants, Vol. 1, Plenum Press, New York & London (1974) and AE Martell & RD Hancock, Metal Complexes in Aqueous Solution, Plenum Press, New York & London (1996), both of which are incorporated herein, for reference. When related to
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46/57 chelators, the term salts and derivatives thereof means salts and derivatives which comprise the same functional structure (for example, the same chemical structure) as the chelator to which they refer and which have similar or better chelating properties. This term includes alkali metal, alkaline earth, ammonium, substituted ammonium salts (i.e. monoethanolammonium, diethanolammonium, triethanolammonium), chelating esters with an acidic portion and mixtures of them, in particular, all sodium, potassium or ammonium salts. The term derivatives also includes chelating surfactant compounds, such as those exemplified in US Patent No. 5,284,972, and large molecules that comprise one or more chelating groups that have the same functional structure as the original chelators, such as polymeric EDDS (ethylenediamine disuccinic acid), described in US Patent No. 5,747,440.
[000127] The contents of the EDDS chelator in shampoo compositions can be as low as 0.01% by weight or as high as up to about 10% by weight, but above the highest content (i.e. 10 %, by weight), there may be concerns with the formulation and / or human security. In one embodiment, the EDDS chelator content can be at least about 0.05% by weight, at least about 0.1% by weight, at least about 0.25% by weight, at least about 0.5% by weight, at least about 1% by weight, or at least about 2% by weight of the shampoo composition. Levels above about 4% by weight can be used, but may not result in an additional benefit.
5. Anti-dandruff agent [000128] According to one embodiment, the shampoo composition can comprise an anti-dandruff active, which can be a particulate dandruff active. The anti-dandruff active can be selected from the group consisting of: azole pyridinothione salts, such as imidazole,
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Econazole, climbazole and elubiol; selenium sulfide; coal tar, particulate sulfur; keratolytic agents such as salicylic acid; and mixtures thereof. In one embodiment, the particulate dandruff is a pyridinothione salt.
[000129] Pyridinothione particles are suitable particles of anti-dandruff active. In one embodiment, the anti-dandruff active is a 1hydroxy-2-pyridinothione salt and is in particulate form. In one embodiment, the concentration of anti-dandruff pyridinothole particulate is in the range of about 0.01% by weight to about 5% by weight or from about 0.1% by weight to about 3% , by weight, or from about 0.1% by weight, to about 2% by weight. In one embodiment, pyridinothione salts are those formed from heavy metals such as zinc, tin, cadmium, magnesium, aluminum and zirconium, generally zinc, typically the zinc salt of 1-hydroxy-2-pyridinothione (known as zinc pyridination or ZPT), commonly 1-hydroxy-2pyridinothione salts in the form of a platelet particle. In one embodiment, the 1-hydroxy-2-pyridinothione salts in the form of platelet particles have an average particle size of up to about 20 microns, or up to about 5 microns, or up to about 2.5 microns . Salts formed from other cations, such as sodium, may also be suitable. Anti-dandruff pyridinothione actives are described, for example, in US Patent No. 2,809,971; US patent No. 3,236,733; US patent No. 3,753,196; US patent No. 3,761,418; US patent No. 4,345,080; US patent 4,323,683; US patent 4,379,753; and in US patent No. 4,470,982.
[000130] The anti-dandruff active can also be selected from polyvalent metal salts of pyrithione; the composition further comprises one or more antifungal and / or antimicrobial actives. The embodiments of the present invention can also comprise a combination of antimicrobial assets.
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48/57 [000131] In one embodiment, the composition comprises an effective amount of a layered material containing zinc. In one embodiment, the composition comprises from about 0.001% by weight to about 10% by weight or from about 0.01% by weight to about 7% by weight or about 0.1% by weight, to about 5% by weight, of a zinc lamellar material (ZLM), by total weight of the composition.
[000132] Many ZLMs exist naturally in the form of minerals. In one embodiment, ZLM is selected from the group consisting of: hydrozincite (zinc carbonate hydroxide), auricalcite (zinc-copper carbonate hydroxide), rosasite (cobrezinc carbonate hydroxide) and mixtures thereof. Related zinc-containing minerals can also be included in the composition. Natural ZLMs can also occur in which anionic layer species, such as clay-type minerals (eg, phyllosilicates) contain zinc gallery ions resulting from ion exchange. All of these natural materials can also be obtained synthetically or formed in situ in a composition or during a production process.
[000133] Another common class of ZLMs, of which many, but not all, are synthetic, is that of double lamellar hydroxides, or double hydroxide salts. In one embodiment, the composition comprises basic zinc carbonate. Basic zinc carbonate, which can also be commercially called zinc carbonate, or basic zinc carbonate, or hydroxy zinc carbonate, is a synthetic version consisting of materials similar to naturally occurring hydrozincite.
[000134] In embodiments having a layered material containing zinc and a pyrithione or a polyvalent metal pyrithione salt, the ratio of layered material containing zinc and pyrithione or polyvalent metal pyrithione salt is about 5: 100 to 10: 1 or about 2:10 to about 5: 1 or about 1: 2 to about 3: 1.
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6. Gel nets [000135] The shampoo composition may also comprise fatty alcohol gel nets. These gel networks are formed by the combination of fatty alcohols and surfactants in the ratio of about 1: 1 to about 40: 1, about 2: 1 to about 20: 1 and / or about 3: 1 to about 10: 1. The formation of a gel network involves heating a dispersion of the fatty alcohol in water with the surfactant to a temperature above the melting point of the fatty alcohol. During the mixing process, the fatty alcohol melts, allowing the surfactant to be partitioned into fatty alcohol droplets. The surfactant brings water into the fatty alcohol. This turns drops of isotropic fatty alcohol into drops of the liquid crystalline phase. When the mixture is cooled below the melting temperature of the chain, the liquid crystal phase is converted into a solid crystalline gel network. The gel network provides a stabilizing benefit to hair compositions. In addition, it provides the benefits of the feeling of conditioning. [000136] Fatty alcohol may be included in the fatty alcohol gel network at a content, by weight, of about 0.05% by weight to about 14% by weight. For example, fatty alcohol may be present in an amount ranging from about 1% by weight to about 10% by weight and / or from about 6% by weight to about 8%, in weight.
[000137] Fatty alcohols useful for the present invention are those having from about 10 to about 40 carbon atoms, from about 12 to about 22 carbon atoms, from about 16 to about 22 carbon atoms and / or from about 16 to about 18 carbon atoms. These fatty alcohols can be straight or branched, and can be saturated or unsaturated. Some non-limiting examples of fatty alcohols include cetyl alcohol, stearyl alcohol, beenyl alcohol and mixtures of these substances. Mixtures of cetyl and stearyl alcohols at a ratio of about 20:80 to about
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80:20 are also suitable.
[000138] Preparation of the gel net: A container is loaded with water and the water is heated to about 74 ° C. Cetyl alcohol, stearyl alcohol and SLES surfactant are added to the heated water. After incorporation, the resulting mixture is passed through a heat exchanger, where it is cooled to about 35 ° C. Upon cooling, the fatty alcohols and the surfactant crystallized to form a crystalline gel network. Table 3 presents the components and their respective amounts for the composition of the gel network.
Table 3
Components of the gel network Ingredient % by weight Water 78.27% Cetyl alcohol 4.18% Stearyl alcohol 7.52% Lauret-3 sodium sulfate (28% active) 10.00% 5-Chlorine-2-methyl-4-isothiazoline-3-one, Kathon CG 0.03%
Product form [000139] The shampoo compositions of the present invention can be presented in typical shampoo formulations. They can be in the form of solutions, dispersion, emulsions, powders, talc, encapsulated, spheres, sponges, solid dosage forms, foams and other application mechanisms. Compositions of the modalities of the present invention can be hair tonics, hair products without rinsing, such as products for treatment and styling, hair products with rinsing, such as shampoos and treatment products; and any other form that can be applied to the hair.
[000140] According to one modality, the shampoo compositions can be supplied in the form of a solid dissolvable and porous structure, with a percentage of open cells from about 80% to about 100%, as revealed in the publications of US patent application
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2009/0232873; and 2010/0179083, which are incorporated herein by reference in their entirety.
[000141] The shampoo composition can have a viscosity of 4,000 cP to 20,000 cP, or from about 6,000 cP to about 12,000 cP, or from about 8,000 cP to about 11,000 cP, measured at 26.6 ° C with a Brookfield R / S Plus rheometer at 2 s ^-1 . cP stands for centipoises., Method of manufacture [000142] Shampoo compositions are generally prepared conventionally. Such methods include mixing the ingredients in one or more steps to a relatively uniform state, with or without heating, cooling, applying a vacuum and the like. The compositions are prepared in order to optimize the stability (physical, chemical or photostability) and / or to apply the active materials. The shampoo composition can be a single phase or a single product, or the shampoo composition can be separate phases or separate products. If two products are used, the products can be used together, at the same time or sequentially. Method of Use [000143] The shampoo compositions of the present invention can be applied to the hair and removed by rinsing with water.
Examples [000144] The exemplified compositions can be prepared using conventional formulation and mixing techniques. It should be understood that other modifications of the composition for hair treatment, within the scope of the practice of those skilled in the art of formulating hair treatment products, can be carried out without deviating from the character and scope of this invention. All parts, percentages and reasons for this document are expressed in weight, unless otherwise specified. Some components can be obtained from suppliers in the form of
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52/57 diluted solutions. The fixed quantity reflects the weight percentage of the active material, unless otherwise specified.
[000145] Table 1 includes examples of specific structures for the silicone quaternary polymers described in Section A of this application.
Table 1
Variable Quaternary silicone polymer A Quaternary silicone polymer B Quaternary silicone polymer C Quaternary silicone polymer D Quaternary silicone polymer E M lauric ester lauric ester lauric ester lauric ester lauric ester Y K-S-K K-S-K K-S-K K-S-K K-S-K K CH2-CHOH-CH2-O-C3H6 CH2-CHOH-CH2-O-C3H6 CH2-CHOH-CH2-O-C3H6 CH2-CHOH-CH2-O-C3H6 CH2-CHOH-CH2-O-C3H6 s PDMS block with368 siloxane units PDMS block with368 siloxane units PDMS block with368 siloxane units PDMS block with450 siloxane units PDMS block with368 siloxane units R, R ² methyl methyl methyl methyl methyl T C6H12 C6H12 C6H12 C6H12 C6H12 THE CH2-COO- CH2-COO- CH2-COO- CH2-COO- CH2-COO- THE' CO-CH2 CO-CH2 CO-CH2 CO-CH2 CO-CH2 AND Ethylene oxide (CH2CH2-O) with an average degree of ethoxylation of 2 Ethylene oxide (CH2CH2-O) with an average degree of ethoxylation of 34 Propylene oxide (CH2CH (CHs) -O) with an average propoxylation grade of 3.5 Propylene oxide (CH2CH (CH3) -O) with an average degree of propoxylation of 3.5 Ethylene oxide (CH2CH2-O) with an average degree of ethoxylation of 2
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Variable Quaternary silicone polymer A Quaternary silicone polymer B Quaternary silicone polymer C Quaternary silicone polymer D Quaternary silicone polymer E Reason forsilicone blocks: blocks ofoxidealkylene 1: 1 9: 1 9: 1 9: 1 7: 3 ViscosityTotal 4,700 mPa.s 2,800 mPa.s 2,600 mPa.s. 5,400 mPa.s. 6,000 mPa.s. [000146] The following examples in Table 2 illustrate moc alities of
silicone emulsions, as described in Section A of this application.
Table 2
Silicone emulsionTHE B Ç D AND Water q.s. q.s. q.s. q.s. q.s. Sodium Laurete Sulfate ¹ 5.0 - - 5.0 5.0 C11-15 Pareth-5 ² - 1.4 1.0 C11-15 Pareth-12 ³ - 2.0 Quaternary silicone polymer A 20.0 Quaternary silicone polymer B10.0 Quaternary silicone polymer C 10.0 Quaternary silicone polymer D 20.0Quaternary silicone polymer E 20.0
¹ sodium lauret-1-sulfate, from Stepan ² Tergitol 15-S-5, from The Dow Chemical Company ³ Tergitol 15-S-12, from The Dow Chemical Company [000147] The following examples in Table 3 illustrate modalities of present invention in which the silicone polymer is emulsified.
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Table 3
11 12 13 14 15 16 17 18 19 20 Water q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. Sodium Laurete Sulfate ¹ 13.0 12.0 10.5 10.5 10.5 10.5 10.5 12.0 12.0 12.0 Sodium Lauryl Sulfate ² 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 CMEA ³ - - 0.8 - - - 0.8 - -Cocoamidopropylbetaína ⁴ 1.7 1.7 1.0 1.0 1.0 1.0 1.0 1.7 1.7 1.0 guar-hydroxypropyltrimony chloride ⁵ 0.325 0.3 - - - - - 0.30 - - Polyquaternium-10 ⁶ 0.075 - - - - - - - 0.30 - Polyquaternium -6 ⁷ 0.075 - 0.25 - - - - - - - Silicone emulsion A 5.0 2.5 Silicone emulsion B3.75 2.5 Silicone emulsion C 2.5 5.0 Silicone emulsion D 5.0 1.25Silicone Emulsion E 1.25 3.75 Glycerin ⁸ 0.5 0.5 - - - - - - - - EGDS ⁹ - - 1.5 - - - 1.5 - - - Trihydroxystearin ¹⁰ 0.1 0.1 - 0.1 0.1 0.1 - 0.1 0.1 0.1 Fragrance, preservatives, Up until Up until Up until Up until Up until Up until Up until Up until Up until Up until viscosity adjustment 3% 3% 3% 3% 3% 3% 3% 3% 3% 3%
¹ sodium lauret-1-sulfate, from Stepan ² sodium lauryl sulfate, from P&G ³ Ninol Comf, from Stepan ⁴ Amphosol HCA-B, from Stepan ⁵ NHance-3196, from ASI ⁶ Ucare Polymer KG-30M, from The Dow Chemical Company ⁷ Mirapol 100, by Rhodia Inc.
⁸ Superol V glycerin USP, from P&G ⁹ pure EGDS, from Evonik ¹⁰ Thixcin R from Elementis
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Data [000148] With reference to table 4, applicants surprisingly found that their emulsified silicone polymer (QAS 4996) in shampoo shows statistically and significantly improved dry conditioning performance when compared to the corresponding emulsified polydimethylsilicone (PDMS) reference standards .
Table 4
Composition Frictional force (g)Shampoo with silicone quaternary polymer C a1% - mixed emulsion 218.97 THE Shampoo with 1% PDMS (330,000 cs) - mixed emulsion 237.63 B Shampoo with 1% PDMS (5,000 cs) - mixed emulsion 259.74 B
[000149] * Compositions obtained from Momentive Performance
Materials [000150] The measurements in table 4 were obtained by measuring the frictional force (g) using the Instron Friction Method (IFM).
Instron's Friction Method (IFM) [000151] Dry conditioning performance is assessed by the frictional strength of the hair, measured by an instrument called Instron's Friction Meter (Instron Mini 55, Instron, Inc .; Canton, MA, USA).
• First, a 20 g hair lock is cleaned with drinking water at a flow rate of 5.7 L / min (1.5 gpm) at about 38 ° C (100 ° F).
• 2 ml of Pantene Fine Hair Solutions Flat to Volume shampoo are then applied to the lock of hair using a syringe, applying half of the syringe to the front and half of the syringe to the back of the lock.
• The Flat to Volume shampoo is then massaged into the hair using milking movements, with the thumb on the front of the
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56/57 stir and fingers on the back for 30 seconds.
• The wick is then rinsed with drinking water at a flow rate of 5.7 L / min (1.5 gpm) at about 38 ° C (100 ° F) for 30 seconds, while massaging the hair with milking movements, with thumb on the front and fingers on the back of the lock.
• The application of the shampoo is repeated.
• 2 ml of the shampoo, which comprises a conditioning composition, is then applied to the hair using a syringe, applying half of the syringe to the front and half of the syringe to the back of the lock.
• The conditioning composition is then massaged into the hair using milking movements, with the thumb on the front of the stir and the fingers on the back, for 30 seconds.
• The lock is at rest for 30 seconds.
• The hair lock is then rinsed with drinking water at a flow rate of 5.7 L / min (1.5 gpm) at about 38 ° C (100 ° F) for 30 seconds, while massaging the hair with milking movements , with thumb on the front and fingers on the back of the lock.
• Excess water is removed from the wick using your fingers like a squeegee, running down the wick twice.
• The wick is hung in a car and taken to a CT / CH room at about 21 ° C (70 ° F) and about 50% ambient humidity to dry and balance for one night.
• The frictional force (g) between the surface of the hair and the foam block along the hair is measured using the Instron Mini 55. [000152] The dimensions and values presented in the present invention should not be understood as being strictly limited to exact numerical values mentioned. Instead, unless otherwise specified, each of these dimensions is intended to
Petition 870190090224, of 9/11/2019, p. 60/81
57/57 mean both the mentioned value and a range of functionally equivalent values around that value. For example, a dimension shown as 40 mm is intended to mean about 40 mm.
[000153] Each document cited in the present invention, including any patent or patent application in cross-referenced or related reference, and any patent or patent application in which this application claims priority or benefit, is hereby fully incorporated herein by reference, except when expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art in relation to any invention presented or claimed in this document, or that it, alone or in any combination with any other reference or references, teaches, suggest or present any invention like this. In addition, if there is a conflict between any meaning or definition of a term mentioned in this document and any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document will take precedence.
[000154] Although particular embodiments of the present invention have been illustrated and described, it should be apparent to those skilled in the art that various other changes and modifications can be made without departing from the character and scope of the invention. Therefore, it is intended to cover in the appended claims all such changes and modifications that fall within the scope of the present invention.

