Topical formulations comprising polyalkoxylated polyol polyesters with Guerbet acids
阅读说明：本技术 包含具有格尔伯特酸的聚烷氧基化多元醇聚酯的局部制剂 (Topical formulations comprising polyalkoxylated polyol polyesters with Guerbet acids ) 是由 塞缪尔·Q·林 徐·秦 于 2019-03-29 设计创作，主要内容包括：本申请涉及包含具有格尔伯特酸的聚烷氧基化多元醇聚酯的局部制剂。本文所含的化合物涉及聚烷氧基化多元醇聚酯,其具有允许产品被倾倒但保留在其所施加的所需表面上的粘度。所述化合物的实施例可以通过下式举例说明：Q-[(OA)<Sub>n</Sub>-OR]<Sub>m</Sub>。(The present application relates to topical formulations comprising polyalkoxylated polyol polyesters with guerbet acids. The compounds contained herein relate to polyalkoxylated polyol polyesters having a viscosity that allows the product to be poured but remain on the desired surface to which it is applied. Examples of such compounds may be illustrated by the following formula: q- [ (OA) n ‑OR] m 。)
1. A polyalkoxylated polyol polyester having the formula:
Q-[(OA)n-OR]m
formula-2
Q is a radical of a natural or synthetic organic polyol compound having 6 to 50 carbon atoms forming a linear, branched, cyclic, saturated or unsaturated structure wherein one or more carbon atoms independently have the formula- [ (OA)n-OR]Wherein n is 6 to 25,
wherein the remaining carbon atoms of the 6 to 50 carbon atoms are independently substituted with hydrogen, oxygen, or nitrogen;
a is selected from-C2H4-or-C3H6-；
R is independently selected from hydrogen or-COR1，
R1Independently selected from C6-C34Alkyl, preferably derived from a guerbet acid; c6-C22Hydroxyalkyl radicals, preferably derived from guerbet acids; or C6-C34Alkenyl radicals, preferably derived from Guerbet acids,
n is an integer selected from 1 to 125, and may be the same or different for each polyalkoxylated hydrophilic arm; and COR1Is not less than 2.5, preferably not less than 3, and most preferably not less than 4; and is
m is an integer selected from 6 to 25, and preferably 6 to 12.
2. The polyalkoxylated polyol polyester according to claim 1, wherein the C derived from a Guerbet acid6-C34The alkyl group has the formula:
where n is 1-120, preferably 3, 5, 7, 9 or 13.
3. The polyalkoxylated polyol polyester of claim 1 or 2, wherein each hydrophilic poly (alkylene glycol) arm (- [ (OA)n-OR]) N of (a) is equal to 25 to 120, more preferably 30 to 85, and most preferably 30 to 70.
4. Polyalkoxylated polyol polyester according to claim 1 or 2, wherein R1Derived from stearic acid, isostearic acid, oleic acid, guerbet acid or mixtures thereof.
5. Polyalkoxylated polyol polyester according to claim 1 or 2, wherein R1Comprising guerbet acid and isostearic acid moieties.
6. The polyalkoxylated polyol polyester according to claim 1 or 2, wherein the Guerbet acid moiety has from 18 to 24 carbon atoms.
7. The polyalkoxylated polyol polyester according to claim 1 or 2, wherein Q is a group of the following polyol compounds:
sugar alcohol of the general formula HOCH2(CHOH)xCH2OH；
A disaccharide having a glycosidic bond;
(C6H10O5)n0wherein n0 is 2 to 20;
dipentaerythritol;
a dendritic polymer polyol; and
polyglycerol having 3 to 10 glycerol units with 6 or more hydroxyl groups.
8. Polyalkoxylated polyol polyester according to claim 1 or 2, wherein Q is selected from the polyols of the following compounds:
sugar alcohol of the general formula HOCH2(CHOH)xCH2OH；
A disaccharide having a glycosidic bond;
(C6H10O5)n0wherein n0 is 2 to 20;
dipentaerythritol; and
a dendritic polymer polyol.
9. A polyalkoxylated polyol polyester according to claim 1 or 2, wherein Q is selected from polyols of sorbitol, trehalose, mannitol, dipentaerythritol, sucrose, lactose, chitobiose, cellobiose and maltose.
10. A cosmetic, dermatological or pharmaceutical composition comprising a polyalkoxylated polyol polyester according to any one of the preceding claims or a mixture thereof.
11. The cosmetic, dermatological or pharmaceutical composition according to claim 10, wherein Q is the group of sorbitol:
12. the cosmetic, dermatological or pharmaceutical composition according to claim 10 or 11, further comprising:
water;
1-50% by weight of a surfactant selected from the group consisting of: anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof;
0.1 to 10 weight percent of the polyol polyester of formula-2; and
0.1 to 50% by weight of other ingredients selected from the group consisting of: skin and hair benefit actives, stabilizers, other thickeners, colorants, preservatives, and pearlizing agents.
13. The cosmetic, dermatological, or pharmaceutical composition of claim 10, further comprising:
water;
2-50 wt% of a surfactant selected from the group consisting of: sulfate-free anionic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof;
0.1 to 10% by weight of the polyalkoxylated polyol polyester of formula-2; and
0.1 to 50% by weight of other ingredients selected from the group consisting of: skin and hair benefit actives, stabilizers, other thickeners, colorants, and preservatives.
