WO2021151828A1

WO2021151828A1 - The use of a polylysine for increasing the gloss of hair

Info

Publication number: WO2021151828A1
Application number: PCT/EP2021/051597
Authority: WO
Inventors: Anna Maria MÜLLER-CRISTADORO; Monika Barbenheim; Daniela Prinz; Zuebeyde DOGAN; Catherine Weichold
Original assignee: Basf Se
Priority date: 2020-01-30
Filing date: 2021-01-25
Publication date: 2021-08-05

Abstract

The present invention relates to the use of a branched polylysine or of a branched polylysine, in which 1 to 80 % of the amino groups present in the branched polylysine are derivatized so that they bear one or two substituents, wherein these substituents are selected from the group consisting of acyl groups having 6 to 24 C-atoms, substituents having the formula -CH2- CH(OH)-R or the formula -CHR-CH2(OH), wherein R is an alky moiety with 2 to 20 C-atoms, substituents having the formula -C(=O)-NH-R, wherein R is an alky moiety with 2 to 20 C- atoms, substituents of the formula -CH2-CH2-C(=O)OR1, wherein R1 is an alkyl group having 6 to 24 C-atoms, substituents formed by the reaction of the amino groups present in the branched polylysine with polyisobutylene succinic anhydride (PIBSA), and mixtures thereof, for increasing the gloss of hair compared to untreated hair.

