WO2024260382A1

WO2024260382A1 - Betaine modified poly (amino acid) s or protein hydrolysate

Info

Publication number: WO2024260382A1
Application number: PCT/CN2024/100195
Authority: WO
Inventors: Hsin I PENG; Alexandros LAMPROU; Catherine Weichold
Original assignee: BASF China Co Ltd; BASF SE
Current assignee: BASF China Co Ltd; BASF SE
Priority date: 2023-06-20
Filing date: 2024-06-19
Publication date: 2024-12-26
Anticipated expiration: 2025-12-20

Abstract

The present invention relates to cationic biopolymers containing betaine-derived moieties, particularly betaine-quaternized poly (amino acid)s. The invention also relates to personal care compositions, particularly hair care compositions, comprising the cationic biopolymers containing betaine-derived moieties, and also use of the cationic biopolymers containing betaine-derived moieties in personal care compositions, particularly as a conditioning agent and/or as a cationic surfactant.

Description

BETAINE MODIFIED POLY (AMINO ACID) S OR PROTEIN HYDROLYSATE

Technical Field

The invention relates to cationic biopolymers containing betaine-derived moieties, particularly betaine-quaternized poly (amino acid) s. The invention also relates to personal care compositions, particularly hair care compositions, comprising the cationic biopolymers containing betaine-derived moieties, and also use of the cationic biopolymers containing betaine-derived moieties in personal care compositions, particularly as a conditioning agent and/or as a cationic surfactant.

Background

Cationic polymers are used as conditioning agents in personal care compositions, for example in hair care compositions. Requirements for hair conditioning agents include, for example, a considerable reduction in the required combing force in wet and also dry hair, good detangling upon the first comb through and good compatibility with further formulation components. In addition, cationic polymers prevent electrostatic charging of the hair.

Numerous cationic polymers suitable as a conditioning agent in hair care compositions are commercially available, including petroleum-based and bio-based. Bio-based cationic polymers derived from renewable materials (e.g., biomass) are of particular interests due to the sustainability of biomass resource. Well-known bio-based cationic polymers include for example quaternized celluloses, quaternized guar gums and quaternized hydrolyzed vegetable wheat proteins. Those cationic polymers derived from renewable materials are generally prepared by using Quab reagent such as glycidyltrimethylammonium chloride or 3-chloro-2-hydroxypropyltrimethylammonium chloride as a quaternizing reagent. The Quab reagent is efficient for quaternization and easy to synthesize. However, the Quab reagent is toxic and causes lesser degradation to the polymer backbone, which is disadvantageous from process safety and environmental friendliness.

It will be desirable if cationic polymers suitable as the conditioning agent may be derived from a green (i.e., eco-friendly) quaternizing reagent.

WO2013/188508A1 describes an antimicrobial composition comprising a cationic glycine betaine component derived from a natural source (e.g., sugar beets) , wherein the cationic glycine betaine component comprises a cationic glycine betaine ester and/or a cationic glycine betaine amide, particular alkyl (ene) betainate methane sulfonates and betainyl amino alkyl (ene) methane sulfonates, having a hydrophobic group attached to a carboxylate group through an ester or amide linkage. The cationic glycine betaine component may be prepared from glycine betaine in the presence of methane sulfonic acid (MSA) as the catalyst, with fatty alcohols to provide the cationic glycine betaine ester having a hydrophobic group attached to carboxylate ester linkage, or with an alcohol to provide a cationic glycine betaine ester and then with a fatty amine to provide the cationic glycine betaine amide having a hydrophobic group attached to carboxylic amide linkage.

It is described that the glycine betaine esters and amides serve as cationic surfactants which have effective antimicrobial activity. The present patent application does not describe any cationic polymer derived from glycine betaine suitable as a conditioning agent in personal care compositions.

There is a need to provide cationic polymers suitable as a conditioning agent in personal care compositions, which may be derived from an eco-friendly (e.g., biodegradable) polymers by quaternization with a green reagent and could still endow the personal care compositions.

Summary of Invention

It is an object of the present invention to provide eco-friendly cationic polymers with desirable conditioning performance, particularly hair conditioning performance and/or hair repairing performance.

It was found by the inventors that the object can be achieved by betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates.

It is a further object of the present invention to provide a process for preparing cationic polymers suitable as a conditioning agent without using a toxic quaternization reagent.

It was found by the inventors that the further object can be achieved by preparing cationic polymers using a betaine ester as the quaternization reagent.

Accordingly, in the first aspect, the present invention relates to betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates, which have at least one amide linkage of formula “-C (O) -NH-” in which the “-C (O) -” moiety is a carbonyl group originating from betaine and the “-NH-” moiety is an imino moiety originating from any free amino group of a poly (amino acid) or a protein hydrolysate.

In some embodiments according to the first aspect, the present invention relates to betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates, which have at least one amide linkage of formula “-C (O) -NH-” in which the “-C (O) -” moiety is a carbonyl group originating from betaine and the “-NH-” moiety is an imino moiety originating from any free amino group of a poly (amino acid) or a protein hydrolysate, wherein the poly (amino acid) is polylysine, the protein hydrolysate is vegetable protein hydrolysate or wheat protein hydrolysate.

In the second aspect, the present invention relates to a process for preparing betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates, which includes subjecting a cationic betaine ester and a poly (amino acid) or a protein hydrolysate to an aminolysis reaction to form at least one amide linkage of formula “-C (O) -NH-” therebetween.

In some embodiments according to the second aspect, the present invention relates to a process for preparing betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates, which includes steps of

(i) subjecting betaine and an alcohol to an acid-catalyzed esterification reaction to provide a cationic betaine ester; and

(ii) subjecting the cationic betaine ester from step (i) and a poly (amino acid) or a protein hydrolysate to an aminolysis reaction to form at least one amide linkage of formula “-C (O) -NH-” therebetween.

In some further embodiments according to the second aspect, the present invention relates to a process for preparing betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates, which includes steps of

(i) subjecting betaine and an alcohol to an acid-catalyzed esterification reaction in the presence of methane sulfonic acid to provide a cationic betaine ester; and

In some alternative or other embodiments according to the second aspect, the present invention relates to a process for preparing betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates, which includes steps of

(i) subjecting betaine and a C_2-5-monoalcohol or a vicinal C_2-6-polyol to an acid-catalyzed esterification reaction, preferably in the presence of methane sulfonic acid, to provide a cationic betaine ester; and

In the third aspect, the present invention relates to a personal care composition, particularly a hair care composition, which comprises the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to the first aspect or the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates obtained and/or obtainable from the process according to the second aspect.

In some embodiments according to the third aspect, the present invention relates to a shampoo composition or a hair conditioner composition, which comprises the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to the first aspect or the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates obtained and/or obtainable from the process according to the second aspect.

In the fourth aspect, the present invention relates to a method for hair conditioning or hair repairing, which includes treating hair with the hair care composition according to the third aspect.