14. The cosmetic, dermatological or pharmaceutical composition according to any one of claims 10, 11 and 13,
it further comprises:
water;
from about 1% to 30% by weight of a skin and hair active selected from the group consisting of: UV filters, moisturizers, conditioners, preservatives, deodorant actives, reducing agents for permanent products, colorants for hair coloring, anti-aging actives, protein/protein derivatives, fragrances, petrolatum, vegetable oils, cationic conditioning polymers and mixtures thereof; and
about 1 to 10% by weight of said polyalkoxylated polyol polyester of formula-1
Technical Field
Background
Rheology or material flow studies are applied to consumer products such as shower gels, shampoos, liquid detergents, dish detergents, hand washes, skin care lotions or creams, hair conditioners, hair styling products, etc. to develop a specific viscosity profile. This profile is critical to the consumer's product preferences and final purchasing decisions.
Consumers prefer products with such rheological profiles: the product is stable in the container, low enough in viscosity to be easily poured from the container, and also thick enough to be applied to the body, hair or fabric without dripping from the consumer's hands or the surface to which it is applied. In addition, the product must stabilize and maintain a consistent rheological profile during storage in the warehouse, while in transit, and while on the shelf for many years.
There are many commercial thickeners that use esters of polyalkoxylated polyols and fatty acids to thicken surfactant-containing formulations. Examples of commercial products include polyethylene glycol 6000 distearate, also known under the INCI name PEG-150 distearate; PEG 120 methyl glucose dioleate and PEG 120 methyl glucose trioleate (glucmate)TMDOE 120 and GlucomateTMVLT); PEG-150 pentaerythritol tetrastearate (Crothix)TMCrothix (TM) Liquid and VersathixTM) (ii) a PEG-150 polyglyceryl-2 tristearate (Genapol LT); PEG/PPG-120/10-trimethylolpropane trioleate (Arlypon TT). The number of hydrophilic polyalkoxylated arms was two in PEG-150 distearate, three in Arlypon TT, four in Genapol LT and Crothix, Crothix Liquid and Versathix, and five in Glucomate DOE 120.
US5,192,462 (Gloor et al) relates to thickeners comprising tetraesters made from fatty acids and polyoxyethylene pentaerythritol having four hydrophilic poly (ethylene glycol) arms. Its preferred chemical structure is PEG-150 pentaerythritol tetrastearate, in which all four hydrophilic poly (ethylene glycol) arms are capped with stearic fatty acid and are the base of Crothix, Crothix Liquid, and Versathix Liquid.
US7,709,011 and US7,553,495 (both Klug et al) relate to thickeners of oxyalkylated polyglycerol esters with fatty acids for topical formulations containing surfactants, as shown below.
Wherein A is of the formula-C2H4-or C3H6A radical of formula-B is hydrogen or a radical of formula-COR, wherein at least one symbol B is a radical of formula-COR-, R is C7-C34Alkyl radical, C7-C21Hydroxyalkyl or alkenyl, n is a number from 1 to 30, and x, y, z are numbers from 0 to 100, wherein the sum of x, y and z is from 50 to 250. (see column 1, lines 43-48).
For those skilled in the art, the number of hydrophilic poly (ethylene glycol) arms is equal to n + 2. When n is 30 and x + y + z is 250, the average number of ethylene glycol units or (x + y + z)/(n +2) is [250/(30+2) ] and a maximum of about 7.81.
Disclosure of Invention
The examples of the present invention teach novel polyalkoxylated polyol polyesters according to formula-2 (below) which are the reaction product of (a) a fatty acid and (b) a polyalkoxylated polyol.
Q-[(OA)n-OR]m
Formula-2
Wherein Q is a radical of a natural or synthetic organic polyol compound having 6 to 50 carbon atoms forming a linear, branched, cyclic, saturated or unsaturated structure wherein each carbon atom is independently represented by the formula- [ (OA)n-OR]Wherein each of said 6 to 50 carbon atoms may be independently substituted with hydrogen, oxygen, or nitrogen; a is selected from-C2H4-or-C3H6-; r is independently selected from hydrogen or-COR1Wherein R is1Independently selected from C6-C34Alkyl radical, C6-C22Hydroxyalkyl radical, C2-C22Alkenyl, and preferably C16-C32The stearic acid moiety, isostearic acid moiety, oleic acid moiety, branched Guerbet acid (Guerbet acid) moiety of (a), or mixtures thereof, and the most preferred embodiment has oleic acid, or alternatively a mixture of isostearic acid and Guerbet acid; COR (continuous operating reference)1Has an average total number (based on two or more, preferably more, polyalkoxylated polyol polyesters conforming to formula-2) of not less than 2.5, preferablySelecting ≥ 3, and most preferably ≥ 4; n is an integer selected from 1 to 125, and may be the same or different for each polyalkoxylated hydrophilic arm; each (OA)nThe average number of n units is from 25 to 120, preferably from 30 to 85, and most preferably from 30 to 70; and m is an integer selected from 6 to 25, preferably 6 to 12.
In one embodiment, the invention relates to the following items:
1. a polyalkoxylated polyol polyester having the formula:
Q-[(OA)n-OR]m
formula-2
Q is a radical of a natural or synthetic organic polyol compound having 6 to 50 carbon atoms forming a linear, branched, cyclic, saturated or unsaturated structure wherein one or more (preferably all) of the carbon atoms independently have the formula- [ (OA)n-OR]Wherein n is 6 to 25,
wherein the remaining carbon atoms of said 6 to 50 carbon atoms are independently replaced by hydrogen, oxygen (preferably-OH) or nitrogen (preferably-NH)2) Particularly preferably hydrogen;
a is selected from-C2H4-or-C3H6-；
R is independently selected from hydrogen or-COR1，
R1Independently selected from C6-C34Alkyl, preferably derived from a guerbet acid; c6-C22Hydroxyalkyl radicals, preferably derived from guerbet acids; or C6-C34Alkenyl radicals, preferably derived from Guerbet acids,
n is an integer selected from 1 to 125, and may be the same or different for each polyalkoxylated hydrophilic arm; and COR1Is not less than 2.5, preferably not less than 3, and most preferably not less than 4; and is
m is an integer selected from 6 to 25, and preferably 6 to 12.
