Polyol esters from bio-based feedstocks for use as emollients in personal care applications

Abstract

Provided are personal care compositions containing ester polyol esters, ester polyol esters, methods of making the same, and uses of the ester polyol esters in personal care compositions.

Description

Technical Field

[0001] This invention relates to personal care compositions containing polyol esters, polyol ester compounds, the use of polyol esters in personal care compositions, and methods for manufacturing polyol esters. Background Technology

[0002] The listing or discussion of previously disclosed documents in this specification should not be construed as an admission that such documents are part of the prior art or common knowledge.

[0003] A common problem associated with personal care compositions such as emollients is the persistent, undesirable residue on the skin after application, especially oily or greasy residues. Such residues can cause skin irritation and are unpleasant for the user.

[0004] Ester polyol esters are products of the reaction of a polyol with more than one equivalent of an ester, resulting in the esterification of more than one hydroxyl group in the polyol, as described in US 9,885,006 B2. Ester polyol esters are commonly used as lubricants and have not previously been described as useful emollients. Summary of the Invention

[0005] The inventors have surprisingly discovered that polyol esters possess the properties necessary for effective emollients. For example, polyol esters can be applied to human skin as a thin oil film, keeping the skin moisturized without leaving oily residue. Polyol esters are also non-irritating, stable, and can be produced from renewable raw materials.

[0006] Therefore, the present invention provides the following.

[0007] 1. A personal care composition comprising an ester polyol ester of formula Ia and an ester polyol ester of formula Ib.

[0008]

[0009] Wherein, in equation Ia:

[0010] Each R 1a Independently, it is a straight-chain or branched alkyl chain having 1 to 17 carbon atoms;

[0011] Each R 2a Independently for being controlled by more than one R 1a’ The C(O)O- group substituted with a straight-chain or branched alkyl chain having 2 to 12 carbon atoms;

[0012]

[0013] In equation Ib:

[0014] L is a straight-chain alkylene chain with 1 to 18 carbon atoms;

[0015] Each R 2b Independently for being controlled by more than one R 1a” The C(O)O- group substituted with a straight-chain or branched alkyl chain having 2 to 12 carbon atoms; and

[0016] Each R 1a’ and R 1a” It is independently a straight-chain or branched alkyl chain having 1 to 17 carbon atoms.

[0017] 2. The personal care composition according to Item 1, wherein the ester polyol ester of Formula Ia is the ester polyol ester of Formula Ic:

[0018]

[0019] in

[0020] Each R 1c Alkyl chains of monocarboxylic acids independently selected from the group consisting of: acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, nonanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid.

[0021] Each R 2c Independently defined as a moiety formed by removing a primary hydroxyl group from a primary polyol selected from the group consisting of: glycerol, diglycerol, ethylene glycol, diethylene glycol, 1,2-propanediol, bis(1,2-propanediol), 2-methyl-1,3-propanediol (2-MePG), trimethylolpropane (TMP), di-trimethylolpropane (Di-TMP), neopentyl glycol (NPG), pentaerythritol (PE), dipentaerythritol (diPE), and sorbitol, wherein the moiety is bonded to the remainder of the molecule at the site of the removed primary hydroxyl group, and the remaining hydroxyl functional groups in the moiety are of formula R. 1c Esterification of monocarboxylic acids with -COOH.

[0022] 3. The personal care composition according to Project 2, wherein each R 1c An alkyl chain of a monocarboxylic acid independently selected from the group consisting of: hexanoic acid, nonanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, decanoic acid, and lauric acid, wherein each of the R groups is optionally present. 1c An alkyl chain of a monocarboxylic acid selected independently from the group consisting of octanoic acid and decanoic acid.

[0023] 4. The personal care composition according to item 3, wherein R 1c It is an alkyl chain of octanoic acid.

[0024] 5. The personal care composition according to any one of the preceding items, wherein the ester polyol ester of formula Ib is the ester polyol ester of formula Id:

[0025]

[0026] in:

[0027] L is a straight-chain alkylene chain with 2 to 14 carbon atoms;

[0028] Each R 2d Independently defined as a moiety formed by removing a primary hydroxyl group from a primary polyol selected from the group consisting of: glycerol, diglycerol, ethylene glycol, diethylene glycol, 1,2-propanediol, bis(1,2-propanediol), 2-methyl-1,3-propanediol (2-MePG), trimethylolpropane (TMP), di-trimethylolpropane (Di-TMP), neopentyl glycol (NPG), pentaerythritol (PE), dipentaerythritol (diPE), and sorbitol, wherein the moiety is bonded to the remainder of the molecule at the site of the removed primary hydroxyl group, and the remaining hydroxyl functional groups in the moiety are of formula R. 1c Esterification of monocarboxylic acids with -COOH;

[0029] Each R 1c Alkyl chains of monocarboxylic acids independently selected from the group consisting of: acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, nonanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid, wherein each of the R groups is optionally present. 1c An alkyl chain of a monocarboxylic acid selected independently from the group consisting of octanoic acid and decanoic acid.

[0030] 6. The personal care composition according to item 5, wherein L is a straight-chain alkylene chain having 4 to 12 carbon atoms.

[0031] 7. The personal care composition according to item 5, wherein L is a C8 linear alkylene chain.

[0032] 8. The personal care composition according to any one of items 2 to 7, wherein R 2c and / or R 2d It is the part that has the following formula:

[0033]

[0034] The dashed lines represent the connection points with the rest of the molecule, where each R... 1c Independently representing the alkyl chain of a monocarboxylic acid selected from the group consisting of: acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, nonanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid, wherein each of the R groups is optionally represented by an alkyl chain. 1c An alkyl chain of a monocarboxylic acid selected independently from the group consisting of octanoic acid and decanoic acid.

