Betaine-modified poly(amino acid) or protein hydrolysate

Abstract

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

Description

[Technical Field]

[0001] The present invention relates to a cationic biopolymer containing a betaine-derived portion, particularly a betaine quaternized poly(amino acid). The present invention also relates to a personal care composition, particularly a hair care composition, containing a cationic biopolymer containing a betaine-derived portion, and also to the use of a cationic biopolymer containing a betaine-derived portion in a personal care composition, particularly as a conditioning agent and / or cationic surfactant. [Background technology]

[0002] Cationic polymers are used as conditioning agents in personal care compositions, such as hair care compositions. Requirements for hair conditioning agents include, for example, a significant reduction in the amount of combing force required for both wet and dry hair, good detangling during the initial combing, and good compatibility with other formulation ingredients. In addition, cationic polymers prevent electrostatic charging of the hair.

[0003] Many cationic polymers suitable as conditioning agents in hair care compositions are commercially available, including petroleum-based and bio-based varieties. Bio-based cationic polymers derived from renewable materials (e.g., biomass) are of particular interest due to the sustainability of biomass resources. Well-known bio-based cationic polymers include, for example, quaternized cellulose, quaternized guar gum, and quaternized hydrolyzed vegetable wheat protein. These renewable material-derived cationic polymers are generally prepared by using Quab reagents such as glycidyltrimethylammonium chloride or 3-chloro-2-hydroxypropyltrimethylammonium chloride as quaternization reagents. Quab reagents are effective for quaternization and are easy to synthesize. However, Quab reagents are toxic and decompose less into the polymer main chain, which is disadvantageous in terms of process safety and environmental considerations.

[0004] It would be desirable if cationic polymers suitable as conditioning agents could be derived from environmentally friendly quaternization reagents.

[0005] International Publication No. 2013 / 188508A1 describes antimicrobial compositions containing cationic glycine betaine components derived from natural resources (e.g., sugar beets), which include cationic glycine betaine esters and / or cationic glycine betaine amides, particularly alkyl(len)betainate methanesulfonates and betainylaminoalkyl(len)methanesulfonates in which a hydrophilic group is bonded to a carboxylate group via an ester or amide bond. Cationic glycine betaine components can be prepared by obtaining cationic glycine betaine esters in which a hydrophobic group is bonded to a carboxylate ester bond using a fatty alcohol in the presence of methanesulfonic acid (MSA) as a catalyst, or by obtaining cationic glycine betaine esters using an alcohol and then obtaining cationic glycine betaine amides in which a hydrophobic group is bonded to a carboxylic acid amide bond using a fatty amine.

[0006] Glycine betaine esters and amides have been described as functioning as cationic surfactants with effective antimicrobial activity. This patent application does not describe at all cationic polymers derived from glycine betaine that are suitable as conditioning agents in personal care compositions.

[0007] There is a need to provide cationic polymers suitable as conditioning agents in personal care compositions, which can be derived from environmentally friendly (e.g., biodegradable) polymers by quaternization with environmentally conscious reagents and can still be added to personal care compositions. [Overview of the project] [Problems that the invention aims to solve]

[0008] The object of the present invention is to provide an environmentally friendly cationic polymer having desirable conditioning performance, particularly hair conditioning performance and / or hair repair performance.

Means for Solving the Problems

[0009] The inventors of the present invention have discovered that this object can be achieved by a betaine quaternized poly(amino acid) or a betaine quaternized protein hydrolyzate.

[0010] A further object of the present invention is to provide a process for preparing a cationic polymer suitable as a conditioning agent without using a toxic quaternizing reagent.

[0011] The inventors of the present invention have discovered that this further object can be achieved by preparing a cationic polymer using a betaine ester as a quaternizing reagent.

[0012] Thus, in a first aspect, the present invention relates to a betaine quaternized poly(amino acid) or a betaine quaternized protein hydrolyzate having at least one amide bond of the formula “—C(O)—NH—”, wherein the “—C(O)—” moiety is a carbonyl group derived from betaine, and the “—NH—” moiety is an imino moiety derived from any free amino group of the poly(amino acid) or the protein hydrolyzate.

[0013] In some embodiments according to the first aspect, the present invention relates to a betaine quaternized poly(amino acid) or a betaine quaternized protein hydrolyzate having at least one amide bond of the formula “—C(O)—NH—”, wherein the “—C(O)—” moiety is a carbonyl group derived from betaine, and the “—NH—” moiety is an imino moiety derived from any free amino group of the poly(amino acid) or the protein hydrolyzate, the poly(amino acid) is polylysine, and the protein hydrolyzate is a vegetable protein hydrolyzate or a wheat protein hydrolyzate.

[0014] In a second aspect, the present invention relates to a process for preparing a betaine quaternized poly(amino acid) or a betaine quaternized protein hydrolysate, comprising subjecting a cationic betaine ester and a poly(amino acid) or protein hydrolysate to an aminolysis reaction to form at least one amide bond of the formula "-C(O)-NH-" between them.

[0015] In some embodiments according to the second aspect, the present invention relates to a process for preparing betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysates, (i) A step of providing a cationic betaine ester by subjecting betaine and alcohol to an acid-catalyzed esterification reaction, (ii) A step of subjecting the cationic betaine ester from step (i) and a poly(amino acid) or protein hydrolysate to an aminolysis reaction to form at least one amide bond of the formula "-C(O)-NH-" between them. Regarding processes that include this.

[0016] In some further embodiments according to the second aspect, the present invention relates to a process for preparing betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysates, (i) A step of providing a cationic betaine ester by subjecting betaine and an alcohol to an acid-catalyzed esterification reaction in the presence of methanesulfonic acid, (ii) A step of subjecting the cationic betaine ester from step (i) and a poly(amino acid) or protein hydrolysate to an aminolysis reaction to form at least one amide bond of the formula "-C(O)-NH-" between them. Regarding processes that include this.

[0017] In some alternative or other embodiments according to the second aspect, the present invention relates to a process for preparing betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysates, (i) Preferably betaine and C in the presence of methanesulfonic acid 2~5 - Monoalcohol or Vicinal C2~6 - A step of subjecting a polyol to an acid-catalyzed esterification reaction to provide a cationic betaine ester, (ii) A step of subjecting the cationic betaine ester from step (i) and a poly(amino acid) or protein hydrolysate to an aminolysis reaction to form at least one amide bond of the formula "-C(O)-NH-" between them. Regarding processes that include this.

[0018] In a third aspect, the present invention relates to a personal care composition, particularly a hair care composition, comprising a betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate obtained and / or obtainable from a process according to the first aspect or the second aspect.

