Cationic galactomannan from guar and process for its production

Abstract

The present invention relates to a cationic galactomannan derived from guar and having a mannose / galactose molar ratio in the range of 2.5:1 and 5:1, a process for its production and its performance and use in home and personal care formulations.

Description

Related applications

[0001] This application claims priority to European Patent Application 24315010.9, filed on 12 January 2024, the entire contents of each of these applications are incorporated herein by reference for all purposes. Technical Field

[0002] This invention relates to cationic galactomannans obtained from guar gum, methods for producing such cationic galactomannans, and performance properties (such as conditioning agents) for home and personal care applications. Background Technology

[0003] Galactomannan is a polysaccharide composed of a mannose backbone with galactose side groups, which can be obtained from various legumes. Cationic galactomannan is commonly used in personal care products, such as hair or skin care products. References may include US 2008 / 0112907, US 2003 / 0211952, or WO 2013 / 011122.

[0004] According to JP 2006241330, cationic modified galactomannan derived from tara gum has improved conditioning properties in household and personal care products, especially hair and body wash products, compared to cationic modified galactomannan derived from guar gum.

[0005] Global interest in better personal care products continues to grow.

[0006] Guar gum is a polysaccharide composed of galactose and mannose as basic sugar units. The main chain is a straight chain of mannose residues linked by β-1,4, and on average, galactose residues are linked by α-1,6 at every other mannose residue, forming short side units.

[0007] Unlike other legumes, tara gum is a natural additive obtained by grinding the endosperm of the seeds of Caesalpinia spinosa. Structurally, it is a galactomannan polymer composed of a backbone of β-1,4-linked mannose units, with approximately α-1,6-linked galactose side chains on every three mannose units.

[0008] Similarly, galactomannans derived from Sophora japonica and Cassia tora are composed of polymers with a backbone of β-1,4-linked mannose units, in which approximately every four and five mannose units have α-1,6-linked galactose side chains, respectively.

[0009] However, the main drawback of using tara gum is the difficulty in obtaining the raw material, as it comes from tall trees rather than shrubs, which limits its widespread use due to its high cost. Another disadvantage is that the annual yield is low because the supplying trees only grow in specific areas.

[0010] As described in U.S. Patent 5,234,825, the regulation of galactose content in galactomannan can be altered to some extent by using galactosidases capable of removing intrinsically linked galactose units from the main chain.

[0011] However, this method has some drawbacks, primarily due to the difficulty in achieving proper and extensive contact of the enzyme with all its components caused by the viscosity of guar gum, which ultimately significantly affects the mannose / galactose molar ratio. Furthermore, this ratio can also be affected by the incomplete removal of residual galactose cleaved during the enzymatic reaction.

[0012] Finally, residual galactose may be particularly relevant, especially when cationization is performed, as any residual galactose may also be cationized, thus affecting the final properties of cationic galactomannan.

[0013] In view of the above, there is a need to develop a method for preparing cationic inverted galactomannans that are structurally similar to cationic galactomannans derived from other legumes (especially natural tarara gum), have good conditioning properties for use in home and personal care compositions, are cost-effective to prepare, and therefore have a wide range of applications. Summary of the Invention

[0014] In conducting research in this field, the applicant has now developed a method for preparing an innovative cationic galactomannan using a cost-effective and simple enzymatic approach. This cationic galactomannan has a precisely controlled mannose / galactose ratio similar to that of galactomannans from other legumes, but is derived from guar gum.

[0015] Therefore, the present invention is based on a cationic galactomannan containing a mannose / galactose molar ratio in the range of 2.5:1 to 5:1.

[0016] The cationic galactomannan is derived from guar gum.

[0017] Preferably, the cationic galactomannan contains a mannose / galactose ratio of 2.5:1 to 3.5:1.

[0018] Furthermore, the present invention also aims to provide a method for preparing the cationic galactomannan while precisely controlling the mannose / galactose ratio.

