JP2020164465A - Topical formulation containing gelbeic acid-containing polyalkoxylated polyol polyester - Google Patents

Abstract

To provide a polyalkoxylated polyol polyester that has a suitable rheology profile and is stable during storage and transportation.SOLUTION: A polyol ester represented by the following formula. Q-[(OA)n-OR]m (formula-2). [In the formula, Q is a group of natural or synthetic organic polyol compound having 6 to 50 carbon atoms; A is selected from -C2H4- or -C3H6-; R is independently selected from hydrogen or -COR1, and R1 is independently selected from C6-C34-alkyl preferably derived from gelbeic acid, C6-C22-hydroxyalkyl preferably derived from gelbeic acid, or C6-C34-alkenyl preferably derived from gelbeic acid.].SELECTED DRAWING: None

Description

Priority Claim This non-provisional application is a partial continuation of U.S. Patent Application No. 15/652679 filed on July 18, 2017, which was filed on February 1, 2017 in the United States. Claims the priority of US Patent Application No. 62/499642 and US Patent Application No. 62/495444 filed on September 15, 2016, the contents of which are incorporated herein by reference in their entirety. To.

Fields of Embodiment The fields of the invention and embodiments thereof are polyalkoxyylated to produce a viscosity that allows the product to be poured and further to be retained on the desired surface to which it is applied. Regarding polyol polyester.

Background of the embodiment Rheology, or study of material flow, shower gels, shampoos, liquid detergents, dishwashing liquids, hand soaps, skin care lotions or creams, hair conditioners, hair styling to create specific viscosity profiles. Applies to consumer products such as agents. Such profiles are important for consumer product preferences and final purchase decisions.

The consumer has a viscosity low enough to stabilize the product in the container and easily pour it out of the container, yet on the body, hair, or fabric without dripping from the consumer's hands or applied surface. You will prefer products with a rheological profile that are thick enough to apply. In addition, the product must be stable during warehousing, transportation, and potentially years of shelf storage, and must maintain a consistent rheological profile.

There are many commercially available thickeners that use esters of polyalkoxylated polyols and fatty acids to thicken surfactant-containing formulations. Examples of commercial products include polyethylene glycol distearate 6000 (also known as INCI name for PEG-150 distearate); PEG-120 methylglucose dioleate and PEG-120 methylglucose trioleate (Glucomate ™ DOE 120 and Glucomate ™ VLT); PEG-150 pentaerythrityl tetrastearate (Crosix ™, Crothix ™ Liquid, and Versazix ™); PEG-150 polyglyceryl-2 tristearate (Genapol LT); trio PEG / PPG-120 / 10 trimethylolate propane (Arlypon TT) is included. The number of hydrophilic polyalkoxylification arms is 2 for PEG-150 distearate, 3 for Arlypon TT, 4 for Genapol LT and Crothix, Crothix Liquid, and Versathix, and 5 for Glucomate DOE 120. is there.

U.S. Pat. No. 5,192,462 (Gloor et al.) Relates to a thickener containing a tetraester consisting of a fatty acid and polyoxyethylene pentaerythritol, having four hydrophilic poly- (ethylene glycol) arms. Its preferred chemical structure is PEG-150 pentaerythrityl tetrastearate, in which all four hydrophilic poly (ethylene glycol) arms are capped with fatty acid stearate, on the basis of Crothix, Crothix liquid, and Versathix Liquid. is there.

U.S. Pat. No. 7,709,011 and U.S. Pat. No. 7,553,495 (both Krug et al.) Concern thickeners of oxyalkylated polyglycerol esters containing fatty acids for surfactant-containing topical formulations as shown below.

In the formula, A formula _-C 2 _{H 4} - or _C 3 _{H 6} - is a radical, B is a group of hydrogen or the formula -COR, wherein at least one symbol B is a group of the formula -COR- R is C _7- C ₃₄ -alkyl, C _7- C ₂₁ -hydroxyalkyl or alkenyl, n is a number from 1 to 30, and x, y, z are numbers from 0 to 100. Here, the sum of x, y, and z is 50-250. (See column 1, lines 43-48).

To those skilled in the art, the number of hydrophilic poly- (ethylene glycol) -arms is equal to n + 2. When n = 30 and x + y + z = 250, the average number of ethylene glycol units or (x + y + z) / (n + 2) is [250 / (30 + 2)], which is about 7.81 at the maximum.

Outline of Embodiments The embodiments of the present invention teach a novel polyalkoxylated polyol polyester according to formula-2 (below), which is a reaction product of (a) fatty acid and (b) polyalkoxylated polyol.
Q-[(OA) _n- OR] _m
Equation-2
In the formula, Q is a group of natural or synthetic organic polyol compounds having 6 to 50 carbon atoms forming a linear, branched, cyclic, saturated or unsaturated structure, and each carbon atom is independent. , Which are substituted with 6 to 25 groups having the formula − [(OA) _{n −} OR], where each of the 6 to 50 carbon atoms is independently substituted with hydrogen, oxygen or nitrogen. even if well; A is _-C 2 _{H 4} - or _-C 3 _{H 6} - is selected from; R is independently selected from hydrogen or -COR _1, wherein, _{R 1} is, independently, C Selected from _6- C ₃₄ alkyl, C _6- C ₂₂ -hydroxyalkyl, C _2- C ₂₂ alkenyl, preferably stearic acid moiety, isostearic acid moiety, oleic acid moiety, C _16- C ₃₂ branched gelbet. an acid moiety or a mixture thereof, most preferred embodiment, oleic acid, or have a mixture of any of isostearic acid (isotearic acid) and Guerbet acid; average total number of COR ₁ (2 or more, preferably multiple , Based on polyalkenylated polyol polyester according to formula-2) is ≧ 2.5, preferably ≧ 3, most preferably ≧ 4; n is an integer selected from 1-125 and each polyalkenylation The hydrophilic arms may be the same or different; (OA) the average number of n per _n units is 25 to 120, preferably 30 to 85, most preferably 30 to 70; m is 6-25, preferably. Is an integer selected from 6-12.