权利要求:
Claims (14)
[1]
1. Shampoo composition, characterized by the fact that it comprises:
a) a silicone polymer comprising:
1. one or more quaternary groups;
ii. at least one block of silicone comprising more than 200 units of siloxane;
iii. at least one structural unit of polyalkylene oxide; and iv. at least one terminal ester group in which said silicone polymer has a viscosity of up to 100,000 mPa.s, in which said silicone polymer is a pre-emulsified dispersion with a particle size less than 1 micron and
b) a detersive surfactant.
[2]
2. Composition according to claim 1, characterized by the fact that said silicone block comprises from 300 to 600 units of siloxane.
[3]
3. Shampoo composition according to claim 1 or 2, characterized by the fact that said silicone polymer is present in an amount of 0.05% to 15%, by weight of the composition.
[4]
Shampoo composition according to any one of claims 1 to 3, characterized in that said silicone polymer is present in an amount of 0.1% to 10%, by weight of the composition.
[5]
Shampoo composition according to any one of claims 1 to 4, characterized in that said silicone polymer is present in an amount of 0.15% to 5%, by weight of the composition.
[6]
6. Composition of shampoo, according to any one
Petition 870190090224, of 9/11/2019, p. 62/81
2/6 of claims 1 to 5, characterized by the fact that said silicone polymer is defined by the following chemical structure:
M — Y - [- (N + R2 — T — N + R2) —Y—] m - [- (NR ² —A — E — A'— NR ² ) - Y—] k — M (Ia) in what:
m is an average value from above 0 to 100 k is an average value from above 0 to 50 k
M represents a terminal group, comprising terminal ester groups selected from among
-OC (O) -Z
-OS (O) 2-Z
-OS (O2) O-Z
-OP (O) (O-Z) OH
-OP (O) (OZ) 2 where Z is selected from monovalent organic residues having up to 40 carbon atoms, where A and A 'are each independently selected from a single bond or a divalent organic group having up to 10 carbon atoms and one or more hetero atoms, and
E is a group of polyalkylene oxide with the following general formula:
- [CH2CH2O] q— [CH2CH (CH3) O] r— [CH2CH (C2H5) O] s— with q = 0 to 200, r = 0 to 200,
Petition 870190090224, of 9/11/2019, p. 63/81
3/6 s = 0 to 200, and q + r + s = 1 to 600,
R is selected from monovalent organic groups having up to 22 carbon atoms and optionally one or more hetero atoms, and in which the free valences in the nitrogen atoms are linked to carbon atoms, R ² is selected from hydrogen or R,
Y is a group with the formula:
—K — S — K— and —A — E — A'— or — A'— E — A—, with
S =

