EP3661969A1

EP3661969A1 - Cosmetic compositions comprising biobased polymer

Info

Publication number: EP3661969A1
Application number: EP18745586.0A
Authority: EP
Inventors: Parag Kulkarni; Kyle CHOI; Peter Hoessel; Zhen Yuan QU; Ben Chuan ZHU; Yang Zhang
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2017-08-03
Filing date: 2018-07-24
Publication date: 2020-06-10
Also published as: BR112020001913A2; WO2019025233A1; CN110997729B; CN110997729A

Abstract

The present invention relates to a biobased polymer to be applied for personal care and having conditioning properties on skin and hair, and especially on hair. The invention relates to cosmetic compositions, especially hair care compositions, hair cleaning compositions or hair styling compositions, comprising the biobased polymer, as well as to a process for preparing said biobased polymer and to the use of said biobased polymer for improving the appearance and manageability of hair

Description

Cosmetic Compositions Comprising Biobased Polymer Field of the invention

The present invention relates to a cationic crosslinked biobased polymer, having conditioning properties on skin and hair, to be applied for personal care purposes, especially for hair care. The invention also relates to cosmetic compositions, especially hair care compositions, such as hair cleansing compositions, hair conditioning compositions and/or hair styling compositions, comprising the cationic crosslinked biobased poly- mer, as well as the use of said cationic crosslinked biobased polymer for improving the manageability and appearance of hair. The invention relates further to the manufacture of hair care compositions comprising the cationic crosslinked biobased polymer, and to a process for preparing said cationic crosslinked biobased polymer. Background of the invention

Cationic polymers with quaternary ammonium functional groups are used quite extensively in personal care products and personal care applications. These polymers have shown in the past substantive conditioning effects when used in hair care formulations, and have also found wide acceptance in skin care products.

One important class of such quaternary ammonium polymers are cationically charge- modified polymers, which derive either from various animal and plant sources, including guar gum, cellulose, proteins, polypeptides, chitosan, lanolin, starches or from man-made polymers, such as amino silicones.

However, in modern times, environmental and sustainability aspects get more and more attention, and the demand for ecologically conceived products raise. Thus there is a need that conditioning agents are "biobased", in the sense of being derived from natural origins such the cationic crosslinked biobased polymers according to the pre- sent invention, especially such as cationic crosslinked biobased polysaccharides according to the present invention.

In the past "biobased polymers" or "biopolymers" have been used widely in personal care and household products, due to their conditioning property that improve the sen- sorial characteristics of the object to which they are applied on, generally skin, hair or fabrics. Additionally to their conditioning effect, they are also known for having thickening effects in the formulations and compositions they are used in.

These properties make them especially suitable for cosmetic compositions, e.g. for the preparation of rinse-off products like hair shampoos, two-in-one shampoos, body washes, hair and body washes, hair conditioners as well as leave-on products such hair treatments, including all types of hair care products as well as lotions and creams, and also hair styling compositions. They show silky-feel on hair, ease the combing of the hair and have antistatic properties on the hair by improving deposition efficiency of conditioning agents or by itself.

Hair is subjected to a wide variety of severe stress, for example as a result of environmental influences, such as UV irradiation, air pollution or hot and/or dry weather conditions, mechanical stresses, such as combing or dry blowing as well as chemical stresses or combined chemical and mechanical stresses of various hair treatments, like washing, bleaching, coloring, perming, etc., which can lead to hair damage. Said damage includes e.g. dryness, reduced elasticity, brittleness, split ends, dullness, matt appearance, reduced fullness, rough surface and reduced mechanical strength. This leads to impaired combability, reduced glossiness, increased electrostatic charging and tendency to break and/or split.

There is therefore a need for hair cosmetic compositions with a complex profile of properties which counteract the negative effects of stressed hair in a diverse manner. They should show good conditioning efficacy as well as protective and hair-damage repairing properties. Of relevance is further a good formulation ability of the compo- nents used, which is e.g. characterized by compatibility with other ingredients commonly applied in hair care compositions and, moreover, the finished products should have good application properties. For instance, a good thickening effect enables to reduce the use of additional thickeners to the lowest possible extent. In addition to the aforementioned desired properties, the consumers often prefer "green" products, for the manufacture of which as many components of "natural origin" as possible are used.

Conditioners known from the prior art often comprise cationic surfactants and/or cati- onic hair polymers. These attaches to the hair and lead to an improvement in combability and shine of the hair, the polymers at the same time often improving the consistency of these preparations. Although cationic surfactants, such as e.g. cetyltrime- thylammonium chloride (CTAC) or behenyl trimethylammonium chloride (BTAC), generally have good conditioning properties, on account of their poor biodegradability, they are not consistent with use in a "natural" hair conditioner. Moreover, cationic surfactants and polymers, depending on the composition of the overall formulation in which they are used, also have some disadvantages under certain circumstances. For example, the sensory behavior of such conditioners on the hair is in some cases in need of improvement, which can become noticeable from a coated, slippery, but also sometimes harsh, somewhat sticky feel to the touch.

Furthermore, silicone oils and/or hair polymers containing silicone groups are often used in conditioning hair cosmetic compositions, such as hair conditioners or two-in- one shampoos. The desired effects when using silicone are e.g. the generation of shine, improvement in the combability or the enclosure of split ends or other kind of hair damage (especially in repair shampoos). However, due to various properties, the use of silicones alone in a "natural" hair conditioner is undesired. For example, hair damage is often merely concealed by silicone-containing conditioners and not permanently repaired. The actual condition of the hair under the silicone is no longer evi- dent, and targeted compensating care becomes difficult. Moreover, especially water- insoluble silicones have a tendency to "build-up" on the hair, and it becomes heavy and lifeless. Under the silicone layer, the hair can dry out unnoticed, which can lead to increased split ends and hair breakage. Thus, there is still a need for conditioning hair cosmetic compositions, for which manufacture the applied conditioning agents are derived from natural sources, without compromising on the conditioning properties and formulating benefits, and hence the use of conventional non-naturally derived components and/or silicone compounds can be reduced or avoided.

As mentioned above, besides their conditioning power, the general capability of bi- obased polymers, such as biobased polysaccharides, to thicken and regulate the rhe- ology of the solutions, in which they are dissolved, is also applied in industry, especially with regard to formulation technologies of personal care compositions. Cationic polymer-based conditioners are known to revitalize the hair, protecting it against environmental damage and offsetting the physical stress created as described above, e.g. by daily styling routines such as combing and blow-drying, or by occasional hair styling treatments as permanent hair treatments like bleaching, coloring and perming. These cationic derivatives act as conditioning and thickening agents in hair care applications and exhibit as well skin protection properties and their emollient characteristics providing smooth feel. Polymeric conditioners help hair and skin look and feel better by improving the physical condition of these cutaneous and keratotic surfaces. Hair conditioners are intended primarily to make wet hair easier to detangle and comb and to make dry hair smoother, shinier, and more manageable.

In particular, among cationic polysaccharides, cationic derivatives of biobased polysaccharides, e.g. hydroxyethyl cellulose, guar gum, cassia gum or starch, have shown good result in improving the wet and dry combing force reduction of hair washed with shampoo formulated therewith. Nevertheless, the performance of different cationic polymers in these applications has been found to still have some weakness in their conditioning performance, e.g. like guar and pectins or to be lacking achieving a good balance between wet and dry combing force reduction and good homogeneity of the formulation. For example, cationic celluloses have been found to deliver good clarity in cleansing surfactant systems, but not being effective enough in wet and dry combing force reduction.

It had been suggested in the art that only high molecular weight cationic polymers could deliver the conditioning effect desired in cleansing systems. For practical purposes, high molecular weight cationic guar for instance is generally defined as having a typical molecular weight no lower than 300,000 Daltons, typically in a range of 0.3- 5.0 million.

However, in view of the use of high molecular weight cationic guar conditioning polymers available for use in hair shampoos, body washes, conditioners etc., it is obvious that they have their drawbacks, such as e.g. their incompatibility with surfactant sys- terns used. In addition, they contribute unfavorably to the final product viscosity, which may not be desirable. High molecular weight cationic guar polymers are further known to be difficult to disperse and dissolve in aqueous solution.

For example, WO 2014/027120 A2, Lamberti Spa, (2013), describes a personal care and household care compositions comprising a conditioner and rheology modifier based on a cationic galactomannan or cationic xyloglucan derived from tamarind gum.

The xyloglucan gum suitable for obtaining the cationic derivative has preferably a Brookfield RVT viscosity, measured at 25 °C and 20 rpm on a 1.0 % by weight aque- ous solution, of between 50 and 10,000 mPa*s and a weight average molecular weight (Mw) typically of between 100,000 and 1,000,000 Dalton and has a cationic degree of substitution comprised between 0.01 and 3.

US 2007172441 Al, (2007) presents a cationic polymer, which when used a hair treatment composition for damaged hair, shows excellent conditioning effects. JP2003064102 A discloses a cationic polymer, by which stiff feeling in drying and conditioning effect in rinsing are improved in case of hair cosmetics. Furthermore, stiff feeling to the skin is supposed to be eliminated, as well as problems regarding the stability in cosmetic formulations and greasy touch and slimy touch are improved.