2. The polyalkoxylated polyol polyester according to item 1, wherein the C derived from a Guerbet acid6-C34The alkyl group has the formula:
where n is 1-120, preferably 3, 5, 7, 9 or 13.
3. The polyalkoxylated polyol polyester of clauses 1 or 2, wherein each hydrophilic poly (alkylene glycol) arm (- [ (OA)n-OR]) Is equal to 25 to 120, more preferably 30 to 85, and most preferably 30 to 70.
4. The polyalkoxylated polyol polyester according to any one of the preceding items, wherein R1Derived from stearic acid, isostearic acid, oleic acid, guerbet acid or mixtures thereof.
5. The polyalkoxylated polyol polyester according to any one of the preceding items, wherein R1Comprising guerbet acid and isostearic acid moieties.
6. The polyalkoxylated polyol polyester according to any one of the preceding items, wherein the Guerbet acid moiety has from 18 to 24 carbon atoms.
7. The polyalkoxylated polyol polyester according to any one of the preceding items, wherein Q is the group of the following polyol compounds:
sugar alcohol of the general formula HOCH2(CHOH)xCH2OH；
A disaccharide having a glycosidic bond;
(C6H10O5)n0wherein n0 is 2 to 20;
dipentaerythritol;
a dendritic polymer polyol; and
polyglycerol having 3 to 10 glycerol units with 6 or more hydroxyl groups.
8. The polyalkoxylated polyol polyester according to any one of the preceding items, wherein Q is selected from the polyols of the following compounds:
sugar alcohol of the general formula HOCH2(CHOH)xCH2OH；
A disaccharide having a glycosidic bond;
(C6H10O5)n0wherein n0 is 2 to 20;
dipentaerythritol; and
a dendritic polymer polyol.
9. The polyalkoxylated polyol polyester according to any one of the preceding items, wherein Q is selected from polyols of sorbitol, trehalose, mannitol, dipentaerythritol, sucrose, lactose, chitobiose, cellobiose, and maltose.
10. A cosmetic, dermatological or pharmaceutical composition comprising a polyalkoxylated polyol polyester according to any one of the preceding items or a mixture thereof.
11. The cosmetic, dermatological or pharmaceutical composition according to item 10, wherein Q is the group of sorbitol:
12. the cosmetic, dermatological and pharmaceutical composition according to item 10 or 11, further comprising:
water;
1-50% by weight of a surfactant selected from the group consisting of: anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof;
0.1 to 10 weight percent of the polyol polyester of formula-2; and
0.1 to 50% by weight of other ingredients selected from the group consisting of: skin and hair benefit actives, stabilizers, other thickeners, colorants, preservatives, and pearlizing agents.
13. The cosmetic, dermatological, and pharmaceutical composition of clause 10, further comprising:
water;
2-50 wt% of a surfactant selected from the group consisting of: sulfate-free anionic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof;
0.1 to 10% by weight of the polyalkoxylated polyol polyester of formula-2; and
0.1 to 50% by weight of other ingredients selected from the group consisting of: skin and hair benefit actives, stabilizers, other thickeners, colorants, and preservatives.
14. The cosmetic, dermatological, and pharmaceutical composition of any one of items 10 to 13, further comprising:
water;
from about 1% to 30% by weight of a skin and hair active selected from the group consisting of: UV filters, moisturizers, conditioners, preservatives, deodorant actives, reducing agents for permanent products, colorants for hair coloring, anti-aging actives, protein/protein derivatives, fragrances, petrolatum, vegetable oils, cationic conditioning polymers and mixtures thereof; and
about 1 to 10% by weight of said polyalkoxylated polyol polyester of formula-1
In another embodiment the present invention relates to cosmetic, dermatological and pharmaceutical preparations comprising polyalkoxylated polyol polyesters of formula-2.
The polyesters of the embodiments of the present invention are suitable as thickeners, rheology modifiers, solubilizers, conditioners and dispersants for aqueous, aqueous/alcoholic and surfactant-containing formulations, and as emulsifiers and suspending agents for thickening and thickening emulsions and suspensions. Examples of such surfactant-containing preparations, emulsions and suspensions are shampoos, bath preparations, shower gels, foam baths, facial cleansers, hand soaps, bar soaps, shaving creams, hair conditioners, deodorants, lotions, creams, ointments, wet wipes, antiperspirants, sunscreens, and the like. Embodiments of the present invention are also suitable as thickeners and rheology modifiers for fabric care products, such as fabric conditioners and liquid laundry detergents. Therefore, the present invention also providesRelates to a composition comprising or consisting of two or more, preferably more, polyalkoxylated polyol polyester molecules of formula-2 as described herein, wherein COR1Is defined based on all polyalkoxylated polyol polyester molecules of formula-2 contained in the composition.
The preparations, cleaning preparations, emulsions and suspensions according to the invention preferably comprise from 0.05% to 20% by weight, particularly preferably from 0.1% to 10% by weight, particularly preferably from 0.5% to 5% by weight, based on the final formulation, of polyalkoxylated polyol polyesters of the formula-1.