In the fifth aspect, the present invention relates to use of the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to the first aspect or the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates obtained and/or obtainable from the process according to the second aspect in personal care compositions, such as hair care compositions, particularly as a conditioning agent and/or as a cationic surfactant.

Brief Description of the Drawings

Figure 1a shows a photo of hair strand after treatment with a polylysine.

Figure 1b shows a photo of hair strand after treatment with a betaine quaternized polylysine.

Detailed Description

The singular forms “a” , “an” and “the” include plural referents unless the context clearly dictates otherwise. The terms “comprise (s) ” , “comprising” , etc. are used interchangeably with “contain (s) ” , “containing” , etc. and are to be interpreted in a non-limiting, open manner. That is, e.g., further components or elements can be present. The expressions “consist (s) of” or “consisting of” or cognates can be embraced within “comprise (s) ” or “comprising” or cognates. The terms “include (s) ” , “including” , etc. are to be interpreted in a non-limiting, open manner.

Herein, the terms “personal care composition” and “hair care composition” are used in respective broadest sense. The term “personal care composition” is intended to refer to a product or composition suitable for topical application on mammalian skin, hair or other keratinous tissues. The term “hair care composition” is intended to a product or composition suitable for topical application on mammalian hair, including, but are not limited to shampoo and conditioner.

Herein, the term “vicinal” within the context of polyols or diols means that the polyols or diols have hydroxyl groups on adjacent carbons.

Herein, the term “betaine” refers to and may be used interchangeably with “glycine betaine” .

Herein, the term poly (amino acid) and poly (amino acid) s refer to and may be used interchangeably with “polypeptide” .

Herein, any percentage given for a component of a composition is calculated in reference to the active ingredient thereof with exclusion of impurities which may be present in commercially available or as-prepared forms of such components (for example, residual solvents or by-products) , based on the weight of the total composition, unless otherwise specified. Also, all proportions are by weight, unless specified otherwise.

Betaine-quaternized Poly (amino acid) s or Betaine-quaternized Protein Hydrolysates

In the first aspect, the present invention provides betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates, which have at least one amide linkage of formula “-C (O) -NH-” in which the “-C (O) -” moiety is a carbonyl moiety originating from betaine and the “-NH-” moiety is an imino moiety originating from any free amino group of a poly (amino acid) or a protein hydrolysate.

Betaine, known as trimethylglycine or glycine betaine, is a natural compound widely distributed in animals, plants, and microorganisms, which is mostly extracted from sugar beet molasses. Betaine contains a positively charged trimethyl ammonium moiety and a negatively charged carboxylate group, which may be represented by the following formula (I)

In the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to the present invention, the “-NH-” moiety in the amide linkage of formula “-C (O) -NH-” is an imino moiety originating from any free amino group of a poly (amino acid) or a protein hydrolysate.

It is known that poly (amino acid) s or protein hydrolysates will have one or more free amino groups (i.e., -NH₂) in the molecules thereof. Any of the free amino groups may react and form an amide linkage, for example with betaine ester intermediate via an aminolysis reaction as described hereinbelow.

Preferably, the poly (amino acid) to be quaternized may be poly (basic amino acid) s, including homopolymers of a basic amino acid and copolymers of a basic amino acid with one or more amino acids. Basic amino acids mean amino acids contain more amino group than carboxyl group. Natural basic amino acids include for example lysine and arginine. According to the present invention, polylysines, homopolymers or copolymers of lysine, particularly homopolymers of lysine (i.e., homopolylysines) are preferred.

There is no restriction to the polymeric structures of the polylysines, which may have a linear or branched structure. The polylysines may have a K-value in the range of 9 to 25, more preferably 10 to 21, as determined with 1 wt%solution of respective polylysines in water at 23 ℃ according to DIN ISO 1628-1.

The protein hydrolysates suitable for the present invention may comprise certain free amino acids in relatively high molar fractions. Preferably, the protein hydrolysate to be quaternized may be vegetable protein hydrolysate, soy protein hydrolysate, rice protein hydrolysate, almond protein hydrolysate, wheat protein hydrolysate, pea protein hydrolysate, sunflower protein hydrolysate, wheat gluten protein hydrolysate, maize protein hydrolysate, barley protein hydrolysate, sorghum protein hydrolysate, potato protein hydrolysate, coffee protein hydrolysate, cotton protein hydrolysate or sesame protein hydrolysate. Suitable protein hydrolysates, particularly wheat and vegetable protein hydrolysates, may have a molecular weight (M_w) in the range of 800 to 10,000 Dalton, preferably 1,000 to 8,000 Dalton. In some embodiments, the protein hydrolysate can be also animal derived protein hydrolysates, for example, milk protein hydrolysate, egg white protein hydrolysate, fish protein hydrolysate, meat hydrolysate, blood protein hydrolysate, hair protein hydrolysate, feather protein hydrolysate and fish meal protein hydrolysate.

Suitable polylysines and protein hydrolysates may be prepared in accordance with known processes or may be commercially available ones.

The betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates may be obtained from an aminolysis reaction between a cationic betaine ester and a poly (amino acid) or a protein hydrolysate to form the at least one amide linkage of formula “-C (O) -NH-” therebetween. By the aminolysis reaction, the ester bond in the cationic betaine ester will be converted to an amide bond wherein the nitrogen atom of the amide bond is derived from the free amino group (s) of the poly (amino acid) or the protein hydrolysate. The aminolysis reaction may be illustrated via the following Scheme 1:

wherein

R in formula (II) is any radical derived from the alcohol forming the cationic betaine ester, for example alkyl, alkyl substituted with a hydroxy group, preferably 2-hydroxyalkyl which is optionally further substituted with a hydroxy group,

P in formula (III) is the remaining moiety of the poly (amino acid) or protein hydrolysate, and

n in formula (III) is a number of at least 1.

It will be understood that n in formula (III) may be 2 or higher when the poly (amino acid) or the protein hydrolysate containing 2 or more free amino groups. For example, polylysines contain multiple free amino groups in the molecules, and then the betaine-quaternized polylysines will contain multiple amide moieties as indicated in the brackets in formula (III) accordingly.

The carbonyl (-C (O) -) in the amide linkage shown in formula (III) originates from the cationic betaine ester and initially from betaine forming the cationic betaine ester, and the imino (-NH-) in the amide linkage shown in formula (III) originates from any free amino group of the poly (amino acid) or protein hydrolysate.

Preferably, the cationic betaine ester taking part in the aminolysis reaction may be cationic betaine ester of monoalcohols such as C_2-5-monoalcohols, or of polyols such as C_2-6-polyols. Examples of the C_2-5-monoalcohols may include, but are not limited to, ethanol, n-propanol, n-butanol, n-pentanol. The C_2-6-polyols may be C_2-6-diols or C_2-6-triols. Examples of the C_2-6-polyols may include, but are not limited to glycerol, ethylene glycol, diethylene glycol, 1, 2-propanediol, 1, 2-butanediol, 1, 2-pentanediol, 1, 2-hexanediol, 2, 3-butanediol, 2, 3-pentanediol, 2, 3-hexanediol. Preferably, the C_2-6-polyols are vicinal C_2-6-diols or C_2-6-triols. Examples of suitable vicinal polyols will be described herein below within the context of the process for preparing betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to the second aspect of the present invention.