Description

The Use of a Polymer for Increasing the Gloss of Hair The present invention relates to the use of a branched polylysine or of a branched polylysine, in which 1 to 80 % of the amino groups present in the branched polylysine are derivatized so that they bear one or two substituents, wherein these substituents are selected from the group consisting of acyl groups having 6 to 24 C-atoms, substituents having the formula -CH₂- CH(OH)-R or the formula -CHR-CH₂(OH), wherein R is an alky moiety with 2 to 20 C-atoms, substituents having the formula -C(=O)-NH-R, wherein R is an alky moiety with 2 to 20 C- atoms, substituents of the formula -CH₂-CH₂-C(=O)OR¹, wherein R¹ is an alkyl group having 6 to 24 C-atoms, substituents formed by the reaction of the amino groups present in the branched polylysine with polyisobutylene succinic anhydride (PIBSA), and mixtures thereof, for increasing the gloss of hair compared to untreated hair. The surface of hair, especially of human hair, can be damaged by hair treatment, e. g. by bleaching, by heat treatments and UV-irradiation. This leads not only to more hair breakage, but also to a matt appearance of the hair. Therefore, there is a need for substances that enhance the gloss appearance by a glossing effect. Methods to measure the degree of hair gloss (also sometimes described as hair shine) focus largely either on optical measuring devices with dedicated software, or on consumer perception evaluations. In both cases treated hair tresses are fixed on cylinders, which are then placed in a so-called gloss-box (black box which avoids light reflection from additional surfaces). Inside the gloss-box the hair tresses are illuminated with a daylight lamp and the effect recorded either with a polarization camera or ranked by panelists. Often hair gloss is achieved via whole formulations / combinations of ingredients. Currently, there are very limited single ingredients available on the market, for which improved gloss performance is directly claimed. These ingredients are mostly silicone-based and include amodimethicone, phenyltrimethicone, aminopropyl phenyl trimethicone, and diphenylsiloxy phenyl trimethicone. For some emollients a positive effect on hair gloss is also claimed, e.g. PPG-3 caprylyl ether. Problems connected with these options are low level of naturalness and sustainability on the one hand. On the other hand, the sensorial perception is often negatively affected, with a greasy look / feel and build-up effect. Single ingredients which are both natural- based and have a purely positive impact on the overall sensorial experience, including hair gloss, have long been the focus of research. In the following, key examples of state of the art for hair gloss are listed: EP 1100442 describes the use of high refractive index non-volatile polysiloxane fluids mixed with suitable non-volatile spreading agents. This type of chemistry is widely used in hair care products claiming hair gloss, in particular hair serums, whose primary purpose is to enhance hair shine. Another more recent example of the use of non-volatile polysiloxane fluids is EP 3 162408 A1, where the polysiloxane fluid is part of a formulation also containing a polyether siloxane copolymer as co-surfactant. In EP 2433615 A1 the composition of a cosmetic product to promote hair shine is presented, with the product most importantly containing large amounts of sunflower glycerides together with a defined amount of silica. The use of silica can be presumed to be to adjust the level of shininess versus oiliness. EP 1543814 A1 describes the use of ethoxylated esters such as PEG/PPG-8/3 Laurate in silicone-free hair care compositions providing long-lasting shine. US6190647 B1 describes the use of copolymers, using an ethylene derivative as one of the monomers, in hair treatment compositions for increasing the luster of hair. As these compositions also always contain polysiloxanes, it is not clear whether the claimed copolymers are actually the primary responsible for any enhanced hair luster. In WO 2017/075306 A1 a method is provided, where are leave-on composition comprising an O/W polysiloxane emulsion with specific viscosity and pH is applied by spraying to hair, the emulsion having a defined particle size and leading to film formation on the hair fibers. Film formation on surfaces can be connected to the level of shine these surfaces appear to have. WO 2010/127923 A2 relates to copolymers e.g. based on N-vinylpyrrolidone and/or N- vinylcaprolactam being used in aerosol hairspray or hair foam formulations, and suitable for temporarily shaping hair and providing shine. EP 1064918 A1 describes the use of metals, metal alloys, various metalloids etc. in hair care compositions with the independent claim of giving shine to hair. Often hair gloss is achieved via whole formulations / combinations of ingredients. Currently, there are very limited single ingredients available on the market, for which improved gloss performance is claimed. These ingredients are mostly silicone-based and include amodimethicone, phenyltrimethicone, aminopropyl phenyl trimethicone, and diphenylsiloxy phenyl trimethicone. For some emollients a positive effect on hair gloss is also claimed, e.g. PPG-3 caprylyl ether. Problems connected with these options are low level of naturalness and sustainability on the one hand. On the other hand, the sensorial perception is often negatively affected, with a greasy look / feel and build-up effect. Single ingredients which are both natural- based and have a purely positive impact on the overall sensorial experience, including hair gloss, have long been the focus of research. Lysine is an amino acid. There are two enantiomers of lysine, L-lysine and D-lysine. Lysine has two amino groups, one at the alpha-position, one at the epsilon-position. Linear L- polylysine is produced by natural fermentation and it is referred to as epsilon-Polylysine or Ɛ- Polylysine. This fermentation can be carried out with bacteria strains of the genus Streptomyces, e. g. Streptomyces albulus. Branched polylysine is formed when both amino-groups of lysine (alpha and epsilon) react in a polycondensation reaction with the carboxylic acid group of lysine. WO 2007/060119, US 201/0123148, and WO 2016/062578 disclose a process for making branched polylysine. Derivatives of branched polylysine are also disclosed. Inter alia, polylysine reacted with saturated or unsaturated long-chain carboxylic acids is disclosed (WO 2016/062578, page 9, lines 29 to 30). WO 2013/013889 discloses the use of hyperbranched polylysine as shale inhibitor. The use of linear (not branched) polylysine in hair care applications is known. EP 2036536 A1 discloses the use of polyamines in conditioning applications (hair care (curly hair) and antifrizz application). polylysine is mentioned. EP 1563826 A1 describes the use of polylysine in spray applications (having a conditioner effect). JP 62221616 describes the use of polylysine in hair cosmetic applications having a conditioning effect. The material obtained by bacteria is linear and in epsilon form. JP 2007169192 and JP 2007153791 describe hair cosmetics and shampoo formulations respectively with polylysine or its