Cleaning compositions according to embodiments of the present invention may further comprise at least one of the following: all conventional anionic, cationic, zwitterionic, nonionic and amphoteric surfactants; all conventional skin and hair benefit actives such as cosmetic oils, petrolatum, vegetable oils, hydrogenated vegetable oils, UV filters, proteins, shine agents, anti-aging agents, amino acids, biological actives, moisturizers, conditioning polymers, silicones, cationic polymers, sucrose polyesters, anti-dandruff zinc salts, hydroxy acids, skin whitening agents; all conventional stabilizers, such as silica, 12-hydroxystearic acid, hydrogenated castor oil, ethylene glycol distearate, bentonite and hectorite clays, fatty acids, fatty alcohols; all conventional thickeners, such as hydroxyethyl cellulose, xanthan gum, polyacrylates, modified or unmodified starches, and the like; all conventional dyes, colorants, pearlescers, fragrances, chelating agents, solvents, humectants, salts and the like.
The total amount of surfactant used in the composition of the invention may be between 5 and 70 wt%, preferably between 10 and 40 wt%, most preferably between 12 and 35 wt%, based on the final composition.
Definition of
As used above, and throughout this disclosure, the following terms are to be understood to have the following meanings, unless otherwise indicated. In the absence of a definition, the conventional definition known to those skilled in the art prevails.
As used herein, the terms "comprising," "including," and "containing" are used in their open, non-limiting sense.
As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.
To provide a more concise description, some of the quantitative representations given herein are not appropriate for the term "about". It is understood that, whether the term "about" is used explicitly or not, every quantity given herein is meant to refer to the actual given value, and it is also meant to refer to the approximation to such given value that would reasonably be inferred based on the ordinary skill in the art, including equivalents and approximations due to the experimental and/or measurement conditions for such given value. Whenever a yield or amount is given as a percentage, such yield or amount refers to the mass of an entity (weight percent), for which the yield is given relative to the maximum amount of the same entity that can be obtained under the particular stoichiometric conditions. Unless otherwise specified, concentrations given in percentages refer to mass ratios.
As used herein, "alkyl" means a straight or branched saturated chain having 1 to 34 or more carbon atoms. Alkyl groups may be unsubstituted or substituted. Alkyl groups containing three or more carbon atoms may be straight-chain, branched-chain or cyclic.
As used herein, "alkenyl" includes unbranched or branched hydrocarbon chains having one or more double bonds therein and having 1 to 34 or more carbon atoms. The double bond of the alkenyl group may be unconjugated or conjugated to another unsaturated group. Alkenyl groups may be unsubstituted or substituted.
The term "hydroxy" means an OH group;
the term "hydroxyalkyl" means an alkyl group as defined above wherein the alkyl group has an OH group disposed thereon.
The term "alkoxy" or "alkoxylated" as used herein includes-O- (alkyl), wherein alkyl is as defined above.
As used herein, the term "composition" is intended to encompass a product comprising the specified ingredients in the specified amounts, as well as any product which results, directly or indirectly, from combination of the specified ingredients in the specified amounts.
The term "amino" as used herein means a substituent containing at least one nitrogen atom.
As used herein, the term "substituted" means that a particular group or moiety bears one or more suitable substituents, wherein a substituent may be attached at one or more positions to the particular group or moiety.
As used herein, the term "unsubstituted" means that the specified group bears no substituents.
Any atom represented herein having a valence that is not met or specified is considered to have a sufficient number of hydrogen atoms to meet the valence of the atom. For example, "substituted with oxygen" or "substituted with nitrogen" means that the substituents are oxygen bonded to one hydrogen (-OH) through one bond or without hydrogen (O) through two bonds and nitrogen bonded to two hydrogen (-NH2) through one bond or with one hydrogen (NH) through two bonds.
All patents or patent applications cited herein are incorporated by reference in their entirety.
Detailed Description
In one embodiment, there is a polyalkoxylated polyol polyester of formula-2, wherein Q is defined as the group of a natural or synthetic organic polyol compound, wherein the group structure is derived from a polyol by removal of one or more, preferably all, of the corresponding OH "groups, has the elements carbon, hydrogen, oxygen, and nitrogen, and is straight, branched, cyclic, saturated, or unsaturated, and wherein Q has from 6 to 50 carbon atoms, and is independently substituted with 6 to 25 groups having the formula- [ (OA)n-OR]By substitution of a group of
Q-[(OA)n-OR]m
Formula-2
Wherein A is selected from-C2H4-or-C3H6-; n is 1 to 125; r is independently selected from hydrogen or-COR1(ii) a And R is1Independently selected from C6-C34Alkyl radical, C6-C22Hydroxyalkyl radical, C2-C34An alkenyl group; wherein R is1Preferably stearic acid moiety, isostearic acid moiety, oleic acid moiety, having 1A guerbet acid moiety of 2 to 32 carbon atoms or mixtures thereof. - [ (OA)n-OR]"is a group attached to the Q group. Highly preferred R1Is an oleic acid moiety; another highly preferred example is a mixture of isostearic acid and guerbet acid. In some embodiments, the Guerbet acid has 12 to 32 carbons, more preferably about 16-32 carbons, more preferably 18-24 carbons, and most preferably 20 carbons, and COR1Is not less than 2.5, preferably not less than 3, and most preferably not less than 4; and m is an integer selected from 6 to 25, preferably 6 to 12. N per hydrophilic poly (alkylene glycol) arm may range from 1 to 125, and the average number of n is from 25 to 120, preferably from 30 to 85, and most preferably from 30 to 70.