However, in view of the above said, there is still a desire for alternative cationic polymers derived from natural origins, which can improve the appearance, manageability and styling of the hair, like the look and feel of the hair, when the hair is treated with hair compositions.

Summary of the invention

The objective of the present invention is to provide a cationic biobased polymer, such as a polysaccharide, preferably a polysaccharide derived from a natural source, to be applied for personal care, and having conditioning properties on skin and hair, and especially on hair, and having good formulation abilities.

The objective can be achieved by the use of the cationic crosslinked biobased polymer according to the present invention.

Another objective of the present invention is further to provide a process for preparing said cationic crosslinked biobased polymer, especially polysaccharide, wherein (i) the biobased polymer, especially polysaccharide, is reacted with cationizing agent in the presence of alkaline hydroxide to obtain cationic biobased polymer, especially biobased polysaccharide, and (ii) the cationic biobased polymer, especially a polysaccharide, obtained from step (i) is crosslinked with bi-epoxy based crosslinker.

Another objective of the present invention is further to provide cosmetic compositions, especially hair care compositions, hair cleaning compositions or hair styling compositions, comprising said cationic crosslinked biobased polymer, especially biobased poly- saccharide, according to the invention. Another objective of the present invention is also the use of said crosslinked biobased cationic polymer, especially polysaccharide, for improving the appearance and manageability of hair.

Detailed description of the invention

The present invention relates to personal care compositions comprising a cosmetically acceptable cationic crosslinked biobased polymer derived from natural source, which has been chemically modified, and with especially efficient conditioning properties on hair. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art and in the technical field to which this invention belongs.

Expressions "a", "an", "the", when used to define a term, include both the plural and singular forms of the term.

In a first aspect, the present invention relates to a cationic biobased or bioderived crosslinked polymer, preferably a cationic biobased crosslinked polysaccharides, for use in cosmetic and personal care applications.

The "biobased" or "bioderived" polymers to be used in the present invention can be derived and obtained from different natural sources, especially from terrestrial land plants, but as well from aquatic plants or microorganisms. The biobased polymer is preferably derived from aquatic sources like seaweed extracts or algae extracts. In such cases the biobased polymer used for preparing the cationic crosslinked polymer according to the present invention is for instance selected from alginates, carrageenans or agar. The biobased polymer more preferably derived from terrestrial sources like land plants such as trees, shrub and fruit exudates. Such natural sources, the biobased polymer is derived from, are for instance Tamarind (Tamarindus indica), Cassia (Cassia tora or Senna obtusifolia), Locust (or Carob) tree (Ceratonia siliqua), Honey Locust (Gleditsia triacanthos), Tara tree (Cesalpina spinosa), Konjac (Amorphophallus konjac) Gum trees like Gum acacia or arabic tree (Acacia Senegal), Gum ghatti (Anogeissus latifolia) or Gum guar (Cyamopsis tetragonoloba).

Most preferably the biobased polymer is derived from the group of natural gums including guar gum and tara gum as well as gum arabicum, gum gahatti and gum trag- acanth, the group of pectins, the group of polyfructoses including inulin, the group of starches including amylose, amylopectin and starch derivatives like pullulan, the group of celluloses, their derivatives and mixtures thereof including hemicellulose, ethylhexylethylcellulose (EHEC), hydroxybutylmethylcellulose (HBMC), hydroxyethyl- methylcellulose (HEMC), hydroxypropylmethylcellulose (HPMC), methyl cellulose (MC), carboxymethyicellulose (CMC), hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC) and cetyl hydroxyethylcellulose, the group of polymannans including polyglu- comannan and polygalactomannan, the group of guar and chemically modified guars such as CMHP Guar, Jaguar® 8012, Jaguar® 8060 or the group of polysaccharides derived from tamarind extracts incluidng tamarind kernel powder, deoiled kernel powder or derivated carboxymethl kernel powder; as well as mixtures of the foregoing. The biobased polymer may optionally also be derived and obtained from non-plant sources such as chitosan, which is obtained by deacetylation of chitin, a structural element in the exoskeleton of crustaceans and cell walls of fungi. Alternatively, the biobased polymer may also be derived from microorganism like Xan- thomonas campestris Leuconostoc mesenteroides, Streptococcus mutans, Sphingo- monas elodea (formerly Pseudomonas elodea) or other subspecies. In such cases the biobased polymer used for preparing the cationic crosslinked biobased polymer according to the present invention is for instance selected from xanthan, dextran, gellan and welan gums. These biobased polymers, preferably the polysaccharides, and their extraction, purification, production and derivatization have been largely described in scientific and patent literature, like polyfructose and Xanthan in WO10014219; polygalactomannans e.g. in US5473059, US4758282, US5733584, W09818828, US3467647, WO12170171, DE3114783, and US2009137438 and tamarind derived polysaccharides in e.g. US2009137438, EP0011951, Carbohydrate Polymers 69 (2007) 251-155; cellulose-based compounds e.g. in Biomacromolecules Vol.9, No.8 (2008), US3833527, J.Agric.Food Chem. 2008, 56, 1582-1588 (the latter also touching chitosan); starch- based compounds e.g. in Macromol. Mater. Eng. (2002), 287, 495-502 and European Polymer Journal 43 (2007), 4940 - 4950; dextrans and pectins e.g. in European Polymer Journal 52 (2014), 53 - 75; Inulin e.g. in Biomacromolecules Vol.2, No. l (2001); all of which are incorporated herein by reference. Preferred biobased polymers, especially preferred polysaccharides, according to the present inventions are guar (including guar flour, guar gum (Cyamopsis tetragonolo- ba) or guar splits as well chemically modified guars such as CMHP Guar, Jaguar^® 8012, Jaguar^® 8060) or derived from tamarind extracts like e.g. tamarind kernel powder, deoiled kernel powder or derivated carboxymethl kernel powder; as well as mix- tures thereof.

Preferred are also starches (including amylose, amylopectin as well as starch derivatives like pullulan) as well as cellulose and cellulose mixtures (such as hemicellulose or cellulose derivatives like ethers, such as ethylhexylethylcellulose (EHEC), hydroxy- butylmethylcellulose (HBMC), hydroxyethylmethylcellulose (HEMC), hydroxypropylme- thylcellulose (HPMC), methyl cellulose (MC), carboxymethyicellulose (CMC), hydroxy- ethylcellulose (HEC), hydroxypropylcellulose (HPC) and cetyl hydroxyethylcellulose and also dextrans.

In the present invention, the more preferred biobased polysaccharides are derived from guars, and in particular from Raw Tamarind Kernel powder (hereinafter called as TKP).

Preparation of the cationic crosslinked biobased polymer

In second aspect, the present invention provides a process for preparing a cationic crosslinked biobased polymer according to the present invention, especially a cationic crosslinked biobased polysaccharide, comprising the steps wherein (i) the biobased polymer is reacted with cationizing agent in the presence of alkaline hydroxide to obtain cationic biobased polymer, and (ii) the cationic biobased polymer obtained from step (i) is crosslinked with bi-epoxy based crosslinker.

According to the present invention, step (i) can be carried out in a similar way as described in WO 2014/027120, meaning that in a step a) a biobased polysaccharide is reacted with a cationizing agent and with sodium hydroxide (or equivalent amount of another alkaline hydroxide) in water or in a water/alcohol mixture. In a step b) de- scribed in WO 2014/027120, sodium hydroxide (or equivalent amount of another alkaline hydroxide) is added to the obtained mixture and the mixture is stirred for from 10 to 300 minutes at temperature comprised between 30 °C and 90 °C and in step c) the pH of the mixture is optionally corrected with an acid. The final mixture obtained from step b) or c) is directly dried and milled.

Cationizing reagents that can be used for the cationic modification of polymeric substrates are e.g. quaternary ammonium salts with a reactive chemical group. Suitable cationizing reagents to be used in step (i) are e.g. glycidylalkylammonium salts including but not limited to glycidyltrimethylammonium chloride, glycidyltriethylammonium chloride, glycidyltripropylammonium chloride, glycidylethyldimethylammonium chloride, glycidyidiethylmethylammonium chloride, and their corresponding bromides and iodides; or other commercially available cationizing reagents, e.g. from QUAB® Serie available from SKW QUAB Chemicals, Inc. such as the 3-chloro-2-hydroxypropyl-alkyl- dimethylammonium chlorides 3-chloro-2-hydroxypropyltrimethylammonium chloride ("CHPTAC"), 2,3-epoxypropyltrimethylammonium chloride ("EPTAC"), 3-chloro-2- hydroxypropyldimethyldodecylammonium chloride ("CHPDLAC"), 3-chloro-2- hydroxypropylcocoalkyldimethylammonium chlorid ("CHPCDAC"), (3-chloro-2- hydroxypropyldimethylstearylammonium chloride ("CHPDSAC") or other similar compounds like 3-chloro-2-hydroxypropylethyldimethylammonium chloride, and their re- spective corresponding bromides and iodides.