[7]
7. Shampoo composition according to the claim
6, characterized by the fact that the K residues in said portion —K— S — K— are identical or different and are bonded to the silicon atom of residue S by a C-Si bond.
[8]
8. Composition of shampoo, according to any one
Petition 870190090224, of 9/11/2019, p. 64/81
4/6 of claims 1 to 7, characterized by the fact that said silicone polymer is defined by the following chemical structure:
M — Y - [- (N + R2 — T — N + R2) —Y—] m - [- (N + R22 — A — E — A'— N + R22) - Y—] k — M (Ib ) on what:
m is an average value from above 0 to 100 k is an average value from above 0 to 50 k
M represents a terminal group, comprising terminal ester groups selected from among
-OC (O) -Z
-OS (O) 2-Z
-OS (O2) O-Z
-OP (O) (O-Z) OH
-OP (O) (OZ) 2 where Z is selected from monovalent organic residues having up to 40 carbon atoms, where A and A 'are each independently selected from a single bond or a divalent organic group having up to 10 carbon atoms and one or more hetero atoms, and
E is a group of polyalkylene oxide with the following general formula:
- [CH2CH2O] q— [CH2CH (CH3) O] r— [CH2CH (C2H5) O] s— with q = 0 to 200, r = 0 to 200,
Petition 870190090224, of 9/11/2019, p. 65/81
5/6 s = 0 to 200, and q + r + s = 1 to 600,
R is selected from monovalent organic groups having up to 22 carbon atoms and optionally one or more hetero atoms, and in which the free valences in the nitrogen atoms are linked to carbon atoms, R ² is selected from hydrogen or R,
Y is a group with the formula:
—K — S — K— and —A — E — A'— or — A'— E — A—, with
S =