[0019] In particular, according to the invention, in a first production method step, guar gum is subjected to a reaction with at least one enzyme to obtain a modified galactomannan having a controlled mannose / galactose ratio, and in a second step, the modified galactomannan is reacted with at least one cationic agent.

[0020] It has been demonstrated that by using the method of the present invention, not only can the mannose / galactose ratio of cationic galactomannans be controlled, but also the degree of substitution (DS) and molecular weight (Mw) of such cationic galactomannans can be controlled.

[0021] Advantageously, cationic galactomannan with a controlled mannose / galactose ratio not only exhibits excellent performance in personal care compositions, but also has high biodegradability.

[0022] The present invention also relates to the use of the cationic galactomannan having a controlled mannose / galactose ratio as a conditioning agent, stabilizer, thickener, film-forming agent, surface modifier, emulsifier, deposition aid, rheology modifier, and flocculant.

[0023] Finally, the present invention also relates to a composition, preferably a home and personal care composition, comprising at least one cationic galactomannan according to the invention. Detailed Implementation

[0024] definition:

[0025] Throughout the specification (including the claims), the terms “comprising one” or “comprising a” shall be construed as synonymous with the term “comprising at least one”, unless otherwise specified, and “between” and “to” shall be construed as including the limits.

[0026] As used herein, unless otherwise indicated, the term "average" refers to the exponential average.

[0027] As used herein, “weight percentage”, “wt%”, “percentage by weight”, “% by weight”, and variations thereof refer to the concentration of a substance when the weight of the substance is divided by the total weight of the composition and multiplied by 100.

[0028] Throughout the specification (including the claims), unless otherwise indicated, the term "average" means exponential average.

[0029] Throughout the specification (including the claims), all process terms shall be understood to be synonymous with the term method.

[0030] It should be noted that, for the sake of continuity of illustration, unless otherwise indicated, limit values ​​are included within the range of given values.

[0031] If any disclosure of any patent, patent application, or publication incorporated herein by reference conflicts with the specification of this application to the extent that it may make the terminology unclear, then this specification shall take precedence.

[0032] This invention relates to cationic galactomannans containing mannose / galactose molar ratios in the range of 2.5:1 and 5:1.

[0033] The cationic galactomannan is derived from guar gum.

[0034] As used herein, the term "cationic group" refers to a positively charged group and a partially charged group. As used herein, the expression "partially charged group" refers to those groups that may become positively charged depending on the pH of the formulation. Such groups may also be referred to as "potentially cationic groups." As used herein, the term "cation" means at least partially cationic. Thus, the terms "cationizing agent," "cationic group," and "cationic moiety" include ammonium (which has a positive charge) as well as primary, secondary, and tertiary amines and their precursors (which are capable of producing positively charged compounds).

[0035] In preferred embodiments, the mannose / galactose ratio is 2.5:1 and 3.5:1. In particular, the mannose / galactose ratio of the cationic galactomannan of the present invention is on average 3:1.

[0036] As used herein, the mannose / galactose ratio refers to the mannose / galactose molar ratio present in the modified galactomannan or cationic galactomannan of this invention.

[0037] The mannose / galactose ratio of the modified galactomannan of this invention can be measured by... 1 The method was performed using 1H NMR spectroscopy.

[0038] Once you get 1 The 1H NMR spectrum was integrated and normalized to 1 for the multiplet signal (calibrated at 5.2 ppm) corresponding to the cleaved mannose anomer. The other three target signals (corresponding to the cleaved galactose anomer) were typically between 5.30 and 5.29 ppm. Another signal (corresponding to the linked mannose anomer) was typically around 4.89 ppm. The last target signal was typically around 4.61 and 4.60 ppm and corresponded to the linked galactose anomer.

[0039] Therefore, the mannose / galactose ratio can be calculated as follows:

[0040] .