salt in combination with quaternized amines, again for conditioning applications. WO 2015/128566 describes a treatment which consists in the application of polyamines (polylysine is mentioned) to keratin fibers and thereafter the application of an activated ester to the creatine fibers. Repair effects are mentioned. US 20090074700 describes the use of polyamines (polylysine is mentioned) together with acids and insoluble material to impart shine on hair. WO 2019/175041 discloses the use of a branched polylysine or of a branched polylysine, in which 1 to 80 % of the amino groups present in the branched polylysine are derivatized so that they bear one or two substituents, for bringing about a hair repair effect. Parameters to characterize branched polylysine (apart from the differentiation between L- and D-lysine) are the average molar mass, either the number average Mn or the weight average Mw, the polydispersity PD = Mw/Mn (measured via gel permeation chromatography), the degree of branching, and the amine number. These parameters can be determined by methods known in the art and/or as disclosed in WO 2016/062578. In general, it is assumed that the backbone of branched polylysine as well as the side chains of branched polylysine both have amide groups formed by alpha-amino groups and by epsilon amino-groups. The relative amount of alpha- and epsilon amide groups in the backbone and in the side chains is not known. The problem underlying the present invention is to provide a substance or a composition having a hair glossing effect. Preferably the said substance or composition should be fully sustainable, i. e. should not have the disadvantages of known substances or compositions having a hair glossing effect. This problem is solved by the use according to clam 1. The subject-matters of the dependent claims are preferred embodiments of the present invention. Branched polylysine according to the present invention is a polylysine that comprises at least one repeating unit per polylysine-molecule which is a lysine-moiety and which is bound to another lysine-moiety via its alpha-amino group and to yet another lysine-moiety via its epsilon- amino group. A cosmetically acceptable solvent according to the present invention can be any cosmetically acceptable solvent. The person skilled in the art knows which substances can be used as cosmetically acceptable solvent. Numerous documents and databases are available as references to identify cosmetically acceptable solvents, e. g. the latest edition of the International Cosmetic Ingredient Dictionary and Handbook published by the Personal Care Products Council or the Cosmetic Ingredient Database cosing on the internet pages of the European Commission. Preferably, the cosmetically acceptable solvent is water or ethanol or a mixture of water and ethanol. “A composition suitable for treating hair” according to the present invention can be any composition suitable for treating hair. It can be a composition suitable for cleansing hair, especially a shampoo, it can be a composition for conditioning hair (a conditioner), it can be a mask. In the branched polylysine according to the present invention and in the branched polylysine according to the present invention in which amino groups are derivatized the lysine repeating units can be derived from L-lysine or from D-lysine or from a mixture of L- and D-lysine, especially from a racemic mixture. Preferably these repeating units are derived from L-lysine. The branched polylysine to be used according to the present invention and the branched polylysine to be used according to the present invention, in which amino groups are derivatized (in the latter case based on/calculated with respect to the polylysine framework, without derivatization) typically have the following properties: • The number average of the molar mass Mn is 300 to 5000 g/mol. • The weight average of the molar mass MW is 500 to 10000 g/mol, preferably 1000 to 5000 g/mol. • The polydispersity PD (= Mw/Mn) is 1.2 to 4, preferably 1.2 to 3, more preferably 1.2 to 2.5 • The amine number is 350 to 600 mgKOH/g, preferably 350 to 500 mgKOH/g. • The degree of branching DB is 0.15 to 0.5, preferably 0.2 to 0.35, more preferably 0.2 to 0.3. The definition of amine number and of “degree of branching” DB can be found in the examples section of the present text. The branched polylysine according to the present invention can be made by heating a mixture comprising lysine and water, especially as described in WO 2016/062578. The branched polylysine in which 1 to 80 %, preferably 1 to 30 %, more preferably 1 to 20 %, and especially 4 to 10 %, of the amino groups present in the branched polylysine are derivatized so that they bear one or two substituents, as it is defined in the claims of the present text, can be made by reacting branched polylysine with carboxylic acids, esters of carboxylic acids, anhydrides of carboxylic acids, epoxy compounds, isocyanates, or with compounds obtainable via Michael addition of amino groups to Michael donor fatty chains (e. g. acrylates or methacrylates), or with PIBSA (polyisobutylene succinic anhydride). Typically, the branched polylysine, in which 1 to 80 %, preferably 1 to 30 %, more preferably 1 to 20 %, and especially 4 to 10 %, of the amino groups present in the branched polylysine are derivatized so that they bear one or two substituents, as it is defined in the claims of the present text, has the following properties: • The number average of the molar mass Mn is 300 to 5000 g/mol. • The weight average of the molar mass MW is 500 to 10000 g/mol, preferably 1000 to 5000 g/mol. • The polydispersity PD (= Mw/Mn) is 1.2 to 4, preferably 1.2 to 3, more preferably 1.2 to 2.5 • The amine number is 350 to 600 mgKOH/g, preferably 350 to 500 mgKOH/g. • The degree of branching DB is 0.15 to 0.5, preferably 0.2 to 0.35, more preferably 0.2 to 0.3. The definition of amine number and of “degree of branching” DB can be found in the examples section of the present text. According to the present invention the surfactant can be any surfactant. It can be selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, a zwitterionic surfactant, and mixtures thereof. The surfactants according to the present invention can be selected amongst the surfactants described in US 2017/0333734 (BASF internal reference PF 77681 US02) in paragraphs [0029] to [0032]. Further cosmetically acceptable ingredients different from the branched polylysine, different from the branched polylysine in which amino groups are derivatized, and different from the surfactant, can be any cosmetically acceptable ingredients known to the person skilled in the art. These further cosmetically acceptable ingredients can be selected amongst the ingredients described in US 2017/0333734 (BASF internal reference PF 77681 US02) in paragraphs [0033] to [0066]. Furthermore, numerous documents and databases are available as references to identify cosmetically acceptable ingredients, e. g. the latest edition of the International Cosmetic Ingredient Dictionary and Handbook published by the Personal Care Products Council or the Cosmetic Ingredient Database cosing on the internet pages of the European Commission.