[9]
9. Shampoo composition according to claim
8, characterized by the fact that the K residues in said portion —K— S — K— are identical or different and are bonded to the silicon atom of residue S by a C-Si bond.
[10]
10. Shampoo composition according to the claim
Petition 870190090224, of 9/11/2019, p. 66/81
6/6
8 or 9, characterized by the fact that:
m is> 0 to 10, k is> 0 to 10,
M is -OC (O) -Z,
Z is a hydrocarbon chain with 0 to 40 carbons q = 0 - 50, r = 0 - 50, q + r is at least 1, s = 0,
R2 is methyl n = 300 - 500
[11]
Shampoo composition according to any one of claims 1 to 10, characterized in that said silicone polymer has a viscosity of 500 to 50,000 mPa.s.
[12]
Shampoo composition according to any one of claims 1 to 11, characterized in that said silicone polymer has a viscosity of 500 to 5,000 mPa.s.
[13]
13. Shampoo composition according to any one of claims 1 to 11, characterized in that said detersive surfactant is present in an amount of 0.5% to 20%, by weight of the composition.
[14]
14. Method for providing improved cleaning and conditioning benefits for the skin and / or hair, characterized in that it comprises the step of washing the hair and / or the skin with said shampoo composition, as defined in any of the claims 1 to 13.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