[0041] The cationic galactomannan of the present invention has the desired cationicity and conditioning properties, while maintaining good biodegradability.

[0042] Typically, the cationicity of cationic galactomannans can be expressed as the degree of substitution (DS).

[0043] The degree of cationic substitution can be determined before or after acidic methanol extraction. Acidic methanol extraction can be considered a washing step, which allows the removal of other quaternary ammonium compounds present at the end of the reaction, which are byproducts of residual cationizing agents or unreacted cationizing agents.

[0044] Generally, the degree of cationic substitution (DS) after acidic methanol extraction 阳离子 ) 萃取 The degree of cationic substitution (DS) was lower than that prior to extraction. 阳离子 In this invention, the degree of cationic substitution (DS) determined after acidic methanol extraction is... 阳离子 ) 萃取 More precise.

[0045] As used in this article, (DS) 阳离子 ) or (DS) 阳离子 This involves the degree of cation substitution measured prior to acidic methanol extraction.

[0046] As used in this article, (DS) 阳离子 ) 萃取 or (DS) 阳离子 ) 萃取 This involves the degree of cationic substitution measured after acidic methanol extraction.

[0047] As used in this article, the term "degree of cation substitution" (DS) is used to express this concept. 阳离子 ) or (DS) 阳离子 ) 萃取 This refers to the average number of moles of cationic groups per mole of sugar unit. (DS) 阳离子 ) or (DS) 阳离子 ) 萃取 It can be done 1 H NMR measurements.

[0048] Once you get 1The H NMR spectrum was normalized to 1 by integrating the multiplets (typically between 5.4 and 4.4 ppm) corresponding to the anomeric protons of the sugar. The target peak (corresponding to the methyl protons of the quaternary ammonium group on the cationic galactomannan) was centered at approximately 3.1–3.2 ppm. Given the presence of three methyl groups on the nitrogen atom to achieve the ammonium functional group, the peak was integrated for nine protons. Therefore, in the case of the cationic agent 2,3-epoxypropyltrimethylammonium chloride, (DS... 阳离子 The calculation of ) is as follows:

[0049] .

[0050] The degree of cationic substitution was measured prior to the extraction process (DS). 阳离子 ) and afterwards (DS) 阳离子 ) 萃取 Therefore, the true value of the degree of cationic substitution is considered to be the value measured after the removal of cationic impurities.

[0051] Generally, the degree of cationic substitution of the cationic galactomannan of the present invention can be determined before or after the extraction step. In some embodiments, the extraction step is carried out by an acidic methanol extraction step. The ratio of methanol to acid, preferably concentrated HCl having about 37% acid v / v, can be from about 25:1 to 100:1, preferably about 50:1. Furthermore, in some embodiments, the acidic methanol extraction step can be considered a washing step, which can remove other quaternary ammonium compounds that may be present at the end of the cationization reaction, including but not limited to one or more residual cationizing agents, byproducts of one or more unreacted cationizing agents, or mixtures thereof.

[0052] The extraction step can be performed in a variety of ways. As noted above, in some embodiments, the extraction step can be performed by acidifying methanol (50:1, MeOH / HCl). 浓37%The extraction is performed (v / v). Alternatively, cationic galactomannan can be added to acidic methanol at a concentration of approximately 1% under stirring. After adding acidic methanol to the cationic galactomannan, the mixture is brought to reflux temperature and maintained at reflux temperature for approximately 45 minutes. At the end of this extraction step, the acidic methanol can be decanted and the process can be repeated. In some embodiments, the extraction step comprises one to three, preferably three, consecutive steps: adding acidic methanol to the cationic galactomannan and refluxing the mixture for a specified period of time, wherein after each intermediate step, the acidic methanol is removed and replaced with fresh acidic methanol. After the extraction step is completely completed, the cationic galactomannan can be filtered and washed with pure methanol, ethanol, or another suitable solvent. The purified cationic galactomannan is then dried and ground, and then subjected to further processing. 1 HNMR analysis.