There is no particular restriction to the counter anion of the cationic polymers, i.e., betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates. Generally, the counter anion may be the same as the counter anion of the cationic betaine ester for preparing the cationic polymers, for example chloride, sulfate and sulfonate, generally sulfonate, particularly methanesulfonate.

The betaine-quaternized poly (amino acid) s may have a degree of modification (DM) in the range of 5%to 60%, for example 5%to 25%, 5%to 20%, or 5%to 15%, particularly 7%to 15%.

For the betaine-quaternized poly (amino acid) s, the degree of modification (DM) is determined in accordance with the following equation:

wherein

△ mole of free amino groups before and after modification refers to a differeence of mole of free amino groups before modification minus mole of free amino groups after modification, and

the moles of free amino groups are determined by ¹H NMR in D₂O.

The betaine-quaternized protein hydrolysates may have a degree of modification (DM) in the range of 2%to 40%, for example 3%to 35%or 5 to 30%, particularly 5 to 25%.

For the betaine-quaternized protein hydrolysates, the degree of modification (DM) is determined in accordance with the following equation by o-phthalaldehyde (OPA) method:

wherein

△ mole of free amino groups before and after modification refers to a differeence of mole of free amino groups before modification minus mole of free amino groups after modification.

Preparation Process

In the second aspect, the present invention relates to a process for preparing betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates, which includes subjecting a cationic betaine ester and a poly (amino acid) or a protein hydrolysate to an aminolysis reaction to form at least one amide linkage of formula “-C (O) -NH-” therebetween. The aminolysis reaction will occur between the ester bond in the cationic betaine ester and the free amino group (s) of the poly (amino acid) or protein hydrolysate such that an amide bond is formed. The aminolysis reaction may be illustrated via the Scheme 1 as described hereinabove.

Suitable cationic betaine ester taking part in the aminolysis reaction may be cationic betaine ester of monoalcohols such as C_2-5-monoalcohols, or polyols such as C_2-6-polyols. Examples of the C_2-5-monoalcohols may include, but are not limited to, ethanol, n-propanol, n-butanol, n-pentanol. The C_2-6-polyols may be C_2-6-diols or C_2-6-triols. Examples of the C_2-6-polyols may include, but are not limited to glycerol, ethylene glycol, diethylene glycol, 1, 2-propanediol, 1, 2-butanediol, 1, 2-pentanediol, 1, 2-hexanediol, 2, 3-butanediol, 2, 3-pentanediol, 2, 3-hexanediol. Preferably, the C_2-6-polyols are vicinal C_2-6-diols or C_2-6-triols, such as glycerol, ethylene glycol, 1, 2-propanediol, 1, 2-butanediol, 1, 2-pentanediol and 1, 2-hexanediol, with 1, 2-propanediol and glycerol being more preferable.

Suitable counter anions of the cationic betaine ester may include, but are not limited to chloride, sulfate and sulfonate, generally sulfonate, particularly methanesulfonate. The counter anion is generally derived from the acid catalyst for the esterification reaction of betaine.

Suitable poly (amino acid) s and protein hydrolysates are those as described hereinabove for the first aspect of the present invention. Any general description and preference of poly (amino acid) s and protein hydrolysates as described hereinabove are applicable here for the second aspect of the present invention.

The aminolysis reaction may be carried out under conventional conditions. For example, the reaction may be carried out at an elevated temperature (e.g., 40℃ to 80 ℃) under an inert atmosphere, optionally in the presence of an organic base such as triethylamine, triethanolamine or dibutylamine. The cationic betaine ester and poly (amino acid) s or protein hydrolysates may be used at a ratio of 0.5 : 1 to 60 : 1 mol, preferably of 2 : 1 to 60 : 1, more preferably of 4 : 1 to 50 : 1, calculated as moles of the cationic betaine ester to moles of amino acid monomer units.

In some embodiments, the process for preparing betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates may further include a step of preparing the cationic betaine ester. Accordingly, the process for preparing betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates may include steps of

In those embodiments, the alcohol may be monoalcohols such as C_2-5-monoalcohols, or polyols such as C_2-6-polyols. Examples of the C_2-5-monoalcohols may include, but are not limited to, ethanol, n-propanol, n-butanol, n-pentanol. The C_2-6-polyols may be C_2-6-diols or C_2-6-triols. Examples of the C_2-6-polyols may include, but are not limited to glycerol, ethylene glycol, diethylene glycol, 1, 2-propanediol, 1, 2-butanediol, 1, 2-pentanediol, 1, 2-hexanediol, 2, 3-butanediol, 2, 3-pentanediol, 2, 3-hexanediol. Preferably, the C_2-6-polyols are vicinal C_2-6-diols or C_2-6-triols, such as glycerol, ethylene glycol, 1, 2-propanediol, 1, 2-butanediol, 1, 2-pentanediol and 1, 2-hexanediol, with 1, 2-propanediol and glycerol being more preferable.

The acid-catalyzed esterification reaction may be carried out in the presence of any suitable acid catalysts, for example hydrochloric acid, sulfuric acid or hydrofluoric acid, or methane sulfonic acid (MSA) , preferably methane sulfonic acid (MSA) . It is known use of methane sulfonic acid for protonation of the carboxylate function of betaine is beneficial in providing a green route to obtain betaine esters since MSA is considered natural and readily biodegradable, easy-to-handle, recyclable, and less aggressive than common organic acids conventionally used such as hydrochloric acid, sulfuric acid or hydrofluoric acid. The acid-catalyzed esterification reaction in the presence of methane sulfonic acid may be illustrated via the following Scheme 2:

wherein ROH represents any alcohol as described hereinabove.

The acid-catalyzed esterification reaction may be carried out under conventional conditions. For example, the reaction may be carried out under heating at a temperature in the range of 120 ℃ to 180 ℃, with applying a reduced pressure (e.g., 50 mbar to 100 mbar) to remove water as formed continuously. A stoichiometric excess of the alcohol may be used, as it may function as both reactant and solvent, with no additional solvent being needed. The acid catalyst, for example MSA, may be used in a stoichiometric or slightly superstoichiometric molar ratio of MSA to betaine, for example 1 : 1 to 2 : 1, preferably 1.1 : 1 to 1.5 : 1. Optionally, the obtained cationic betaine ester in the product mixture may be used directly to the further aminolysis reaction with the poly (amino acid) or protein hydrolysates, or the cationic betaine ester may be used after separation and purification by conventional means.

It may be contemplated that the process for preparing betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates may also be carried out with cationic esters of betaine derivative such that poly (amino acid) s or protein hydrolysates quaternized with betaine derivative may be obtained. Suitable betaine derivatives may be for example N-alkyl betaines such as N-coco-N, N-dimethylammonium glycinates and N-oleyl-N, N-dimethylammonium glycinates, N-alkylamido betaines such as N-acylamino-propyl-N, N-dimethylammonium glycinates, particularly N-cocoamidopropyl-N, N-dimethylammonium glycinate, N-lauramidoamidopropyl-N, N-dimethylammonium glycinate. Corresponding cationic esters of those betaine derivative may react with poly (amino acid) s or protein hydrolysates via an aminolysis reaction to provide N-alkyl or N-alkylamino derivatives of the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates as described herein.