In one embodiment, the invention refers to the following items:
1. 1. formula:
Q-[(OA) _n- OR] _m
Equation-2
Polyalkoxylated polyol polyester having
Q is a group of natural or synthetic organic polyol compounds having 6 to 50 carbon atoms forming a linear, branched, cyclic, saturated or unsaturated structure and is one or more (preferably all). The carbon atom (of) independently has a substituent of the formula-[(OA) _n- OR] (in the formula, n = 6-25).
Here, the remaining carbon atoms of the 6 to 50 carbon atoms are independently substituted with hydrogen, oxygen (preferably -OH), or nitrogen (preferably -NH ₂ ), particularly preferably hydrogen;
A is, _-C 2 _{H 4} - or _-C 3 _{H 6} - is selected from;
R is independently selected from hydrogen or -COR ₁ and
R ₁ is independently and preferably C _6- C ₃₄ -alkyl derived from gelbeic acid; preferably C _6- C ₂₂ -hydroxyalkyl derived from gelbe acid; or preferably C derived from gelbe acid. Selected from _6- C ₃₄ -alkenyl,
n is an integer selected from 1-125 and may be the same or different for each polyalkoxylated hydrophilic arm; the average total number of COR ₁ is ≧ 2.5, preferably ≧ 3, most preferably. ≧ 4; and m is an integer selected from 6-25, preferably 6-12, polyalkoxylated polyol polyester.

（式中、ｎ＝１−１２０、好ましくは３、５、７、９、又は１３である）を有する、項目１に記載のポリアルコキシル化ポリオールポリエステル。 2. The C _6- C ₃₄ -alkyl derived from gelbeic acid has the following formula:

The polyalkoxylated polyol polyester according to item 1, which has (in the formula, n = 1-120, preferably 3, 5, 7, 9, or 13).

3. 3. N per hydrophilic poly- (alkylene glycol) arm (-[(OA) _n- OR]) is equal to 25 to 120, more preferably 30 to 85, most preferably 30 to 70, in item 1 or 2. The polyalkoxylated polyol polyester described.

4. R ₁ is, stearic acid, isostearic acid, oleic acid, Guerbet acids, or is derived from a mixture thereof, polyalkoxylated polyol polyester according to any one of items 1 3.

5. R ₁ is, Guerbet and isostearic (isotearic) including partial, polyalkoxylated polyol polyester according to any one of items 1 4.

6. The polyalkoxylated polyol polyester according to any one of items 1 to 5, wherein the gerve portion has 18 to 24 carbon atoms.

7. Q is the group of the following polyol compounds:
HOCH ₂ (CHOH) _x CH ₂ OH sugar alcohol with the general formula;
Disaccharides with glycosidic bonds;
(C ₆ H ₁₀ O ₅ ) _n0 (in the formula, n0 is 2 to 20);
G-pentaerythritol;
The polyalkoxypolyester polyester according to any one of items 1 to 6, which is a dendrimer polyol; and a polyglyceryl having 3 to 10 glycerin units having 6 or more hydroxyl groups.

8. Q is a polyol of the following compound:
HOCH ₂ (CHOH) _x CH ₂ OH sugar alcohol with the general formula;
Disaccharides with glycosidic bonds;
(C ₆ H ₁₀ O ₅ ) _n0 (in the formula, n0 is 2 to 20);
The polyalkoxylated polyol polyester according to any one of items 1 to 7, which is selected from dipentaerythritol; and dendrimer polyol.

9. The polyalkoxylated polyol polyester according to any one of items 1 to 8, wherein Q is selected from polyols of sorbitol, trehalose, mannitol, dipentaerythritol, sucrose, lactose, chitobiose, cellobiose, and maltose.

10. A cosmetic, skin or pharmaceutical composition comprising the polyalkoxylated polyol polyester according to any one of items 1 to 9 or a mixture thereof.

である、項目１０に記載の化粧用、皮膚用又は薬学的組成物。 11. The basis of sorbitol whose Q is as follows:

The cosmetic, skin or pharmaceutical composition according to item 10.

12.
water;
1% -50% by weight surfactant selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof;
From the group consisting of 0.1% to 10% by weight polyol polyester of formula-2; and active agents, stabilizers, additional thickeners, colorants, preservatives, and pearl colorants beneficial to the skin and hair. The cosmetic, skin, and pharmaceutical composition according to item 10 or 11, further comprising 0.1% to 50% by weight of other ingredients selected.

13.
water;
2% -50% by weight surfactant selected from the group consisting of sulfate-free anionic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof;
Selected from the group consisting of 0.1% to 10% by weight polyalkoxylated polyol polyester of formula-2; and active agents, stabilizers, additional thickeners, colorants, and preservatives beneficial to the skin and hair. The cosmetic, skin, and pharmaceutical composition according to item 10, further comprising 0.1% to 50% by weight of other ingredients.

をさらに含む、項目１０から１３のいずれか１項に記載の化粧用、皮膚用、及び薬学的組成物。 14.
water;
UV filters, moisturizers, conditioners, preservatives, deodorants, reducing agents for permanent wave products, coloring agents for coloring hair, anti-aging activators, proteins / protein derivatives, fragrances, petrolatum, vegetable oils, cationic About 1% to 30% by weight of skin and hair active ingredients selected from the group consisting of conditioning polymers and mixtures thereof; and about 1% to 10% by weight of polyalkylated polyol polyester of formula-1.

The cosmetic, skin, and pharmaceutical composition according to any one of items 10 to 13, further comprising.

In other embodiments of the invention, there are cosmetic, dermatological, and pharmaceutical formulations comprising the polyalkoxylated polyol polyester of formula-2.

The polyesters of embodiments of the present invention can be used as thickeners, rheology modifiers, solubilizers, conditioners, and dispersants for aqueous, aqueous / alcoholic, and surfactant-containing formulations, as well as emulsions and suspensions. It is suitable as an emulsifier and a suspending agent having a thickening action and a bodying action for the purpose. Examples of these surfactant-containing formulations, emulsions, and suspensions include shampoos, shower formulations, shower gels, foam baths, facial cleansers, hand soaps, solid soaps, shaving creams, hair conditioners, deodorants, lotions, etc. Creams, ointments, wet wipes, antiperspirants, sunscreens, etc. 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. Accordingly, the present invention also relates to compositions comprising or consisting of two or more, preferably a large number of polyalkoxylated polyol polyester molecules of formula-2 as described herein. The average total number of ₁ is defined based on all the polyalkoxylated polyol polyester molecules of formula-2 contained in the composition.