[0053] According to one embodiment of the invention, the cationic galactomannan has a degree of cation substitution (DS) for the cationic substituent in the range of 0.01 to 1.0. 阳离子 ) 萃取 .

[0054] In a preferred embodiment, the cationic galactomannan has a degree of cation substitution (DS) for the cationic substituent in the range of 0.01 to 0.4. 阳离子 ) 萃取 .

[0055] In a more preferred embodiment, the cationic galactomannan has a degree of cation substitution (DS) for the cationic substituent in the range of 0.05 to 0.2. 阳离子 ) 萃取 .

[0056] The degree of cationization of cationic galactomannans can also be expressed as charge density. The degree of cationic substitution can be converted into charge density using several methods.

[0057] A preferred method for calculating the charge density of cationic galactomannans uses a method that precisely quantifies the equivalent amount of quaternary ammonium groups on the galactomannan. For cationic galactomannans obtained by reacting galactomannan with 3-chloro-2-hydroxypropyltrimethylammonium chloride or 2,3-epoxypropyltrimethylammonium chloride, the cationic charge density can be calculated from the degree of cationic substitution using the following formula:

[0058] Cation charge density in milliequivalents per gram (meq / g) = .

[0059] Generally, the above formula depends on the groups grafted onto the galactomannan.

[0060] As used herein, the term "charge density" refers to the ratio of the positive charge on a monomer unit included in a polymer to the molecular weight of that monomer unit. The product of charge density and polymer molecular weight determines the number of positively charged sites on a given polymer chain.

[0061] According to the present invention, the cationic galactomannan has a charge density of about 0.06 to about 3.2 meq / g, for example about 0.06 to about 1.8 meq / g, and for example 0.06 to 1.2 meq / g after acidic methanol extraction.

[0062] Regarding the average molecular weight (Mw) of the cationic galactomannan of the present invention, generally, the cationic galactomannan can have an average molecular weight (Mw) of at least about 10,000 Da. The cationic galactomannan of the present invention can also typically have an average molecular weight (Mw) of up to about 2,500 kDa. In preferred embodiments, the cationic galactomannan of the present invention can have an average molecular weight (Mw) of more than about 200,000 Da and more preferably more than 600,000 Da.

[0063] In another preferred embodiment, the average molecular weight of the cationic galactomannan described herein is less than about 2,500 kDa, more preferably less than 1,900 kDa.

[0064] According to a particularly preferred embodiment, the average molecular weight of the cationic galactomannan includes 600 kDa to about 1,900 kDa.

[0065] As used herein, the “average molecular weight” of cationic galactomannan means the weight-average molecular weight of the galactomannan.

[0066] The average molecular weight of cationic galactomannans was measured using SEC-MALS (size exclusion chromatography with multi-angle light scattering detection). Molecular weight was measured using a value of 0.140 for dn / dc. The Wyatt MALS detector was calibrated using a 22.5 kDa polyethylene glycol standard. All calculations of the molecular weight distribution were performed using Wyatt's ASTRA software. For cationic galactomannans, samples were prepared as 0.05% solutions in a mobile phase (100 mM NaNO3, 200 ppm NaN3, 20 ppm pDADMAC) and filtered through a 0.45 μm PVDF filter prior to analysis. 100 µL of the filtered solution was injected and then passed through a pre-column with three OH pak SB-806 M columns at 35°C. For modified galactomannan, the sample was prepared as a 0.05% solution in the mobile phase (100 mM NaNO3, 200 ppm NaN3) and filtered through a 0.45 μm PVDF filter before analysis. 100 µL of the filtered solution was injected and then passed through a pre-column with three OH pak SB-806 M columns at 35°C.