[0019] In some embodiments according to the third aspect, the present invention relates to a shampoo composition or hair conditioner composition comprising a betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate obtained and / or obtainable from a process according to the first aspect or the second aspect.

[0020] In a fourth aspect, the present invention relates to a method for hair conditioning or hair repair, comprising treating hair with a hair care composition according to the third aspect.

[0021] In a fifth aspect, the present invention relates to the use of betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysates obtained and / or obtainable from a process according to the first aspect or the second aspect, in personal care compositions, such as hair care compositions, particularly as conditioning agents and / or cationic surfactants. [Brief explanation of the drawing]

[0022] [Figure 1a] The image shows a hair bundle after treatment with polylysine. [Figure 1b] The image shows a hair bundle after treatment with betaine quaternized polylysine. [Modes for carrying out the invention]

[0023] The singular forms "a," "an," and "that" refer to multiple objects unless the context explicitly indicates otherwise. Terms such as "contains" and "includes" are interchangeable with terms such as "contains" and "includes," and should be interpreted in a non-restrictive, open-ended manner. In other words, for example, there may be further components or elements. Expressions such as "consist of" or "made up of" or similar expressions can be encompassed by "contains" or similar expressions. Terms such as "contains" and "includes" should be interpreted in a non-restrictive, open manner.

[0024] In this specification, the terms “personal care composition” and “hair care composition” are used in their broadest sense. The term “personal care composition” is intended to refer to a product or composition suitable for topical application to the skin, hair, or other keratinous tissue of mammals. The term “hair care composition” is intended to refer to a product or composition, including but not limited to shampoos and conditioners, suitable for topical application to the hair of mammals.

[0025] In this specification, the term "vicinal" in relation to polyols or diols means that the polyol or diol has a hydroxyl group on an adjacent carbon.

[0026] In this specification, the term "betaine" refers to "glycine betaine" and may be used interchangeably.

[0027] In this specification, the terms poly(amino acid) and poly(amino acid) refer to "polypeptide" and may be used interchangeably.

[0028] In this specification, any proportions of the components of a composition are calculated based on the total weight of the composition, with respect to the active ingredient, excluding any impurities (e.g., residual solvents or by-products) that may be present in the commercially available or as-prepared form of that component. All proportions are also given by weight, unless otherwise specified.

[0029] Betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysate In a first aspect, the present invention provides a betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate having at least one amide bond of the formula "-C(O)-NH-", the "-C(O)-" portion being a carbonyl portion derived from betaine, and the "-NH-" portion being an imino portion derived from any free amino group of the poly(amino acid) or protein hydrolysate.

[0030] Betaine, also known as trimethylglycine or glycine betaine, is a naturally occurring compound widely distributed in animals, plants, and microorganisms, and is mostly extracted from sugar beet molasses. Betaine contains a positively charged trimethylammonium moiety and a negatively charged ruboxylate group, which can be represented by the following formula (I). [ka]

[0031] In the betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate according to the present invention, the "-NH-" portion in the amide bond of formula "-C(O)-NH-" is an imino portion derived from any free amino group of the poly(amino acid) or protein hydrolysate.

[0032] Poly(amino acid) or protein hydrolysates are known to have one or more free amino groups (i.e., -NH2) within their molecules. Any of these free amino groups can react with a betaine ester intermediate to form an amide bond, for example, via the aminolysis reaction described below.

[0033] Preferably, the quaternized poly(amino acid) may be poly(basic amino acid), which includes homopolymers of basic amino acids and copolymers of basic amino acids with one or more amino acids. Basic amino acids mean that the amino acid contains more amino groups than carboxyl groups. Examples of naturally occurring basic amino acids include lysine and arginine. According to the present invention, polylysine, lysine homopolymers or copolymers, and especially lysine homopolymers (i.e., homopolylysine) are preferred.

[0034] The polymer structure of polylysine is not limited and may have a linear or branched structure. The K value of polylysine, measured using a 1% by weight solution of each polylysine in water at 23°C according to DIN ISO 1628-1, may be in the range of 9 to 25, more preferably 10 to 21.

[0035] Protein hydrolysates suitable for the present invention may contain specific free amino acids in a relatively high mole fraction. Preferably, the protein hydrolysates to be quaternized may be plant protein hydrolysates, soy protein hydrolysates, rice protein hydrolysates, almond protein hydrolysates, wheat protein hydrolysates, pea protein hydrolysates, sunflower protein hydrolysates, wheat gluten protein hydrolysates, corn protein hydrolysates, barley protein hydrolysates, sorghum protein hydrolysates, potato protein hydrolysates, coffee protein hydrolysates, cotton protein hydrolysates, or sesame protein hydrolysates. Suitable protein hydrolysates, particularly wheat and plant protein hydrolysates, have a molecular weight (M) in the range of 800 to 10,000 daltons, preferably 1,000 to 8,000 daltons. w) may have. In some embodiments, the protein hydrolysate may also be an animal-derived protein hydrolysate, such as milk protein hydrolysate, egg white protein hydrolysate, fish protein hydrolysate, meat hydrolysate, blood protein hydrolysate, hair protein hydrolysate, feather protein hydrolysate, and fishmeal protein hydrolysate.

[0036] Suitable polylysines and protein hydrolysates may be prepared according to known methods or may be commercially available.

[0037] Betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysates can be obtained from an aminolysis reaction between a cationic betaine ester and a poly(amino acids) or protein hydrolysate to form at least one amide bond of the formula "-C(O)-NH-" between them. In this aminolysis reaction, the ester bond of the cationic betaine ester is converted to an amide bond, and the nitrogen atom of the amide bond originates from the free amino group of the polyamino acid or protein hydrolysate. The aminolysis reaction can be illustrated by Scheme 1 below. [ka] During the ceremony, In formula (II), R is any group derived from the alcohol forming the cationic betaine ester, such as alkyl, alkyl substituted with a hydroxyl group, preferably optionally further substituted with a hydroxyl group, 2-hydroxyalkyl. In formula (III), P is the remaining portion of the poly(amino acid) or protein hydrolysate. In equation (III), n is a number of at least 1.

[0038] It will be understood that in formula (III), n can be 2 or more when the poly(amino acid) or protein hydrolysate contains two or more free amino groups. For example, polylysine contains multiple free amino groups within the molecule, and thus, the betaine quaternized polylysine will contain multiple amide groups as shown within the parentheses of formula (III).

[0039] The carbonyl (-C(O)-) of the amide bond shown in formula (III) is derived from the cationic betaine ester and the betaine that originally forms the cationic betaine ester, and the imino group (-NH-) of the amide bond shown in formula (III) is derived from any free amino group of the poly(amino acid) or protein hydrolysate.