The preferred cationizing agents are glycidyltrimethylammonium chloride, glycidyltri- ethylammonium chloride, glycidyltripropylammonium chloride, especially glycidyltrimethylammonium chloride. Preferably, the cationizing agents are used in amount of from 20 to 95 wt%, based on the biobased polymers. More preferably the cationizing agents are used in amount of from 35 to 90 wt%, based on the biobased polymers. Most preferably the cationizing agents are used in amount of from 50 to 85 wt%, based on the biobased polymers. In step (i), suitable alkaline hydroxides include but are not limited to sodium hydroxide, potassium hydroxide or mixture thereof.

Preferably, the weight ratio of the cationizing agents to the alkaline hydroxides is (5- 200) : 1.

More preferably the weight ratio of the cationizing agents to the alkaline hydroxides is (10-100) : 1.

Most preferably the weight ratio of the cationizing agents to the alkaline hydroxides is (20-70) : l.

In step (i), the reaction conditions such as the reaction temperature, the reaction time and the solvents etc. are not particularly limited. Preferably, the reaction is carried out at a temperature of from 30 to 80°C, more preferably 40 to 70°C, most preferably 50 to 65°C. Preferably, the reaction time is from 10 min to 30 hours, more preferably 20 min to 20 hours, most preferably 30 min to 10 hours.

Preferably, the solvent is selected from water, alcohol or mixture thereof, more pref- erably alcohol such as ethanol or isopropanol, most preferably isopropanol. The amount of the solvent is not particularly limited, a person skilled in the art can select the amounts according to the reaction.

The procedure of the invention can comprise one or more further derivatization steps, for example hydroxyalkylation, carboxyalkylation, hydrophobization steps, or combination thereof.

In this case, the cationic crosslinked biobased polymer, especially the polysaccharides, of the invention may also contain further substituent groups such as hydroxyalkyl sub- stituents, wherein the alkyl represents a straight or branched hydrocarbon moiety having 1 to 5 carbon atoms (e.g., hydroxyethyl, or hydroxypropyl, hydroxybutyl), hydrophobic substituents, carboxyalkyl substituents, or combinations thereof.

The process for introducing a hydroxyalkyl substituent on a polysaccharide is well known in the art. Typically, the hydroxyalkylation of a polysaccharide is obtained by the reaction with reagents such as alkylene oxides, e.g. ethylene oxide, propylene oxide, butylene oxide and the like, to obtain hydroxyethyl groups, hydroxypropyl groups, or hydroxybutyl groups, etc.

The hydrophobization of the cationic crosslinked biobased polymer, especially the pol- ysaccharides, of the invention is obtained by the introduction of hydrophobic groups.

The introduction of hydrophobic groups on polysaccharides is described for example in EP 323627 and EP 1786840. Typical derivatizing agents bringing a hydrophobic group include linear or branched C₂-C₂4 alkyl and alkenyl halides, linear or branched alkyl and alkenyl epoxides containing a C₆-C₂4 hydrocarbon group and alkyl and alkenyl glycidyl ethers containing a C₄- C₂₄ linear or branched hydrocarbon group as well as alkyl- and alkenyl^-hydroxy-y- chloropropyl ethers. A suitable glycidyl ether hydrophobizing agent can be, for example, butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, hexa- decyl glycidyl ether, behenyl glycidyl ether and nonylphenyl glycidyl ether. Representative alkyl epoxides include, but are not limited to, 1,2-epoxy hexane, 1,2- epoxy octane, 1,2-epoxy decane, 1,2-epoxy dodecane, 1,2- epoxy tetradecane, 1,2- epoxy hexadecane, 1,2-epoxy octadecane and 1,2-epoxy eicosane as well as epoxy derivatives of triglycerides. Exemplary halide hydrophobizing agents include, but are not limited to, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, neopentyl, hexyl, octyl, decyl, dodecyl, myristyl, hexadecyl, stearyl and behenyl bromides, chlorides, and iodides.

In a preferred embodiment of the invention, the cationic crosslinked biobased polymer comprises a cationic substituent as well as a hydrophobic substituent. For instance, in one preferred embodiment of the invention, the cationic substituent is 2-hydroxy-3- (trimethylammonio)propyl ether chloride and the hydrophobic substituent contains a linear alkyl or alkenyl chain containing between 6 and 24 carbon atoms or a mixture of such alkyls or alkenyls.

The cationic crosslinked biobased polymer, especially the polysaccharides, of the invention may contain both hydroxyalkyi substituents and hydrophobic substituents. The cationic crosslinked biobased polymer, especially the polysaccharides, of the invention may be carboxyalkylated.

Halo-carboxylic acids or their salts may be used for the preparation of carboxyalkyl cationic polysaccharides. The preferred halo-carboxylic acid is chloroacetic acid.

The derivatization reactions (cationization, carboxyalkylation, hydroxyalkylation, hy- drophobization) can follow any order. However, when the cationic crosslinked bi- obased polysaccharides of the invention also contain hydroxyalkyi substituents, the latter may be introduced in the last step, after the cationization step a) and the optional hydrophobization have occurred.

The characterizing step of the procedure of the invention is step (ii). Step (ii) can be performed simultaneously at the same time with the step (i), or subsequently at any time after step (i).

In one further aspect, the present invention provides a cationic crosslinked biobased polymer, especially polysaccharide, crosslinked with bi-epoxy based crosslinker. In the present invention, the term " bi-epoxy " means comprising at least two epoxy groups.

The at-least bi-epoxy based crosslinker preferably contains 2 to 10, more preferably 2 to 8 and most preferably 2 to 6 epoxy groups. The at-least bi-epoxy based crosslinker preferably contains 2 epoxy groups.

Preferred crosslinking agents to be used in the invention are selected from GP 682 (an epoxy functional dimethylpolysiloxane copolymer fluid with a low level of epoxy groups) or other commonly known crosslinkers like Poly( ethylene glycol) diglycidyl ether, Poly(propylene glycol) diglycidyl ether, Poly(oxy-l,2-ethanediyl), a-hydro-ω- (oxiranylmethoxy)-, ether with 2,2'-[oxybis(methylene)]bis[2-(hydroxymethyl)-l,3- propanediol] (6: 1), Oxirane, 2,2'-[9H-fluoren-9-ylidenebis(4,l-phenyleneoxy-2,l- ethanediyloxymethylene)]bis or Poly(oxy-l,2-ethanediyl), a-hydro-G)-(2- oxiranylmethoxy)-, ether with 2-ethyl-2-(hydroxymethyl)-l,3-propanediol (3: 1).

Especially preferred crosslinkers are GP 682, which is available from Genesee Polymers Corporation (http://www.gpcsilicones.com/fluids/epoxfunsilfluid/gp682.htm) and Poly(propylene glycol)diglycidyl ether. In step (ii), the reaction conditions such as the reaction temperature, the reaction time and the solvents etc. are not particularly limited. The reaction in step (ii) can be carried out under the reaction conditions as described in step (i).

After step (ii), the pH of cationic polysaccharide can opportunely be adjusted. Any acid may be selected to adjust the pH of the reaction mixture, including strong acids such as hydrochloric acid and sulfuric acid or weak acids such as acetic acid, lactic acid, citric acid, carbon dioxide and fumaric acid. In preferred embodiments a weak acid such as lactic acid is used. The amount of acid used is the amount which is necessary to reach the desired pH value, which is usually from 4 to 11, preferably 5 to 9, more preferably 6 to 8.

Further treatments can be also performed before step a) or soon after step b).

In another embodiment, the cationic crosslinked biobased polysaccharides are depol- ymerized by known methods, such as oxidation, for example with alkali or hydrogen peroxide, or by other depolymerization reactions, such as enzymatic or thermal depol- ymerisation, or acid hydrolysis. The depolymerized cationic galactomannan or xyloglu- can used in this invention are preferably prepared by treatments with alkali. In a preferred embodiment, the depolymerized cationic crosslinked biobased polysaccharides of the invention is prepared by reducing the molecular weight of the galactomannan or xyloglucan before any derivatization. Depolymerization can be performed using the already mentioned methods. At the end of the preparation procedure, the cationic crosslinked biobased polysaccharides according to the invention are dried and recovered using means known in the art and under the conventional conditions. Examples of such means include oven drying, air drying, fluidized bed drying, filtering, centrifuging, addition of solvents, freeze drying and the like. The use of oven drying is particularly recommended. Finally, the dried product can be milled in a conventional manner to get fine powder. The cationic biobased crosslinked polysaccharides have a weight average molecular weight (M_w) of from 0.3 to 3 m , preferably from 1 to 2 m. The cationic biobased crosslinked polysaccharides have a RVT Brookfield viscosity of from 35 to 4500 mPas, preferably from 300 to 3000 mPas, at 1% by weight in water, 20 rpm and 20°C.