Based on the final formulation, the formulations, cleansing formulations, emulsions and suspensions according to the invention are preferably 0.05% to 20% by weight, particularly preferably 0.1% to 10% by weight, particularly preferably. Includes 0.5% to 5% by weight of the polyalkylated polyol polyester of formula-1.

The cleansing composition according to embodiments of the present invention comprises the following components: all conventional anionic, cationic, biionic, nonionic and amphoteric surfactants; beneficial activity for all normal skin and hair. Agents such as hairdressing oils, vaseline, vegetable oils, hardened vegetable oils, UV filters, proteins, shining agents, anti-aging agents, amino acids, physiological activators, moisturizers, conditioning polymers, silicones, cationic polymers, sucrose polyesters. , Anti-mold zinc salts, hydroxy acids, skin whitening agents, etc .; all conventional stabilizers, such as silica, 12-hydroxystearic acid, hardened castor oil, ethylene glycol distearate, bentonite and hectolite clay, fatty acids, fats. Group alcohols, etc .; all conventional thickeners, such as hydroxyethyl cellulose, xanthan gum, polyacrylates, processed or unprocessed starches; all conventional dyes, colorants, pearl colorants, fragrances, chelating agents, solvents, etc. At least one of moisturizers, salts and the like can be further included.

The total amount of surfactant used in the composition of the present invention is between 5% by weight and 70% by weight, preferably between 10% by weight and 40% by weight, most preferably 12% by weight, based on the final composition. It can be between% and 35% by weight.

Definitions As used above and throughout this disclosure, the following terms should be understood to have the following meanings, unless otherwise indicated. If there is no definition, conventional definitions known to those skilled in the art will regulate.

As used herein, the terms "including," "containing," and "comprising" are used in their unlimited, non-limiting sense.

As used herein, the singular forms "a", "an", and "the" include a plurality of referents unless the context clearly indicates otherwise.

To provide a more concise explanation, some of the quantitative expressions given herein are not modified by the term "about". Regardless of whether the term "about" is used explicitly, any quantity given herein is meant to refer to an actual given value, and such a given value. Refers to an approximation to such a given value that would be reasonably inferred based on conventional art in the art, including equivalents and approximations from experimental and / or measurement conditions to the value. It is understood that this also means. Whenever a yield or quantity is given as a percentage, such yield or quantity is given with respect to the maximum amount of entity that may be obtained under certain stoichiometric conditions. Refers to mass (weight percent). Unless otherwise specified, the concentration shown as a percentage refers to the mass ratio.

As used herein, "alkyl" means a linear or branched saturated chain with 1 to 34 or more carbon atoms. The alkyl group may be unsubstituted or substituted. Alkyl groups containing 3 or more carbon atoms may be linear, branched, or cyclized.

As used herein, an "alkenyl" is non-branched or branched, having one or more double bonds therein and having 1 to 34 or more carbon atoms. Contains hydrocarbon chains. The double bond of an alkenyl group can be unconjugated or conjugated to another unsaturated group. The alkenyl group may be unsubstituted or substituted.

The term "hydroxyl" means an OH group.

The term "hydroxyalkyl" means the alkyl group defined above, where the alkyl group has an OH group located on it.

As used herein, the term "alkoxy" or "alkoxylation" includes -O- (alkyl), where alkyl is defined above.

As used herein, the term "composition" refers to a product containing a particular amount of a particular ingredient, as well as any product that arises directly or indirectly from a particular amount of a particular combination of ingredients. Intended to include things.

As used herein, the term "amino" means a substituent containing at least one nitrogen atom.

As used herein, the term "substituted" means that a particular group or moiety has one or more suitable substituents, wherein the substituent is one or more. It may be attached to a specific group or part at the position of.

As used herein, the term "unsubstituted" means that a particular group has no substituents.

Any atom represented herein with an unfilled or unspecified valence is assumed 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 substituent is a double bond via a single bond with one hydrogen (-OH) or without a hydrogen. It is either (= O) oxygen-bonded through, or (-NH2) nitrogen-bonded via a single bond with two hydrogens, or (= NH) through a double bond with one hydrogen. ) It means that it is nitrogen-bonded.

All patents or patent applications cited herein are hereby incorporated by reference in their entirety.

Detailed Description of Embodiments of the Invention In one embodiment, there is a polyalkoxypolymerized polyol polyester of formula-2, in which Q is defined as the group of a natural or synthetic organic polyol compound, wherein the structure of the group is: Derived from the polyol by removal of one or more, preferably all of the respective OH groups, having carbon, hydrogen, oxygen and nitrogen elements, linear, branched, cyclic, saturated, or unsaturated. , In the formula, Q has 6 to 50 carbon atoms and is independently substituted with 6 to 25 groups having the formula-[(OA) _n- OR].
Q-[(OA) _n- OR] _m
Equation-2
In the formula, A _-C 2 _{H 4} - or _-C 3 _{H 6} - is selected from; n is 1-125; R is independently selected from hydrogen or -COR _{1; R 1} is independently , C _6- C ₃₄ -alkyl, C _6- C ₂₂ -hydroxyalkyl, C _2- C ₃₄ -alkenyl; in the formula, R ₁ is preferably stearic acid moiety, isostearic acid moiety, oleic acid moiety, A gerbe moiety having 12 to 32 carbon atoms, or a mixture thereof. "-[(OA) _n- OR]" is a group attached to the group of Q. Highly preferred R ₁ is oleic acid moiety; another highly preferred embodiment is a mixture of isostearic acid and Guerbet acids. In some embodiments, the gelbeic acid has 12 to 32 carbons, more preferably about 16-32 carbons, even more preferably 18-24 carbons, and most preferably 20 carbons. , The average total number of COR ₁ is ≧ 2.5, preferably ≧ 3, most preferably ≧ 4; m is an integer selected from 6-25, preferably 6-12. The n of each hydrophilic poly- (alkylene glycol) -arm can be in the range 1-125, with an average number of n of 25 to 120, preferably 30-85, most preferably 30 to 70.