The product of the process for preparing betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates as described herein may be a reaction mixture comprising the resulted betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates. The reaction mixture may be used directly for formulating personal care compositions without purification.

It has been surprisingly found by the inventors that the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates as described herein are particularly useful for hair conditioning in terms of wet and dry combability and hair repairing in terms of structure rigidity.

Personal Care Composition

The betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates may be present in the personal care composition in an amount of 0.01%to 10%by weight, preferably 0.1%to 8%by weight, more preferably 1%to 5%by weight, based on the total amount of the personal care composition.

The personal care composition generally comprises a main surfactant component as well-known in the art. The surfactant component may include at least one of anionic, nonionic, cationic, amphoteric and zwitterionic surfactants. Particularly, the surfactant component may include a nonionic surfactant, a cationic surfactant and optionally at least one of anionic and amphoteric and zwitterionic surfactants.

Suitable nonionic surfactants are, for example, reaction products of aliphatic C_10-22-alcohols or C_6-20-alkyl phenols with 6 to 60 mols of an alkylene oxide such as ethylene oxide and/or propylene oxide per mole of the alcohol or phenols. Also suitable are alkylamine oxides, fatty acid esters of glycerol and glycols such as polyethylene glycols, ethoxylated fatty acid amides, alkyl polyglycosides, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleate, or mono-or dialkylalkanolamides, particularly mono-or dialkylalkanolamides.

The personal care composition may comprise one or more nonionic surfactants in an amount of 0.01%to 30%by weight, preferably 0.1%to 10%by weight, based on the total amount of the personal care composition.

Suitable cationic surfactants are quaternary ammonium compounds and ester quats, in particular quaternized fatty acid trialkanolamine ester salts. Examples of quaternary ammonium compounds include, but are not limited to alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, docosyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, and imidazolium compounds known under the INCI names Quaternium-27, Quaternium-83 and Quaternium-87. The alkyl chains of the above-mentioned surfactants preferably have 10 to 24 carbon atoms. Examples of ester quats include, but are not limited to quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1, 2-dihydroxypropyldialkylamines.

The personal care composition may comprise one or more cationic surfactants in an amount of 0.01%to 10 %by weight, preferably 0.1%to 5%by weight, based on the total amount of the personal care composition.

Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkylsulfonates, alkylarylsulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isothionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, in particular respective alkali metal and alkaline earth metal salts, ammonium salts, or alkanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates may have between 1 to 10 ethylene oxide and/or propylene oxide units, preferably 1 to 3 ethylene oxide units, in the molecule. Examples of the anionic surfactants include, but are not limited to sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauryl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate, or any combinations thereof. The alkyl sulfates and/or alkyl ether sulfates may be particularly mentioned as the anionic surfactant in the personal care composition.

The personal care composition may optionally comprise one or more anionic surfactants in an amount of 0.01%to 10%by weight, preferably 0.1%to 5%by weight, based on the total amount of the personal care composition.

Suitable amphoteric or zwitterionic surfactants are, for example, alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates or propionates, alkyl amphodiacetates or dipropionates. Examples of the amphoteric surfactants include, but are not limited to cocodimethylsulfopropylbetaine, laurylbetaine, cocamidopropylbetaine or sodium cocamphopropionate.

The personal care composition may optionally comprise one or more amphoteric or zwitterionic surfactants in an amount of 0.1%to 20%by weight, preferably 3%to 10%by weight, based on the total amount of the personal care composition.

The personal care composition may further comprise an additional cationic polymer which is different from the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates. Suitable additional cationic polymers are for example homopolymers or copolymers of ester or amide derivatives of acrylic acid or methacrylic acid (e.g. INCI: Polyquaternium-7) , homopolymers of methacryloylethyltrimethylammonium chloride (INCI: Polyquaternium-37) , quaternary copolymers of hydroxyethylcellulose and diallyldimethylammonium chloride (INCI: Polyquaternium-4) , polymeric quaternized ammonium salts of hydroxyethylcellulose which have been modified with a trimethylammonium-substituted epoxide (INCI: Polyquaternium-10, Polyquaternium-67) , depolymerized guar gum derivatives which have been quaternized (INCI: Guar Hydroxypropyl Trimonium Chloride) , amphoteric copolymers (INCI: Polyquaternium-74) , quaternized guar derivatives, and homopolymers of diallyldimethylammonium chloride (DADMAC) (INCI: Polyquaternium-6) .

The personal care composition may optionally comprise one or more additional cationic polymer in an amount of 0.01%to 5%by weight, preferably 0.1%to 2%by weight, based on the total amount of the personal care composition.

The personal care composition may further comprise cosmetically acceptable additives known in the art, for example emulsifiers, stabilizers, thickeners, consistency regulators, solvents, and benefit agents that can provide a positive and/or beneficial effect to the substrate being cleaned, e.g., to the hair.