[0067] Galactomannans can be functionalized by chemical modification using various cationic reactants (also known as cationizing agents). The cationizing agents of the present invention are defined as compounds that, by reacting with the hydroxyl groups of galactomannans, can produce galactomannans comprising at least one cationic group according to the present invention. Specifically, depending on the galactomannan and the hydroxyl groups that can be chemically modified, the cationizing agent can react with available hydroxyl groups of the mannose backbone or skeleton, available hydroxyl groups of galactose units substituted along the mannose backbone or skeleton, or both. Various cationizing agents can be used in this regard. Furthermore, cationic galactomannans can be formed by reacting at least one galactomannan according to the present invention with at least one cationizing agent.

[0068] The cationizing agent of the present invention is defined as a compound containing at least one cationic moiety. The cationizing agent includes agents capable of cationizing galactomannan to produce cationically modified galactomannan.

[0069] According to the present invention, examples of cationic agents for generating the disclosed cationic galactomannan are:

[0070] -Cat epoxides, such as 2,3-epoxypropyltrimethylammonium chloride, 2,3-epoxypropyltrimethylammonium bromide, 2,3-epoxypropyltrimethylammonium iodide, and mixtures thereof;

[0071] 1-Chloroethanol-functionalized cationic nitrogen compounds, such as 3-halo-2-hydroxypropyltrimethylammonium chloride, for example 3-chloro-2-hydroxypropyltrimethylammonium chloride, and mixtures thereof;

[0072] -Catonic olefinically unsaturated monomers or their precursors, such as trimethylammonium propyl methacrylamide chloride, trimethylammonium propyl methacrylamide methyl sulfate, diallyl dimethyl ammonium chloride, vinyl benzyl trimethyl ammonium chloride, cationic monomers of dimethylaminopropyl methacrylamide (tertiary amine) precursors such as N-vinylformamide, N-vinylacetamide (whose units can be hydrolyzed or grafted onto ethyleneamine units after polymerization), and mixtures thereof.

[0073] In particular, the cationizing agent for producing the cationic galactomannan of the present invention can be selected from 2,3-epoxypropyltrimethylammonium chloride, 2,3-epoxypropyltrimethylammonium bromide, 2,3-epoxypropyltrimethylammonium iodide, 3-halo-2-hydroxypropyltrimethylammonium chloride (including, for example, 3-chloro-2-hydroxypropyltrimethylammonium chloride), and combinations thereof.

[0074] In a preferred embodiment, the cationic galactomannan of the present invention is cationicized by at least one cationic agent selected from 2,3-epoxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride and mixtures thereof.

[0075] According to the present invention, cationic groups can be introduced into modified galactomannan by reacting the modified galactomannan starting material with a derivatizing agent comprising reactive functional groups and at least one cationic moiety (or a precursor of the cationic moiety).

[0076] A suitable set of derivatizing agents typically contains reactive functional groups, such as epoxy groups, halogen groups, ester groups, acid anhydride groups or olefinic unsaturated groups, and at least one cationic moiety or a precursor of such cationic moiety.

[0077] As used herein, the term "derivative" means an agent containing at least a cationic moiety grafted onto galactomannan. The term "derivative" encompasses the term "cationizing agent." In one embodiment of the invention, the cationic moiety may be attached to a reactive functional group of the derivatizing agent via a divalent linking group (such as an alkylene or oxyalkylene group). Suitable cationic moieties include, but are not limited to, primary, secondary, or tertiary amino groups, quaternary ammonium groups, sulfonium or phosphonium groups, and combinations thereof.

[0078] The derivatizing agent may comprise a cationic moiety or a precursor of a cationic moiety containing a cationic nitrogen moiety, more typically a quaternary ammonium moiety. Typical quaternary ammonium moieties are trialkylammonium moieties (such as trimethylammonium, triethylammonium, or tributylammonium moieties), aryldialkylammonium moieties (such as benzyldimethylammonium moieties), and ammonium moieties in which the nitrogen atom is a member of a cyclic structure (such as pyridinium and imidazoline moieties), each of which is combined with a counterion (typically chloride, bromide, iodide, or acetate counterions). In one embodiment, the cationic substituent is attached to the reactive functional group of the cationic agent via an alkylene or oxyalkylene linking group.