[0040] Preferably, the cationic betaine ester involved in the aminolysis reaction is a cationic betaine ester of a monoalcohol such as C 2~5 -monoalcohol or a polyol such as C 2~6 -polyol. Examples of C 2~5 -monoalcohol include, but are not limited to, ethanol, n-propanol, n-butanol, n-pentanol. Examples of C 2~6 -polyol can be a C 2~6 -diol or a C 2~6 -triol. Examples of C 2~6 -polyol 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, etc. Preferably, the C 2~6 -polyol is a vicinal C 2~6 -diol or a C 2~6 -triol. Examples of suitable vicinal polyols are described below in connection with the process for preparing the betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate according to the second aspect of the present invention.

[0041] There are no particular restrictions on the counterions of cationic polymers, i.e., betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysates. Generally, the counter anions may be the same as those of cationic betaine esters used to prepare cationic polymers, and may be, for example, chlorides, sulfates and sulfonates, generally sulfonates, and especially methanesulfonates.

[0042] Betaine quaternized poly(amino acid) can have a degree of modification (DM) ranging from 5% to 60%, for example, 5% to 25%, 5% to 20%, or 5% to 15%, particularly 7% to 15%.

[0043] For betaine quaternized poly(amino acid) compounds, the degree of modification (DM) is determined according to the following formula.

number

[0044] Betaine quaternized protein hydrolysates may have a degree of modification (DM) ranging from 2% to 40%, for example, 3% to 35% or 5% to 30%, particularly 5% to 25%.

[0045] For betaine quaternized protein hydrolysates, the degree of modification (DM) is determined by the o-phthalaldehyde (OPA) method according to the following formula.

number

[0046] Preparation process In a second aspect, the present invention relates to a process for preparing betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysates, comprising subjecting a cationic betaine ester and a poly(amino acids) or protein hydrolysate to an aminolysis reaction to form at least one amide bond of the formula "-C(O)-NH-" between them. The aminolysis reaction occurs between the ester bond in the cationic betaine ester and the free amino group of the poly(amino acids) or protein hydrolysate to form an amide bond. The aminolysis reaction can be illustrated by Scheme 1 above.

[0047] Suitable cationic betaine esters involved in the aminolysis reaction are C 2~5 - Monoalcohols such as monoalcohols or C 2~6 -It may be a cationic betaine ester of polyols such as polyols. 2~5 -Examples of monoalcohols include, but are not limited to, ethanol, n-propanol, n-butanol, and n-pentanol. 2~6 -Polyols are C 2~6 -diol or C 2~6 - It could be a triol. 2~6 -Examples of polyols 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, and 2,3-hexanediol. Preferably, C 2~6 -Polyols are Vicinal C 2~6 -diol 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 preferred.

[0048] Suitable counter anions for cationic betaine esters include, but are not limited to, chlorides, sulfates, and sulfonates, generally sulfonates, and especially methanesulfonates. The counterions generally originate from the acid catalyst for the esterification reaction of betaine.

[0049] Suitable poly(amino acids) and protein hydrolysates are as described above in relation to the first aspect of the present invention. The general descriptions and preferences regarding poly(amino acids) and protein hydrolysates described above also apply herein to the second aspect of the present invention.

[0050] The aminolysis reaction can be carried out under conventional conditions. For example, the reaction can be carried out at a high temperature (e.g., 40°C to 80°C) under an inert atmosphere, optionally in the presence of an organic base such as triethylamine, triethanolamine, or dibutylamine. Cationic betaine esters and poly(amino acids) or protein hydrolysates can be used in a ratio of 0.5:1 to 60:1 moles, preferably 2:1 to 60:1, and more preferably 4:1 to 50:1, calculated as the number of moles of cationic betaine ester to the number of moles of amino acid monomer units.

[0051] In some embodiments, the process for preparing betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysates may further include the step of preparing cationic betaine esters. Therefore, the process for preparing betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysates is (i) A step of providing a cationic betaine ester by subjecting betaine and alcohol to an acid-catalyzed esterification reaction, (ii) A step of subjecting the cationic betaine ester from step (i) and a poly(amino acid) or protein hydrolysate to an aminolysis reaction to form at least one amide bond of the formula "-C(O)-NH-" between them. It may include.

[0052] In those embodiments, the alcohol is C 2~5 - Monoalcohols such as monoalcohols or C 2~6 -It may be a polyol such as a polyol. 2~5 -Examples of monoalcohols include, but are not limited to, ethanol, n-propanol, n-butanol, and n-pentanol. 2~6 -Polyols are C 2~6 -diol or C 2~6 - It could be a triol. 2~6 -Examples of polyols 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, and 2,3-hexanediol. Preferably, C 2~6 -Polyols are Vicinal C 2~6 -diol 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 preferred.

[0053] The acid-catalyzed esterification reaction can be carried out in the presence of any suitable acid catalyst, such as hydrochloric acid, sulfuric acid, hydrofluoric acid, or methanesulfonic acid (MSA), preferably methanesulfonic acid (MSA). Methanesulfonic acid (MSA) is naturally occurring, readily biodegradable, easy to handle, reusable, and less aggressive than conventionally used organic acids such as hydrochloric acid, sulfuric acid, or hydrofluoric acid. Therefore, using methanesulfonic acid for the protonation of the carboxylate group of betaine is known to be beneficial in providing an environmentally friendly route for obtaining betaine esters. An acid-catalyzed esterification reaction in the presence of methanesulfonic acid can be illustrated by Scheme 2 below. [ka] In the formula, ROH represents any of the above alcohols.

[0054] Acid-catalyzed esterification reactions can be carried out under conventional conditions. For example, the reaction may be carried out by heating at a temperature in the range of 120°C to 180°C while applying reduced pressure (e.g., 50 to 100 millibars) and continuously removing the water produced. Alcohols can be used in stoichiometric excess amounts, as they can function as both reactant and solvent without requiring additional solvents. The acid catalyst (e.g., MSA) may be used in a stoichiometric or slightly stoichiometrically excess molar ratio of MSA to betaine, for example, 1:1 to 2:1, preferably 1.1:1 to 1.5:1. Optionally, the cationic betaine ester obtained in the product mixture may be used directly in further aminolysis reactions with poly(amino acids) or protein hydrolysates, or the cationic betaine ester may be used after separation and purification by conventional means.

[0055] The process for preparing betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysates may also be carried out using cationic esters of betaine derivatives so as to yield poly(amino acids) or protein hydrolysates quaternized with the betaine derivative. Suitable betaine derivatives may be N-alkylbetaines, e.g., N-coco-N,N-dimethylammonium glycinate and N-oleyl-N,N-dimethylammonium glycinate, N-alkylamidebetaines, e.g., N-acylaminopropyl-N,N-dimethylammonium glycinate, particularly N-cocoamidopropyl-N,N-dimethylammonium glycinate and N-lauramidopropyl-N,N-dimethylammonium glycinate. The cationic esters of these corresponding betaine derivatives react with the poly(amino acids) or protein hydrolysate via an aminolysis reaction to produce N-alkyl or N-alkylamino derivatives of the betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysates described herein.