[0035] 9. The personal care composition according to any one of items 2 to 7, wherein R 2c and / or R 2d It is the part that has the following formula:

[0036]

[0037] The dashed lines represent the connection points with the rest of the molecule, where each R... 1c Independently representing the alkyl chain of a monocarboxylic acid selected from the group consisting of: acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, nonanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid, wherein each of the R groups is optionally represented by an alkyl chain. 1c An alkyl chain of a monocarboxylic acid selected independently from the group consisting of octanoic acid and decanoic acid.

[0038] 10. The personal care composition according to Item 1, wherein the ester polyol ester of Formula Ia is an ester polyol ester of Formula IIa, and / or the ester polyol ester of Formula Ib is an ester polyol ester of Formula IIb:

[0039]

[0040] In equation IIa, each A independently represents a straight chain C. 5-9 Alkyl chain, or straight chain or branched C 14-17 Alkyl chain;

[0041]

[0042] In equation IIb:

[0043] Each A independently represents a straight chain C. 5-9 Alkyl chain, or straight chain or branched C 14-17 Alkyl chains; and

[0044] n is an integer between 6 and 10.

[0045] 11. The personal care composition according to item 10, wherein in formula IIa and / or IIb:

[0046] (i) Each A represents C independently. 6-8 Alkyl, optionally representing C7 alkyl; or

[0047] (ii) Each A independently represents an alkyl chain of a monocarboxylic acid selected from the group consisting of palmitic acid and stearic acid, optionally representing an alkyl chain of isostearic acid or stearic acid, and more optionally representing an alkyl chain of isostearic acid.

[0048] 12. The personal care composition according to item 10 or 11, wherein n is an integer from 7 to 9, optionally wherein n is 8.

[0049] 13. The personal care composition according to any one of items 10 to 12, wherein each A represents a C7 alkyl group and n is an 8.

[0050] 14. The personal care composition according to Item 1, wherein the ester polyol ester of Formula Ia is an ester polyol ester of Formula IIc, and / or the ester polyol ester of Formula Ib is an ester polyol ester of Formula IId:

[0051]

[0052] In equation IIc, each A independently represents a straight chain C. 5-9 Alkyl chain, or straight chain or branched C 14-17 Alkyl chain;

[0053]

[0054] In equation IId:

[0055] Each A independently represents a straight chain C. 5-9 Alkyl chain, or straight chain or branched C 14-17 Alkyl chains; and

[0056] n is an integer between 6 and 10.

[0057] 15. The personal care composition according to item 13, wherein in formula IIc and / or IId:

[0058] (i) Each A represents C independently. 6-8 Alkyl, optionally representing C7 alkyl; or

[0059] (ii) Each A independently represents an alkyl chain of a monocarboxylic acid selected from the group consisting of palmitic acid and stearic acid, optionally representing an alkyl chain of isostearic acid or stearic acid, and more optionally representing an alkyl chain of isostearic acid.

[0060] 16. The personal care composition according to item 13 or 14, wherein n is an integer from 7 to 9, optionally wherein n is 8.

[0061] 17. The personal care composition according to any one of items 13 to 15, wherein:

[0062] (i) Each A represents a C7 alkyl group and n is 8; or

[0063] (ii) The compound of formula IIc is trimethylolpropane triisostearate.

[0064] 18. The personal care composition according to any one of the preceding items, wherein the weight ratio of the ester polyol ester of formula Ia, Ic, IIa or IIc to the ester polyol ester of formula Ib, Id, IIb or IId is from 95:5 to 30:70.

[0065] 19. The personal care composition according to item 18, wherein:

[0066] (a) The weight ratio of the polyol ester of formula Ia, Ic or IIa to the polyol ester of formula Ib, Id or IIb is 90:10 to 80:20.

[0067] (b) The weight ratio of the polyol ester of formula Ia, Ic or IIa to the polyol ester of formula Ib, Id or IIb is 60:40 to 70:30; or

[0068] (c) The weight ratio of the polyol ester of formula Ia, Ic or IIa to the polyol ester of formula Ib, Id or IIb is 40:60 to 50:50.

[0069] 20. The personal care composition according to any one of the preceding items, wherein the ester polyol esters of formula Ia, Ib, Ic, Id, IIa, IIb, IIc or IId are present in the personal care composition in a ratio produced by a reaction between the following:

[0070] Formula R 2a -OH or R 2b Polyols with -OH groups;

[0071] Formula R 1a Monocarboxylic acids with -COOH; and

[0072] Dicarboxylic acids of the formula HOOC-L-COOH

[0073] The molar ratio of monocarboxylic acid to dicarboxylic acid in the reaction mixture is from 99.99:0.01 to 99:1 (e.g., about 99.97:0.03 to about 99.7:0.3, or about 99.95:0.05, about 99.875:0.125, or about 99.78:0.22).

[0074] The ratio of hydroxyl to carboxyl groups in the reaction mixture is about 0.940 to about 0.955.

[0075] 21. The personal care composition according to item 20, wherein the reaction is quenched once the acid value reaches a value of less than 20 mg KOH / g and the hydroxyl value reaches a value of less than 5 mg KOH / g.

[0076] 22. The personal care composition according to item 20 or 21, wherein the mixture of ester polyol esters of formula Ia, Ib, Ic, Id, IIa, IIb, IIc or IId produced by the reaction has a dynamic viscosity of 20 to 90 cps at 25°C, preferably, the dynamic viscosity at 25°C is selected from the following:

[0077] (a) 20-30 cps;

[0078] (b) 35-45 cps; or

[0079] (c)80-90cps.