Formulations comprising the cationic crosslinked biobased polymer

In another aspect, the present invention provides cosmetic compositions, especially hair care compositions, hair cleaning compositions or hair styling compositions, comprising said cationic crosslinked biobased polymer, especially polysaccharide. The cosmetic compositions, especially hair care compositions, hair cleaning compositions or hair styling compositions, according to the present invention can be obtained by add- ing the cationic crosslinked biobased polymer, especially polysaccharide of the present invention, to a cosmetic formulation by a commonly known method. Other additional components generally used in such cosmetic compositions are not limited to specific ones. Preferably, the hair treatment compositions according to the invention are in the form of a hair rinse, hair mask, shampoo, hair spray, hair foam, hair mousse, hair gel, setting foam, hair tonic, hair setting composition, end fluid, neutralizer for permanent waves, hair colorant and hair bleach or "hot-oil-treatments". Hair sprays can be in the form of aerosol sprays or pump sprays without propellant gas. Hair foams can be pre- sent as aerosol foams comprising propellants or pump foams without propellant gas.

However, the cosmetic compositions prepared according to the present invention are not limited to the above and are not limited in their formulation, and any appropriate cosmetic and formulation additive, usually used in common cosmetic compositions, and other than those derived herein below, may be added as long as it does not interfere with the effects originally expected from the composition.

The final cosmetic composition according to the present invention should be cosmeti- cally or dermatologically acceptable as whole and should contain a non-toxic physiologically acceptable medium as well as cosmetically or dermatologically acceptable additives, and should be suitable to be applied to the hair and skin for cosmetic purposes. The expression "cosmetically acceptable" means a composition or an agent, which is non-toxic and physiologically acceptable and has optionally further a pleasant ap- pearance, odor, feel and/or taste.

The resulting cosmetic composition according to the present invention may be prepared by conventional techniques into the final products, which are preferably the aforementioned hair care and hair treatment compositions like hair shampoos, hair rinses, hair conditioners, hair gels, hair waxes, hair styling compositions, hair mousses, hair lotions, hair mists and so forth.

The cosmetic compositions according to the present invention comprise from 0.05 to 20 wt%, preferably from 0.1 to 10 wt%, more preferably from 0.2 to 5 wt% the cati- onic crosslinked biobased polymer, especially polysaccharide.

Preferably, the hair cosmetic composition according to the invention comprises at least one cosmetically acceptable carrier. Preferably, the carrier component is selected from water, water-miscible organic solvents, preferably C2-C4-alkanols, in particular etha- nol, oils, fats, waxes, esters of C6-C30-monocarboxylic acids with mono-, di- or trihy- dric alcohols, saturated acyclic and cyclic hydrocarbons, fatty acids, fatty alcohols, propellant gases and mixtures thereof.

Hair sprays and hair foams preferably comprise predominantly or exclusively water- soluble or water-dispersible components. If the compounds used in the hair sprays and hair foams according to the invention are water-dispersible, they can be used in the form of aqueous microdispersions with particle diameters of usually 1 to 350 nm, preferably 1 to 250 nm. The solids contents of these preparations are here usually in a range from about 0.5 to 20% by weight.

Additional components of the cosmetic compositions according to the present inven- tion may be selected with regard to their function, such as surfactants, like anionic, non-ionic, cationic and amphoteric surfactants, solvents like water or alcohols, solubil- izers like ethanol, ethylene glycol, propylene glycol, etc., moisture retainers like glycerin, trehalose, sorbitol, maltitol, dipropylene glycol, 1,3-butylene glycol, sodium hya- luronate, etc., antioxidants like tocopherol, BHT, etc., UV absorbants like benzophe- none derivatives, paraamino benzoate derivatives, methoxy cinnamate derivatives, etc., UV-scattering agents like inorganic compounds such as zinc oxide, zirconium oxide, titanium oxide, etc., thickeners, metal chelating agents like edetic acid salts, etc., pH-adjusting agents, bactericides, preserving agents like phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid as well as silver complexes e.g. known under the name Surfacine®, hair growth stimulants, emollients, vitamins, antiinflammatory agents and anti-dandruff agents such as zinc pyrithione, selenium sulfide, salicylic acid, coal tar, sulfur, ketoconozole and climbazole.

Furthermore, dyes like cochineal red A (C.I. 16255), patent blue V (C.I.42051), indigo tin (C.I.73015), chlorophyllin (C.I.75810), quinoline yellow (C.I.47005), titanium dioxide (C.I.77891), indanthrene blue RS (C.I. 69800), madder lake (C.I.58000), luminescent dyes such as luminol, pigments like inorganic white pigments such as titanium dioxide, inorganic red pigments such as iron oxide (Indian red), iron titanate, etc., inorganic green pigments such as cobalt titanate, etc., iron oxide-treated mica titanium, carbon black-treated mica titanium and any other auxiliary substances such as foam- ing-promoting agents, dispersants, fillers, being conventionally added to cosmetic formulations.

The cosmetic compositions of the present invention may further comprise substances generally known to be comprised in cosmetic compositions for their multifunctional properties with regard to cosmetic and/or formulating effects, such as amino acids (alginin, glutamic acid, etc.), higher alcohols, higher fatty acids like lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, oleic acid, un- decylenic acid, tall oil fatty acid, coconut oil fatty acid, palm oil fatty acid, palm kernel fatty acid, linolic acid, linoleic acid, eicosapentaenoic acid, docosahexanoic acid, etc. and esters thereof like hexyl laurate, isopropyl myristate, octyldodecyl myristate, myristic acid myristate, myristic acid-2-hexyldecyl, glycerin trimyristate, isopropyl palmitate, palmitic acid-2-heptylundecyl, palmitic acid-2-hexyldecyl, butyl stearate, isocetyl stearate, 12-hydroxystearic acid cholesteryl, cetostearylalcohol, cetyl octan- ate, hexyldecyldimethyl octanate, isocetyl isostearate, trimethylolpropane triisos- tearate, decyl oleate, oleic acid oil, cetyl lactate, myristyl lactate, ethyl acetate, butyl acetate/amyl acetate, acetic acid lanolin, 2-ethylhexanoic acid cetyl, 2-ethylhexyl palmitate, di-2-ethylhexylic acid ethylene glycol, tri-2-ethylhexylic acid trimethylol propane, tri-2-ethylhexylic acid glycerin, tetra-2-ethylhexylic acid pentaerythritol, cetyl-2- ethyl hexanoate, diisobutyl adipate, adipic acid-2-heptylundecyl, adipic acid-2- hexyldecyl, dipentaerythritol fatty acid ester, neopentyl glycol dicaprylate, diisostearyl malate, di-2-heptylundecanoic acid glycerin, tri-2-heptylundecanoic acid glyceride, caster oil fatty acid methyl ester, acetoglyceride, N-lauryl-L-glutamic acid-2- octyldodecyl ester, di-2-ethylhexyl sebacate, diisopropyl sebacate, succinic acid-2- ethylhexyl, triethyl citrate, ethyl laurate, mink oil fatty acid ester, etc.) as well as waxes like carnauba wax, candelilla wax, etc., hydrocarbon oils like liquid paraffin, squalane, etc. or essential oils.

Further examples of suitable additional components can be found in the other refer- ences cited herein as well in the International Cosmetic Ingredient Dictionary and Handbook (9th ed. 2002).

These additives may in total be present in the composition in a proportion from 80 wt% to 99.95 wt%, preferably from 90 to 99,9 wt%, more preferably from 95 to 99,8 wt%, relative to the total weight of the composition. Especially when the cosmetic compositions according to the invention are hair cleansing compositions such as shampoos, they comprise additionally surfactants such as anionic, non-ionic, cationic or amphoteric surfactants. The anionic surfactant may include C₈-C₂4 alkyl sulfate, C₈-C₂4 alkyl ether sulfate, C₈- C₂₄ alkyl benzene sulfonate, C₈-C₂₄ alkyl phosphate, C₈-C₂₄ polyoxyalkylenealkyl ether phosphate, C₈-C₂₄ alkyl sulfosuccinate, C₈-C₂₄ polyoxyalkylenealkyl ether sulfosuccin- ate, C₈-C₂₄ acyl alaninate, C₈-C₂₄ acyl N-methyl-[beta]-alaninate, C₈-C₂₄ acyl gluta- mate, C₈-C₂₄ acyl isethionate, C₈-C₂₄ acyl sarcosinate, C₈-C₂₄ taurinate, C₈-C₂₄ acyl me- thyl taurinate, [alpha]-sulfofatty acid ester salt, ether carbonate, polyoxyalkylene fatty acid monoethanol amide sulfonate or C₈-C₂₄ long chain carboxylate, wherein C₈-C₂₄ means having any number from 8 to 24 carbon atoms.)

The nonionic surfactant may include alkanol amide, glycerin fatty acid ester, polyoxy- alkylenealkyl ether, polyoxyalkyleneglycol ether, polyoxyalkylenesorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyalkylenesorbit fatty acid ester, sorbit fatty acid ester, polyoxyalkyleneglycerin fatty acid ester, polyoxyalkylene fatty acid ester, poly- oxyalkylenealkylphenyl ether, tetrapolyoxyalkylene ethylenediamine-condensed substances, sucrose fatty acid ester, polyoxyalkylene fatty acid amide, polyoxy- alkyleneglycol fatty acid ester, polyoxyalkylene castor oil derivatives, polyoxyalkylene- hardened castor oil derivatives, or alkylpolyglycoside, polyglycerin fatty acid ester.