Gerveic acid is a primary carboxylic acid with a well-defined bibranch of the carbon chain (Equation-3). This unique branched structure results in lower melting points, lower viscosities, and better solubility. An example of a commercial product is ISOCARB® from Sasol, ranging from 12 carbons to 32 carbons. The preferred range of carbons is 16 to 32 carbons, most preferably 18 to 24 carbons, and the most preferred number of carbons is 20.

（式中、ｎ＝１−１２０である）を有し、式中、ｎ＝１−１２０である。記号「

」は、−ＣＯＲ_１の炭素原子へのその部分の結合部位を示す。言い換えれば、「ゲルベ酸から誘導される」とは、Ｒ_１（アルキル、アルケニル又はヒドロキシアルキル）が、−ＣＯＯＨと一緒にゲルベ酸を形成することを意味する。本発明のポリアルコキシル化ポリオールポリエステル（式−２）は、１つ又は複数の反応段階により調製される。ポリアルコキシル化ポリオールは、６から２０個のヒドロキシル基を有するポリオール化合物を、該ポリオール化合物と、ＫＯＨ、ＮａＯＨ、又はカルシウム金属などの塩基触媒との混合物を真空下で１００℃−２００℃で乾燥した後、１３０℃−２００℃で、エチレンオキシド又はプロピレンオキシドによりアルコキシル化することによって調製される。アルキレンオキシドを、圧力下で１０−２０時間にわたって反応器中に計量供給する。エチレンオキシド、プロピレンオキシド、又はエチレンオキシドとプロピレンオキシドの混合物を使用することができ、その結果、一級−ＯＨ基、二級−ＯＨ基、又はそれらの混合物が得られる。 The branched gelbeic acid-derived part has the following formula:

(In the formula, n = 1-120), and in the formula, n = 1-120. symbol"

”Indicates the binding site of that portion of −COR _{1 to} the carbon atom. In other words, the term "derived from a Guerbet acid", R 1 _(alkyl, alkenyl or hydroxyalkyl) are means to form a Guerbet acid with -COOH. The polyalkoxylated polyol polyester (formula-2) of the present invention is prepared by one or more reaction steps. The polyalkoxylated polyol is a polyol compound having 6 to 20 hydroxyl groups, and a mixture of the polyol compound and a base catalyst such as KOH, NaOH, or calcium metal is dried under vacuum at 100 ° C.-200 ° C. It is then prepared by alkoxylation with ethylene oxide or propylene oxide at 130 ° C.-200 ° C. The alkylene oxide is metered into the reactor under pressure for 10-20 hours. Ethylene oxide, propylene oxide, or a mixture of ethylene oxide and propylene oxide can be used, resulting in a primary-OH group, a secondary-OH group, or a mixture thereof.

The organic polyol compound (Q) of the embodiment of the present invention can be a natural or synthetic polyol having at least 6 hydroxyl groups, examples of which are shown from (but limited to) the following compounds: Not done).
1. 1. General formula HOCH ₂ (CHOH) _x CH ₂ OH, a sugar alcohol also called a polyhydric alcohol or a polyalcohol having at least 6 hydroxyl groups. Examples include mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, maltotritol, maltotetraitol, and polyglycitol. Not limited to these.
2. Disaccharides are formed from two monosaccharides by dehydration via glycosidic bonds. Examples include, but are not limited to, trehalose, sucrose, lactose, maltose and the like. They contain 6 or more hydroxyl groups.
3. 3. _(C 6 _H 10 _{O 5)} dextrin having a chemical structure of _n, wherein, n is 2 to 20.
4. G-pentaerythritol 5. Dendrimer polyol. For example, Bolton® H2004, H2003, and H20 have 6, 12, and 16 terminal hydroxyl groups, respectively.
6.6 Polyglyceryl having 3 to 10 glycerin units with more than 6 hydroxyl groups.

After the reaction, each hydroxyl group of the starting polyol compound will grow into a hydrophilic poly- (alkylene glycol) arm. The lengths of all arms may be the same or different depending on the reaction conditions.

The next reaction is an esterification reaction between the polyalkoxylated polyol compound and the fatty acid, so that part or all of the hydrophilic poly- (alkylene glycol) arm is capped with the fatty acid ester. The reaction is carried out between 120 ° C. and 250 ° C. with or without a catalyst until the desired acid value or degree of esterification is achieved. A preferred method is to use an esterification catalyst such as alkylbenzene sulfonic acid, methanesulfonic acid, organotin catalyst, organic titanate catalyst. A preferred molar ratio of fatty acids to alkoxylated polyol compounds is to form esters of 30% -100% hydrophilic poly- (alkylene glycol) arms. For example, if the starting polyol compound is sorbitol, which will result in 6 poly- (alkylene glycol) arms per sorbitol molecule, the molar ratio would be 2.4-6. If it is trehalose that will result in eight poly- (alkylene glycol) arms, its molar ratio is 3.2 to 8. Most preferred is to form at least four or more aliphatic ester cap arms.

In another embodiment, Q is the portion of the organic group 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 formulation comprising the polyalkoxylated polyol polyester (formula-1) of the present invention. The polyalkenylized polyol polyesters of the present invention are used as thickeners, rheology modifiers, solubilizers, conditioners, and dispersants for aqueous, aqueous / alcoholic, and surfactant-containing formulations; in emulsions and suspensions. It is suitable as an emulsifier and a suspending agent having a thickening action and a bodying action. These surfactant-containing formulations, emulsions, and suspensions include, for example, shampoos, shower formulations, shower gels, foam baths, wash pigments, hand soaps, solid soaps, shaving creams, hair conditioners, deodorants, lotions, etc. Creams, ointments, wet wipes, antiperspirants, sunscreens, etc.