Examples Methods and Definitions Concentrations % means % by weight, unless defined differently. Degree of Branching (DB) The degree of branching (DB) of branched polylysine is defined according to H. Frey et al., Acta Polymer., 48, pages 30 to 35 (1997) as DB [%] = 100 x 2D/(2D+L) wherein D denotes the fraction of dendritic units and L denotes the fraction of linear units in the sample that is concerned. DB was determined by ¹H NMR. Amine Number The amine number (unit: mg KOH/g), also referred to as amino number, was determined by titration. It was determined as described in WO 2016/062578 according to the formula given on page 13 of WO 2016/062578: Calculation:

with Amine number = Fraction of total amine, calculated as mg KOH/g V_P = Consumption of standard solution up to the inflection point [ml] V_B = Consumption of standard solution in blank value titration [ml] t = titer of the standard solution c = concentration of the standard solution [=0.1 mol/l] 56.1 = molar weight of KOH [g/mol] E = weight of sample taken [g]. Average Molar Mass Mn (number average) and Mw (weight average) Mn and Mw were determined by gel permeation chromatography as described in WO 2016/062578 (see page 12 of WO 2016/062578, wherein trifluoroacete means trifluoroacetic acid):

Mw and M_nwere determined by size exclusion chromatography under the following con- ditions:

Solvent: 0.1% (w/w) trifluoroacetate, 0.1 M NaCI in distilled water Flow: 0.8 ml/min Injection volume: 100 μl

Column material: hydroxylated polymethacrylate (TSKgel G3000PWXL)

Calibration: poly(2-vinylpyridine) standards in the molar mass range from 839 to 1.020.000 g/mole (from PSS, Mainz, Germany)

Polydispersity

PD is defined as PD = Mw/Mn

Experiments Carried Out

Example 1 : branched polylysine 1

1700 g of a 50% aqueous solution of L-Lysine were placed in a 2I four-necked flask equipped with a stirrer a condensation column, a thermometer and a nitrogen inlet. The L-Lysine solution was heated to the boiling point. Then the temperature of the external heat source was increased according to the following profile: 1 h at 150 °C, 1h at 160, 1h at 170 and 1 h at 180 °C while water was distilled off. The pressure was then decreased to 200 mbar while the external heat source was maintained at 180 °C and the reaction for circa 1 + ½ hours continued under vacuum (200 mbar). The warm reaction melt was collected in an aluminum vessel. At room temperature, a solid material was obtained.