The amphoteric surfactant may include C₈-C₂₄ alkyl amidopropylbetaine, C₈-C₂₄ alkyl carboxybetaine, C₈-C₂₄ alkyl sulfobetaine, C₈-C₂₄ alkyl sulfobetaine, C₈-C₂₄ alkyl hy- droxysulfobetaine, C₈-C₂₄ alkyl amidopropylhydroxysulfobetaine, C₈-C₂₄ alkyl hydroxy- phosphobetaine, C₈-C₂₄ alkyl aminocarboxylate, C₈-C₂₄ alkyl imidazoliumbetaine, C₈-C₂₄ alkyl amineoxide, C₈-C₂₄ alkyl phosphate or esters containing a tertiary or quaternary nitrogen group, wherein C₈-C₂₄ means having any number from 8 to 24 carbon atoms and being linear or branched. The cationic surfactants may include alkyltrimethyl ammonium salts, dialkyldimethyl ammonium salts, alkylpyridium salts, alkyldimethylbenzyl ammonium salts, benzetho- nium chloride or benzalkonium chloride. Especially when the cosmetic compositions according to the invention are hair conditioning compositions such as hair conditioners, they may comprise additionally further conditioning agents.

The conditioning effect may be enhanced e.g. by adding silicone (methylpolysiloxane, methylphenylsiloxane, high polymeric methylpolysiloxane, cyclic polysiloxane, polyeth- er-modified silicone, amino-modified silicone, etd.) to a hair treatment composition or skin care composition of the present invention. The amount of a silicone added is preferably 5% by weight or lower with respect to the total weight of the entire composition.

Especially in view of the applicability of the cosmetic compositions according to the invention as hair treatment compositions, they may comprise additionally further viscosity and rheology modifying agents. Thus in addition to the cationic crosslinked biobased polymer, especially the polysaccharide, according to the present invention, consistency regulators and thickeners, e.g. anionic or nonionic polymers, may be added to a hair treatment composition or skin care composition of the present invention in order to adjust the viscosity of the composition or improve the performance of the composition, e.g. in maintaining the set style, as long as the addition of the polymer does not interfere with the expected effects of the composition of the present invention.

Suitable consistency regulators are primarily fatty alcohols or hydroxy fatty alcohols having 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides, fatty acids or hydroxy fatty acids. Preference is given to a combination of these sub- stances with alkyl oligoglucosides and/or fatty acid N-methylglucamides of identical chain length and/or polyglycerol poly-12-hydroxystearates. Suitable thickeners are, for example, Aerosil grades (hydrophilic silicas), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethylcellulose and hydrox- yethyl- and hydroxypropylcellulose, also relatively high molecular weight polyethylene glycol mono- and diesters of fatty acids. Bentonites have also proven to be particularly effective, such as, e.g. Bentone Gel VS-5PC (Rheox), which is a mixture of cyclopenta- siloxane, disteardimonium hectorite and propylene carbonate. Further suitable surfactants, such as, for example ethoxylated fatty acid glycerides, esters of fatty acids with polyols, such as, for example, pentaerythritol or trimethylolpropane, fatty alcohol eth- oxylates with a narrowed homolog distribution or alkyl oligoglucosides, and also electrolytes, such as sodium chloride and ammonium chloride. Further mentioned may also be sodium polynaphthalenesulfates, acrylate/aminoacrylate/C10-30-alkyl PEG-20 itaconate copolymers and polyacrylamidomethylpropanesulfonic acid. Suitable polymeric thickeners are, for example, optionally modified polymeric natural substances (carboxymethylcellulose and other cellulose ethers, hydroxyethyl- and propylcellulose and the like), as well as synthetic polymeric thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyi- mines, polyamides). These include the polyacrylic and polymethacrylic compounds which have in part already been specified previously, for example the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, (INCI name: Carbomer). Such polyacrylates and polyacrylic acids are available inter alia from BF Goodrich under the tradename Carbopol®, e.g. Carbopol 940 (molecular weight ca. 4 000 000), Carbopol 941 (molecular weight ca. 1 250 000) or Carbopol 934 (molecular weight ca. 3 000 000) or as Pemulen™ grades from Noveon; Synthalens® from Sigma; Keltrol® grades from Kelco; Sepigel™ grades from Seppic; Salcare® grades Allied Colloids), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone. Also included are acrylic acid copolymers as are available for example from Rohm & Haas under the trade- names Aculyn® and Acusol®, e.g. the anionic, non associative polymers Aculyn 22, Aculyn 28, Aculyn 33 (crosslinked), Acusol 810, Acusol 823 and Acusol 830 (CAS 25852-37-3). Also of specific suitability are associative thickeners, e.g. based on modified polyurethanes (HEUR) or hydrophobically modified acrylic or methacrylic acid copolymers (HASE thickeners, High Alkali Swellable Emulsion).

The use amount of the additional thickeners is preferably in a range from 0.001 to 5% by weight, preferably 0.1 to 3%, based on the total weight of the composition.

In case the cosmetic compositions according to the present invention are formulated as hair sprays or aerosol foams, propellants like mixtures of propane/butane, pentane, dimethyl ether, 1,1 difluoroethane (HFC-152a), carbon dioxide, nitrogen or compressed air are added thereto.

Of course, as for all cosmetic products, the use of perfumes and fragrances are very important, the smell or odour of thecosmteic formulation to be applied matters. Per- fume oils which may be mentioned are mixtures of natural and synthetic fragrances. Natural fragrances are extracts from flowers (lily, lavender, rose, jasmine, neroli, ylang ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peels (bergamot, lemon, oranges), roots (mace, angelica, celery, cardamom, costus, iris, calmus), woods (pinewood, sandalwood, guaiacwood, cedarwood, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), needles and branches (spruce, fir, pine, dwarf-pine), resins and balsams (galbanum, ele- mi, benzoin, myrrh, olibanum, opoponax). Animal raw materials are also suitable, such as, for example, civet and castoreum. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon types. Fra- grance compounds of the ester type are e.g. benzyl acetate, phenoxyethyl isobutyr- ate, p-tert-butyl cyclohexyl acetate, linalyl acetate, dimethylbenzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethylmethyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include e.g. the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclame- naldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones include e.g. the io- nones, isomethylionone and methyl cedryl ketone, the alcohols include anethole, cit- ronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons include primarily the terpenes and balsams. However, preference is giv- en to using mixtures of different fragrances which together produce a pleasant scent note. Essential oils of relatively low volatility, which are mostly used as aroma components, are also suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliba- num oil, galbanum oil, labolanum oil and lavandine oil. Preferably, bergamot oil, dihy- dromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, hexylzimtaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, boisambrene forte, ambroxan, indole, he- dione, sandelice, lemon oil, mandarin oil, orange oil, allyl amyl glycolate, cyclovertal, lavandin oil, clary sage oil, -damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillate, irotyl and floramat, alone or in mixtures, are used.

Suitable aromas are, for example, peppermint oil, spearmint oil, anise oils, star anise oil, caraway oil, eucalyptus oil, fennel oil, lemon oil, wintergreen oil, clove oil, menthol and the like.

For illustrating purposes hair shampoo according to the present invention are shown herein below.

Hair shampoo formulation I comprising additional silicone conditioner

Surfactant I Sodium laureth sulfate (SLES) 15 wt%

Surfactant II Cocamidopropyl betaine (CAPB) 3 wt%

Conditioning agent I Cationic crosslinked biobased

according to the invenpolymer derivative of the inven0.5 wt%

tion tion

Conditioning agent II Dimethicone 2%

Electrolyte Sodium chloride 1 wt% Carrier Deionized water To 100 wt%

Preservative Citric acid q.s.

Hair shampoo formulation II comprising additional silicone conditioner

Surfactant I Ammonium laureth sulfate 12 wt%

Surfactant II Cocamidopropyl betaine (CAPB) 3 wt%

Surfactant III Sodium cocoamphoacetate 3 wt%

Conditioning agent I Cationic crosslinked biobased

polymer derivative of the in0.5 wt%

vention

Conditioning agent II Amodimethicone 2 wt%

Electrolyte Sodium chloride 1 wt%

Carrier DI water To 100 wt%

Preservative Citric acid q.s.

Hair shampoo formulation III comprising no additional silicone conditioner

Surfactant I Sodium lauryl glucose carbox- ylate (and) Lauryl glucoside 15 wt%

Surfactant I Cocamidopropyl betaine (CAPB) 3 wt%

Conditioner I cationic crosslinked biobased

polymer derivative of the inven0.5 wt%

tion

Electrolyte Sodium chloride 1 wt%

Carrier DI water To 100 wt%

Preservative Citric acid q.s.