[0080] 23. The personal care composition according to any one of the preceding items, wherein the total mass percentage of the ester polyol esters of formula Ia, Ic, IIa or IIc and the ester polyol esters of formula Ib, Id, IIb or IId in the personal care composition is 0.5 to 65% by weight, preferably 0.5 to 15% by weight, for example 0.5 to 12% by weight.

[0081] 24. A personal care composition according to any one of items 1, 2, 5, 8 and 9, wherein the ester polyol ester of formula Ia, Ib, Ic, Id, IIa or IIb is derived from a bio-based raw material, optionally wherein the bio-based raw material comprises palmitic acid.

[0082] 25. The personal care composition according to any one of the preceding items is an emollient composition.

[0083] 26. Use of the ester polyol ester as described in any one of items 1 to 25 in a personal care composition, optionally wherein the ester polyol ester comprises a first ester polyol ester of formula Ia, Ic, IIa or IIc and a second ester polyol ester of formula Ib, Id, IIb or IId.

[0084] 27. Compounds of formula IIa or IIc:

[0085]

[0086] Each A independently represents C. 6-8 alkyl.

[0087] 28. The compound according to item 27 has the following structure:

[0088]

[0089] 29. Compounds of formula IIb or IId:

[0090]

[0091] Each A independently represents C. 6-8 Alkyl and n are integers from 6 to 10.

[0092] 30. The compound according to item 29 has the following structure:

[0093]

[0094] 31. A method for preparing an ester polyol ester, the method comprising preparing a reaction mixture containing:

[0095] Polyols are selected from the group consisting of glycerol, trimethylolpropane and combinations thereof;

[0096] sebacic acid; and

[0097] bitter,

[0098] The method includes the step of esterifying glycerol with sebacic acid and caprylic acid.

[0099] The reaction mixture has a hydroxyl to carboxyl ratio (HCR) corresponding to the molar ratio of hydroxyl to carboxyl groups, the HCR being less than about 1, and the molar ratio of octanoic acid to sebacic acid is from 99.99:0.01 to 99:1 (e.g., from about 99.97:0.03 to about 99.7:0.3, e.g., about 99.95:0.05, about 99.875:0.125, or about 99.78:0.22).

[0100] 32. The method according to item 31, wherein the hydroxyl to carboxyl ratio (HCR) of the reaction mixture is less than about 0.97, preferably about 0.92 to about 1, more preferably about 0.92 to about 0.97, further preferably about 0.93 to about 0.95, and still more preferably about 0.940 to about 0.955.

[0101] 33. The method described in item 31 or 32, wherein the reaction is quenched once the acid value reaches a value below 20 mg KOH / g and the hydroxyl value reaches a value below 5 mg KOH / g.

[0102] 34. The method according to any one of items 31 to 33, wherein the dynamic viscosity of the mixture of ester polyol esters produced by said method is 20 to 90 cps at 25°C, preferably selected from the following:

[0103] (a) 20-30 cps;

[0104] (b) 35-45 cps; or

[0105] (c)80-90cps. Attached Figure Description

[0106] Figure 1 The structure of the polyol ester formed from glycerol and caprylic acid is shown.

[0107] Figure 2 The structure of the polyol ester formed from glycerol, sebacic acid and caprylic acid is shown.

[0108] Figure 3 Toxicity data for the compounds described in this invention, as tested by OECD 492, are shown.

[0109] Figure 4 Toxicity data for the compounds described in this invention, as tested by OECD 439, are shown.

[0110] Some embodiments of this disclosure are described more fully below with reference to the accompanying drawings. Detailed Implementation

[0111] This invention provides a personal care composition comprising an ester polyol ester of formula Ia and an ester polyol ester of formula Ib.

[0112]

[0113] Wherein, in equation Ia:

[0114] Each R 1a Independently, it is a straight-chain or branched alkyl chain having 1 to 17 carbon atoms;

[0115] Each R 2a Independently for being controlled by more than one R 1a’ The C(O)O- group substituted with a straight-chain or branched alkyl chain having 2 to 12 carbon atoms;

[0116]

[0117] In equation Ib:

[0118] L is a straight-chain alkylene chain with 1 to 18 carbon atoms;

[0119] Each R 2b Independently for being controlled by more than one R 1a” The C(O)O- group substituted with a straight-chain or branched alkyl chain having 2 to 12 carbon atoms; and

[0120] Each R 1a’ and R 1a” It is independently a straight-chain or branched alkyl chain having 1 to 17 carbon atoms.

[0121] In the embodiments herein, the term "comprising" can be interpreted as requiring the features mentioned, but not limiting the presence of other features. Optionally, the word "comprising" can also refer to the situation where only the listed components / features are present (e.g., the word "comprising" can be replaced by the phrases "consisting of" or "substantially consisting of"). It is expressly anticipated that both broader and narrower interpretations can be applied to all aspects and embodiments of the invention. In other words, the word "comprising" and its synonyms can be replaced by the phrases "consisting of" or "substantially consisting of" or their synonyms, and vice versa.

[0122] In embodiments herein, the term "ester polyol ester" refers to a compound formed by the esterification of at least two hydroxyl groups in a polyol. In embodiments of the invention, the ester polyol ester has at least 90% esterification of the polyol hydroxyl groups, for example, at least 95%, at least 99%, at least 99.5%, or, for example, about 100% esterification of the polyol hydroxyl groups. The term "polyol ester" may be used interchangeably with "ester polyol ester" herein.

[0123] In the embodiments described herein, the term "alkyl" refers to the formula -C n H 2n+1 The alkyl group is a monovalent group. The alkyl group can be straight-chain or branched. In some embodiments of the invention, the alkyl group can be straight-chain. In other embodiments of the invention, the alkyl group can be branched.