The skilled person is able to select according to general knowledge in the art of formulating personal care compositions such as shampoos, shower gels and liquid hand soaps, and the vast literature there-related, appropriate such optional ingredients for application purposes. For example, the personal care composition may further comprise one or more benefit agents, such as emollients, moisturizers, skin conditioning agents, or hair conditioning agents such as silicones such as volatile silicones, gums or oils, or non-amino silicones and mixtures thereof, mineral oils, esters, such as butyl myristate, cetyl palmitate, decyloleate, glyceryl laurate, glyceryl ricinoleate, glyceryl stearate, glyceryl isostearate, hexyl laurate, isobutyl palmitate, isocetyl stearate, isopropyl isostearate, isopropyl laurate, isopropyl linoleate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, propylene glycol monolaurate, propylene glycol ricinoleate, propylene glycol stearate, and propylene glycol isostearate, animal fats, including acetylated lanolin alcohols, lanolin, lard, mink oil and tallow, and fatty acids and alcohols, including behenic acid, palmitic acid, stearic acid, behenyl alcohol, cetyl alcohol, eicosanyl alcohol and isocetyl alcohol; vitamins or their derivatives, such as vitamin B complex, including thiamine, nicotinic acid, biotin, pantothenic acid, choline, riboflavin, vitamin B6, vitamin B12, pyridoxine, inositol, carnitine, vitamins A, C, D, E, K and their derivatives, such as vitamin A palmitate, and pro-vitamins, e.g., panthenol (pro vitamin B5) , panthenol triacetate and mixtures thereof; antioxidants; free-radical scavengers; abrasives, natural or synthetic; dyes; hair coloring agents; bleaching agents; hair bleaching agents; UV absorbers, such as benzophenone, bornelone, PABA (Para Amino Benzoic Acid) , butyl PABA, cinnamidopropyl trimethyl ammonium chloride, disodium distyrylbiphenyl disulfonate, potassium methoxycinnamate; anti-UV agents, such as butyl methoxydibenzoylmethane, octyl methoxycinnamate, oxybenzone, octocrylene, octyl salicylate, phenylbenzimidazole sulfonic acid, ethyl hydroxypropyl aminobenzoate, menthyl anthranilate, aminobenzoic acid, cinoxate, diethanolamine methoxycinnamate, glyceryl aminobenzoate, titanium dioxide, zinc oxide, oxybenzone, octyl dimethyl PABA (padimate O) , red petrolatum; antimicrobial agents; antibacterial agents, such as bacitracin, erythromycin, triclosan, neomycin, tetracycline, chlortetracycline, benzethonium chloride, phenol, parachlorometa xylenol (PCMX) , triclocarban (TCC) , chlorhexidine gluconate (CHG) , zinc pyrithione, selenium sulfide; antifungal agents; melanin regulators; tanning accelerators; depigmenting agents, such as retinoids such as retinol, kojic acid and its derivatives such as, for example, kojic dipalmitate, hydroquinone and its derivatives such as arbutin, transexamic acid, vitamins such as niacin, vitamin C and its derivatives, azelaic acid, placertia, licorice, extracts such as chamomile and green tea, where retinol, kojic acid, and hydroquinone are preferred; skin lightening agents such as hydroquinone, catechol and its derivatives, ascorbic acid and its derivatives; skin coloring agents, such as dihydroxyacetone; liporegulators; weight-reduction agents; anti-acne agents; anti-seborrhoeic agents; anti-ageing agents; anti-wrinkle agents; keratolytic agents; anti-inflammatory agents; anti-acne agents, such as tretinoin, isotretinoin, motretinide, adapalene, tazarotene, azelaic acid, retinol, salicylic acid, benzoyl peroxide, resorcinol, antibiotics such as tetracycline and isomers thereof, erythromycin, anti-inflammatory agents such as ibuprofen, naproxen, hetprofen, botanical extracts such as alnus, arnica, artemisia capillaris, asiasarum root, calendula, chamomile, nidium, comfrey, fennel, galla rhois, hawthorn, houttuynia, hypericum, jujube, kiwi, licorice, magnolia, olive, peppermint, philodendron, salvia, sasa albomarginata, imidazoles such as ketoconazole and elubiol; refreshing agents; cicatrizing agents; vascular-protection agents; agents for the reduction of dandruff (Anti-dandruff agent) , seborrheic dermatitis, or psoriasis, such as pyrithione salts, being formed from heavy metals such as zinc, tin, cadmium, magnesium aluminum, sodium and zirconium, like zinc pyrithione, shale oil and derivatives thereof such as sulfonated shale oil, selenium sulfide, sulfur, salicylic acid, coal tar, povidone-iodine, imidazoles such as ketoconazole, dichlorophenyl imidazolodioxalan, clotrimazole, itraconazole, miconazole, climbazole, tioconazole, sulconazole, butoconazole, fluconazole, miconazolenitrite and any possible stereo isomers and derivatives thereof such as anthralin, piroctone olamine (Octopirox) , selenium sulfide, ciclopirox olamine, anti-psoriasis agents such as vitamin D analogs, e.g. calcipotriol, calcitriol, and tacaleitrol, vitamin A analogs such as esters of vitamin A, including vitamin A palmitate, retinoids, retinols, and retinoic acid, corticosteroids such as hydrocortisone, clobetasone, butyrate, clobetasol propionate; antiperspirants or deodorants, such as aluminum chlorohydrates, aluminum zirconium chlorohydrates; immunomodulators; nourishing agents; depilating agents, such as calcium thioglycolate, magnesium thioglycolate, potassium thioglycolate, strontium thioglycolate; agents for combating hair loss; reducing agents for permanent-waving; reflectants, such as mica, alumina, calcium silicate, glycol dioleate, glycol distearate, silica, sodium magnesium fluorosilicate; essential oils and fragrances.

It will be understood that the personal care composition will comprise water as a vehicle or medium.

In some embodiments, the personal care composition is a hair care composition, such as shampoo composition and a conditioner composition.

Embodiments

Various embodiments are listed below. It will be understood that the embodiments listed below may be combined with all aspects and other embodiments in accordance with the scope of the invention.

Embodiment 1: Betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates, which have at least one amide linkage of formula “-C (O) -NH-” in which the “-C (O) -” moiety is a carbonyl moiety originating from betaine and the “-NH-” moiety is an imino moiety originating from any free amino group of a poly (amino acid) or a protein hydrolysate.

Embodiment 2: the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to the embodiment 1, wherein the betaine-quaternized poly (amino acid) s have a degree of modification (DM) in the range of 5%to 60%, for example 5%to 25%, 5%to 20%, or 5%to 15%, particularly 7%to 15%.

Embodiment 3: the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to the embodiment 1 or 2, wherein the poly (amino acid) s are poly (basic amino acid) s, particularly polylysines.

Embodiment 4: the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to the embodiment 3, wherein the polylysines have a K-value in the range of 9 to 25, more preferably 10 to 21.

Embodiment 5: the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to the embodiment 1, wherein the betaine-quaternized protein hydrolysates have a degree of modification (DM) in the range of 2%to 40%, for example 3%to 35%or 5 to 30%, particularly 5 to 25%.

Embodiment 6: the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to the embodiment 1 or 5, wherein the protein hydrolysates are vegetable protein hydrolysate, soy protein hydrolysate, rice protein hydrolysate, almond protein hydrolysate, wheat protein hydrolysate, pea protein hydrolysate, sunflower protein hydrolysate, wheat gluten protein hydrolysate, maize protein hydrolysate, barley protein hydrolysate, sorghum protein hydrolysate, potato protein hydrolysate, coffee protein hydrolysate, cotton protein hydrolysate or sesame protein hydrolysate.

Embodiment 7: the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to the embodiment 1, 5 or 6, wherein the protein hydrolysate has a molecular weight M_w in the range of 800 to 10,000 Dalton, preferably 1,000 to 8,000 Dalton.

Embodiment 8: the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to any of the embodiments 1 to 7, wherein the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates are obtained from an aminolysis reaction between a cationic betaine ester and a poly (amino acid) or a protein hydrolysate to form the at least one amide linkage of formula “-C (O) -NH-” therebetween.

Embodiment 9: a process for preparing betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates, which includes subjecting a cationic betaine ester and a poly (amino acid) or a protein hydrolysate to an aminolysis reaction to form at least one amide linkage of formula “-C (O) -NH-” therebetween.

Embodiment 10: the process according to the embodiment 9, wherein the cationic betaine ester is selected from cationic betaine ester of monoalcohols such as C_2-5-monoalcohols, or polyols such as C_2-6-polyols.

Embodiment 11: the process according to the embodiment 10, wherein the cationic betaine ester is selected from cationic betaine ester of ethanol, n-propanol, n-butanol and n-pentanol.