Applications and uses of the cationic crosslinked biobased polymer

The cationic crosslinked biobased polymer, especially polysaccharide, according to the present invention can be used and applied to hair and skin in personal care through different methods and various uses, thereby improving the appearance, manageability and/or styling ability of hair. These methods and uses according to the present invention are listed herein below for illustrative purposes. In one aspect, the present invention provides the use of said cationic crosslinked bi- obased polymer, especially polysaccharide, for improving the touch, the feel and/or the hair fullness of hair washed with hair shampoo formulated herewith or treated with a hair conditioning composition formulated herewith. In one aspect, the present invention provides the use of said cationic crosslinked bi- obased polymer, especially polysaccharide, for improving the combability and/or the detangling effect of wet or dry hair washed with hair shampoo formulated herewith or treated with a hair conditioning composition formulated herewith. In one aspect, the present invention provides the use of said cationic crosslinked bi- obased polymer, especially polysaccharide, for improving the conditioning efficacy of other conditioning agents present in hair care composition formulated herewith.

In one aspect, the present invention provides the use of said cationic crosslinked bi- obased polymer, especially polysaccharide, for providing shininess and/or glossiness to the hair washed with hair shampoo formulated herewith or treated with a hair conditioning composition formulated herewith.

In one aspect, the present invention provides the use of said cationic crosslinked bi- obased polymer, especially polysaccharide, for good washout efficacy or improved wash-out behavior, especially of hair styling compositions, on the hair washed with hair shampoo formulated herewith.

In one aspect, the present invention provides the use of said cationic crosslinked bi- obased polymer, especially polysaccharide, for reducing electrostatic charging of the hair washed with hair shampoo formulated herewith or treated with a hair conditioning composition formulated herewith.

In one aspect, the present invention provides the use of said cationic crosslinked bi- obased polymer, especially polysaccharide, for protecting the hair during chemical and/or mechanical treatments of the hair, when a hair care composition formulated herewith has been applied to the hair before (as pre-treatment) or after (as after- treatment). In one aspect, the present invention provides the use of said cationic crosslinked biobased polymer, especially polysaccharide, for preventing or reducing split ends of the hair treated with a hair care composition formulated herewith.

In another aspect, the present invention provides the use of said cationic crosslinked biobased polymer, especially polysaccharide for styling hair with hair styling compositions formulated herewith.

In yet another aspect, the present invention provides the use of said crosslinked biobased cationic polymer, especially polysaccharide, in shower gels and body washes for combined hair and skin care or skin care only.

As mentioned further above, due its natural origin, the cationic crosslinked biobased polymer, especially polysaccharide, according to the present invention is especially suitable for being formulated and applied in cosmetic compositions designed for and with ecological objectives.

Hence, in yet another aspect, the present invention provides the use of said cationic crosslinked biobased polymer, especially polysaccharide for realization of an ecological and/or natural ("green") conditioner concept. EXAMPLES

The look, feel or haptic properties of hair, like its shine, fullness and smell, play an important role in the quality and the acceptance of cosmetic hair formulations. The feel of hair determines whether or not cosmetic formulations are perceived of providing a beneficial effect on the hair. So far this interaction between the hands and fingers with the hair needs to be detected and evaluated in in-use tests, but should also be correlated with analytical test methods.

The assessment of feel, suppleness and glossiness may e.g. be correlated with the results of test methods like resistance forces measurement while wet and dry combing, surface analyses of the hair with scanning electron microscopy (SEM) and atomic force microscopy (AFM).

The examples given below are intended to illustrate the invention without restricting it. The preparation examples provided, as well as the formulation examples, may serve as general reference examples and may be applied to the derivatization of other biobased polymers, especially to other biobased polysaccharide, and their use.

I. Preparation of a cationic crosslinked biobased polymers according to the inven- tion

The Tamarind Kernel Powder (TKP) used in the examples below is available from Vishnu Gum & Chemicals (Polysaccharide Content 73.41%; Water Solubility: precipitate; Ash content: 1.89; Moisture Content: 8.2; Nitrogen Content: 2.64; Charge Density: 0).

Preparation Example P. l :

36 g of Tamarind Kernel Powder (TKP) was mixed with 75.4 g of iso-Propanol in the SYSTAG Reactor. 17.6 g of an aqueous solution of 3.86wt% sodium hydroxide was added within 20 min during stirring. The inner temperature was raised to 60°C within 10 min and then 28.4 g of an aqueous solution of 75wt % Glycidyltrimethylammonium Chloride aqueous solution was added within 30 min resulting in cationic intermediate compound c-TKP. Afterwards, 9 mg of Polyethylene Glycol Diglycidyl Ether was added. The inner temperature was kept at 60°C for 5 hours. Then the mixture was cooled to 25°C within 10 min. After 2 days, the pH to 6.5 was adjusted with lactic acid. The mixture was filtered to get the solid. The solid was washed first twice with a mixture of 160 ml IPA (isopropanol) and 80 ml water, and then once with solely 160 ml IPA. The solid end product (cc-TKP-Pl) was put into the oven at 50°C for 12 h. Then the dried product was milled to get fine powder.

The charge density (CD) is calculated from the cationic substitution and defined in mil- liequivalents per gram (meq/g) describing the amount of cationic charge per gram of polymer. The CD of the cationic crosslinked biobased polymer (cc-TKP-Pl) is 0.8 meq/g.

Preparation Example P.2:

36 g of Tamarind Kernel Powder (TKP) was mixed with 75.4 g of iso-Propanol in the SYSTAG Reactor. 17.6 g of dosing aqueous solution of 3.86wt % sodium hydroxide was added within 20 min during stirring. The inner temperature was raised to 60°C within 10 min and then 28.4 g of 75wt% of an aqueous solution of 2-hydroxypropyl- N-trimethyl ammonium chloride was added within 30 min resulting in cationic intermediate compound c-TKP. Afterwards, 39.8 mg of GP-682 was added. The inner temperature was kept at 60°C for 5 hours. Then the mixture was cooled to 25°C within 10 min. After 2 days, the pH to 6.5 was adjusted with lactic acid. The mixture was fil- tered to get the solid. The solid was first washed twice with a mixture of 160 ml IPA (isopropanol) and 80 ml water for two times, and then once with solely 160 ml IPA. The solid end product (cc-TKP-P2) was put into the oven at 50°C for 12 h. Then the dried product was milled to get fine powder. The charge density (CD) is calculated from the cationic substitution and defined in mil- liequivalents per gram (meq/g) describing the amount of cationic charge per gram of polymer. The CD of the cationic crosslinked biobased polymer (cc-TKP-P2) is 1.1 meq/g.

II. Formulation examples comprising a cationic crosslinked biobased polymers according to the invention

The formulations to be used in test methods hereinafter were prepared as follows:

The cationic crosslinked biobased polymer according to the invention, the cc-TKP-P2 derivative obtained in preparation example P.2 was slowly dispersed in water under stirring. The dispersion was heated up to 70 °C, the respective surfactants were added subsequently while stirring for another 30 min. Then the formulation was cooled down to room temperature and the silicone compound was added, if it was required in the final formulation. The pH value of the final formulation was adjusted to a pH of 6 to7 with citric acid, and sodium chloride was added while stirring uniformly.

The comparative formulations examples, comprising no polymer, comparative poly- mers and the cationic but non-crosslinked c-TKP derivate were prepared accordingly.

1. Blank Formulations (with and without silicone additive)

Table F. l

Ingredients (weight %) Blank Formulation

B. l B.2

SLES¹ 10% 10%

CAPB² 4% 4%

Dimethicone³ / 1%

NaCI 1% 1% Water to 100% to 100%

¹ Sodium laureth sulfate (Surfactant)

² Cocamidopropyl betaine (Surfactant)

³ Polydimethylsiloxane (Silicone conditioner)

Formulation examples comprising cationic crosslinked biobased polymer accordi to the present invention :

Table F.2

Sodium laureth sulfate (Surfactant)

Cocamidopropyl betaine (Surfactant)

Polydimethylsiloxane (Silicone conditioner)

3. Formulation examples comprising comparative conditioning polymers: Table F.3

¹ Sodium laureth sulfate (Surfactant)

² Cocamidopropyl betaine (Surfactant)

³ Polydimethylsiloxane (Silicone conditioner)

⁴ Polyquaternium-10 (comparative polymer)

⁵ Guar Hydroxypropyltrimonium Chloride (comparative polymer)

⁶ Guar Hydroxypropyltrimonium Chloride (comparative polymer)

III. Testing methods and test results

A. Pre-treatment of hair strands for testing

In all testing methods shown herein below, hair strands (black Chinese hair, available from International Hair Importers (IHIP, New York)) were pre-treated according to scheme below.

A. l Cleansing

All hair strands were pre-cleansed using a solution of sodium lauryl ether sulfate, 2EO (C12-C14 alcohol basis) 12% active matter, pH 6.5), followed by an extensive rinsing procedure.

A.2 Drying

After cleansing, the hair strands were dried over 24 hours in the climate-controlled room.