[0079] In a preferred embodiment, the cationic galactomannan of the present invention comprises a cationic group selected from the following: an amino group selected from primary amino, secondary amino, tertiary amino and combinations thereof; a quaternary ammonium group; a sulfonium group; a phosphonium group; and combinations thereof.

[0080] In another preferred embodiment, the cationic group of the galactomannan of the present invention is selected from trialkylammonium groups, such as trimethylammonium groups, triethylammonium groups, or tributylammonium groups; aryl dialkylammonium groups, such as benzyl dimethylammonium groups; ammonium groups wherein the nitrogen atom is a member of a ring structure, such as pyridinium groups and imidazoline groups; and combinations thereof.

[0081] According to embodiments of the present invention, cationic galactomannan may optionally contain other derivatized groups, such as cationic hydrophobic groups or hydrophobic groups. Suitable hydrophobic groups include hydroxyalkyl groups, preferably hydroxypropyl groups.

[0082] Advantageously, the cationic galactomannan of the present invention is biodegradable.

[0083] The term biodegradable means that a compound / product or any article of manufacture degrades naturally and returns to nature without causing any harmful impact on the environment. As used herein, biodegradability is measured according to the inherent biodegradability test OECD 302, and specifically, a compound / product is considered biodegradable under OECD 302B (as modified and discussed). Specifically, OECD 302B provides test criteria for determining whether a chemical substance is considered biodegradable (including inherently biodegradable). Test method OECD 302B means, and as used herein, that the method is used without any preconditioning of the inoculum (i.e., inherent final biodegradation of the inoculum without preconditioning), as modified in the following ways: (i) regarding the percentage of biodegradation of the tested sample, a sample is considered biodegradable if at least 60% of the tested sample is biodegradable during the test period; and (ii) the biodegradation is determined using the OxiTop®-IDS sensor available from Xylem Analytics. Therefore, for example, based on the foregoing and as used herein, a material is considered biodegradable under OECD 302B if at least 60% of it is biodegradable over 60 days (the testing period). As used herein, the inoculum used in OECD 302B as modified and described above means that the inoculum was sampled from the environment and was not cultured specifically to enhance the biodegradability of cationic galactomannan (i.e., the inoculum was not pre-adapted).

[0084] In one embodiment, the cationic galactomannan of the present invention is obtained by reacting a modified galactomannan derived from guar gum having a controlled mannose / galactose ratio with at least one cationic agent.

[0085] According to the invention, in the first step, guar gum is subjected to a reaction with at least one enzyme to obtain modified galactomannan as defined above.

[0086] exist Figure 1 The enzymatic method of the present invention is described in the document.

[0087] The obtained modified galactomannan has a controlled mannose / galactose ratio, such as, for example Figure 1 As shown.

[0088] The method of the present invention allows for extensive cleavage not only by enabling the enzyme to reach all the necessary sites of guar gum, but also by completely removing the galactose residues cleaved from guar gum.

[0089] For enzymatic reactions, guar gum is first swollen with water.

[0090] Guar gum is swollen with water, and after grinding, swollen guar gum is produced in the form of "grated parmesan." To control the swelling state of the guar gum, the total water content to guar gum weight ratio is between 1.5:1 g / g, preferably between 1:1 g / g. If the amount of water is too high, a paste or slurry will form and should be avoided, as enzymatic contact with guar gum during the enzymatic reaction is detrimental. If the water content is too low, insufficient swelling of the guar gum is obtained, and the resulting enzymatic reaction is severely affected by insufficient contact between the enzyme and the guar gum. In both cases, the accessibility of guar gum is insufficient for the reaction to occur properly.