BE406221A|1933-11-15|

---

US2438091A|1943-09-06|1948-03-16|American Cyanamid Co|Aspartic acid esters and their preparation|

---

BE498391A|1944-10-16|

---

BE498392A|1945-11-09|

---

US2528378A|1947-09-20|1950-10-31|John J Mccabe Jr|Metal salts of substituted quaternary hydroxy cycloimidinic acid metal alcoholates and process for preparation of same|

---

US2658072A|1951-05-17|1953-11-03|Monsanto Chemicals|Process of preparing amine sulfonates and products obtained thereof|

---

US2809971A|1955-11-22|1957-10-15|Olin Mathieson|Heavy-metal derivatives of 1-hydroxy-2-pyridinethiones and method of preparing same|

---

US3236733A|1963-09-05|1966-02-22|Vanderbilt Co R T|Method of combatting dandruff with pyridinethiones metal salts detergent compositions|

---

US3761418A|1967-09-27|1973-09-25|Procter & Gamble|Detergent compositions containing particle deposition enhancing agents|

---

US3753196A|1971-10-05|1973-08-14|Kulite Semiconductor Products|Transducers employing integral protective coatings and supports|

---

US3929678A|1974-08-01|1975-12-30|Procter & Gamble|Detergent composition having enhanced particulate soil removal performance|

---

US4345080A|1980-02-07|1982-08-17|The Procter & Gamble Company|Pyridinethione salts and hair care compositions|

---

US4323683A|1980-02-07|1982-04-06|The Procter & Gamble Company|Process for making pyridinethione salts|

---

US4379753A|1980-02-07|1983-04-12|The Procter & Gamble Company|Hair care compositions|

---

US4529586A|1980-07-11|1985-07-16|Clairol Incorporated|Hair conditioning composition and process|

---

US4470982A|1980-12-22|1984-09-11|The Procter & Gamble Company|Shampoo compositions|

---

DE3216585C2|1982-05-04|1984-07-26|Th. Goldschmidt Ag, 4300 Essen|Process for the production of finely divided, stable O / W emulsions of organopolysiloxanes|