Embodiment 12: the process according to the embodiment 10, wherein the cationic betaine ester is selected from cationic betaine ester of C_2-6-diols or C_2-6-triols, particularly vicinal C_2-6-diols or C_2-6-triols.

Embodiment 13: the process according to the embodiment 12, wherein the cationic betaine ester is selected from cationic betaine ester of glycerol, ethylene glycol, diethylene glycol, 1, 2-propanediol, 1, 2-butanediol, 1, 2-pentanediol, 1, 2-hexanediol, 2, 3-butanediol, 2, 3-pentanediol, 2, 3-hexanediol, with 1, 2-propanediol and glycerol being preferable.

Embodiment 14: the process according to any of the embodiments 9 to 13, wherein the poly (amino acid) s are poly (basic amino acid) s, particularly polylysines.

Embodiment 15: the process according to the embodiment 14, wherein the polylysines have a K-value in the range of 9 to 25, more preferably 10 to 21.

Embodiment 16: the process according to any of the embodiments 9 to 13, wherein the protein hydrolysates are vegetable protein hydrolysate, soy protein hydrolysate, rice protein hydrolysate , almond protein hydrolysate, wheat protein hydrolysate, pea protein hydrolysate, sunflower protein hydrolysate, wheat gluten protein hydrolysate, maize protein hydrolysate, barley protein hydrolysate, sorghum protein hydrolysate, potato protein hydrolysate, coffee protein hydrolysate, cotton or sesame protein hydrolysate.

Embodiment 17: the process according to any of the embodiments 9 to 13 and 16, wherein the protein hydrolysate has a molecular weight M_w in the range of 800 to 10,000 Dalton, preferably 1,000 to 8,000 Dalton.

Embodiment 18: the process according to any of the embodiments 9 to 17, wherein the betaine-quaternized poly (amino acid) s have a degree of modification (DM) in the range of 5%to 60%, for example 5%to 25%, 5%to 20%, or 5%to 15%, particularly 7%to 15%, or the betaine-quaternized protein hydrolysates have a degree of modification (DM) in the range of 2%to 40%, for example 3%to 35%or 5 to 30%, particularly 5 to 25%.

Embodiment 19: the process according to any of the embodiments 9 to 18, which further includes a step of subjecting betaine and an alcohol to an acid-catalyzed esterification reaction to provide the cationic betaine ester.

Embodiment 20: the process according to the embodiment 19, wherein the acid-catalyzed esterification reaction is carried out in the presence of methane sulfonic acid.

Embodiment 21: a personal care composition, particularly a hair care composition, which comprises the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to any of the embodiments 1 to 8 or the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates obtained and/or obtainable from the process according to any of the embodiments 9 to 20.

Embodiment 22: the personal care composition according to the embodiment 21, wherein the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates are present in the personal care composition in an amount of 0.01%to 10%by weight, preferably 0.1%to 8%by weight, more preferably 1%to 5%by weight, based on the total amount of the personal care composition.

Embodiment 23: the personal care composition according to the embodiment 21 or 22, which is a shampoo composition or a conditioner composition.

Embodiment 24: a method for hair conditioning or hair repairing, which includes treating hair with the hair care composition according to any of the embodiments 21 to 23.

Embodiment 25: Use of the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to any of the embodiments 1 to 8 or the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates obtained and/or obtainable from the process according to any of the embodiments 9 to 20 in personal care compositions, such as hair care compositions, particularly as a conditioning agent and/or as a cationic surfactant.

Examples

Aspects of the present invention will be more fully illustrated by the following examples, which are set forth to illustrate certain aspects of the present invention and are not to be construed as limiting thereof.

I. Preparation Examples

Example 1

A 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser with reduced-pressure connection with a Dean-Stark receiver, was charged with 47 g of betaine and 42 g of methanesulfonic acid. The mixture as obtained was stirred at ambient temperature for 1 hour under N₂ purge. Then, 147 g of glycerol was added to the mixture, which was then heated with stirring to an internal temperature of 140℃, with continuous water separation under a reduced pressure of 100 mbar. A transparent glycerol betainate intermediate was collected after 4 hours of distillation and stored in a sealed container. A conversion of approximately 60%was achieved, as determined by ¹H NMR.

A 250 ml three-neck flask equipped with a stirrer, an internal thermometer, and a gas inlet tube was charged with 21 g of dried wheat protein hydrolysate (WP) , 100 g of the glycerol betainate intermediate, and 3 g of triethylamine. The mixture as obtained was stirred at 60℃ for 24 hours under N₂ purge. The product, a single phase, brown-colored solution was collected and stored in a sealed container. Degree of modification is approximately 5%, based on o-phthalaldehyde (OPA) method.

Example 2

A 250 ml three-neck flask equipped with a stirrer, an internal thermometer, and a gas inlet tube was charged with 21 g of dried wheat protein hydrolysate (WP) , 100 g of the betainate intermediate as prepared in Example 1, 15 g of sodium bicarbonate and 2 g of triethylamine. The mixture as obtained was stirred at 60℃ for 24 hours under N₂ purge. The product, a single phase, brown-colored solution was collected and stored in a sealed container. Degree of modification is approximately 21%, based on OPA method.

Example 3

A 250 ml three-neck flask equipped with a stirrer, an internal thermometer, and a gas inlet tube was charged with 21 g of dried wheat protein hydrolysate (WP) , 100 g of the betainate intermediate as prepared in Example 1 and 21 g of triethylamine. The mixture as obtained was stirred at 60℃ for 24 hours under N₂ purge. The product, a single phase, brown-colored solution was collected and stored in a sealed container. Degree of modification, based on OPA method is approximately 43%.

Example 4

A 250 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser with reduced-pressure connection with a Dean-Stark receiver, was charged with 23 g of betaine and 22 g of methanesulfonic acid. The mixture as obtained was stirred at ambient temperature for 1 hour under N₂ purge. Then, 125 g of n-butanol was added to the mixture, which was then heated with stirring to an internal temperature of 130℃, with continuous water separation under reduced pressure of 550 mbar. A transparent butanol betainate intermediate was collected after 4 hours of distillation and used immediately after preparation for the next step. A conversion of approximately 92%was achieved, as determined by ¹H NMR.

A 250 ml four-neck flask equipped with a stirrer, an internal thermometer, and a condenser with reduced-pressure connection with a Dean-Star receiver, was charged with 38.5 g of dried vegetable protein hydrolysate (Kera-P LM) and 100 g of the butanol betainate intermediate under N₂ purge. The mixture was stirred at 60℃ for 14 hours under a reduced pressure of 35 mbar. The product, a viscous brown slurry, was collected and stored in a sealed container. The product was dialyzed with a dialysis bag of molecular weight cut-off of 1000 Da, lyophilized, and stored in a sealed container. Degree of modification is approximately 10%, based on ¹H NMR. The active content is 100%.