A.3 Bleaching

The cleansed and dry hair strands were bleached by applying hydrogen peroxide (17% active matter, pH 9.4). A.4 General hair treatment step with hair shampoo

If not stated differently in the individual test descriptions herein below, the treatment step with a hair shampoo composition is performed as follows:

Bleached hair strands are individually wetted for 1 min under rinsing device with water at 38°C. Then 0.5 g hair shampoo/2 g hair (respectively 0.25g hair shampoo/lg hair) is applied to the wet hair strands and soaked for 5 min. Afterwards the hair strands are rinsed for 1 min under tap water in order to remove shampoo residues.

In general the procedure may be repeated once with combing 3 times in between and after, but repetition may vary depending on the examples. The hair shampoo formulations applied in the testing methods comprise either no conditioning polymer (blank formulations, Table F. l), the cationic crosslinked biobased polymer according to the invention (table F.2) or the comparative conditioning polymer (Table F.3).

After the cleansing, bleaching and drying, the hair strands were ready to be tested in the following testing methods Tl, T2, T3 and T4.

T.l Combing force measurement

The physical measurements of combing forces on hair strands enable objectively measured results on how products like hair shampoos or hair conditioners perform with regards to conditioning and detangling efficacies. In a pre-post design, the reduction of wet or dry combing forces is determined to substantiate the efficacy. The advantage of these testing method is its objectivity due to high precision and reliability.

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

1.1 Preparation of the hair strands for the wet combing test.

The first step for the investigation of wet combability was the preparation of the hair strands for the determination of the reference values. The preparation included swelling for 30 minutes in tap water of the hair strands. After the reference measurement was taken, the hair strands were treated with 0.25 g of the respective shampoo formulation per 1 g of hair and incubated for 5 minutes. Then the hair strands were well rinsed with tap water for about 1 minute at room temperature. This treatment with the shampoo formulation was repeated once, and the measurement was performed.

1.2 Preparation of the hair strands for the dry combing test The first step for the investigation of dry combability was the preparation of the hair strands for the determination of the reference values. The preparation included the equilibration of the hair strands for 12 hours at a room temperature of 23°C and 50% relative humidity. Then the reference measurement was taken. The hair strands were treated with 0.25 g of the respective shampoo formulation per 1 g of hair and incubated for 5 minutes. Then the hair strands were well rinsed with tap water for about 1 minute at room temperature. This treatment with the shampoo formulation was repeated. The hair strands were dried, and the dried hair strands were equilibrated at the conditions given above. Then the combing measurement was performed.

1.3 Determination of combing work

The conditioning performance of the respective shampoo formulations was evaluated by measuring the reduction in work or energy associated with combing the hair strands.

Combing force was measured by a Zwicki Z2.5 Dynamic Testing Machine (Zwick Roell, Germany) before and after treatment with the test formulation according to the description above. The percent change in combing work reduction was then calculated as the ratio of the difference between post and pre-treatment combing work to pre- treatment combing work as shown below. As such, negative values indicate a reduc- tion in combing work due to the treatment (conditioning) and positive values indicate an increase in combing work due to the treatment. The recorded force-displacement curves were integrated to calculate the combing work.

The residual combing work is calculated as following :

_, . , . . . . combing work after treatment

Residual combing work = ^Λ

combine work before treatment

Change in combing work (%) = (Treated - Untreated) χ 100

The data provided in the table T. l below (see also Figure 1) show that the cationic crosslinked biobased polymer according to the invention is well capable of improving the manageability of hair, especially also in comparison to other known conditioning agents or its cationic non-crosslinked derivative.

Table T. l

T.2 Surface evaluation of conditioning effect with AFM method

Conditioners deposit onto the hair and the change of hair properties are of analytical interest as these properties are closely tied to product performance. Although the amount of conditioners deposited on the fiber is very small in quantity, it is still con- ceivable that mainly the surface is moisturized. This is especially true of cationic polymeric conditioners, which deposit preferentially on the surface of the fiber, rather than penetrate into the cortex. The binding interaction between conditioner and the hair surface is one of the important factors in determining the conditioner thickness distribution and consequently the proper functions of conditioner. In this test, atomic force microscopy (AFM) was used to obtain the local conditioner thickness distribution and adhesive forces while mapping of various shampoo formulations on hair surfaces. The conditioner thickness was evaluated by measuring the forces on the atomic force microscopy tip as it approached, contacted and pushed through the conditioner layer.

AFM Height and Phase Imaging in Tapping Mode was used to obtain the morphological information of the sample.

Freshly auto-cleaved mica was used as a substrate for deposition of the cationic cross- linked biobased conditioning polymer of the present invention as well as for the comparative conditioning agents. 2.1 AFM test conditions

A soft silicon nitride (SiN) tip was used for the testing. The AFM measurement was done at room temperature in dry conditions. The atomic force microscopy measurements were performed with a Digital Instruments Nanoscope Dimension 3000 SPM (Veeco, Mannheim, Germany) in the tapping mode. The surface topography of the hair and hard-soft contrasts were measured.

2.2 AFM sample preparation:

The mica surfaces were preferably even, flat and free from scratches and contamination. All the samples were tested with an 0.025 wt% aqueous polymer solution of the respective conditioning polymer.

2.3 AFM sample treatment

The shampoo formulations were diluted to comprise 0.025 wt% of the condition agent (either the cationic crosslinked biobased polymer or the comparative conditioning agent).

The mica substrates were dipped in the solutions for ca. 10 sec, and subsequently dipped in water for ca. 10 sec to remove residual non absorbed polymer, in order to get a monolayer.

2.4 AFM test results and evaluation

As can be seen from the results. The cationic crosslinked cc-TKP-P2 offered bette performance than its non-crosslinked c-TKP counterpart. The cationic c-TKP deriva tive, which was not crosslinked, showed comparable performance as commercialized PQ-10 (Ucare™ JR-400) and a guar based conditioning polymer (Jaguar® Excel). This may be attributed to different morphologies of crosslinked conditioning polymers vs the non-crosslinked conditioning polymers.

As can be demonstrated, see Table T.2 and Figure 2 from the AFM images, the cation- ic crosslinked cc-TKP-P2 according to the present invention, showed larger particle sizes. Table T.2:

T.3 Silicon residual analysis on hair with SEM/EDS

The analysis of silicone residues on hair was performed by imaging with scanning electron microscopy (SEM) and with electron dispersive x-ray spectroscopy (EDS). The addition of an EDS detector to an SEM microscope allows for elemental analysis and can show morphology and elemental distribution on a sample surface.

3.1 Hair pre-treatment

The hair strands were pre-treated in order remove any preceding residues from the hair. A solvent mixture comprising O-xylene and 2-propanol in a ratio of 1 : 1 was prepared. Each hair strand was dipped down into 50 ml solvent mixture each, and heated up to 80°C and then stored therein for 1 hour while swirling the hair strand sample a few times with spatula. The dipping procedure was repeated three times. Afterwards, the hair strand was washed with 200ml of ethanol three times, as well as three times with 200ml deionized water.

3.2 Hair treatment with hair shampoo

The pre-treated hair strands were individually wetted for 1 min under rinsing device with water at 38°C. Then 0.5 g shampoo/2 g hair (respectively 0.25g shampoo/lg hair) was applied to the wet hair strands and soaked for 5 min. Afterwards the hair strands were rinsed for 1 min under rinsing device in order to remove shampoo residues. After cleansing, the hair strands were dried over 24 hours in the climate- controlled room.

Measurement, for evaluating the silicone residue on the hair, were taken after the above washing process was performed once, 5 times and 10 times.

3.3 Test results and evaluation

In comparison to the hair shampoo formulation comprising a cationic non-crosslinked guar derivative (comparative formulation C. IO), the cationic crosslinked TKP derivative cc-TKP-P2 according to the present invention (formulation F.3) brought less silicon build-up with higher frequency of treatment, and on the other side a better deposition at first time, compared to comparative cationic guar derivative.

Table T.3 : Silicone content on hair surface in %

The results of the SEM analysis show, that the cationic crosslinked conditioning polymer according to the present invention show better a compatibility with silicon agent, but is still soluble in aqueous solution. Thus, the deposited silicon can be easily washed away by cationic crosslinked biobased conditioning polymer according to the present invention, preventing silicone residues to build up. (Figure 3).

T.4 Hair sensory test

4.1. Test procedure and test design As mentioned above, the look, feel and the haptic properties of hair play an important role in the quality and the acceptance of cosmetic hair formulations. Thus, this acceptance needs to be evaluated when developing and testing new hair cosmetic formulations by in-use tests with test persons.

A panel of 11 trained volunteers tested parameters of different formulations in order to compare two differently treated strands for their sensory properties. Accordingly, 11 hair strands per formulation according to the invention (F.4) and per comparison (C. l l) were prepared (see hair strands pre-treatment A. l to A.4), so that each panel- ist uses an individual strand only once.

The tests were performed in an air-conditioned room with a temperature of 23°C and a relative humidity of 50%.