Based on the final formulation, the cleansing formulations, emulsions and suspension formulations according to the embodiments of the present invention are preferably 0.05% to 20% by weight, particularly preferably 0.1% to 10% by weight. Particularly preferably, it contains 0.5% by weight to 5% by weight of the polyalkylated polyol polyester of formula-2 or formula-3.

The cleansing composition according to an embodiment of the present invention comprises the following components: all conventional anionic, cationic, diionic, nonionic and amphoteric surfactants; active agents beneficial to the skin and hair, eg, Hairdressing oils, vaseline, vegetable oils, hardened vegetable oils, UV filters, proteins, shining agents, anti-aging agents, amino acids, physiological activators, moisturizers, conditioning polymers, silicones, cationic polymers, sucrose polyesters, anti-slip zinc Salts, hydroxy acids, skin whitening agents, etc .; stabilizers such as silica, 12-hydroxystearic acid, hardened castor oil, ethylene glycol distearate, bentonite and hectolite clay, fatty acids, fatty alcohols, etc .; other thickening Agents such as hydroxyethyl cellulose, xanthan gum, polyacrylates, processed or unprocessed fatty acids, etc .; and polyethylene glycol can be further included. The cleansing composition can be in the form of a liquid, paste, gel, or solid.

The total amount of surfactant used in the composition of the embodiments of the present invention is most, based on the final composition, between 5% by weight and 70% by weight, preferably between 10% by weight and 40% by weight. It can preferably be between 12% by weight and 35% by weight.

Each of these components in the cleansing composition as well as the desired optional ingredients are described below.

A. Detergency Surfactants Conventional detergency surfactants can be selected from anionic, cationic, nonionic, amphoteric / zwitterionic surfactants, or mixtures thereof. Details of these conventional detergency surfactants are described, for example, in US Pat. No. 7659235 (B2); US Pat. No. 8361450 (B2); US Pat. No. 8802607 (B2); US Pat. No. 3929678; US Pat. No. 2528378 (these are incorporated herein by reference); and M.D. C. It is known in McCutcheon's, Emulsifiers and Detergents, 1989, published by the publisher. Anionic surfactants may include alkyl sulphates or alkyl ether sulphates, including alkyl glycerol ether sulphates. They may also contain sulfate-free anionic surfactants, as shown below.

Aliphatic sulfonates such as primary alkanes (eg C _8- C ₂₂ ) sulfonates, primary alkane disulfonates, C _8- C ₂₂ alkene sulfonates, alkyl glyceryl ether sulfonates, aromatic alkyl sulfonates, or C _8- C ₂₂ Hydroxyalkane sulfonate.

Alkyl sulfosuccinates (mono - including and dialkyl, e.g., _C 6 _{-C 22} sulfosuccinates). Alkyl and acyl taurates, alkyl and acyl glycinates, sulfoacetates, alkyl phosphates, alkyl phosphate esters, alkyloxy alkyl phosphates, and acyl lactates, C _8- C ₂₂ monoalkyl succinates, and maleates. Aliphatic acyl isethionic acid salts, which are typically prepared by the reaction of isethionic acid salts, such as alkali metal isethionic acid salts, with aliphatic fatty acids of 8-20 carbon atoms. For example, commercially available products of aliphatic acyl isethionates include, for example, DEFI, Hostapon SCI-78C, Jordapon CI pillar, YA-SCI-85, Islux LQ-CLR-SB and the like. Formula R- (CH ₂ CH ₂ O) An anionic carboxylic acid salt surfactant having _n CO ₂ M, in which R is C _8- C ₂₀ alkyl; n is 1 to 20; M is a cation such as sodium and potassium. Another class of anionic surfactants is soaps or salts of fatty acids. Examples of the sulfonic acid derivative of alkylpolyglucoside include sodium laurylglucosides hydroxypropylsulfonate and sodium decylglucosides hydroxypropylsulfonate.

Other sulfate-free mild surfactants are a class of alkanoyl surfactants prepared from amino acids. The alkyl group is an alkyl group from C ₈ to C ₂₀ , preferably C ₁₂ to C ₁₆ . Surfactants of this category may include, for example, alkanoyl sarcosinate, alkanoyl glycinate, and alkanoyl glutamate. Commercially available products include, for example, Ajinomoto's Amisoft (registered trademark), Amilite (registered trademark), and Sino Lion's Eversoft.

Preferred anionic surfactants are sulfate-free mild surfactants and mixtures thereof. The weight ratio of the anionic surfactant in the composition according to the embodiment of the present invention is in the range of 5% by weight to 35% by weight, preferably 10% by weight to 25% by weight.

Amphoteric or zwitterionic surfactants are surfactants that have both positive and negative charges. They can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, where the aliphatic group can be a straight chain or a branched chain, where among the aliphatic groups. one is a _{C 18} carbon atoms from _{C 8,} including one anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples include conventional betaines such as N-alkyl-N, N-dimethylammonium glycinate, coco-amidopropyl betaine; C _12- C ₁₈ -alkyldimethyl-sulfopropyl betaine, and amine oxides. Etc. may be included. The proportion of the amphoteric surfactant in the composition according to the embodiment of the present invention is 0.5% by weight to 30% by weight, preferably 1% by weight to 15% by weight.

Nonionic surfactants include alkoxylated fatty alcohols, acids, amides or alkylphenols; long chain tertiary amine oxides; long chain tertiary phosphine oxides; dialkyl sulfoxides; US Pat. No. 5,389,279 and US Pat. No. 5,09814. Sugar amides according to No.; alkyl polyglucosides according to US Pat. No. 4,565,647 and US Pat. No. 3,723,325 (all of which are incorporated herein by reference) may be included. Preferred nonionic surfactants are alkyl polyglucosides and alkyl polyglucamides. Examples of commercial products may include BASF's Plantaren® series, Dow Chemicals' Ecosense® series, Clariant's Gluco Tain®, and Colonial Chemicals' Poly Suga Mulse. The proportion of nonionic surfactant according to the embodiment of the present invention is in the range of 1% by weight to 20% by weight, preferably 1% by weight to 15% by weight.