[0124] In the embodiments described herein, the term "alkylene" refers to formula -C n H 2n - A divalent group. The alkylene group can be straight-chain or branched. In some embodiments of the invention, the alkylene group is typically straight-chain.

[0125] The terms “formulation” and “composition” are used interchangeably in this document.

[0126] In some embodiments of the present invention, the ester polyol ester of formula Ia may be the ester polyol ester of formula Ic:

[0127]

[0128] Among them, each R 1c Alkyl chains of monocarboxylic acids independently selected from the group consisting of: acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, nonanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid.

[0129] Each R 2cIndependently defined as a moiety formed by removing a primary hydroxyl group from a primary polyol selected from the group consisting of: glycerol, diglycerol, ethylene glycol, diethylene glycol, 1,2-propanediol, bis(1,2-propanediol), 2-methyl-1,3-propanediol (2-MePG), trimethylolpropane (TMP), di-trimethylolpropane (Di-TMP), neopentyl glycol (NPG), pentaerythritol (PE), dipentaerythritol (diPE), and sorbitol, wherein the moiety is bonded to the remainder of the molecule at the site of the removed primary hydroxyl group, and the remaining hydroxyl functional groups in the moiety are of formula R. 1c Esterification of monocarboxylic acids with -COOH.

[0130] In some aspects of these implementation schemes, the various R 1c The alkyl chain of a monocarboxylic acid may be independently selected from the group consisting of: hexanoic acid, nonanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, decanoic acid, and lauric acid. In specific aspects of these embodiments, each R... 1c It can be an alkyl chain of a monocarboxylic acid selected from the group consisting of octanoic acid and decanoic acid. For example, R 1c It can be an alkyl chain of octanoic acid.

[0131] In some embodiments of the present invention, the ester polyol ester of formula Ib may be the ester polyol ester of formula Id:

[0132]

[0133] Where L is a straight-chain alkylene chain with 2 to 14 carbon atoms;

[0134] Each R 2d Independently defined as a moiety formed by removing a primary hydroxyl group from a primary polyol selected from the group consisting of: glycerol, diglycerol, ethylene glycol, diethylene glycol, 1,2-propanediol, bis(1,2-propanediol), 2-methyl-1,3-propanediol (2-MePG), trimethylolpropane (TMP), di-trimethylolpropane (Di-TMP), neopentyl glycol (NPG), pentaerythritol (PE), dipentaerythritol (diPE), and sorbitol, wherein the moiety is bonded to the remainder of the molecule at the site of the removed primary hydroxyl group, and the remaining hydroxyl functional groups in the moiety are of formula R. 1c Esterification of monocarboxylic acids with -COOH;

[0135] Each R 1c Independently, an alkyl chain of a monocarboxylic acid selected from the group consisting of: acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, nonanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid. In some aspects of these embodiments, each R... 1c It can be an alkyl chain of a monocarboxylic acid selected from the group consisting of octanoic acid and decanoic acid.

[0136] In some aspects of these embodiments, L may be a straight-chain alkylene chain with 4 to 12 carbon atoms, for example, a C8 straight-chain alkylene chain.

[0137] In some aspects of the above embodiments of the present invention, R 2c and / or R 2d It can be a part that has the following formula:

[0138]

[0139] The dashed lines represent the connection points with the rest of the molecule, where each R... 1c Independently representing an alkyl chain of a monocarboxylic acid selected from the group consisting of: acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, nonanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid. In some aspects of these embodiments, each R... 1c It can be an alkyl chain of a monocarboxylic acid selected from the group consisting of octanoic acid and decanoic acid.

[0140] In some other aspects of the above embodiments of the present invention, R 2c and / or R 2d It can be a part that has the following formula:

[0141]

[0142] The dashed lines represent the connection points with the rest of the molecule, where each R... 1c Independently representing an alkyl chain of a monocarboxylic acid selected from the group consisting of: acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, nonanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid. In some aspects of these embodiments, each R... 1c It can be an alkyl chain of a monocarboxylic acid selected from the group consisting of octanoic acid and decanoic acid.

[0143] In some embodiments of the present invention, the ester polyol ester of formula Ia may be the ester polyol ester of formula IIa, and / or the ester polyol ester of formula Ib may be the ester polyol ester of formula IIb:

[0144]

[0145] In equation IIa, each A independently represents a straight chain C. 5-9 Alkyl chain, or straight chain or branched C 14-17 Alkyl chain;

[0146]

[0147] In equation IIb:

[0148] Each A independently represents a straight chain C. 5-9 Alkyl chain, or straight chain or branched C 14-17 Alkyl chains; and

[0149] n is an integer between 6 and 10.

[0150] In some aspects of these implementation schemes, each A can independently represent a straight chain C. 5-9 Alkyl chains, such as straight-chain C 6-8 Alkyl, such as a straight-chain C7 alkyl. In some aspects of these embodiments, n is an integer from 7 to 9, for example 8. In certain aspects of these embodiments, each A represents a C7 alkyl and n is 8. A specific example of a compound of formula IIb that may be mentioned herein is an octanoylglycerol / sebic acid copolymer.

[0151] In other respects, each A can independently represent a straight chain or a branched chain C. 14-17 The alkyl chain optionally represents an alkyl chain of a monocarboxylic acid selected from the group consisting of palmitic acid and stearic acid, more preferably an alkyl chain of isostearic acid or stearic acid, and even more preferably an alkyl chain of isostearic acid. In these respects, n is an integer from 6 to 10, optionally an integer from 7 to 9, for example 8.