Example 5

A 250 ml four-neck flask equipped with a stirrer, an internal thermometer, and a condenser with reduced-pressure connection with a Dean-Star receiver, was charged with 21 g of ε-polylysine (from JNC Corp., lyophilized, Kv=20.2) and 100 g of the betainate intermediate as prepared in Example 4 under N₂ purge. The mixture as obtained was stirred at 140 ℃ for 5 hours under a reduced pressure of 35 mbar. The product, a viscous brown slurry, was collected and stored in a sealed container. The product was dialyzed with a dialysis bag of molecular weight cut-off of 1000 Da, lyophilized, and stored in a sealed container. Degree of modification is approximately 12%, based on ¹H NMR. The active content is 100%.

Example 6

A 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with reduced-pressure connection and a Dean-Stark receiver, was charged with 100 g of an aqueous solution of L-lysine (50 wt%) . The mixture as obtained was heated with stirring to an internal temperature of 160 ℃, with continuous water separation. After a reaction time of 1 hour, water was distilled off further under reduced pressure (670 mbar) . Finally, 264 g of water distillate was collected and the highly viscous polymer was discharged to a silicone container as fast as possible while it was still hot and flowable. The K-value of the branched lysine homopolymer was determined as 11.0.

A 250 ml three-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with reduced-pressure connection and a Dean-Stark receiver, was charged with 27 g of the branched lysine homopolymer, 100 g of the betainate intermediate as prepared in Example 1, and 4 g of dibutylamine under N₂ purge. The mixture was stirred at 125℃ for 3 hours under a reduced pressure of 10 mbar. The product, a single phase, brown-colored viscous solution was collected and stored in a sealed container. Degree of modification based on ¹H NMR is approximately 51%. The active content is 29.5%.

Comparative Example 1

A 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser, was charged with 68 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quab reagent) , 40 g of the branched polylysine homopolymer as prepared in Example 6, and 100 g of D. I. water. The reaction was allowed to proceed for 16 h at room temperature, meanwhile the pH was maintained at 8 by controlled addition of a 48 wt%aqueous NaOH solution, using a control unit of Systag FlexyCube automated lab reactor, equipped with a peristaltic pump and a pH probe with high temperature electrolyte. Afterwards, the polymer was precipitated with excess methanol (1 : 10 by weight) and filtered. Upon three successive precipitation steps, the product was dried over 16 h in a vacuum oven at 40℃ to obtain the final product. The degree of modification (DM) of the polymer as determined by ¹H NMR is 88%.

II. Tests of Hair Care Performance

II. 1 Hair Conditioning Performance with Respect to Combability

The physical measurement of combing forces on hair strands enables objectively measured results on how products like hair shampoos or hair conditioners perform with regards to conditioning and detangling efficacies. In a pre-post design, the reduction of wet and dry combing forces was determined to substantiate the efficacy.

Prior to measurement, hair strands were detangled until no loops or coils remain. Next, the strands were positioned into a clamp and combed into the testing comb which is part of the tensile tester. The combing force reduction is given in percent and calculated from the force ratio between treated hair strands value and blank value (untreated hair strands) . Each formulation was tested with 5 Caucasian hair strands from IHIP, using a wet and dry combing device. For the wet combing test 1 g of hair strands with a length of 12 cm, and for the dry combing test 2 g of hair stands with a length of 15 cm, were used.

The first step for investigating dry combability was preparation of the hair strands for the determination of the reference values. The preparation included equilibration of the hair strands for 12 hours at a room temperature of 23 ℃ and 50%relative humidity. Then the measurement for the untreated hair strands was taken. The hair strands were treated with 0.25 g of the respective washing formulations as shown in Table 1 per 1 g of hair and incubated for 5 minutes. Then the hair strands were well rinsed with tap water for about 1 minute at room temperature. This treatment with the washing formulation was repeated. The hair strands were dried, and the dried hair strands were equilibrated at the conditions given above. Then the combing measurement was performed.

The conditioning performance of the respective washing formulations was evaluated by measuring the change in work or energy associated with combing the hair strands, recorded as residual combing work. The combing work was calculated from integrating the recorded force-displacement curves. Combing force was measured by a Zwicki Z2.5 Dynamic Testing Machine (Zwick Roell, Germany) before and after treatment with the test formulations..

The residual combing work is calculated as following:

Residual combing work = (combing work after treatment) / (combing work before treatment) x 100%

Table 1

II. 1 Hair Repairing Performance

The hair repairing performance was investigated by measuring the enthalpy and temperature of keratin denaturization from differential scanning calorimetry (DSC) . Enthalpy is a measure for the content of alpha-helical material in the keratin and is an indication of structural rigidity of hair.

Prior to measurement, virgin and bleached hair strands were treated with 0.25 g of a washing solution per 1 g of hair and incubated for 5 minutes. Then the hair strands were well rinsed with tap water for about 1 minute at 38℃. The hair strands were dried, and the dried hair strands were equilibrated (22℃, humidity of 50%for 24 hours) . Before application of respective repairing formulations, hair strands were rinsed under 38 ℃ water for 1 min and excess water was removed. Then, the hair strands were treated with 0.125 g of the respective repairing formulations per 1 g of hair, brushed over 5 times on each side of the hair strand, and incubated for 5 minutes. Then, the hair strands were well rinsed with tap water for about 1 minute at 38 ℃. The hair strands were dried, and the dried hair strands were equilibrated.

For DSC analysis, a DSC Q100 (TA Instruments, Eschborn, Germany) was used in combination with high volume pans (100μL, 30bar pressure resistance) . Hair strands were equilibrated at 22 ℃ and 50%RH for 24 hours to normalize the water content prior to being cut into snippets. The denaturation temperatures of human hair proteins were determined as described by Wortmann et al . (J. Appl . Polym . Sci . 48 (1993 ) 137 ) using a heating rate of 2K /min.

Enthalpy was calculated using the manufacturer supplied software, and enthalpy recovery is calculated as:

Enthalpy recovery (%) = [ (Enthalpy_placebo-Enthalpy_sample) / (Enthalpy_{virgin (untreated)} -Enthalpy_placebo) ] × 100%

Table 2

It can be seen the formulations F7 and F9 comprising the betaine-quaternized protein hydrolysate and the betaine-quaternized polylysine respectively exhibit excellent repairing effect to the damaged (i.e., bleached) hair, which is much better than formulations F6 and F8 comprising corresponding unquaternized protein hydrolysate and polylysine respectively.

II. 3 Hair Conditioning Performance with Respect to Appearance

The hair strands were first bleached using the following protocol: 100g of bleaching mixture was prepared from 33.3g bleaching powder (Schwarzkopt Igora) and 66.7 g developer (Schwarzkopf Igora 12%) . Bleaching mixture was applied to 20g of hair (10 strands) with a hair dyeing brush and left for 30 min. Hair strands were then rinsed for 5 min, followed by subsequent combing and air drying. The bleached hair strands were rinsed for 1 min. Then, 0.5 g of test formulations (e.g. 10%a. m. in demineralized water with pH 4) were applied to hair strands with a hair dyeing brush. After 3 minutes of exposure, the hair strands were rinsed for 1 min. The hair strands were combed while wet, and combed again after dried. Subsequently, the hair strands were assessed visually.