The polymer was characterized by gel permeation chromatography, degree of branching and amino number:

Mn: 2150 g/mol Mw: 3650 g/mol PD: 1.7 degree of branching measured via ¹H-NMR = 0.28 amino number: 410 mg KOH/g Example 2: branched polylysine 2 1700 g of a 50% aqueous solution of L-Lysine were placed in a 2l four-necked flask equipped with a stirrer a condensation column, a thermometer and a nitrogen inlet. The L-Lysine solution was heated to the boiling point. Then the temperature of the external heat source was increased according to the following profile: 1 h at 150 °C, 1h at 160, 1h at 170 and 1 h at 180°C while water was distilled off. The pressure was then decreased to 200 mbar while the external heat source was maintained at 180 °C and the reaction for circa 2 hours continued under vacuum (200 mbar). The warm reaction melt was collected in an aluminum vessel. At room temperature, a solid material was obtained. The polymer was characterized by gel permeation chromatography, degree of branching and amino number: Mn: 2070 g/mol Mw: 4070 g/mol PD: 2 degree of branching measured via ¹H-NMR = 0.3 amino number: 366 mgKOH/g Example 3: branched polylysine modified with oleic acid (modification of 10 % of the amino end groups with oleic acid) 50 g of branched polylysine, made according to the procedure described in example 1 (not dissolved in water) was melted at 120 °C and 10,25 g oleic acid were added under stirring. The pressure was then decreased to 200 mbar while the external heat source was maintained at 180 °C and the reaction continued for circa 1 hour under vacuum (200 mbar). At room temperature, a solid material was obtained. Application Examples Application method (see table on the following pages): X g test substance Y g additive Ad 100 g: demineralized water or ethanol as solvent (I. e.: The total amount of test substance, additive and solvent was 100 g in each case.) The components were mixed together to give a homogeneous blend.20 μl of this mixture were then applied to a hair strand using a hair dye brush, brushing for 1 minute. The hair strand had a weight of 2 g and was either virgin Caucasian hair or medium-bleached Caucasian hair. Subsequently, the hair strand was clamped on a metal roll and evaluated in the gloss box against correspondingly prepared hair strands, which were either untreated or treated with benchmarks. As positive benchmark the ingredient Shineblend Max from Innospec was used, while shea butter (Cetiol^® SB45) was the negative benchmark (both benchmarks were applied as a 50 % solution in ethanol). Results of hair gloss evaluation on virgin hair (3 panelists):

The results show that treatment with branched polylysine results in a gloss enhancing effect, which is superior to that of the selected positive benchmark, Shineblend Max. The effect of branched polylysine is also higher than that achieved with linear epsilon-polylysine (comparative example 12). The gloss effect of the branched polylysine modified with oleic acid (comparative examples 8 and 9) is not as good as that of the underivatized branched polylysine and strongly depends on the solvent used. Sensorial comparisons (11 panelists): Formulation 2017-94-1 Formulation 2017-94-2 Formulation 2017-94-4 30 % branched polylysine 2 10 % branched polylysine 2 50 % Shineblend Max 70 % ethanol 40 % argan oil 50 % ethanol 50 % ethanol The results of the sensorial comparisons in the sensorial diagram (Fig. 1) confirm that formulations containing branched polylysine are significantly superior to the silicone positive benchmark (formulation 2017-94-4), both in terms of gloss effect and with respect to the general acceptance by the panelists.