[0056] The products of the processes for preparing the betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysates described herein may be reaction mixtures containing the obtained betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysates. These reaction mixtures may be used directly to formulate personal care compositions without purification.

[0057] Surprisingly, the inventors have found that the betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysates described herein are particularly useful in terms of structural rigidity for hair conditioning in terms of combability in both wet and dry conditions, and for hair repair in terms of structural rigidity.

[0058] Personal care composition In a third aspect, the present invention relates to a personal care composition, particularly a hair care composition, comprising a betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate obtained or obtainable from a process according to the first aspect or the second aspect.

[0059] Betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysate 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, and more preferably 1% to 5% by weight, based on the total amount of the personal care composition.

[0060] Personal care compositions generally contain major surfactant components well known in the art. These surfactant components may include at least one of anionic, nonionic, cationic, amphoteric, and bipolar surfactants. In particular, the surfactant components may include a nonionic surfactant, a cationic surfactant, and optionally at least one of anionic, amphoteric, and bipolar ionic surfactants.

[0061] Suitable nonionic surfactants include, for example, aliphatic C 10~22- Alcohol or C 6~20 -The reaction product of alkylphenol and alkylene oxide such as ethylene oxide and / or propylene oxide in an amount of 6 to 60 moles per mole of alcohol or phenol. Alkylamine oxides, fatty acid esters of glycerol and glycol, such as polyethylene glycol, 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, are also preferred.

[0062] The personal care composition may contain 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.

[0063] Suitable cationic surfactants are quaternary ammonium compounds and ester quaternary ammonium compounds, particularly quaternary fatty acid tricanolamine ester salts. Examples of quaternary ammonium compounds include, but are not limited to, alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, and trialkylmethylammonium chloride, such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, docosyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, and tricetylmethylammonium chloride, as well as imidazolium compounds known by the INCI names quaternium-27, quaternium-83, and quaternium-87. The alkyl chain of the above-mentioned surfactants preferably has 10 to 24 carbon atoms. Examples of quaternary ammonium ester compounds include, but are not limited to, quaternary ester salts of fatty acids and triethanolamine, quaternary ester salts of fatty acids and diethanolalkylamine, and quaternary ester salts of fatty acids and 1,2-dihydroxypropyldialkylamine.

[0064] The personal care composition may contain 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.

[0065] Suitable anionic surfactants include, for example, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alcoyl sarcosinates, acyl taurates, acyl isothionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, and α-olefin sulfonates, particularly alkali metal and alkaline earth metal salts, ammonium salts, or alkanolamine salts. Alkyl ether sulfates, alkyl ether phosphates, and alkyl ether carboxylates may have 1 to 10 ethylene oxide and / or propylene oxide units, preferably 1 to 3 ethylene oxide units, in their molecules. Examples of 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 combination thereof. Alkyl sulfates and / or alkyl ether sulfates may be mentioned in particular as anionic surfactants in personal care compositions.

[0066] The personal care composition may optionally contain 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.

[0067] Suitable amphoteric or bipolar surfactants include, for example, alkyl betaines, alkylamidopropyl betaines, alkyl sulfobetaines, alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates or propionates, alkyl amphodiaacetates or dipropionates. Examples of amphoteric surfactants include, but are not limited to, cocodimethylsulfopropyl betaine, lauryl betaine, cocamidopropyl betaine, or sodium cocampopropionate.

[0068] The personal care composition may optionally contain one or more amphoteric or bipolar 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.

[0069] The personal care composition may further contain additional cationic polymers different from betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysates. Suitable additional cationic polymers include, for example, homopolymers or copolymers of esters 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), quaternized ammonium salt polymers of hydroxyethylcellulose modified with trimethylammonium-substituted epoxides (INCI: Quaternium-10, Polyquaternium-67), quaternized depolymerized guar gum derivatives (INCI: Guar Hydroxypropyltrimonium Chloride), amphoteric copolymers (INCI: Polyquaternium-74), quaternized guar derivatives and homopolymers of diallyldimethylammonium chloride (DADMAC) (INCI: Polyquaternium-6).

[0070] The personal care composition may optionally contain one or more additional cationic polymers 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.

[0071] The personal care composition may further contain additives that are acceptable as cosmetics and known in the art, such as emulsifiers, stabilizers, thickeners, viscosity modifiers, solvents, and beneficial agents that can provide good and / or beneficial effects to the base material to be cleaned, such as hair.