III. Biodegradability of Polymers

Biodegradation was tested in triplicate using the OECD 301 F manometric respirometry method. 30 mg/mL test substance was inoculated into wastewater taken from Mannheim Wastewater Treatment Plant and incubated in a closed flask at 25℃ for 56 days. The consumption of oxygen during this time is measured as the change in pressure inside the flask using an OxiTop C (WTW) . Evolved CO₂ is absorbed using an NaOH solution. The amount of oxygen consumed by the microbial population during biodegradation of the test substance, after correction using a blank, is expressed as a percentage of the ThOD (Theoretical Oxygen Demand) . The percentage indicates the biodegradation extent. The test results are summarized in Table 3.

Table 3

It can be seen that the betaine-quaternized poly (amino acid) s and the betaine-quaternized protein hydrolysates according to the present invention have a better biodegradability than corresponding Quab quaternized poly (amino acid) s and Quab quaternized protein hydrolysates (Examples 1 to 3 vs. WQTP dialyzed, and Example 6 vs. Comparative Example 1) . It can also be found that betaine quaternization does not substantially reduce the biodegradability of poly (amino acid) s and protein hydrolysates (Examples 1 to 3 vs Gluadin WP dialyzed, Example 4 vs. Kera-P LM, Example 5 vs. ε-Polylysine) .

Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It will be apparent to those of skill in the art that various modifications and variations can be made to the method and apparatus of the present invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention include modifications and variations that are within the scope of the appended claims and their equivalents.

Claims

Betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates, which have at least one amide linkage of formula “-C (O) -NH-” in which the “-C (O) -” moiety is a carbonyl moiety originating from betaine and the “-NH-” moiety is an imino moiety originating from any free amino group of a poly (amino acid) or a protein hydrolysate.
The betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to claim 1, wherein the betaine-quaternized poly (amino acid) s have a degree of modification (DM) in the range of 5%to 60%, for example 5%to 25%, 5%to 20%, or 5%to 15%, particularly 7%to 15%.
The betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to claim 1 or 2, wherein the poly (amino acid) s are poly (basic amino acid) s, particularly polylysines.
The betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to claim 3, wherein the polylysines have a K-value in the range of 9 to 25, more preferably 10 to 21.
The betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to claim 1, wherein the betaine-quaternized protein hydrolysates have a degree of modification (DM) in the range of 2%to 40%, for example 3%to 35%or 5 to 30%, particularly 5 to 25%.
The betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to claim 1 or 5, wherein the protein hydrolysates are vegetable protein hydrolysate, soy protein hydrolysate, rice protein hydrolysate, almond protein hydrolysate, wheat protein hydrolysate, pea protein hydrolysate, sunflower protein hydrolysate, wheat gluten protein hydrolysate, maize protein hydrolysate, barley protein hydrolysate, sorghum protein hydrolysate, potato protein hydrolysate, coffee protein hydrolysate, cotton protein hydrolysate or sesame protein hydrolysate.
The betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to claim 1, 5 or 6, wherein the protein hydrolysate has a molecular weight M_w in the range of 800 to 10,000 Dalton, preferably 1,000 to 8,000 Dalton.
The betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to any of claims 1 to 7, wherein the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates are obtained from an aminolysis reaction between a cationic betaine ester and a poly (amino acid) or a protein hydrolysate to form the at least one amide linkage of formula “-C (O) -NH-” therebetween.
A process for preparing betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates, which includes subjecting a cationic betaine ester and a poly (amino acid) or a protein hydrolysate to an aminolysis reaction to form at least one amide linkage of formula “-C (O) -NH-” therebetween.
The process according to claim 9, wherein the cationic betaine ester is selected from cationic betaine ester of monoalcohols such as C_2-5-monoalcohols, or polyols such as C_2-6-polyols.
The process according to claim 10, wherein the cationic betaine ester is selected from cationic betaine ester of ethanol, n-propanol, n-butanol and n-pentanol.
The process according to claim 10, wherein the cationic betaine ester is selected from cationic betaine ester of C_2-6-diols or C_2-6-triols, particularly vicinal C_2-6-diols or C_2-6-triols..
The process according to claim 12, wherein the cationic betaine ester is selected from cationic betaine ester of glycerol, ethylene glycol, diethylene glycol, 1, 2-propanediol, 1, 2-butanediol, 1, 2-pentanediol, 1, 2-hexanediol, 2, 3-butanediol, 2, 3-pentanediol, 2, 3-hexanediol, with 1, 2-propanediol and glycerol being preferable.
The process according to any of claims 9 to 13, wherein the poly (amino acid) s are poly (basic amino acid) s, particularly polylysines.
The process according to claim 14, wherein the polylysines have a K-value in the range of 9 to 25, more preferably 10 to 21.
The process according to any of claims 9 to 13, wherein the protein hydrolysates are vegetable protein hydrolysate, soy protein hydrolysate, rice protein hydrolysate , almond protein hydrolysate, wheat protein hydrolysate, pea protein hydrolysate, sunflower protein hydrolysate, wheat gluten protein hydrolysate, maize protein hydrolysate, barley protein hydrolysate, sorghum protein hydrolysate, potato protein hydrolysate, coffee protein hydrolysate, cotton or sesame protein hydrolysate.
The process according to any of claims 9 to 13 and 16, wherein the protein hydrolysate has a molecular weight M_w in the range of 800 to 10,000 Dalton, preferably 1,000 to 8,000 Dalton.
The process according to any of claims 9 to 17, wherein the betaine-quaternized poly (amino acid) shave a degree of modification (DM) in the range of 5%to 60%, for example 5%to 25%, 5%to 20%, or 5%to 15%, particularly 7%to 15%, or the betaine-quaternized protein hydrolysates have a degree of modification (DM) in the range of 2%to 40%, for example 3%to 35%or 5 to 30%, particularly 5 to 25%.
The process according to any of claims 9 to 18, which further includes a step of subjecting betaine and an alcohol to an acid-catalyzed esterification reaction to provide the cationic betaine ester.
The process according to claim 19, wherein the acid-catalyzed esterification reaction is carried out in the presence of methane sulfonic acid.
A personal care composition, particularly a hair care composition, which comprises the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to any of claims 1 to 8 or the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates obtained and/or obtainable from the process according to any of claims 9 to 20.
The personal care composition according to claim 21, wherein the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates are present in the personal care composition in an amount of 0.01%to 10%by weight, preferably 0.1%to 8%by weight, more preferably 1%to 5%by weight, based on the total amount of the personal care composition.
The personal care composition according to claim 21 or 22, which is a shampoo composition or a conditioner composition.
A method for hair conditioning or hair repairing, which includes treating hair with the hair care composition according to any of claims 21 to 23.
Use of the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates according to any of claims 1 to 8 or the betaine-quaternized poly (amino acid) s or betaine-quaternized protein hydrolysates obtained and/or obtainable from the process according to any of claims 9 to 20 in personal care compositions, such as hair care compositions, particularly as a conditioning agent and/or as a cation ic su rfactant.