Claims

1. The use of a branched polylysine or of a branched polylysine, in which 1 to 80 % of the amino groups present in the branched polylysine are derivatized so that they bear one or two substituents, wherein these substituents are selected from the group consisting of

• acyl groups having 6 to 24 C-atoms,

• substituents having the formula -CH₂-CH(OH)-R or the formula -CHR-CH₂(OH), wherein R is an alky moiety with 2 to 20 C-atoms,

• substituents having the formula -C(=O) -NH-R, wherein R is an alky moiety with 2 to 20 C-atoms,

• substituents of the formula -CH₂-CH₂-C(=O)OR¹ wherein R¹ is an alkyl group having 6 to 24 C-atoms,

• substituents formed by the reaction of the amino groups present in the branched polylysine with polyisobutylene succinic anhydride (PIBSA),

• and mixtures thereof, for increasing the gloss of hair compared to untreated hair.

2. The use according to claim 1 , wherein the branched polylysine or the branched polylysine, in which 1 to 80 % of the amino groups present in the branched polylysine are derivatized, is comprised in a composition, wherein the composition further comprises a cosmetically acceptable solvent, preferably water or ethanol or a mixture of water and ethanol, and wherein the branched polylysine or the branched polylysine, in which 1 to 80 % of the amino groups present in the branched polylysine are derivatized, is comprised in this composition in a concentration of 2 - 70 % by weight, preferably 5 - 60 % by weight, more preferably 10 to 50 % by weight.

3. The use according to claim 1 or 2, wherein the branched polylysine or the branched polylysine, in which 1 to 80 % of the amino groups present in the branched polylysine are derivatized, are comprised in a composition, wherein the composition further comprises at least one surfactant selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, a zwitterionic surfactant, and mixtures thereof.

4. The use according to claim 2 or 3, wherein the composition further comprises one or more further cosmetically acceptable ingredients different from the branched polylysine, different from the branched polylysine, in which amino groups are derivatized, different from the solvent, and different from the surfactant.

5. The use according to any of claims 2 to 4, wherein the composition is a composition suitable for cleansing hair or a composition suitable for conditioning hair.

6. The use according to any of claims 2 to 5, wherein the composition comprises 2 – 70 % by weight, preferably 5 – 60 % by weight, more preferably 10 to 50 % by weight of the branched polylysine or of the branched polylysine, in which 1 to 80 % of the amino groups present in the branched polylysine are derivatized, 0.1 to 25 % by weight, preferably 0.5 to 20 % by weight, more preferably 1 to 20 % by weight of the surfactant, and ad 100 % by weight solvent plus the one or more further cosmetically acceptable ingredients.

7. The use according to any of claims 1 to 6, wherein the hair is human hair.

8. The use according to any of claims 1 to 6, wherein a branched polylysine in which amino groups are derivatized is used, wherein the substituents are selected from the group consisting of • acyl groups having 10 to 20 C-atoms, more preferably 18 C-atoms, • substituents having the formula -CH₂-CH(OH)-R or the formula -CHR-CH₂(OH), wherein R is an alky moiety with 2 to 20 C-atoms, • substituents having the formula -C(=O)-NH-R, wherein R is an alky moiety with 2 to 20 C-atoms, • substituents of the formula -CH₂-CH₂-C(=O)OR¹, wherein R¹ is an alkyl group having 6 to 24 C-atoms, • substituents formed by the reaction of the amino groups present in the branched polylysine with polyisobuthylene succinic anhydride (PIBSA), • and mixtures thereof.

9. The use according to claim 7, wherein the substituents are acyl groups having 6 to 24 C- atoms, preferably acyl groups having 10 to 20 C-atoms, more preferably 18 C-atoms.

10. The use according to claim 7 or 8, wherein 1 to 30 %, preferably 1 to 20 %, and especially 4 to 10 %, of the amino groups present in the branched polylysine are derivatized.

11. The use according to any of claims 7 to 9, wherein the substituents are acyl groups derived from oleic acid.