[0152] In some embodiments of the present invention, the ester polyol ester of formula Ia may be the ester polyol ester of formula IIc, and / or the ester polyol ester of formula Ib may be the ester polyol ester of formula IId:

[0153]

[0154] In equation IIc, each A independently represents a straight chain C. 5-9 Alkyl chain, or straight chain or branched C 14-17 Alkyl chain;

[0155]

[0156] In equation IId:

[0157] Each A independently represents a straight chain C. 5-9 Alkyl chain, or straight chain or branched C 14-17 Alkyl chains; and

[0158] n is an integer between 6 and 10.

[0159] In some aspects of these implementation schemes, each A can independently represent a straight chain C. 5-9 Alkyl chains, such as straight-chain C 6-8 Alkyl, such as a straight-chain C7 alkyl. In some aspects of these embodiments, n is an integer from 7 to 9, such as 8. In certain aspects of these embodiments, each A represents a C7 alkyl and n is 8.

[0160] In other respects, each A can independently represent a straight chain or a branched chain C. 14-17 The alkyl chain optionally represents an alkyl chain of a monocarboxylic acid selected from the group consisting of palmitic acid and stearic acid, more preferably an alkyl chain of isostearic acid or stearic acid, and even more preferably an alkyl chain of isostearic acid. In these respects, n is an integer from 6 to 10, optionally an integer from 7 to 9, for example 8.

[0161] A specific example of a compound of formula IIc that may be mentioned in this article is trimethylolpropane triisostearate.

[0162] The weight ratio of polyol esters of formula Ia, Ic, IIa, or IIc to polyol esters of formula Ib, Id, IIb, or IId can be from 95:5 to 30:70. A specific weight ratio will affect the properties of the mixture of polyol esters, such as viscosity and surface tension. Depending on the type of personal care composition, the ratio of polyol esters can be varied to provide the desired physical properties to the personal care composition. For example, as those skilled in the art will understand, the physical properties required for hair wax differ from those required for moisturizing creams.

[0163] The specific weights of the ester polyol esters that can be used in this invention are as described below.

[0164] (a) The weight ratio of the polyol ester of formula Ia, Ic or IIa to the polyol ester of formula Ib, Id or IIb is 90:10 to 80:20.

[0165] (b) The weight ratio of the polyol ester of formula Ia, Ic or IIa to the polyol ester of formula Ib, Id or IIb is 60:40 to 70:30.

[0166] (c) The weight ratio of the polyol ester of formula Ia, Ic or IIa to the polyol ester of formula Ib, Id or IIb is 40:60 to 50:50.

[0167] Typically, the ratio of polyol esters in a personal care composition corresponds to the ratio produced during the preparation process. The ratio of polyol esters of formula Ia, Ic, IIa, or IIc produced by the reaction to polyol esters of formula Ib, Id, IIb, or IId will depend on the ratio of monocarboxylic acid (e.g., octanoic acid) to dicarboxylic acid (e.g., sebacic acid) in the reaction mixture. The greater the amount of dicarboxylic acid, the greater the proportion of polyol esters of formula Ib, Id, IIb, or IId. Because the presence of dicarboxylic acid can lead to the formation of undesirable oligomers in the emollient (and, if present in sufficiently high amounts, to the formation of polymers), the concentration of dicarboxylic acid is typically kept low. For example, the molar ratio of monocarboxylic acid to dicarboxylic acid in the reaction mixture is typically from 99.99:0.01 to 99:1 (e.g., from about 99.97:0.03 to about 99.7:0.3). Specific molar ratios that may be mentioned in this article include approximately 99.95:0.05, approximately 99.875:0.125, and approximately 99.78:0.22.

[0168] Therefore, in some embodiments of the present invention, ester polyol esters of formula Ia, Ib, Ic, Id, IIa, IIb, IIc, or IId are present in the personal care composition in a ratio produced by a reaction between the following:

[0169] Formula R 2a -OH or R 2b Polyols with -OH groups;

[0170] Formula R 1a Monocarboxylic acids with -COOH; and

[0171] Dicarboxylic acids of the formula HOOC-L-COOH

[0172] The molar ratio of monocarboxylic acid to dicarboxylic acid in the reaction mixture is from 99.99:0.01 to 99:1 (e.g., about 99.97:0.03 to about 99.7:0.3, or about 99.95:0.05, about 99.875:0.125, or about 99.78:0.22).

[0173] The ratio of hydroxyl to carboxyl groups in the reaction mixture is about 0.940 to about 0.955.

[0174] In some embodiments of the invention, the reaction that produces ester polyol esters is quenched when the acid value reaches below 20 mg KOH / g and the hydroxyl value reaches below 5 mg KOH / g. This has the effect of stopping the reaction when the amounts of free acid and hydroxyl groups are low, and the reaction is almost complete. This helps to reduce the formation of unwanted byproducts.

[0175] The mixture of polyol esters produced by the reaction will have a dynamic viscosity. This is a key property affecting how the personal care composition will feel on human skin and can be adjusted by changing the carbon chain length and the ratio of monocarboxylic acid to dicarboxylic acid in the reaction mixture. In some embodiments of the invention, the polyol esters of formula Ia, Ib, Ic, Id, IIa, IIb, IIc, or IId produced by the reaction have a dynamic viscosity of 20 to 90 cps at 25°C, with specific dynamic viscosities at 25°C that may be mentioned herein including 20-30 cps; 35-45 cps; and 80-90 cps.

[0176] The amount of ester polyol esters in a personal care composition will depend on the intended use of the personal care composition. In this document, "amount of ester polyol esters" refers to the total amount of ester polyol esters of formulas Ia, Ib, Ic, Id, IIa, IIb, IIc, and IId in the composition. Typically, the amount of ester polyol esters in a personal care composition can be from 0.5% to 65% by weight. In some embodiments of the invention that may be mentioned herein, the amount of ester polyol esters in a personal care composition can be from about 0.5% to about 15% by weight, for example, from 0.5% to 12% by weight. Specific personal care compositions according to the invention are discussed in the examples below.