Guerbet acids are primary carboxylic acids with well-defined carbon chain twin branches (formula-3). This unique branched structure results in lower melting point, lower viscosity and better solubility. Examples of commercial products are from the Sasol company (Sasol)
The branched guerbet acid derived moiety has the formula:
wherein n is 1-120. Symbol
The organic polyol compound (Q) of the embodiment of the present invention may be a natural polyol or a synthetic polyol having at least six hydroxyl groups, and examples thereof are shown by the following classes of compounds (but not limited thereto):
1. sugar alcohols, also known as polyols having at least six hydroxyl groups (polyhydroxyl/polyalchol), have the general formula HOCH2(CHOH)xCH2And (5) OH. Examples include, but are not limited to, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, heptatol, isomalt, maltitol, lactitol, maltotriose, maltotetraitol, and polyglucitol.
2. Disaccharides, which are formed by dehydration of two monosaccharides via a glycosidic bond. Examples include, but are not limited to, trehalose, sucrose, lactose, maltose, and the like. Which contains six or more hydroxyl groups.
3. Dextrin having the chemical structure (C)6H10O5)nWherein n is 2 to 20.
4. Dipentaerythritol
5. A dendritic polymer polyol. For example,h2003 and H20 have 6, 12 and 16 terminal hydroxyl groups, respectively.
6. Polyglycerol having 3 to 10 glycerol units with 6 or more hydroxyl groups.
After the reaction, each hydroxyl group of the starting polyol compound will grow into a hydrophilic poly (alkylene glycol) arm. The length of all arms may be the same or different depending on the reaction conditions.
The next reaction is an esterification reaction between a polyalkoxylated polyol compound and a fatty acid such that some or all of the hydrophilic poly (alkylene glycol) arms are capped with a fatty acid ester. The reaction is carried out between 120 ℃ and 250 ℃ with or without a catalyst until the desired acid number or degree of esterification is reached. The preferred method is to use an esterification catalyst such as an alkyl benzene sulfonic acid, methane sulfonic acid, an organotin catalyst, an organotitanate catalyst, and the like. The preferred molar ratio of fatty acid to alkoxylated polyol compound is to form an ester having from 30% to 100% hydrophilic poly (alkylene glycol) arms. For example, when the starting polyol compound is sorbitol, the molar ratio will be 2.4 to 6 when six poly (alkylene glycol) arms will be produced per sorbitol molecule. When it is trehalose, the molar ratio is from 3.2 to 8 when eight poly (alkylene glycol) arms will be produced. Most preferably, more than at least four fatty ester terminated arms are formed.
In another embodiment, Q is an organic moiety of sorbitol having 6 carbons, and formula-4 is the chemical structure of the polyol ester from the sorbitol starting compound.
Another embodiment of the present invention is a cosmetic, dermatological and pharmaceutical preparation containing the polyalkoxylated polyol polyester of the present invention (formula-1). The polyalkoxylated polyol polyesters of the present invention are suitable as thickeners, rheology modifiers, solubilizers, conditioners, and dispersants for aqueous, aqueous/alcoholic, and surfactant-containing formulations; as emulsifying and suspending agents with thickening and thickening action for emulsions and suspensions. Such surfactant-containing preparations, emulsions and suspensions are, for example, shampoos, bath preparations, shower gels, foam baths, facial cleansers, hand soaps, bar soaps, shaving creams, hair conditioners, deodorants, lotions, creams, ointments, wet wipes, antiperspirants, sunscreens, etc.
The formulations of the cleaning preparations, emulsions and suspensions according to the invention preferably comprise from 0.05% to 20% by weight, particularly preferably from 0.1% to 10% by weight, particularly preferably from 0.5% to 5% by weight, based on the final formulation, of polyalkoxylated polyol polyesters of the formula-2 or of the formula-3.
Cleaning compositions according to embodiments of the present invention may further comprise the following components: all conventional anionic, cationic, zwitterionic, nonionic and amphoteric surfactants; skin and hair benefit actives such as cosmetic oils, petrolatum, vegetable oils, hydrogenated vegetable oils, UV filters, proteins, shine agents, anti-aging agents, amino acids, bioactives, moisturizers, conditioning polymers, silicones, cationic polymers, sucrose polyesters, anti-dandruff zinc salts, hydroxy acids, skin whitening agents; stabilizers such as silica, 12-hydroxystearic acid, hydrogenated castor oil, ethylene glycol distearate, bentonite and hectorite clays, fatty acids, fatty alcohols, and the like; other thickeners such as hydroxyethyl cellulose, xanthan gum, polyacrylates, modified or unmodified starches, and the like; and polyethylene glycol. The cleaning composition may be in the form of a liquid, paste, gel or solid.
The total amount of surfactant used in the compositions of the present embodiments may be between 5 and 70 wt%, preferably between 10 and 40 wt%, and most preferably between 12 and 35 wt%, based on the final composition.
Each of these components, as well as preferred and optional components, in the cleaning composition are described below.
A. Detersive surfactant
Conventional detersive surfactants can be selected from anionic, cationic, nonionic, amphoteric/zwitterionic surfactants or mixtures thereof. Details of these conventional detersive surfactants are known, such as US7,659,235B 2; US8,361,450B2, respectively; US8,802,607B 2; US 3,929,678; US 2,528,378, incorporated herein by reference; and McCutcheon's, Emulsifiers and Detergents (1989) published by m.c. publishing Co (m.c. publishing Co). Anionic surfactants may include alkyl sulfates or alkyl ether sulfates (including alkyl glyceryl ether sulfates). It may also include sulfate-free anionic surfactants as shown below.