4.2 Sensory assessment on wet hair

After treating the hair with the shampoo the strands are dripping wet. Before starting the assessment, the panelists squeeze the surplus water out of the strands. After this the parameters of wet sensory are tested.

4.3 Sensory assessment on dry hair

After combing the strands 3 times, the hair is dried over 24 hours, and the parameters of dry sensory are tested.

4.4 Test results

The following parameters were evaluated :

More or less hardness, softness and smoothness of the hair, more or less stickiness, oiliness and waxiness of the hair, more or less residues on the hair, difficult or easy hair combing, general hair care feel as well as general acceptance (likewise more or less). The grading was done on a five-point-scale from minus one to plus one, compared to the reference, the test product can be more or less highly pronounced in its properties (+1/-1), more or less slightly pronounced (+0.5/-0.5) or the same (0). After the de- termination of the degree of the parameters, the volunteers gave their associations as a creative statement. The test was performed in the double blind mode. The samples were coded and applied randomly. To evaluate the sensory data, the medians for each parameter were calculated, as well as the average absolute deviation from the median as a measure of the variation of the individual values for each parameter. To calculate the statistical significance of a pair-wise comparison, the Wilcoxon test was carried out. In the chart, the position of the symbol indicates the median, and the average absolute deviation from the median is transformed into the weighted deviation from the median and shown in the chart in the form of shifted lines.

Corresponding results also showed in the wet hair sensory evaluation on Asian hair. The crosslinked cationic biobased polymer according to the invention ccTKP-P2 of formulation example F.4 demonstrated apparent benefits over the comparative condition polymer PQ-10 (Ucare® JR400) of comparative formulation C. ll, which showed again the advantage of the invention (Figure 4).

Claims

1. A cationic crosslinked biobased polymer, preferably selected from a polysaccharide, deriving from a natural source and obtained by cationization and subsequent cross- linking with a bi-epoxy based crosslinker.

2. The cationic crosslinked biobased polymer according to claim 1, wherein the polymer is a polysaccharide.

3. The cationic crosslinked biobased polymer according to claim 1 or 2, wherein the natural sources, the polymer is derived from, are aquatic sources like seaweed extracts or algae extracts.

4. The cationic crosslinked biobased polymer according to claim 1, 2 or 3, wherein the polymer is selected from alginates, carrageenans or agar.

5. The cationic crosslinked biobased polymer according to claim 1 or 2, wherein the natural sources, the polymer is derived from, are microorganism.

6. The cationic crosslinked biobased polymer according to claim 1, 2 or 5, wherein the polymer is selected from xanthan, dextran, gellan and welan gums.

7. The cationic crosslinked biobased polymer according to claim 1 or 2, wherein the natural sources, the polymer is derived from, are land plants.

8. The cationic crosslinked biobased polymer according to claiml, 2 or 7, wherein the natural sources, the polymer is derived from, are selected from Tamarind (Tama- rindus indica), Cassia (Cassia tora or Senna obtusifolia), Locust (or Carob) tree (Ceratonia siliqua), Honey Locust (Gleditsia triacanthos), Tara tree (Cesalpina spi- nosa), Konjac (Amorphophallus konjac) Gum trees like Gum acacia or arabic tree (Acacia Senegal), Gum ghatti (Anogeissus latifolia) or Gum guar (Cyamopsis tetragonoloba)

9. The cationic crosslinked biobased polymer according to any of claims 1, 2, 7 or 8, wherein the polymer is selected from the group of natural gums including guar gum and tara gum as well as gum arabicum, gum gahatti and gum tragacanth, the group of pectins, the group of polyfructoses including inulin, the group of starches including amylose, amylopectin and starch derivatives like pullulan, the group of celluloses, their derivatives and mixtures thereof including hemicellulose, ethylhexylethylcellulose (EHEC), hydroxybutylmethylcellulose (HBMC), hydroxyeth- ylmethylcellulose (HEMC), hydroxypropylmethylcellulose (HPMC), methyl cellulose 5 (MC), carboxymethyicellulose (CMC), hydroxyethylcellulose (HEC), hydroxypropyl- cellulose (HPC) and cetyl hydroxyethylcellulose, the group of polymannans including polyglucomannan and polygalactomannan, the group of guar and chemically modified guars such as CMHP Guar, Jaguar® 8012, Jaguar® 8060 or the group of polysaccharides derived from tamarind extracts incluidng tamarind kernel powder, de- 10 oiled kernel powder or derivated carboxymethl kernel powder; as well as and mixtures of the foregoing.

10. The cationic crosslinked biobased polymer according to any one of the preceding claims, wherein the bi-epoxy based crosslinker contains 2 to 10, preferably 2 to 8, more preferably 2 to 6 epoxy groups, most preferably 2 epoxy groups.

15 11. The cationic crosslinked biobased polymer according to any one of the preceding claims, wherein the bi-epoxy based crosslinker is selected from the group consisting of an epoxy functional dimethylpolysiloxane copolymer, Poly(ethylene glycol) diglyc- idyl ether, Poly(propylene glycol) diglycidyl ether, Poly(oxy-l,2-ethanediyl), a- hydro-co-(oxiranylmethoxy)-, ether with 2,2'-[oxybis(methylene)]bis[2-

20 (hydroxymethyl)-l,3-propanediol] (6: 1), Oxirane, 2,2'-[9H-fluoren-9-ylidenebis(4, l-phenyleneoxy-2,l-ethanediyloxymethylene)]bis-, Poly(oxy-l,2-ethanediyl), a- hydro-co-(2-oxiranylmethoxy)-, ether with 2-ethyl-2-(hydroxymethyl)-l,3- propanediol (3 : 1), preferably from the group consisting of an epoxy functional dimethylpolysiloxane copolymer, Poly(ethylene glycol) diglycidyl ether and

25 Poly(propylene glycol) diglycidyl ether, more preferably from an epoxy functional dimethylpolysiloxane copolymer or Poly(ethylene glycol) diglycidyl ether.

12. A process for preparing the cationic crosslinked biobased polymer according to any one of the preceding claims, wherein in a first step (i) the biobased polymer is reacted with cationizing agent in the presence of alkaline hydroxide to obtain cationic 30 biobased polymer, and in a second step (ii) the cationic biobased polymer obtained from step (i) is crosslinked with bi-epoxy based crosslinker as defined in claim 10 or 11.

13. The process according to claim 12, wherein the cationizing agent is selected from the group consisting of glycidyltrimethylammonium chloride, glycidyltriethylammo- nium chloride, glycidyltripropylammonium chloride, glycidylethyldimethylammonium chloride, glycidyidiethylmethylammonium chloride, 3-chloro-2- hydroxypropyltrimethylammonium chloride, 3-chloro-2- hydroxypropyltriethylammonium chloride, 3-chloro-2- hydroxypropyltripropylammonium chloride and 3-chloro-2- hydroxypropylethyldimethylammonium chloride, as well as the corresponding bromides and iodides of all foregoing.

14. The process according to claim 12 or 13, wherein the alkaline hydroxide used in step (i) is sodium hydroxide or potassium hydroxide or a mixture thereof.

15. A cosmetic composition comprising the cationic crosslinked biobased polymer de- fined in any one of claims 1 to 11.

16. The cosmetic composition according to claim 15, wherein the cosmetic composition is a cosmetic hair composition applied to the hair for cleaning, conditioning or styling purposes.

17. A cosmetic composition according to claim 15 or 16, wherein the cosmetic composi- tion is a hair shampoo, a hair conditioner, a hair treatment, a hair styling composition like a hair styling gel or a hair styling mousse.

18. A cosmetic composition according to claim 15, 16, 17 or 18, wherein the cosmetic composition comprises from 0.05 wt% to 20 wt%, preferably from 0.1 wt% to 10 wt%, more preferably from 0.2 wt% to 5 wt% the cationic crosslinked biobased polymer defined in any one of claims 1 to 11.

19. The use of the cationic crosslinked biobased polymer defined in any one of claims 1 to 11 for hair conditioning by improving the combability and detangling effect on hair washed or treated with a hair shampoo or a hair care composition formulated therewith

20. The use of the cationic crosslinked biobased polymer defined in any one of claims 1 to 11 for hair conditioning by reducing electrostatic charging of the hair washed or

5 treated with a hair shampoo or a hair care composition formulated therewith.

21. The use of the cationic crosslinked biobased polymer defined in any one of claims 1 to 11 for protecting the hair during chemical hair treatments of the hair before or after having been treated with a hair care composition formulated herewith.

22. The use of the cationic crosslinked biobased polymer defined in any one of claims 1 10 to 11 for preventing or reducing split ends of the hair washed or treated with a hair shampoo or a hair care composition formulated therewith.

23. The use of the cationic crosslinked biobased polymer defined in any one of claims 1 to 11 for improving the healthy appearance of the hair by providing glossiness to the hair.

15 24. The use of the cationic crosslinked biobased polymer defined in any one of claims 1 to 11 for styling the hair.

25. The use of the cationic crosslinked biobased polymer defined in any one of claims 1 to 11 for improving the wash-out efficacy of hair styling compositions in hair cleansing composition.

20