---

LU84463A1|1982-11-10|1984-06-13|Oreal|POLYQUATERNARY POLYSILOXANE POLYMERS|

---

LU84894A1|1983-07-01|1985-04-17|Oreal|HAIR COMPOSITION AND METHOD FOR TREATING HAIR|

---

LU85303A1|1984-04-13|1985-11-27|Oreal|HAIR COMPOSITION AND METHOD FOR TREATING HAIR|

---

GB2161172B|1984-07-03|1988-06-02|Beecham Group Plc|Conditioning shampoo compositions|

---

USRE34584E|1984-11-09|1994-04-12|The Procter & Gamble Company|Shampoo compositions|

---

US4902499A|1986-04-04|1990-02-20|The Procter & Gamble Company|Hair care compositions containing a rigid silicone polymer|

---

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|

---

US5104646A|1989-08-07|1992-04-14|The Procter & Gamble Company|Vehicle systems for use in cosmetic compositions|

---

US5106609A|1990-05-01|1992-04-21|The Procter & Gamble Company|Vehicle systems for use in cosmetic compositions|

---

CA2056859A1|1990-12-07|1992-06-08|Euan S. Reid|Hair treatment composition|

---

US5166297A|1991-03-25|1992-11-24|Siltech Inc.|Silicone ester quaternary compounds|

---

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|

---

MX9305744A|1992-09-22|1994-05-31|Colgate Palmolive Co|SHAMPOO HAIR CONDITIONER CONTAINING POLYMERS CATIONIC CONDITIONERS.|

---

US5284972A|1993-06-14|1994-02-08|Hampshire Chemical Corp.|N-acyl-N,N',N'-ethylenediaminetriacetic acid derivatives and process of preparing same|

---

US5747440A|1996-01-30|1998-05-05|Procter & Gamble Company|Laundry detergents comprising heavy metal ion chelants|

---

GB9708182D0|1997-04-23|1997-06-11|Dow Corning Sa|A method of making silicone in water emulsions|

---

FR2767473B1|1997-08-25|2000-03-10|Oreal|COSMETIC COMPOSITIONS CONTAINING A POLYOXYALKYLENE AMINE SILICONE BLOCK COPOLYMER AND A CONDITIONING AGENT AND USES THEREOF|

---

JP3297059B2|1997-12-19|2002-07-02|ザ、プロクター、エンド、ギャンブル、カンパニー|Polyvalent cationic silicone polymer|

---

FR2777010B1|1998-04-01|2000-06-16|Oreal|HETEROCYCLIC QUATERNARY POLYAMMONIUM SILICIATED POLYMERS AND THEIR USE IN COSMETIC COMPOSITIONS|

---

GB9816870D0|1998-08-03|1998-09-30|Unilever Plc|Hair treatment compositions|

---

ES2244241T3|1998-08-21|2005-12-01|Unilever N.V.|CONDITIONING COMPOSITIONS.|

---

US6136304A|1998-08-21|2000-10-24|Helene Curtis, Inc.|Conditioning compositions|

---

US5998537A|1998-09-21|1999-12-07|Dow Corning Corporation|Emulsions containing ultrahigh viscosity silicone polymers|

---

EP1000959B1|1998-11-14|2003-04-16|Goldschmidt AG|Polyetherquat functional polysiloxanes|

---

US6649155B1|1999-05-03|2003-11-18|The Procter & Gamble Company|Anti-dandruff and conditioning shampoos containing certain cationic polymers|

---

FR2799956B1|1999-10-20|2001-12-07|Oreal|COSMETIC COMPOSITIONS CONTAINING A VINTLDIMETHICONE / DIMETHICONE COPOLYMER IN AQUEOUS EMULSION AND A THICKENER THEREOF AND USES THEREOF|

---

FR2799971B1|1999-10-20|2001-12-07|Oreal|COSMETIC COMPOSITIONS CONTAINING A VINYLDIMETHICONE / DIMETHICONE COPOLYMER AND A CATIONIC POLYMER AND USES THEREOF|

---

FR2799955B1|1999-10-20|2001-12-07|Oreal|COSMETIC COMPOSITIONS CONTAINING AN EMULSION OF A VINYLDIMETHICONE / DIMETHICONE COPOLYMER AND A CATIONIC SURFACTANT AND USES THEREOF|

---

FR2799972B1|1999-10-20|2001-12-07|Oreal|COSMETIC COMPOSITIONS CONTAINING A VINYL DIMETHICONE / DIMETHICONE COPOLYMER IN AQUEOUS EMULSION AND A THICKENER AND USES THEREOF|

---

FR2799969B1|1999-10-20|2001-12-07|Oreal|COSMETIC COMPOSITIONS CONTAINING A VINYLDIMETHICONE / DIMETHICONE COPOLYMER AND A SILICONE AND USES THEREOF|

---

FR2799970B1|1999-10-20|2001-12-07|Oreal|COSMETIC COMPOSITIONS CONTAINING A VINYLDIMETHICONE / DIMETHICONE COPOLYMER AND A CONDITIONING AGENT AND USES THEREOF|