Aliphatic sulfonates, e.g. primary alkanes (e.g. C)8-C22) Sulfonates, primary alkane disulfonates, C8-C22Olefin sulfonates, alkyl glyceryl ether sulfonates, aromatic alkyl sulfonates or C8-C22A hydroxyalkane sulfonate.
Alkyl sulfosuccinates (including monoalkyl and dialkyl, e.g. C)6-C22Sulfosuccinates). Alkyl and acyl taurates, alkyl and acyl glycinates, alkyl sulfoacetates, alkyl phosphates, alkoxy alkyl phosphates and acyl lactates, C8-C22Monoalkylsuccinates and maleates. Fatty acyl isethionates, which are typically prepared by the reaction of isethionates, such as alkali metal isethionates, and aliphatic fatty acids of 8 to 20 carbon atoms. For example, commercial products of fatty acyl isethionates are DEFI, Hostapon SCI-78C, Jordapon CI print, YA-SCI-85, Iselux LQ-CLR-SB, and the like. Having the formula R- (CH)2CH2O)nCO2M wherein R is C8-C20An alkyl group; n is 1 to 20; and M is a positive ion, such as sodium, potassium, and the like. Another class of anionic surfactants are soaps or fatty acid salts. Sulfonate derivatives of alkyl polyglucosides include, for example, sodium lauryl glucoside hydroxypropyl sulfonate and sodium decyl glucoside hydroxypropyl sulfonate.
Another sulfate-free mild surfactant is a class of alkanoyl surfactants prepared from amino acids. Alkyl is C8To C20Preferably C12To C16An alkyl group. Such surfactants may include, for example, alkanoyl sarcosinates, alkanoyl glycinates and alkanoyl glutamates. For example, the commercial product is of Ajinamoto
Preferred anionic surfactants are sulfate-free mild surfactants and mixtures thereof. The weight proportion of anionic surfactant in the composition according to embodiments of the present invention is in the range of 5 to 35 wt%, preferably 10 to 25 wt%.
Amphoteric or zwitterionic surfactants are surfactants having a positive and a negative charge. It can be broadly described as a derivative of aliphatic quaternary ammonium, phosphonium and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic radicals is C8To C18Carbon atoms and one containing an anionic group, e.g. carboxy, sulfonate, sulfate, phosphate or phosphonate. Examples may include conventional betaines, such as ammonium N-alkyl-N, N-dimethylglycinate, cocamidopropyl betaine; c12-C18Alkyl dimethyl-sulfopropyl betaines and amine oxides. The proportion of amphoteric surfactant in the composition according to embodiments of the present invention is from 0.5% to 30% by weight, and preferably from 1% to 15% by weight.
The nonionic surfactant may include alkoxylated fatty alcohols, acids, amides or alkyl phenols; long chain tertiary amine oxides; long chain tertiary phosphine oxides; a dialkyl sulfoxide; sugar amides, as described in US5,389,279 and US5,009,814; alkyl polyglucosides, as described in US 4,565,647 and US 3,723,325, all of which are incorporated herein by reference. Preferred nonionic surfactants are alkyl polyglucosides and alkyl polyglucosamides. Examples of commercial products may include those of BASF
Cationic surfactants are surfactants having positively charged groups. Suitable cationic surfactants may include quaternary ammonium salts, such as di- (C)10-C24) Alkyl dimethyl ammonium chloride, (C)10-C24) Alkyl trimethylammonium chloride or sulphate, and N-acylaminoethyl-N, N-diethyl-N-methylammonium chloride. Other conventional cationic surfactants are described in the US8,470,305B2 and 8,470,305B2 references, which are incorporated herein by reference. The weight proportion of cationic surfactant in the composition according to embodiments of the invention is in the range of 1 to 10 wt%, and preferably 1 to 7 wt%.
B.Liquid crystal inducer and modifier
Liquid crystal inducers are small nonionic molecules and are believed to dissolve in mixtures of surfactants, thereby altering the surfactant micelles to form stacks of larger structural aggregates of different shapes and sizes, such as lamellar liquid structures or vesicles, rod-like and cubic liquid crystals. An alternative name for liquid crystal inducers is hydrophobic thickeners. It includes the classes alkanolamide, alkylamine oxide or mixtures thereof. Examples of this class include monoethanolamides and diethanolamides, isopropanolamides of fatty acids of 10 to 20 carbon atoms, PPG-hydroxyethyl cocamide, and alkylamine oxides of 10 to 20 carbon atoms. Another class of chemicals in liquid crystal inducers are alkoxylated alkyl alcohols of 8 to 18 carbon atoms, preferably 8 to 12 carbon atoms, and 1 to 4 ethylene oxide units.
The liquid crystal modifier comprises fatty acid and fatty alcohol with 8-20 carbon atoms and aliphatic hydrocarbon with molecular weight less than 400 g/mol. It is believed to change the size and shape of the liquid crystal. US7,655,607B 2 is a reference to ranges and examples of liquid crystal inducers and modifiers, which is incorporated herein by reference.