[0072] Those skilled in the art can select such optional ingredients suitable for the intended purpose of application, in accordance with the ordinary knowledge in the field of formulation technology for personal care compositions such as shampoos, shower gels, and liquid hand soaps, and the vast amount of literature relating thereto. For example, a personal care composition may contain one or more beneficial agents, such as emollients, moisturizers, skin conditioning agents, or hair conditioning agents, such as volatile silicones, gums, or oils, silicones or non-aminosilicones and mixtures thereof, mineral oil, butyl myristate, cetyl palmitate, decyl oleate, 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, esters, acetylated lanolin alcohol, lanolin, lard, mink oil and animal fats, and behenic acid, palmitic acid, etc. Fatty acids and fatty alcohols including thearic acid, behenyl alcohol, cetyl alcohol, eicosanyl alcohol and isocetyl alcohol, vitamins or their derivatives, such as thiamine, nicotinic acid, biotin, pantothenic acid, choline, riboflavin, vitamin B6, vitamin B12, vitamin B group including pyridoxine, inositol, carnitine, vitamins A, C, D, E, K and their derivatives, such as vitamin A palmitate, and provitamins, such as panthenol (provitamin B 5) Panthenol triacetate and mixtures thereof, antioxidants, radical scavengers, abrasives (natural or synthetic), dyes, hair dyes, bleaches, hair bleaching agents, benzophenone, bornelon, PABA (para-aminobenzoic acid), butyl PABA, cinnamidopropyltrimethylammonium chloride, disodium distylylbiphenyl disulfonate, UV absorbers such as potassium methoxycinnamate, 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, octyldimethyl PABA (padimate O), red petrolatum, and other UV protection agents, antibacterial agents, bacitracin, erythromycin, triclosan, neomycin, tetracycline, chlortetracycline, benzethonium chloride, phenol, parabens Antibiotics, antifungal agents, melanin regulators, tanning accelerators, retinoids such as retinol, kojic acid and its derivatives such as kojic acid and kojic acid dipalmitate, hydroquinone and its derivatives such as hydroquinone and arbutin, vitamins such as tranexamic acid and niacin, vitamin C and its derivatives, azelaic acid, placentia, licorice, chamomile and green tea extracts, etc. (here, retinol, kojic acid and hydro Skin whitening agents such as quinone (preferably), hydroquinone, catechol and its derivatives, ascorbic acid and its derivatives, skin colorants such as dihydroxyacetone, lipid regulators, weight-reducing agents, anti-acne agents, anti-seborrheic agents, anti-aging agents, anti-wrinkle agents, keratolytic agents, anti-inflammatory agents, antibiotics such as tretinoin, isotretinoin, motoretinide, adapalene, tazarotene, azelaic acid, retinol, salicylic acid, benzoyl peroxide, resorcinol, tetracycline and its isomers, anti-inflammatory agents such as erythromycin, ibuprofen, naproxen, hetoprofen, ha Plant extracts such as cinnamon, arnica, Artemisia capillaris, Asarum, calendula, chamomile, nydium, comfrey, fennel, gallnut, hawthorn, houttuynia cordata, St. John's wort, jujube, kiwi, licorice, magnolia, olive, peppermint, philodendron, salvia, and bamboo grass; anti-acne agents such as ketoconazole and imidazole such as erbiol; cooling agents; scar-inducing agents; vascular protective agents; pyrithione salts formed from heavy metals such as zinc, tin, cadmium, magnesium, aluminum, sodium, and zirconium, such as zinc pyrithione.This product contains shale oil and its derivatives such as sulfonic acid shale oil, selenium sulfide, sulfur, salicylic acid, coal tar, povidone-iodine, ketoconazole, dichlorophenylimidazolodioxalane, clotrimazole, itraconazole, miconzol, crimbazole, thioconazole, sulconazole, butoconazole, fluconazole, miconzol nitrate, and other imidazoles, as well as any possible stereoisomers and derivatives thereof such as anthraline, piroctone olamine (octopirox), selenium sulfide, cyclopirox olamine, etc., drugs for reducing dandruff (anti-dandruff agents), seborrheic dermatitis or psoriasis, vitamin D analogs such as calcipotriol, calcitriol and tacaretrol, and vitamin A palmitate. It further contains vitamin A analogs such as vitamin A esters, retinoids, retinol, and retinoic acid; corticosteroids such as hydrocortisone, clobetazone, butyrate, and clobetasol propionate; antiperspirants or deodorants such as aluminum chlorohydrate and aluminum zirconium chlorohydrate; immunomodulators; nutritional supplements; hair removal agents such as calcium thioglycolate, magnesium thioglycolate, potassium thioglycolate, and strontium thioglycolate; hair loss prevention agents; reducing agents for perms; reflective agents such as mica, alumina, calcium silicate, glycol dioleate, glycol distearate, silica, and sodium magnesium fluoridosilicate; essential oils; and fragrances.

[0073] It will be understood that personal care compositions may include water as a vehicle or medium.

[0074] In some embodiments, the personal care composition is a hair care composition such as a shampoo composition and a conditioner composition.

[0075] In a fourth aspect, the present invention relates to a method for hair conditioning or hair repair, comprising treating hair with a hair care composition according to the third aspect.

[0076] In a fifth aspect, the present invention relates to the use of betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysates obtained and / or obtainable from a process according to the first aspect or the second aspect, in personal care compositions, such as hair care compositions, particularly as conditioning agents and / or cationic surfactants.

[0077] Embodiment Various embodiments are listed below. It will be understood that the embodiments shown below can be combined with all aspects and other embodiments within the scope of the present invention.

[0078] Embodiment 1: A betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate having at least one amide bond of the formula "-C(O)-NH-", wherein the "-C(O)-" portion is a carbonyl portion derived from betaine, and the "-NH-" portion is an imino portion derived from any free amino group of the poly(amino acid) or protein hydrolysate.

[0079] Embodiment 2: The betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate according to Embodiment 1, wherein the betaine quaternized poly(amino acid) has 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%.

[0080] Embodiment 3: The poly(amino acid) is poly(basic amino acid), particularly polylysine, in the betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate according to Embodiment 1 or 2.

[0081] Embodiment 4: The polylysine is the betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate described in Embodiment 3, having a K value in the range of 9 to 25, more preferably 10 to 21.

[0082] Embodiment 5: The betaine quaternized protein hydrolysate is the betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate according to Embodiment 1, having 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%.

[0083] Embodiment 6: The protein hydrolysate is a plant protein hydrolysate, soy protein hydrolysate, rice protein hydrolysate, almond protein hydrolysate, wheat protein hydrolysate, pea protein hydrolysate, sunflower protein hydrolysate, wheat gluten protein hydrolysate, corn protein hydrolysate, barley protein hydrolysate, sorghum protein hydrolysate, potato protein hydrolysate, coffee protein hydrolysate, cotton protein hydrolysate, or sesame protein hydrolysate, wherein the betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysate is as described in Embodiment 1 or 5.

[0084] Embodiment 7: The protein hydrolysate has a molecular weight M in the range of 800 to 10,000 daltons, preferably 1,000 to 8,000 daltons. w A betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate according to Embodiment 1, 5, or 6, having the above characteristics.

[0085] Embodiment 8: An aminolysis reaction between a cationic betaine ester and a poly(amino acid) or protein hydrolysate, obtained by an aminolysis reaction to form at least one amide bond of the formula "-C(O)-NH-" between them, the betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate according to any one of Embodiments 1 to 7.

[0086] Embodiment 9: A process for preparing a betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate, comprising subjecting a cationic betaine ester and a poly(amino acid) or protein hydrolysate to an aminolysis reaction to form at least one amide bond of the formula "-C(O)-NH-" between them.

[0087] Embodiment 10: Cationic betaine ester is C 2~5 - Monoalcohols such as monoalcohols or C 2~6 - The process according to Embodiment 9, selected from cationic betaine esters of polyols such as polyols.

[0088] Embodiment 11: The process according to Embodiment 10, wherein the cationic betaine ester is selected from cationic betaine esters of ethanol, n-propanol, n-butanol, and n-pentanol.

[0089] Embodiment 12: Cationic betaine ester is C 2~6 -diol or C 2~6 - Triol, especially Vicinal C 2~6 -diol or C 2~6 - The process according to Embodiment 10, selected from cationic betaine esters of triols.

[0090] Embodiment 13: The process according to Embodiment 12, wherein the cationic betaine ester is selected from cationic betaine esters of glycerol, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 2,3-butanediol, 2,3-pentanediol, and 2,3-hexanediol, with 1,2-propanediol and glycerol being preferred.