Cationic surfactants are surfactants that have a positively charged group. Suitable cationic surfactants include quaternary ammonium salts such as di- (C _10- C ₂₄ ) -alkyldimethylammonium chloride, (C _10- C ₂₄ ) -alkyltrimethylammonium chloride or sulfate, and N-. Acylaminoethyl-N, N-diethyl-N-methylammonium chloride and the like may be included. Other conventional cationic surfactants are described in US Pat. Nos. 8470305 (B2) and 8470305 (B2), which are incorporated herein by reference. The weight ratio of the cationic surfactant in the composition according to the embodiment of the present invention is in the range of 1% by weight to 10% by weight, preferably 1% by weight to 7% by weight.

B. Liquid Crystal Inducers and Modifiers Liquid crystal inducers are small nonionic molecules that are solubilized in a mixture of surfactants, thereby filling the surfactant micelles with larger structural aggregates of different shapes and sizes. , For example, lamellar liquid crystal structures or vesicles, rod-shaped and cubic liquid crystals are considered to be changed. Another name for liquid crystal inducers is hydrophobic thickeners. They include the class of alkanoamides, alkylamine oxides or mixtures thereof. Examples of this category include mono- and di-ethanolamides, isopropanolamides of 10-20 carbon atom fatty acids, PPG-hydroxyethyl cocamides of 10-20 carbon atoms and alkylamine oxides. Other classes of chemicals in liquid crystal inducers are 8-18 carbon atoms, preferably 8-12 carbon atoms, and 1-4 ethylene oxide unit alkoxylated alkyl alcohols.

Liquid crystal modifiers include fatty acids and aliphatic alcohols with 8-20 carbon atoms, as well as aliphatic hydrocarbons with a molecular weight of less than 400 g / mol. They are believed to change the size and shape of the liquid crystal. U.S. Pat. No. 7,655,607 (B2) is a reference to the scope and examples of liquid crystal inducers and modifiers, which is incorporated herein by reference.

C. Beneficial Activators for Skin and Hair These beneficial activators can be water-soluble, water-insoluble, or water-dispersible. Water-soluble activators may include, but are limited to, polyols such as glycerin, diglycerin, sorbitol, propylene glycol, propanediol, panthenol, and sugars; α-hydroxy acids and salts thereof; low molecular weight polyethylene glycols. Not done. Water-insoluble and water-dispersible activators for skin and hair include petrolatum, silicones, vegetable oils, essential oils, skin softeners, hydrocarbon oils, aliphatic esters, cationic polymers, high refractive index oils for luster. , Anti-foaming agents, proteins / protein derivatives, etc., but not limited to these. These water-insoluble beneficial agents are usually present in the composition as emulsions or stripes. Non-limiting examples in US Pat. No. 7,262,158 are incorporated herein by reference. Various other skin and hair beneficial activators are vitamins, lipids (sucrose ester, lanolin, cholesterol, etc.), liposomes, essential fatty acids, butter, minerals, antibacterial agents, anti-acne agents, oil control agents, astringents, Oil control agents, scrubs and exfoliating particles, essential oils, sunscreens, hairdressers, dyes, fragrances, cyclodextrins / fragrance complexes, anti-wrinkle actives (amino acids and their derivatives such as N-acetyl- L-cysteine), thiol, anti-fat deposits (caffeine, lanolin, etc.), tanning actives, skin whitening actives, skin soothing agents (bisabolol, aloe vera, dipotassium glycyrrhizinate, etc.) Can be included.

Cationic water-soluble / or dispersible polymers are very useful for compositions according to the invention as conditioning activators or adhesion aids. Suitable cationic polymers for the compositions according to the invention have a cationic charge density in the range of 0.2-8 meq / g and a molecular weight in the range of 10 to 3 million. Those cationic groups 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 CTFA Cosmetic Ingredient Dictionary, 3rd Edition, edited by Estrin, Crosley, and Haynes, and US Pat. No. 8470305 (B2) and US Pat. No. 8,105994 (B2). These are incorporated herein by reference. As a non-limiting example, a copolymer of a vinyl monomer having a cationic protonated amine or a quaternary ammonium functional group and a water-soluble spacer monomer such as acrylamide, methacrylamide, alkyl and dialkylacrylamide, vinylpyrrolidone, vinyl caprolactone, etc. Can be included. Non-limiting 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, and cationic guar gum derivatives. Non-limiting examples include products with the following trade names: Jaguar® from Rhone Poulenc, Aqua® and N-Hance Polymers from Aqualon, UCARE Polymers from Dow Chemical, Nalco. MerQuat from, galactazole from Henkel, etc.

D. Stabilizers and additional thickeners Stabilizers (or structuring systems) are used to form crystal stabilization networks in the composition to allow droplets of lipophilic beneficial agents to coalesce and phase separate in the product. To prevent. Non-limiting examples include hydroxyl-containing fatty acids, aliphatic esters, or aliphatic soapy water-insoluble wax-like substances such as 12-hydroxystearic acid, 9,10-dihydroxystearic acid, and tri-9,10-dihydroxystearic acid. , And tri-12-hydroxystearin and the like. Other classes of stabilizers are C _10- C ₂₂ ethylene glycol fatty acid esters, fumed silica, precipitated silica, smectite clay and the like. Examples of other conventional stabilizers are disclosed in US Pat. No. 6,194,363 and US Pat. No. 9,138,428, which are incorporated herein by reference. Another class of stabilizers is a gel network of aliphatic amphiphiles such as stearic acid and behenyltrimethylammonium chloride, as disclosed in US Pat. No. 8,470,305. Another class of stabilizers is a mixture of unmodified and modified starch with fatty acids, as disclosed in US Pat. No. 6,906,016, all of which are incorporated herein by reference.