C.Skin and hair benefit actives
These benefit actives may be water soluble, water insoluble or water dispersible. Water soluble actives may include, but are not limited to, polyols such as glycerol, diglycerol, sorbitol, propylene glycol (propylene glycol), propylene glycol (propandiol), panthenol, and sugars; alpha-hydroxy acids and salts thereof; low molecular weight polyethylene glycol. Water insoluble and water dispersible skin and hair benefit actives include, but are not limited to, petrolatum, silicones, vegetable oils, essential oils, emollients, hydrocarbon oils, fatty esters, cationic polymers, high refractive index oils for lightening, anti-dandruff agents, protein/protein derivatives, and the like. These water insoluble benefit agents are typically present in the composition as an emulsion or a stripe. Non-limiting examples in US7,262,158 are incorporated herein by reference. Other various skin and hair benefit actives may include vitamins, lipids (sucrose esters, lanolin, cholesterol, etc.), liposomes, essential fatty acids, butter, minerals, antimicrobials, anti-acne agents, oil control agents, astringents, oil control agents, scrub and exfoliate particles, essential oils, sunscreens, styling aids, dyes, perfumes, cyclodextrin/perfume complexes, anti-wrinkle actives (amino acids and derivatives thereof such as N-acetyl-L-cysteine), thiols, anti-cellulite agents (caffeine, theophylline, etc.), tanning actives, skin whitening actives, skin soothing agents (such as bisabolol, aloe, dipotassium glycyrrhizinate, etc.).
Cationic water-soluble/dispersible polymers are very useful as conditioning actives or deposition aids for the compositions according to the invention. Suitable cationic polymers for use in the composition according to the invention have a cationic charge density in the range of from 0.2 to 8meq/g and a molecular weight in the range of from 1,000 to 3,000,000. The cationic groups thereof are nitrogen-containing moieties, such as quaternary ammonium or cationic protonated amino moieties, which can be primary, secondary and tertiary amines. Non-limiting examples of cationic polymers are described by Estringson (Estrin), Crosley (Crosley) and Haynes (Haynes)CTFA Cosmetic Ingredient Dictionary (CTFA Cosmetic Ingredient Dictionary), 3 rd edition and US 8470,305B2 and US8,105,994B 2, which are incorporated herein by reference. Non-limiting examples can include copolymers of vinyl monomers having cationic protonated amine or quaternary ammonium functionalities with water-soluble spacer monomers such as acrylamide, methacrylamide, alkyl and dialkyl acrylamides, vinyl pyrrolidone, vinyl caprolactone, and the like. Non-limiting specific examples are polyquaternium-11, -16, -7, -6, -22, -47, -39. Other suitable cationic polymers include polysaccharide polymers such as cationic cellulose derivatives, cationic starch derivatives, cationic guar gum derivatives, and the like. Non-limiting examples include the following trade names: from Rhone Poulenc
D. Stabilizers and other thickeners
The stabilizer (or structuring system) serves to form a crystalline stabilizing network in the composition, preventing coalescence and phase separation of the droplets of lipophilic benefit agent in the product. Non-limiting examples include hydroxyl-containing fatty acids, fatty esters, or fatty soap water-insoluble waxy materials, such as 12-hydroxystearic acid, 9, 10-dihydroxystearic acid, tris-9, 10-dihydroxystearin, and tris-12 hydroxystearin. Another class of stabilizers is C10-C22Ethylene glycol fatty acid esters, fumed silica, precipitated silica, montmorillonite clay, and the like. Other examples of conventional stabilizers are disclosed in US 6,194,363 and US9,138,428, which are incorporated herein by reference. Another class of stabilizers is the gel network of fatty amphiphiles (e.g. stearic acid and behenyltrimethylammonium chloride), as disclosed in US8,470,305. Another class of stabilizers is unmodifiedBlends of sexual and modified starches and fatty acids, as disclosed in US 6,906,016, all incorporated herein by reference.
Other thickeners useful for stabilizing and altering the viscosity of the composition according to the present invention are polymers. Non-limiting examples include carbohydrate gums such as cellulose gum, microcrystalline cellulose, cellulose gel, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose, methyl/propyl cellulose, guar gum, karaya gum, tragacanth gum, acacia gum, agar gum, xanthan gum, and mixtures thereof; modified and unmodified starch granules having a gelatinization temperature between 30 ℃ and 85 ℃ and pregelatinized cold water soluble starch. Further non-limiting examples include the class of hydrophobically associating, cross-linking, alkali swellable acrylate polymers comprising acidic monomers having hydrophobic end groups and associative monomers as disclosed in US9,161,899, which is incorporated herein by reference. Non-limiting commercial examples are Carbopol aqua sf-1 from Lubrizol, Stabylen 30 from 3V sigma s.p.a., inc (3V sigma s.p.a.), and the Aqupec series from Sumitomo Seika, japan.
Suitable other thickeners may include salts such as sodium chloride and sodium sulfate; cellulose derivatives such as hydroxyethyl cellulose; xanthan gum, guar gum; starch and starch derivatives; carboxyvinyl polymers, e.g.940; polyacrylate emulsions, e.g.
According to the invention, the formulation of emulsions and suspensions comprises water; an oil; an emulsifier; preferably from 0.05 to 20% by weight, particularly preferably from 0.1 to 10% by weight, particularly preferably from 0.5 to 5% by weight, of a polyester of the formula-1; and other conventional ingredients for skin care, hair care and body care. The non-aqueous portion of the emulsion is typically in the range of 2% to 85%, and preferably 5% to 45%. Oils include, but are not limited to, cosmetic oils that are refined vegetable oils, refined synthetic or fermented hydrocarbon oils, silicone oils, and synthetic ester oils.
The following non-limiting examples demonstrate the compositions and outstanding performance of the present invention.