[0091] Embodiment 14: The process according to any one of Embodiments 9 to 13, wherein poly(amino acid) is poly(basic amino acid), particularly polylysine.

[0092] Embodiment 15: The process according to Embodiment 14, wherein the polylysine has a K value in the range of 9 to 25, more preferably 10 to 21.

[0093] Embodiment 16: The process according to any one of Embodiments 9 to 13, wherein the protein hydrolysate is a 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, corn protein hydrolysate, barley protein hydrolysate, sorghum protein hydrolysate, potato protein hydrolysate, coffee protein hydrolysate, cotton or sesame protein hydrolysate.

[0094] Embodiment 17: The protein hydrolysate has a molecular weight M in the range of 800 to 10,000 daltons, preferably 1,000 to 8,000 daltons. w The process according to any one of embodiments 9 to 13 and 16, having the following characteristics.

[0095] Embodiment 18: The process according to any one of Embodiments 9 to 17, wherein the betaine quaternized poly(amino acid) has 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 hydrolysate has 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%.

[0096] Embodiment 19: The process according to any one of Embodiments 9 to 18, further comprising the step of subjecting betaine and alcohol to an acid-catalyzed esterification reaction to provide a cationic betaine ester.

[0097] Embodiment 20: The process according to Embodiment 19, wherein the acid-catalyzed esterification reaction is carried out in the presence of methanesulfonic acid.

[0098] Embodiment 21: A personal care composition, particularly a hair care composition, comprising a betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate obtained and / or obtainable from a process according to any one of Embodiments 1 to 8 or any one of Embodiments 9 to 20, or a betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate.

[0099] Embodiment 22: The personal care composition according to Embodiment 21, wherein the betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate is present in the personal care composition in an amount of 0.01% to 10% by weight, preferably 0.1% to 8% by weight, and more preferably 1% to 5% by weight, based on the total amount of the personal care composition.

[0100] Embodiment 23: A personal care composition according to Embodiment 21 or 22, which is a shampoo composition or a conditioner composition.

[0101] Embodiment 24: A method for hair conditioning or hair repair, comprising treating hair with a hair care composition described in any one of Embodiments 21 to 23.

[0102] Embodiment 25: Use of a betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate obtained and / or obtainable by a process according to any one of Embodiments 1 to 8 or any one of Embodiments 9 to 20, in a personal care composition, such as a hair care composition, particularly as a conditioning agent and / or cationic surfactant. [Examples]

[0103] Aspects of the present invention are illustrated in more detail by the following embodiments, which are provided to illustrate specific aspects of the invention and should not be construed as limiting to them.

[0104] I. Preparation example Example 1 47 g of betaine and 42 g of methanesulfonic acid were placed in a 500 ml four-necked flask equipped with a stirrer, internal thermometer, gas inlet tube, and a vacuum-connected condenser with a Dean-Stark receiver. The resulting mixture was stirred at ambient temperature for 1 hour under N2 purge. Next, 147 g of glycerol was added to the mixture, and it was then heated to an internal temperature of 140°C while stirring, and water was continuously separated under reduced pressure of 100 millibars. After 4 hours of distillation, a clear betaine glycerol intermediate was recovered and stored in a sealed container. 1 A conversion rate of approximately 60% was achieved, as determined by 1H NMR.

[0105] 21 g of dried wheat protein hydrolysate (Gluadin® WP), 100 g of glycerol betaine intermediate, and 3 g of triethylamine were placed in a 250 ml three-necked flask equipped with a stirrer, internal thermometer, and gas inlet tube. The resulting mixture was stirred at 60°C for 24 hours under N2 purging. The resulting single-phase brown solution was collected and stored in a sealed container. The degree of modification was approximately 5% based on the o-phthalaldehyde (OPA) method.

[0106] Example 2 21 g of dried wheat protein hydrolysate (Gluadin® WP), 100 g of the betaine intermediate prepared in Example 1, 15 g of sodium bicarbonate, and 2 g of triethylamine were placed in a 250 ml three-necked flask equipped with a stirrer, internal thermometer, and gas inlet tube. The resulting mixture was stirred at 60°C for 24 hours under N2 purging. The single-phase brown solution product was collected and stored in a sealed container. The degree of modification was approximately 21% based on the OPA method.

[0107] Example 3 21 g of dried wheat protein hydrolysate (Gluadin® WP), 100 g of the betaine intermediate prepared in Example 1, and 21 g of triethylamine were placed in a 250 ml three-necked flask equipped with a stirrer, internal thermometer, and gas inlet tube. The resulting mixture was stirred at 60°C for 24 hours under N2 purging. The single-phase brown solution product was collected and stored in a sealed container. The degree of modification according to the OPA method was approximately 43%.

[0108] Example 4 23 g of betaine and 22 g of methanesulfonic acid were placed in a 250 ml four-necked flask equipped with a stirrer, internal thermometer, gas inlet tube, and a vacuum-connected condenser with a Dean-Stark receiver. The resulting mixture was stirred at ambient temperature for 1 hour under N2 purge. Next, 125 g of n-butanol was added to the mixture, and it was then heated to an internal temperature of 130°C while stirring, and water was continuously separated under reduced pressure of 550 millibars. After 4 hours of distillation, a clear butanol betaine intermediate was recovered and used immediately for the next step. 1 As determined by 1H NMR, a conversion rate of approximately 92% was achieved.

[0109] 38.5 g of dried plant protein hydrolysate (Gluadin® Kera-P LM) and 100 g of butanol betaine intermediate were charged under N2 purge into a 250 ml four-necked flask equipped with a stirrer, internal thermometer, gas inlet tube, and vacuum-connected condenser with Dean-Stark receiver. The mixture was stirred at 60°C for 14 hours under reduced pressure of 35 mmbar. The resulting viscous brown slurry was collected and stored in a sealed container. The product was dialyzed using a dialysis bag with a molecular weight cutoff of 1000 Daltons, freeze-dried, and stored in a sealed container. The degree of modification was: 1 Based on 1H NMR, the concentration is approximately 10%. The active ingredient content is 100%.

[0110] Example 5 21 g of ε-polylysine (JNC, lyophilized, Kv=20.2) and 100 g of the betaine intermediate prepared in Example 4 were charged into a 250 ml four-necked flask equipped with a stirrer, internal thermometer, and a vacuum-connected condenser with a Dean-Stark receiver under N2 purge. The resulting mixture was stirred at 140°C for 5 hours under reduced pressure of 35 mmbar. The resulting viscous brown slurry was collected and stored in a sealed container. The product was dialyzed using a dialysis bag with a molecular weight cutoff of 1000 Daltons, lyophilized, and stored in a sealed container. The degree of modification was: 1 Based on 1H NMR, the concentration is approximately 12%. The active ingredient content is 100%.