According to the present invention, a further thickener for stabilizing the composition and modifying the viscosity of the composition is a polymer. Non-limiting examples include cellulose gum, microcrystalline cellulose, cellulose gel, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose, methyl / propyl cellulose, guar gum, karaya gum, tragacanth gum, arabic gum, acacia gum, agar (gum agar). ), Xanthan gum, and carbohydrate gums such as mixtures thereof; processed and unprocessed starch granules having a gelatinization temperature of 30 ° C.-85 ° C., and pregelatinized cold water soluble starch. As a further non-limiting example, hydrophobic association includes acidic monomers and associative monomers having hydrophobic end groups, as disclosed in US Pat. No. 9,161,899, which is incorporated herein by reference. Includes the category of crosslinked alkali swellable acrylate polymers. Examples of non-limiting commercial products include Lubrizol's Carbopol Aqua SF-1, 3V Sigma S.A. P. A's Stabylen 30 and Sumitomo Seika's Aquepec series in Japan.

Suitable additional thickeners 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 such as Carbopol® 940; Carbopol®. ) Polyacrylate emulsions such as Aqua Sf-1 polymer; polyethylene glycol; and polyvinyl alcohol may be included.

Emulsions and suspension formulations according to the invention are water; oils; emulsifiers; preferably 0.05% to 20% by weight, particularly preferably 0.1% to 10% by weight, particularly preferably 0.5% by weight. Includes% to 5% by weight polyester of formula-1; as well as other conventional ingredients for skin care, hair care, and body care. The non-aqueous portion of the emulsion is usually in the range of 2% to 85%, preferably 5% to 45%. Oils include, but are not limited to, refined vegetable oils, refined synthetic or fermented hydrocarbon oils, silicone oils, and synthetic ester oils.

The following non-limiting examples demonstrate the compositions and excellent performance of the present invention.

Example 1. Synthesis of polyalkoxylated polyol polyesters of formula-3 with different molecular structures. Table 1 lists the preparation of polyesters of formula-3 having a range of molecular weights of alkoxylated sorbitol and fatty acids. The reaction flask used is a 1 liter resin kettle with four necks. Sorbitol was mixed with a KOH or NaOH base catalyst and dried under vacuum at 90 ° C.-110 ° C. X mol of ethylene oxide per mole of sorbitol, or a mixture of ethylene oxide and propylene oxide, is added under pressure and reacted at 140 ° C.-180 ° C. for a reaction time of 10-20 hours. After the reaction, the resulting product was cooled, degassed and filtered to give Sorbeth-xxx. Sorbeth-xxx, oleic or stearic acid components, and catalyst-methanesulfonic acid were added to the flask and subsequently purged with nitrogen gas. The mixture was heated between 120 ° C.-220 ° C. while mixing under nitrogen and collecting water. The reaction was continued until the sum of R ₁ (or acid value) reached the target or almost constant. After cooling the flask to room temperature, the product was collected. The polyester obtained was a waxy solid.

Example 2. The polyester-6 and PEG-150 pentaerythrityl tetrastearate in Table 1 of the present invention (PEG-150 Pentaerytricyl Teterstage) are 6% cocoylglycine potassium (Amilite GCK-11F from Ajinomoto Co., Inc.), 15% cocamide. It was formulated in a non-sulfate personal cleansing composition of propyl betaine (35 wt% activity, trade name-Monteric LMAB), 0.3% EDTA, 78.7% water, and citric acid up to pH 6. Cocoyl glycine potassium surfactants are derived from glycine amino acids and are known to be very mild to the skin. The trade name of PEG-150 pentaerythrityl tetrastearate is CROTHIX by Croda Inc, which is based on US Pat. No. 5,192,462, incorporated herein by reference.

At 2% by weight thickener, the polyester-6 of the present invention resulted in a viscosity of 72900 cP, whereas CROTHIX resulted in a viscosity of 45840 cP. This shows the superior performance of the polyester of the present invention over the prior art.

Example 3. This personal cleansing formulation is based on a surfactant-sodium cocoyl sarcosine derived from other amino acids. Its composition is 29.89% sodium cocoyl sarcosine (trade name-Zschimmer & Schwarz, Ethylene LS 9011, 29 wt% activity), 12.38% cocamidopropyl betaine (trade name-Monative LMAB, 35 wt% activity), 1.8% thickener, 1% cocamide MEA, 0.1% EDTA, 1% NaCl, 53.83% water, and citric acid up to pH 6. At 1.8% by weight in the formulation, the polyester-7 of the present invention resulted in a viscosity of 6960 cP, while CROTHIX resulted in 3640 cP.

Example 4. This personal cleansing formulation is based on two mild non-sulfate surfactants well known in the personal cleansing market: nonionic alkyl polyglucoside surfactants and anionic sodium cocoyl isetionate. The composition is 13% decyl glucoside (trade name-Planteren 2000 NUP according to BASF), 7% sodium cocoyl isetionate (trade name-Pureact I-78C), 7% cocamidopropyl betaine (trade name-Montaric). LMAB), 1% PEG-7 glyceryl cocoate (trade name-Protakem GC-7 by Protameen Inc), 0.35% EDTA, citric acid up to pH 5.5, and water. At the same 1.2% by weight, the polyester-4 and CROTHIX of the present invention thickened the surfactant formulation to 26340 cp and 22200 cP, respectively. The polyester 4 of the present invention also exhibited superior performance over the prior art CROTHIX.

Example 5. This formulation is a classic sulfate surfactant cleansing product: 10.7% sodium lauryl ether sulfate solution (70% by weight activity), 8.58% cocamidopropyl betaine (35% by weight activity), 0. 25% cocamide MEA, 0.2% EDTA, 0.5% NaCl, x% thickener, and 79.57% water. Its pH is 5.5. The polyester-5 of the present invention in Table 1 was compared to three commercially available thickeners in this sulfate cleansing formulation. 1) Product name: CROTHIX, solid form, supplied by Croda. INCI: PEG-150 pentaerythrityl tetrastearate; 2) Trade names: Glutamate DOE-120, Lubizol Inc. Supplied by INCI name: PEG-120 methyl glucose dioleate; 3) trade name: Rewopal PEG 6000 DS, Evonik Inc. Supplied by INCI name: PEG-150 distearate.

This result demonstrates the superior performance of the thickeners of the embodiments of the present invention over many of the commercially available thickeners of the prior art in classical sulfate surfactant personal cleansing products. In this example and other examples, the wide range of polyesters of the embodiments of the present invention are more effective and useful in a wide range of personal cleansing products, including different types of surfactants, than the current commercial products of the prior art. Demonstrated to be a broad thickener.