Examples of the invention
Example 1. Synthesis of polyalkoxylated polyol polyesters of formula-3 having different molecular structures. Table 1 lists the preparation of polyesters of formula-3 having a range of molecular weights of alkoxylated sorbitol and fatty acid. The reaction flask used was a one-liter resin kettle with four necks. Sorbitol is mixed with KOH or NaOH base catalyst and dried under vacuum at 90-110 ℃. X moles of ethylene oxide or a blend of ethylene oxide and propylene oxide per mole of sorbitol are added under pressure and reacted at 140 deg.C to 180 deg.C for a reaction time of 10 to 20 hours. After the reaction, the resulting product was cooled, degassed and filtered to give sorbitol polyether-xxx. The ingredients of sorbitol polyether-xxx, oleic or stearic acid, and catalyst-methanesulfonic acid were added to the flask, then purged with nitrogen. The mixture was heated to between 120-220 ℃ while mixing under nitrogen and collecting the water. Continuing the reaction until R1The sum (or acid number) of (a) is targeted or nearly constant. The product was collected after cooling the flask to room temperature. The resulting polyester was a waxy solid.
Example 2 the polyester-6 of table 1 of the present invention and PEG-150 pentaerythritol tetrastearate were formulated in a non-sulfate personal cleansing composition having 6% potassium cocoyl glycinate (Amilite GCK-11F from Ajinomoto Inc), 15% cocamidopropyl betaine (35% active by weight, trade name-Monteric LMAB), 0.3% EDTA, 78.7% water, and citric acid adjusted to pH 6. Potassium cocoyl glycinate surfactants are derived from glycine amino acids and are known to be very mild to the skin. PEG-150 pentaerythritol tetrastearate is available under the trade name CROTHIX from procumbent corporation (Croda Inc) and is based on US5,192,462, which is incorporated herein by reference.
At 2 wt% thickener, polyester-6 of the present invention gave a viscosity of 72,900cP, while CROTHIX gave a viscosity of 45,840 cP. This indicates the superior performance of the polyesters of the invention over the prior art.
Example 3 this personal cleansing formulation is based on cocoyl sarcosinate, another amino acid derived surfactant. The composition was 29.89% sodium cocoyl sarcosinate (trade name: ProtelanLS9011 from Simplex & Schwarz, 29% active by weight), 12.38% cocamidopropyl betaine (trade name: Monateric LMAB, 35% active by weight), 1.8% thickener, 1% cocamide MEA, 0.1% EDTA, 1% NaCl, 53.83% water, and citric acid adjusted to pH 6. At 1.8% by weight in the formulation, polyester-7 of the present invention produced a viscosity of 69660 cP, while CROTHIX produced 3640 cP.
Example 4. this personal cleansing formulation is based on a nonionic alkyl polyglucoside surfactant and an anionic sodium cocoyl isethionate, two well known mild and non-sulfate surfactants in the personal cleansing market. The composition was 13% decyl glucoside (trade name-Plantaren 2000N UP from BASF corporation), 7% sodium cocoyl isethionate (trade name-Pureac I-78C), 7% cocamidopropyl betaine (trade name-Montaric LMAB), 1% PEG-7 coco glyceride (Protachem GC-7 from Protatami Inc.), 0.35% EDTA, citric acid adjusted to pH 5.5, and water. At the same 1.2 wt%, polyester-4 and CROTHIX of the present invention thickened the above surfactant formulations to 26340cP and 22200cP, respectively. Polyester 4 of the present invention again exhibits superior properties over prior art CROTHIX.
Example 5 this formulation is a typical sulphate surfactant cleaning product: 10.7% sodium lauryl ether sulfate solution (70% active by weight), 8.58% cocamidopropyl betaine (35% active by weight), 0.25% cocamide MEA, 0.2% EDTA, 0.5% NaCl, x% thickener, and 79.57% water. The pH was 5.5. The inventive polyester-5 of table 1 was compared to three commercial thickeners in this sulfate cleaning formulation: 1) trade name: CROTHIX, solid form, supplied by prochloraz. INCI: PEG-150 pentaerythritol tetrastearate; 2) trade name: glucimate DOE-120, supplied by Lubizol Inc. INCI name: PEG-120 methyl glucose dioleate; 3) the commodity name is as follows: rewopal PEG 6000DS, supplied by Evonik Inc. INCI name: PEG-150 distearate.
This result demonstrates the superior performance of the thickeners of the present embodiments over many prior art commercial thickeners in classical sulfate surfactant personal cleansing products. This and other examples show that a wide range of polyesters of the embodiments of the present invention are more effective and versatile thickeners than prior commercial products of the prior art in a variety of personal cleansing products having different types of surfactants.
Example 6 this example illustrates the synthesis of a polyester of formula-1 with a gemini branched guerbet acid. Commercial Guerbet acids used were Isocab-20 (2-octyl-dodecanoic acid) having 20 carbons and Isocab-24 (2-decyl-tetradecanoic acid) having 24 carbons, supplied by the company Sasolr. The same reaction conditions as in example 1 apply here.
Example 7 this example demonstrates the thickening ability of polyester 11(PE-11) in two popular cleaning formulations. SH-1 cleansing formulation (shampoo): 78.9% of water, 6% of potassium cocoyl glycinate, 15% of cocamidopropyl betaine, 0.1% of EDTA and 7% of pH; SH-2 cleansing formulation (also shampoo): water 58.4%, sodium C14-16 olefin sulfonate (39% solids) 30%, cocamidopropyl betaine 11.5%, EDTA 0.1%, pH 7. The polyester-11 of the present invention shows much stronger thickening properties than Crothix-S.
In addition to showing a robust improvement to shampoo formulations with Corthix, formulations with a mixture of guerbet acids also showed a significant improvement over formulations without guerbet acids.
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