[0177] As mentioned herein, one advantage of the present invention is that ester polyol esters can be produced from a variety of raw materials. For example, they can be produced from renewable bio-based raw materials. They can also be produced from synthetic or non-bio-based raw materials. In some embodiments of the invention, particularly when longer chain acids are required, ester polyol esters can be formed from bio-based raw materials containing palmitic acid, which can be derived from palm oil.

[0178] The personal care compositions of the present invention can be any personal care composition in which ester polyol esters may be used. For example, the personal care composition can be a hair care composition or a skin care composition, particularly a moisturizing composition. Examples of hair care compositions include hair masks, hair waxes, shampoos, and conditioners. Examples of skin care compositions include shower gels, skin or body lotions, and body lotions. Any personal care composition of the present invention can be optimized for use on healthy adult skin, infant skin, or other sensitive skin. Specifically, shower gels, skin or body lotions, shampoos, and body lotions can be ideally optimized for use on infant skin or other sensitive skin, such as the skin on a user's face. Those skilled in the art will understand that some personal care compositions are suitable for more than one use and can be used as both hair care and skin care compositions, or have dual functions within the category of hair care or skin care compositions. Examples of dual-function personal care compositions include combined shampoo and shower gels, and combined "two-in-one" shampoo and conditioner compositions.

[0179] To avoid ambiguity, when any numerical range is used herein, the upper and lower limits of any relevant range may be combined to provide new ranges, all of which are specifically considered herein. For example, ester polyol esters used in personal care compositions may have a dynamic viscosity at 25°C selected from any of the following ranges:

[0180] 20 to 90 cps, 20 to 80 cps, 20 to 45 cps, 20 to 35 cps, 20 to 30 cps;

[0181] 30 to 90 cps, 30 to 80 cps, 30 to 45 cps, 30 to 35 cps;

[0182] 35 to 90 cps, 35 to 80 cps, 35 to 45 cps;

[0183] 45 to 90 cps, 45 to 80 cps;

[0184] 80 to 90 cps.

[0185] The present invention also provides the use of ester polyol esters as disclosed herein in personal care compositions. Such use may include the use of first ester polyol esters of formula Ia, Ic, IIa, or IIc and second ester polyol esters of formula Ib, Id, IIb, or IId.

[0186] The present invention also provides certain compounds of formulas IIa, IIb, and IIc. Specifically, the present invention provides compounds of formula IIa or IIc:

[0187]

[0188] Each A independently represents C. 6-8 alkyl.

[0189] In some embodiments of the present invention, the compound of formula IIa may have the following formula:

[0190]

[0191] In some embodiments of the present invention, the compound of formula IIc may have the following formula:

[0192]

[0193] This invention provides compounds of formula IIb or IId:

[0194]

[0195] Each A independently represents C. 6-8 Alkyl and n are integers from 6 to 10.

[0196] In some embodiments of the present invention, the compounds of formula IIb have the following structures:

[0197]

[0198] In some embodiments of the present invention, the compound of formula IId has the following structure:

[0199]

[0200] The present invention also provides a method for preparing ester polyol esters (e.g., ester polyol esters of formulas IIa-IId above), the method comprising preparing a reaction mixture containing the following:

[0201] Polyols are selected from the group consisting of glycerol, trimethylolpropane and combinations thereof;

[0202] sebacic acid; and

[0203] bitter,

[0204] The method includes the step of esterifying glycerol with sebacic acid and caprylic acid.

[0205] The reaction mixture has a hydroxyl to carboxyl ratio (HCR) corresponding to the molar ratio of hydroxyl to carboxyl groups, the HCR being less than about 1, and the molar ratio of octanoic acid to sebacic acid being from 99.99:0.01 to 99:1.

[0206] The molar ratio of octanoic acid to sebacic acid can be from about 99.97:0.03 to about 99.7:0.3, for example, about 99.95:0.05, about 99.875:0.125, or about 99.78:0.22. The reaction can be quenched once the acid value reaches below 20 mg KOH / g and the hydroxyl value reaches below 5 mg KOH / g. Typically, the dynamic viscosity of the mixture of ester polyol esters produced by the reaction at 25°C is 20 to 90 cps. For example, the dynamic viscosity of the mixture of ester polyol esters produced by the reaction at 25°C is 20-30 cps, 35-45 cps, or 80-90 cps.

[0207] As those skilled in the art will understand, other ester polyol esters that can be used in the personal care compositions of the present invention can be prepared by methods corresponding to those described above. Other methods for preparing ester polyol esters are described in US 9,885,006 B2 and in the examples below.

[0208] The ester polyol esters used in this invention can provide personal care compositions with enhanced sensory properties. For example, ester polyol esters are more fluid than many known emollients, which provides a lighter and less oily feel on the skin and results in a lower likelihood of irritation. Ester polyol esters are also highly stable, enhancing the oxidative stability of personal care compositions and making them suitable for long-term storage without the need to add antioxidants to the composition.

[0209] Ester polyol esters, formed from polyols such as glycerol and TMP, are highly branched, allowing for the production of higher molecular weight products with lower viscosity than unbranched ester polyol esters. This improves the spreadability of the resulting compositions, providing the properties discussed above. Ester polyol esters can also have a higher refractive index, resulting in higher gloss, which is particularly desirable in hair care products.

[0210] The embodiments described below illustrate the invention and should not be construed as limiting.

[0211] Example

[0212] Materials and methods

[0213] Sebacic acid was purchased from Megachem, 99.5% purity. Caprylic acid was purchased from KLK Oleochemicals, 99% purity. Glycerol was purchased from KLK Oleochemicals, 99.7% purity.