Example 6. This example shows the synthesis of a polyester of formula-1 containing a bifurcated gelbeic acid. Commercially available gelbeic acids were Sasol-supplied Isocarb-20 (2-octyl-dodecanoic acid) with 20 carbons and Isocarb-24 (2-decyl-tetradecanoic acid) with 24 carbons. It was. The same reaction conditions as in Example 1 were applied here.

Example 7. This example demonstrates the thickening power of polyester 11 (PE-11) in two common cleansing formulations. SH-1 cleansing preparation (shampoo): 78.9% water, 6% cocoylglycine potassium, 15% cocamidopropyl betaine, EDTA 0.1%, pH7; SH-2 cleansing preparation (also shampoo): 58.4 water %, Sodium olefin (C14-16) sulfonate (39% solid) 30%, Cocamidopropyl betaine 11.5%, EDTA 0.1%, pH 7. The polyester-11 of the present invention showed much stronger thickening performance than Crothix-S.

In addition to showing a strong improvement over shampoo formulations with Corthix, formulations with a mixture of gelbeic acid also showed significant improvements over formulations without gelveic acid.

Claims (14)

formula:
Q-[(OA) _n- OR] _m
Equation-2
Polyalkoxylated polyol polyester having
In the formula, Q is the group of a natural or synthetic organic polyol compound that forms a linear, branched, cyclic, saturated or unsaturated structure and has 6 to 50 carbon atoms, with one or more carbons. The atom independently has a substituent of the formula-[(OA) _n- OR] (in the formula, n = 6-25).
(Here, the remaining carbon atoms of 6 to 50 carbon atoms are independently substituted with hydrogen, oxygen or nitrogen);
A is, _-C 2 _{H 4} - or _-C 3 _{H 6} - is selected from;
R is selected independently of hydrogen or -COR ₁ and
R ₁ is preferably C _6- C ₃₄ -alkyl derived from gelbeic acid; preferably C _6- C ₂₂ -hydroxyalkyl derived from gelbe acid; or preferably C _6- C derived from gelbe acid. _34- Selected independently from alkenyl,
n is an integer selected from 1-125 and may be the same or different for each polyalkoxylated hydrophilic arm; the average total number of COR ₁ is ≧ 2.5, preferably ≧ 3, most preferably. ≧ 4; and m is an integer selected from 6-25, preferably 6-12, polyalkoxylated polyol polyester. The C _6- C ₃₄ -alkyl derived from gelbeic acid has the following formula:

The polyalkoxylated polyol polyester according to claim 1, which has (in the formula, n = 1-120, preferably 3, 5, 7, 9 or 13). Claim 1 or 2 in which n per hydrophilic poly- (alkylene glycol) arm (-[(OA) _n- OR]) is equal to 25 to 120, more preferably 30 to 85, most preferably 30 to 70. The polyalkoxylated polyol polyester according to. The polyalkoxylated polyol polyester according to claim 1 or 2, wherein R ₁ is derived from stearic acid, isostearic acid, oleic acid, gelbeic acid or a mixture thereof. The polyalkoxylated polyol polyester according to claim 1 or 2, wherein R ₁ comprises a gerve and an isostear moiety. The polyalkoxylated polyol polyester according to claim 1 or 2, wherein the gerve moiety has 18 to 24 carbon atoms. Q is the group of the following polyol compounds:
HOCH ₂ (CHOH) _x CH ₂ OH sugar alcohol with the general formula;
Disaccharides with glycosidic bonds;
(C ₆ H ₁₀ O ₅ ) _n0 (in the formula, n0 is 2 to 20);
G-pentaerythritol;
The polyalkoxylated polyol polyester according to claim 1 or 2, which is a dendrimer polyol; and a polyglyceryl having 3 to 10 glycerin units having 6 or more hydroxyl groups. Q is a polyol of the following compound:
HOCH ₂ (CHOH) _x CH ₂ OH sugar alcohol with the general formula;
Disaccharides with glycosidic bonds;
(C ₆ H ₁₀ O ₅ ) _n0 (in the formula, n0 is 2 to 20);
The polyalkoxylated polyol polyester according to claim 1 or 2, selected from dipentaerythritol; and dendrimer polyols. The polyalkoxylated polyol polyester according to claim 1 or 2, wherein Q is selected from the polyols of sorbitol, trehalose, mannitol, dipentaerythritol, sucrose, lactose, chitobiose, cellobiose, and maltose. A cosmetic, skin or pharmaceutical composition comprising the polyalkoxylated polyol polyester according to any one of claims 1 to 9 or a mixture thereof. The basis of sorbitol whose Q is as follows:

The cosmetic, skin or pharmaceutical composition according to claim 10. water;
1% -50% by weight surfactant selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof;
From 0.1% to 10% by weight polyol polyester of formula-2; and the group consisting of active agents, stabilizers, additional thickeners, colorants, preservatives, and pearl colorants that are beneficial to the skin and hair. The cosmetic, skin or pharmaceutical composition according to claim 10 or 11, further comprising 0.1% to 50% by weight of other ingredients selected. water;
2% -50% by weight surfactant selected from the group consisting of sulfate-free anionic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof;
Selected from the group consisting of 0.1% to 10% by weight polyalkoxylated polyol polyester of formula-2; and actives, stabilizers, additional thickeners, colorants, and preservatives beneficial to the skin and hair. The cosmetic, skin or pharmaceutical composition according to claim 10, further comprising 0.1% to 50% by weight of other ingredients. water;
UV filters, moisturizers, conditioners, preservatives, deodorants, reducing agents for permanent wave products, coloring agents for coloring hair, anti-aging activators, proteins / protein derivatives, fragrances, petrolatum, vegetable oils, cationic Approximately 1% to 30% by weight of skin and hair active ingredients selected from the group consisting of conditioning polymers and mixtures thereof; and approximately 1% to 10% by weight of polyalkylated polyol polyester of formula-1.

The cosmetic, skin or pharmaceutical composition according to any one of claims 10, 11 and 13, further comprising.