---

FR2802087A1|1999-12-08|2001-06-15|Oreal|COSMETIC COMPOSITIONS CONTAINING QUATERNIZED SILICONE AND A NACRANT AGENT AND USES THEREOF|

---

FR2802085B1|1999-12-08|2002-01-18|Oreal|COSMETIC COMPOSITIONS CONTAINING QUATERNIZED SILICONE AND NON-AMINOUS SILICONE AND USES THEREOF|

---

FR2802086A1|1999-12-08|2001-06-15|Oreal|COSMETIC COMPOSITIONS CONTAINING QUATERNIZED SILICONE AND CATIONIC POLYMER AND USES THEREOF|

---

AU3932800A|2000-03-31|2001-10-15|Procter & Gamble|Hair conditioning composition comprising carboxylic acid/carboxylate copolymer and vinylpyrrolidone copolymer|

---

US6696053B1|2000-05-04|2004-02-24|Unilever Home & Personal Care Usa, Division Of Conopco, Inc.|Leave-on or rinse-out hair care conditioner compositions containing silicone quaternary compounds and thickeners|

---

AU9168701A|2000-07-27|2002-02-13|Ge Bayer Silicones Gmbh And Co|Polyammonium-polysiloxane compounds, methods for the production and use thereof|

---

US7041767B2|2000-07-27|2006-05-09|Ge Bayer Silicones Gmbh & Co. Kg|Polysiloxane polymers, method for their production and the 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|

---

DE60141972D1|2000-11-16|2010-06-10|Procter & Gamble|HYDROPHILIC NETWORK SILICONE|

---

DE10104033A1|2001-01-31|2002-08-14|Wella Ag|Hair care product with diquaternary silicone polymers|

---

GB0102647D0|2001-02-02|2001-03-21|Dow Corning Sa|Cosmetic skin care preparation|

---

BR0208643A|2001-04-06|2004-03-02|Unilever Nv|Hair Care Composition|

---

US6475568B1|2001-05-15|2002-11-05|Crompton Corporation|Block, non-n silicone polyalkyleneoxide copolymers with tertiary amino links|

---

DE10139963A1|2001-08-14|2003-03-06|Wacker Chemie Gmbh|Organopolysiloxanes containing quaternary ammonium groups and process for their preparation|

---

FR2830759B1|2001-10-15|2003-12-12|Oreal|COMPOSITION IN THE FORM OF AN OIL-IN-WATER EMULSION CONTAINING A SILICONE COPOLYMER AND ITS IN PARTICULAR COSMETIC USES|

---

GB0125449D0|2001-10-23|2001-12-12|Unilever Plc|Cosmetic compositions|

---

US6482969B1|2001-10-24|2002-11-19|Dow Corning Corporation|Silicon based quaternary ammonium functional compositions and methods for making them|

---

US6607717B1|2001-10-24|2003-08-19|Dow Corning Corporation|Silicon based quaternary ammonium functional compositions and their applications|

---

MXPA04005044A|2001-11-30|2004-08-11|Procter & Gamble|Shampoo containing a silicone in water emulsion.|

---

WO2003078504A1|2002-03-20|2003-09-25|Ge Bayer Silicones Gmbh & Co. Kg|Branched polyorganosiloxane polymers|

---

BR0308602B1|2002-03-21|2013-12-17|Hair treatment compositions comprising polysiloxane, and hair conditioning method|

---

US20080206355A1|2002-06-04|2008-08-28|The Procter & Gamble Company|Composition comprising a particulate zinc material, a pyrithione or a polyvalent metal salt of a pyrithione and a synthetic cationic polymer|

---

US20040120914A1|2002-06-28|2004-06-24|L'oreal|Composition containing a quaternary silicone, a cation and two cationic polymers and method of use|

---

US7740873B2|2002-06-28|2010-06-22|L'oreal|Composition comprising a quaternary silicone and a liquid fatty alcohol and method of treatment|

---

WO2004024114A2|2002-09-10|2004-03-25|Takasago International Corporation|Compositions comprising silicone-in-water emulsions and fragrances and hair care preparations comprising such compositions|

---

DE10250755B4|2002-10-31|2007-02-08|Merz Pharma Gmbh & Co. Kgaa|A foamable composition based on an O / W emulsion comprising a combination of a silicone-based emulsifier and an anionic surfactant having improved skin action, their preparation and their use|

---

CN100457804C|2002-11-04|2009-02-04|Ge拜尔硅股份有限公司|Linear polyamino and/or polyammonium polysiloxane copolymers I|

---

JP2006505643A|2002-11-04|2006-02-16|ジーイー・バイエル・シリコーンズ・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング・ウント・コンパニー・コマンジツトゲゼルシヤフト|Linear polyamino and / or polyammonium polysiloxane copolymer II|

---

US7585494B2|2002-11-04|2009-09-08|Momentive Performance Materials Gmbh|Formulations used for the treatment of substrate surfaces|

---

AU2003295904A1|2002-11-22|2004-06-18|Petroferm Inc.|Polymers containing quaternary ammonium salts|

---

US20040126349A1|2002-12-31|2004-07-01|Anderson Glen T.|Hair and scalp compositions with a crosslinked silicone elastomer and method of using same|