[0214] Acid value was determined according to ASTM D664.

[0215] Example 1: Reaction process for synthesizing polyol esters

[0216] Polyols, monocarboxylic acids, diacarboxylic acids, and tin oxide catalysts (in amounts specified in Tables 1a and 1b below) were mixed in a reactor protected from oxygen and moisture. The reaction apparatus included a four-necked round-bottom flask equipped with a top stirrer, a nitrogen inlet for covering, a condenser with a Dean Stark device, and a thermocouple / temperature controller. The resulting mixture was initially homogenized at 115°C, and the contents were then sampled to determine the acid value. The reactor temperature was gradually increased to 115°C, 180°C, and finally to a maximum reaction temperature of 210°C. Water was produced by the reaction, which was removed by increasing the temperature and condensed in the condenser. As the rate of water production from condensation slowed and the top temperature decreased, the reactor was bubbled with nitrogen at a rate of 0.2 L / min to accelerate water removal. The reaction was continued until the acid value reached 20 mg KOH / g. Unreacted fatty acids and catalyst were removed by treatment with alkali and clay, as described in US 9,885,006B2. In short, unreacted acid is removed by using the minimum amount of the weakest basic material required to achieve the desired acid value. Residual catalyst is removed using montmorillonite clay adsorbents with a high surface area, resulting in excellent adsorption performance. As-synthesized mixtures of ester polyol esters are specified as references identified in Tables 1a and 1b. PE25, PE50, and PE100 contain... Figure 1 and Figure 2 The two compounds shown are EM25 and EM44, which contain similar compounds formed from C9 monocarboxylic acids and dicarboxylic acids, namely azelaic acid and nonanoic acid.

[0217] The amounts of each reagent used to prepare glycerol polyol esters are shown in Table 1a.

[0218]

[0219] Table 1a: Detailed information on reagents used in the preparation of glycerol polyol esters

[0220] Using the starting materials listed in Table 1b below, the corresponding esters made from trimethylolpropane were prepared by equivalent methods.

[0221]

[0222] Table 1b: Detailed information on reagents used to prepare TMP polyol esters

[0223] Example 2: Physical and chemical properties of ester polyol esters

[0224] Basic physical and chemical analyses of polyol esters were performed using the established standards and in-house methods listed in Table 2. The results are presented in Table 3 and subsequent sections.

[0225]

[0226] Table 2: Testing of polyol esters.

[0227]

[0228] Table 3: Physical and chemical properties of polyol esters

[0229] Surface tension

[0230] The elastic-like tension, also known as surface tension, between the synthesized polyol ester and air was determined using the Du Noüy ring test. This test is based on the principle that the force required to pull the ring through the liquid is related to the surface tension of the liquid. In short, a ring connected to a torque meter is immersed in the synthesized polyol ester. The ring is then removed from the polyol ester, and the force acting on the ring is measured shortly before the liquid film tears. The surface tension is then calculated from the ring diameter and the tear-off force. The results are recorded in Table 4.

[0231] Surface tension has a strong influence on the wettability of materials and is also related to their spreadability. Generally, emollients with low surface tension exhibit rapid spread behavior, and vice versa. This is demonstrated by PE25, which exhibits lower measured surface tension and faster spreadability compared to PE50 and PE100.

[0232] PE 25 25.38 PE 50 29.51 PE 100 27.36

[0233] Table 4: Surface tension of polyol esters

[0234] TGA

[0235] Thermogravimetric analysis (TGA) was used to determine the decomposition temperatures of the reactants and different grades of polyol esters (PE25, PE50, and PE100). TGA is a thermal analysis method that measures the change in mass of the sample during heating.

[0236] For the reactants octanoic acid and glycerol, over 99% by weight of the samples decomposed within the temperature range shown in Table 5. However, for sebacic acid, only 95.24% by weight of the samples decomposed, and its decomposition temperature was higher than that of the other reactants tested. This is attributed to the physical state of sebacic acid as a solid, while the other reactants were in liquid form. Note that the boiling points of all reactants are higher than their decomposition temperatures.

[0237] bitter 150.9 to 193.3 237.0 sebacic acid 247.9 to 283.9 294.4 glycerin 178.7 to 220.9 290.0

[0238] Table 5: Decomposition temperature range of reactants

[0239] Polyol ester samples PE25, PE50, and PE100 were also analyzed. Two decomposition temperature ranges were observed, indicating the presence of two distinct oligomer structures in each sample. The decomposition temperature ranges of two samples were almost identical, suggesting that the oligomers in both samples have the same molecular structure. Generally, higher decomposition temperatures correlate with higher molecular weight oligomers. The results in Table 6 show that PE100 contains a higher percentage (54.80 wt%) of oligomers with higher molecular weights compared to PE25 and PE50.

[0240]

[0241] Table 6: Decomposition Temperature Range of Polyol Esters

[0242] Expansiveness

[0243] The developing ability of polyol ester samples was determined using the following method. At 25°C, a drop of sample (20 μL) was applied to a flat, horizontal surface of ashless paper (Whatman filter paper). The liquid emulsifier sample was allowed to develop for 10 minutes. After 10 minutes, the wetted area was measured, and the results are listed in Table 7.

[0244] Over a 10-minute duration, PE25 recorded the highest unfolded area, followed by PE50 and PE100. PE25 exhibited rapid unfolding capability compared to PE50 and PE100, which had medium and low unfolding capabilities, respectively. Visually, PE25 appeared to be less viscous than PE50 and PE100.