[0111] Example 6 100 g of an aqueous solution (50 wt%) of L-lysine was placed in a 500 ml four-necked flask equipped with a stirrer, internal thermometer, gas inlet tube, vacuum-connected condenser, and Dean-Stark receiver. The resulting mixture was heated to an internal temperature of 160°C while stirring, and water was continuously separated. After 1 hour of reaction, water was further removed under reduced pressure (670 mg / L). Finally, 264 g of water fraction was recovered, and the high-viscosity polymer was discharged into a silicone container as quickly as possible while it was still hot and fluid. The K value of the branched-chain lysine homopolymer was measured to be 11.0.

[0112] 27 g of branched-chain lysine homopolymer, 100 g of the betaine intermediate prepared in Example 1, and 4 g of dibutylamine were placed in a 250 ml three-necked flask equipped with a stirrer, internal thermometer, gas inlet tube, vacuum-connected condenser, and Dean-Stark receiver under N2 purging. The mixture was stirred at 125°C for 3 hours under reduced pressure of 10 mmbar. The resulting single-phase, brownish, viscous solution was collected and stored in a sealed container. 1 The degree of modification based on 1H NMR is approximately 51%. The active ingredient content is 29.5%.

[0113] Comparative Example 1 68 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quab reagent), 40 g of branched-chain polylysine homopolymer prepared in Example 6, and 100 g of DI water were placed in a 500 ml four-necked flask equipped with a stirrer, internal thermometer, gas inlet tube, and condenser. The reaction was allowed to proceed at room temperature for 16 hours, during which time the pH was maintained at 8 by controlled addition of 48 wt% NaOH aqueous solution using a Systag FlexyCube automated laboratory reactor control unit equipped with a peristaltic pump and a pH probe with a high-temperature electrolyte. The polymer was then precipitated with an excess amount of methanol (weight ratio 1:10) and filtered. The precipitation step was repeated three times, and the product was dried in a vacuum oven at 40°C for 16 hours to obtain the final product. 1 The degree of polymer modification (DM), as measured by 1H NMR, is 88%.

[0114] II. Hair care performance test II.1 Conditioning performance related to combability Physical measurement of the combing force applied to hair strands allows for objective measurement results regarding how products such as hair shampoos or conditioners function in terms of conditioning and detangling effects. In pre- and post-design, the decrease in combing force in wet and dry conditions was measured to demonstrate effectiveness.

[0115] Before measurement, the hair bundles were untangled until no loops or coils remained. Next, the hair bundles were placed in clamps and combed through a test comb, which is part of a tensile testing machine. The decrease in combing force was expressed as a percentage and calculated from the ratio of the force of the treated hair bundle to the blank (untreated hair bundle). Each formulation was tested using wet and dry combing equipment with hair bundles from five Caucasians provided by IHIP. 1g of 12cm long hair was used for the wet combing test, and 2g of 15cm long hair was used for the dry combing test.

[0116] The first step in the investigation of dry combability is the preparation of hair bundles for baseline measurement. Preparation includes 12 hours of hair bundle equilibration at room temperature of 23°C and relative humidity of 50%. Next, measurements were taken of untreated hair bundles. The hair bundles were treated with each cleaning compound shown in Table 1 at a rate of 0.25 g per gram of hair and incubated for 5 minutes. After that, the hair bundles were thoroughly rinsed with tap water at room temperature for about 1 minute. This treatment with the cleaning compound was repeated. The hair bundles were dried and the dried hair bundles were equilibrated under the above conditions. Next, combability measurements were taken.

[0117] The conditioning performance of each cleaning compound was evaluated by measuring the change in work or energy associated with combing hair strands and recording it as residual combing work. Combing work was calculated by integrating the recorded force-displacement curve. Combing force was measured using a Zwicki Z2.5 dynamic testing machine (Zwick Roell, Germany) before and after treatment with the test compound.

[0118] The amount of remaining combing work is calculated using the following formula. Residual combing work = (Combing work after processing) / (Combing work before processing) × 100%

[0119] [Table 1]

[0120] II.1 Hair repair performance Hair repair performance was investigated by measuring the enthalpy and temperature of keratin modification using differential scanning calorimetry (DSC). Enthalpy is a measure of the α-helix substance content in keratin and is an indicator of the structural rigidity of hair.

[0121] Before measurement, untreated and bleached hair bundles were treated with 0.25 g of cleansing solution per gram of hair and incubated for 5 minutes. The bundles were then thoroughly rinsed with 38°C tap water for approximately 1 minute. The bundles were dried and then equilibrated (22°C, 50% humidity, 24 hours). Before applying the corresponding repair formulation, the bundles were rinsed with 38°C water for 1 minute to remove excess water. The bundles were then treated with 0.125 g of the corresponding repair formulation per gram of hair, brushed 5 times on both sides, and incubated for 5 minutes. The bundles were then thoroughly rinsed with 38°C tap water for approximately 1 minute. The bundles were dried and then equilibrated.

[0122] For DSC analysis, a DSC Q100 (TA Instruments, Eschborn, Germany) was used in combination with a large-capacity pan (100 μL, 30 bar pressure resistance). Hair bundles were equilibrated at 22°C and 50% RH for 24 hours to normalize the water content, and then cut into small pieces. The denaturation temperature of human hair protein was measured using a heating rate of 2 K / min, as described by Wortmann et al. (J.Appl.Polym.Sci.48(1993)137).

[0123] Enthalpy is calculated using software provided by the manufacturer, and the enthalpy recovery rate is calculated as follows: Enthalpy recovery rate (%) = [(Enthalpy プラセボ - Enthalpy サンプル ) / (enthalpy バージン(未処理) - Enthalpy プラセボ )] × 100%

[0124] [Table 2]

[0125] Formulations F7 and F9, containing betaine quaternized protein hydrolysate and betaine quaternized polylysine, respectively, exhibit superior restorative effects on damaged (i.e., bleached) hair, which are far superior to the corresponding formulations F6 and F8, containing unquaternized protein hydrolysate and polylysine, respectively.

[0126] II.3 Hair Conditioning Performance Related to Appearance First, the hair was bleached using the following protocol: 100g of bleach mixture was prepared from 33.3g of bleach powder (Schwarzkopf Igora) and 66.7g of developer (Schwarzkopf Igora 12%). The bleach mixture was applied to 20g of hair (bundles of 10 strands) using a hair dyeing brush and left for 30 minutes. The hair bundles were then rinsed for 5 minutes, followed by combing and air drying. The bleached hair bundles were rinsed for 1 minute. Next, 0.5g of the test formulation (e.g., 10% of the active ingredient in desalinated water at pH 4) was applied to the hair bundles using a hair dyeing brush. After exposure for 3 minutes, the hair bundles were rinsed for 1 minute. The hair bundles were combed while wet and again after drying. The hair bundles were then visually evaluated.