---

US20040265258A1|2002-12-31|2004-12-30|Robinson Freda E.|Hair care compositions|

---

US20060233720A1|2002-12-31|2006-10-19|Anja Stork|Sprayable oil-like formulations|

---

WO2004069137A2|2003-02-07|2004-08-19|Ge Bayer Silicones Gmbh & Co. Kg|Use of polyamino and/or polyammonium-polysiloxane copolymers|

---

DE10316662A1|2003-04-11|2004-11-11|Ge Bayer Silicones Gmbh & Co. Kg|Reactive amino and / or ammonium polysiloxane compounds|

---

JP4200827B2|2003-06-20|2008-12-24|株式会社デンソー|Impact detection device|

---

US20050048016A1|2003-07-02|2005-03-03|L'oreal|Composition containing a silicone elastomer and a block silicone copolymer|

---

CN101111534B|2005-02-02|2012-08-22|瓦克化学股份公司|Manufacture of stable low particle size organopolysiloxane emulsion|

---

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|

---

US7441684B2|2006-08-02|2008-10-28|Ethicon Endo-Surgery, Inc.|Pneumatically powered surgical cutting and fastening instrument with audible and visual feedback features|

---

US8349300B2|2007-04-19|2013-01-08|The Procter & Gamble Company|Personal care compositions containing at least two cationic polymers and an anionic surfactant|

---

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|

---

US8765170B2|2008-01-30|2014-07-01|The Procter & Gamble Company|Personal care composition in the form of an article|

---

JP5718246B2|2008-12-08|2015-05-13|ザ プロクター アンド ギャンブルカンパニー|Personal care composition in the form of an article having a porous soluble solid structure|

---

BR112012010823B1|2009-10-21|2020-10-06|Stepan Company|VISCOSE LIQUID CLEANING COMPOSITIONS UNDERSTANDING SULPHONATED FATTY ACIDS, ESTERS OR SALTS OF THE SAME AND BETAINES OR SULTAINS AND THE MANUFACTURING PROCESS OF THE SAME|

---

EP2552390B1|2010-03-31|2016-10-12|Unilever PLC|Personal wash cleanser with mild surfactant systems comprising defined alkanoyl compounds and defined fatty acyl isethionate surfactant product and optional skin or hair benefit agent|

---

US20110240065A1|2010-04-01|2011-10-06|Rajan Keshav Panandiker|Care polymers|

---

CA2867315C|2012-03-29|2017-06-27|Michael Albert Snyder|Hair conditioning compositions comprising low viscosity silicone polymers|

---

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|

---

MX352277B|2012-03-30|2017-11-16|Procter & Gamble|Hair conditioning composition comprising mono-alkyl amine cationic surfactant system, deposition polymer, and silicone.|

---

US20150010487A1|2013-07-03|2015-01-08|The Procter & Gamble Company|Shampoo composition comprising low viscosity silicone polymers|FR2661408B1|1990-04-27|1993-09-17|Rhone Poulenc Nutrition Animal|PROCESS FOR THE PREPARATION OF CITRAL.|

---

WO2015047786A1|2013-09-27|2015-04-02|The Procter & Gamble Company|Hair conditioning compositions comprising low viscosity emulsified silicone polymers|

---

MX357742B|2013-09-27|2018-07-23|Procter & Gamble|Hair compositions comprising low viscosity silicone polymers.|

---

WO2017071915A1|2015-10-29|2017-05-04|Unilever Plc|Personal cleansing compositions|

---

EA035252B1|2016-04-01|2020-05-21|Юнилевер Н.В.|Personal cleansing composition|

---

WO2017223076A1|2016-06-20|2017-12-28|Rita Corporation|Surfactant composition|

---

US20180000705A1|2016-06-30|2018-01-04|The Procter & Gamble Company|Shampoo Compositions Comprising a Chelant|

---

US20180000706A1|2016-06-30|2018-01-04|The Procter & Gamble Company|Conditioner Composition Comprising a Chelant|

---

US20180000715A1|2016-06-30|2018-01-04|The Procter & Gamble Company|Hair Care Compositions For Calcium Chelation|

---

US11246816B2|2016-06-30|2022-02-15|The Procter And Gamble Company|Shampoo compositions comprising a chelant|

---

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|

---

US11179312B2|2017-06-05|2021-11-23|Momentive Performance Materials Inc.|Aqueous compositions for the treatment of hair|

---

US10982051B2|2017-06-05|2021-04-20|Momentive Performance Materials Inc.|Aqueous compositions for hair treatment comprising polyorganosiloxanes with polyhydroxyaromatic moieties|

---

US10912732B2|2017-12-20|2021-02-09|The Procter And Gamble Company|Clear shampoo composition containing silicone polymers|

---

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|

法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-02-04| B09A| Decision: intention to grant|

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2020-03-24| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/06/2014, 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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US201361842640P| true| 2013-07-03|2013-07-03|

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US61/842,640|2013-07-03|

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US14/039,886|US9198849B2|2013-07-03|2013-09-27|Shampoo composition comprising low viscosity emulsified silicone polymers|

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US14/039,886|2013-09-27|

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PCT/US2014/044329|WO2015002812A1|2013-07-03|2014-06-26|Shampoo composition comprising low viscosity emulsified silicone polymers|

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