[0245] PE 25 573.97 PE 50 440.61 PE 100 286.67

[0246] Table 7: Development Properties of Polyol Esters

[0247] Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES) ) analyze

[0248] The metal content in polyol esters was determined using ICP-OES (Perkin Elmer Optima DV 5300). The preparation of the equipment, standards, and samples followed standard operating procedure APHA 3120B. The results are shown in Table 3.

[0249] The effectiveness of clay treatment during the purification step was verified because the tin content used as a catalyst during the esterification reaction was less than 1 mg / kg for all three samples.

[0250]

[0251] Table 8: ICP-OES results of polyol esters

[0252] toxicology

[0253] The toxicological properties of polyol esters EM25 and EM44 were evaluated using the test methods listed below. The results are shown in... Figure 3 and 4 In OECD 492, an average tissue survival rate of 60% or higher results in no classification and indicates a non-irritating compound, while an average tissue survival rate of less than 60% results in classification (Category 1 or Category 2) and indicates an irritating compound. In OECD 439, an average tissue survival rate of 50% or higher results in no classification and indicates a non-irritating compound, while an average tissue survival rate of less than 50% results in classification (Category 1 or Category 2) and indicates an irritating compound.

[0254] 1. In Vitro Eye Irritation: OECD 492

[0255] 2. Skin Irritation Test: OECD TG439

[0256] like Figure 3 and 4 The results show that, according to OECD 492 and OECD TG439, ​​EM25 and EM44 are both non-irritating compounds.

[0257] Example 3: Examples of Personal Care Preparations

[0258] Hair care products

[0259]

[0260]

[0261] Table 9: Rinse-off Deep Nourishing Hair Mask Preparations

[0262]

[0263] Table 10: Hair Styling Wax Formulations

[0264]

[0265] Table 11: Naturally Sourced Sulfate-Free Moisturizing Shampoos and Body Washes

[0266]

[0267] Table 12: Hair Conditioner Preparations

[0268] Body care products

[0269]

[0270] Table 13: Skin Emulsion Formulations

[0271]

[0272] Table 14: Spray-type body lotion formulations

[0273] Infant care products

[0274]

[0275] Table 15: Mild Conditioning Shampoo Formulations for Children

[0276]

[0277] Table 16: Mild Baby Shampoo Formulations

[0278]

[0279] Table 17: Moisturizing Light Body Lotion Formulation Example 4: Comparison of Various Chemical Properties with Known Emollients

[0280]

[0281] Table 18: Comparison of chemical properties with known emollients

[0282] The polyol esters EM25 and EM44 have improved viscosity, spreadability, and refractive index relative to their molecular weight. This results in improved sensory properties and advantageously increased gloss.

Claims

1. Use of ester polyol esters in personal care compositions, wherein the ester polyol ester comprises ester polyol ester Ia and ester polyol ester Ib. The ester polyol ester Ia is or ； The ester polyol ester Ib is or 。 2. The use according to claim 1, wherein the weight ratio of ester polyol ester Ia to ester polyol ester Ib is 95:5 to 30:

70.

3. The use according to claim 2, wherein: (a) The weight ratio of ester polyol ester Ia to ester polyol ester Ib is 90:10 to 80:20; (b) The weight ratio of ester polyol ester Ia to ester polyol ester Ib is 60:40 to 70:30; or (c) The weight ratio of ester polyol ester Ia to ester polyol ester Ib is 40:60 to 50:

50.

4. The use according to claim 1, wherein ester polyol ester Ia or ester polyol ester Ib are present in the personal care composition in a ratio produced by the reaction between the following: It is a polyol that is either glycerol or trimethylolpropane; It is a monocarboxylic acid of caprylic acid; and It is a dicarboxylic acid of sebacic acid. The molar ratio of monocarboxylic acid to dicarboxylic acid in the reaction mixture is from 99.99:0.01 to 99:

1. The ratio of hydroxyl to carboxyl groups in the reaction mixture is 0.940 to 0.

955.

5. The use according to claim 4, wherein the reaction is quenched once the acid value reaches a value below 20 mg KOH / g and the hydroxyl value reaches a value below 5 mg KOH / g.

6. The use according to claim 4, wherein the mixture of ester polyol ester Ia and ester polyol ester Ib produced by the reaction has a dynamic viscosity of 20 to 90 cps at 25°C.

7. The use according to claim 1, wherein the total combined mass percentage of ester polyol ester Ia and ester polyol ester Ib in the personal care composition is 0.5 to 65% by weight.

8. The use according to claim 1, wherein the personal care composition is an emollient composition.

9. The use according to claim 1, wherein the ester polyol ester is prepared by a method comprising preparing a reaction mixture containing: Polyols are selected from the group consisting of glycerol, trimethylolpropane and combinations thereof; sebacic acid; and bitter, The method includes the step of esterifying glycerol with sebacic acid and caprylic acid. The reaction mixture has a hydroxyl to carboxyl ratio (HCR) corresponding to the molar ratio of hydroxyl groups to carboxyl groups, where HCR is less than 1, and the molar ratio of octanoic acid to sebacic acid is from 99.99:0.01 to 99:

1. The dynamic viscosity of the mixture of ester polyol esters produced by the method at 25°C is 20 to 90 cps.

10. The use according to claim 9, wherein the hydroxyl to carboxyl ratio (HCR) of the reaction mixture is less than 0.

97.

11. The use according to claim 9, wherein the reaction is quenched once the acid value reaches a value below 20 mg KOH / g and the hydroxyl value reaches a value below 5 mg KOH / g.

12. The use according to claim 9, wherein the dynamic viscosity at 25°C is selected from the following: (a) 20-30 cps; (b) 35-45 cps; or (c) 80-90 cps.

13. The use according to claim 1, wherein the ester polyol ester Ia or ester polyol ester Ib used in the personal care composition has a dynamic viscosity of 20 to 90 cps at 25°C.

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