[0127] [Table 3]

[0128] III. Biodegradability of Polymers Biodegradation was tested using the OECD 301F manometer respiration assay in triple replicates. 30 mg / mL of the test substance was inoculated into wastewater collected from the Mannheim Wastewater Treatment Plant and incubated in a sealed flask at 25°C for 56 days. Oxygen consumption during this period was measured as a change in pressure within the flask using OxiTop C (WTW). The generated CO2 was absorbed using a NaOH solution. The amount of oxygen consumed by the microbial community during the biodegradation of the test substance was corrected using a blank and expressed as a percentage of the ThOD (Theoretical Oxygen Demand). The percentage indicates the degree of biodegradation. The test results are summarized in Table 3.

[0129] [Table 4]

[0130] The betaine quaternized poly(amino acids) and betaine quaternized protein hydrolysates according to the present invention exhibit better biodegradability than the corresponding Quab quaternized poly(amino acids) and Quab quaternized protein hydrolysates (Embodiments 1-3 vs. dialyzed Gluadin® WQTP and Embodiment 6 vs. Comparative Example 1). It can also be found that betaine quaternization does not substantially reduce the biodegradability of the poly(amino acids) and protein hydrolysates (Embodiments 1-3 vs. dialyzed Gluadin WP, Embodiment 4 vs. Gluadin® Kera-P LM, Embodiment 5 vs. ε-polylysine).

[0131] Although the present invention has been described herein with reference to specific embodiments, it should be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It will be apparent to those skilled in the art that various modifications and variations of the methods and apparatus of the present invention can be made without departing from the spirit and scope of the invention. Accordingly, the present invention is intended to include modifications and variations that fall within the scope of the appended claims and their equivalents.

Claims

1. A betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate having at least one amide bond of the formula "-C(O)-NH-", wherein the "-C(O)-" portion is a carbonyl portion derived from betaine, and the "-NH-" portion is an imino portion derived from any free amino group of the poly(amino acid) or protein hydrolysate.

2. The betaine quaternized poly(amino acid) according to claim 1, wherein the betaine quaternized poly(amino acid) has 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%.

3. The poly(amino acid) is poly(basic amino acid), particularly polylysine, as described in claim 1 or 2, for betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate.

4. The polylysine has a K value in the range of 9 to 25, more preferably 10 to 21, as described in claim 3, for betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate.

5. The betaine quaternized protein hydrolysate has 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%, according to claim 1, the betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate.

6. The betaine quaternized poly(amino acids) or betaine quaternized protein hydrolysate according to claim 1 or 5, wherein the protein hydrolysate is a plant protein hydrolysate, soy protein hydrolysate, rice protein hydrolysate, almond protein hydrolysate, wheat protein hydrolysate, pea protein hydrolysate, sunflower protein hydrolysate, wheat gluten protein hydrolysate, corn protein hydrolysate, barley protein hydrolysate, sorghum protein hydrolysate, potato protein hydrolysate, coffee protein hydrolysate, cotton protein hydrolysate, or sesame protein hydrolysate.

7. The protein hydrolysate has a molecular weight M in the range of 800 to 10,000 daltons, preferably 1,000 to 8,000 daltons. ｗ A betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate according to any one of claims 1, 5, or 6.

8. An aminolysis reaction between a cationic betaine ester and a poly(amino acid) or protein hydrolysate, obtained by an aminolysis reaction for forming at least one amide bond of the formula "-C(O)-NH-" between them, according to any one of claims 1 to 7.

9. A process for preparing a betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate, comprising subjecting a cationic betaine ester and a poly(amino acid) or protein hydrolysate to an aminolysis reaction to form at least one amide bond of the formula "-C(O)-NH-" between them.

10. The cationic betaine ester is C ２～５ - Monoalcohols such as monoalcohols or C ２～６ - The process according to claim 9, selected from cationic betaine esters of polyols such as polyols.

11. The process according to claim 10, wherein the cationic betaine ester is selected from cationic betaine esters of ethanol, n-propanol, n-butanol, and n-pentanol.

12. The cationic betaine ester is C ２～６ -diol or C ２～６ - Triol, especially Vicenal C ２～６ -diol or C ２～６ - The process according to claim 10, selected from cationic betaine esters of triols.

13. The process according to claim 12, wherein the cationic betaine ester is selected from cationic betaine esters of glycerol, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 2,3-butanediol, 2,3-pentanediol, and 2,3-hexanediol, with 1,2-propanediol and glycerol being preferred.

14. The process according to any one of claims 9 to 13, wherein the poly(amino acid) is poly(basic amino acid), particularly polylysine.

15. The process according to claim 14, wherein the polylysine has a K value in the range of 9 to 25, more preferably 10 to 21.

16. The process according to any one of claims 9 to 13, wherein the protein hydrolysate is a plant protein hydrolysate, soy protein hydrolysate, rice protein hydrolysate, almond protein hydrolysate, wheat protein hydrolysate, pea protein hydrolysate, sunflower protein hydrolysate, wheat gluten protein hydrolysate, corn protein hydrolysate, barley protein hydrolysate, sorghum protein hydrolysate, potato protein hydrolysate, coffee protein hydrolysate, cotton or sesame protein hydrolysate.

17. The protein hydrolysate has a molecular weight M in the range of 800 to 10,000 daltons, preferably 1,000 to 8,000 daltons. ｗ The process according to any one of claims 9 to 13 or 16, comprising:

18. The process according to any one of claims 9 to 17, wherein the betaine quaternized poly(amino acid) has 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 hydrolysate has 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%.

19. The process according to any one of claims 9 to 18, further comprising the step of subjecting betaine and alcohol to an acid-catalyzed esterification reaction to provide the cationic betaine ester.

20. The process according to claim 19, wherein the acid-catalyzed esterification reaction is carried out in the presence of methanesulfonic acid.

21. A personal care composition, particularly a hair care composition, comprising a betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate as described in any one of claims 1 to 8, or a betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate obtained and / or obtainable from a process described in any one of claims 9 to 20.

22. The personal care composition according to claim 21, wherein the betaine quaternized poly(amino acid) or betaine quaternized protein hydrolysate is present in the personal care composition in an amount of 0.01% to 10% by weight, preferably 0.1% to 8% by weight, and more preferably 1% to 5% by weight, based on the total amount of the personal care composition.

23. The personal care composition according to claim 21 or 22, which is a shampoo composition or a conditioner composition.

24. A method for hair conditioning or hair repair, comprising treating hair with a hair care composition according to any one of claims 21 to 23.

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

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