[0091] The obtained swollen guar gum is then contacted with an enzymatic solution containing at least one enzyme and a buffer solution and subjected to an enzymatic reaction. In particular, the enzymatic solution is obtained using a mixture of at least one enzyme and a buffer solution, the molar concentration of which is between 0.01 and 0.05 M, preferably between 0.01 and 0.03 M, based on the total weight of the enzymatic solution.

[0092] The buffer solution used in this invention may be selected in a non-limiting manner from sodium acetate solution, potassium acetate solution, sodium citrate solution and potassium phthalate solution.

[0093] Modified galactomannan can be obtained by enzymatically cleaving the galactose portion of guar gum.

[0094] The inventors discovered that adding swollen guar gum part-wise to an enzymatic solution containing an enzyme and a buffer solution allows for both good wetting of the guar gum by the enzymatic solution and impregnation of the enzyme on the guar gum. In particular, subjecting the mixture of guar gum and the enzymatic solution to vigorous stirring results in the formation of a macroscopically homogeneous gel.

[0095] Preferably, the swollen guar gum is added to the enzymatic solution at a weight ratio of guar gum to the total weight of the mixture, which is between 0.01 and 0.1, preferably between 0.01 and 0.03, based on the total weight of the mixture.

[0096] The enzymatic reaction is carried out at a temperature of 0°C to 90°C, preferably 30°C to 80°C.

[0097] The enzymatic reaction preferably lasts for at least 5 hours. According to the invention, the enzymatic reaction preferably lasts for 5 to 30 hours, more preferably 5 to 24 hours.

[0098] The enzymatically reacted guar gum was then washed with an alcohol:water mixture to obtain crude, broken galactomannan. The washing mixture contained alcohol:water in a volume ratio of 1:1 to 10:5 (v / v) based on the total volume of the mixture.

[0099] By using a washing solution, galactose residues can be removed from the interface of the reaction mixture, and crude galactomannan can be obtained.

[0100] The crude cleaved galactomannan was then completely dried in an oven at 50°C under atmospheric pressure for 16 hours and ground into a fine powder using a cryogenic grinder.

[0101] The inventors have discovered that an additional washing process allows for the complete removal of galactose units that are broken down and carried into the crude mixture of broken galactomannan.

[0102] In a particularly preferred embodiment, the milled powder is then washed at least four times with an alcohol:water mixture to obtain modified galactomannan.

[0103] The modified galactomannan contains mannose / galactose molar ratios in the range of 2.5:1 and 5:1.

[0104] Specifically, the washing mixture comprises alcohol:water in a volume ratio of 1:1 to 10:5 based on the total volume of the mixture.

[0105] In particular, in order to accurately control the mannose / galactose ratio, additional washing after grinding the crude modified galactomannan is unavoidable.

[0106] Furthermore, by using the method of the present invention, modified galactomannans with a controlled average mannose / galactose ratio can be obtained, which is crucial for obtaining the desired cationicity of cationic galactomannans.

[0107] According to a particularly preferred embodiment, the method for obtaining the modified galactomannan as described above from guar gum follows these steps:

[0108] a. Soak guar gum in water;

[0109] b. Contact the obtained swollen guar gum with an enzyme solution containing at least one enzyme and a buffer, and heat the resulting mixture at a temperature of 30°C to 80°C for 5 to 30 hours to obtain enzymatically reacted guar gum;

[0110] c. Wash the enzymatically reacted guar gum at least four times with a mixture of alcohol and water to obtain crude broken galactomannan;

[0111] d. After the crude broken galactomannan is completely dried, it is ground into a fine powder and washed at least four times with a mixture of alcohol and water to obtain modified galactomannan.

[0112] The modified galactomannan contains mannose / galactose molar ratios in the range of 2.5:1 and 5:1.

[0113] According to the present invention, the alcohol may be selected from, but is not limited to, isopropanol, methanol, and ethanol. According to a preferred embodiment, the selected alcohol is isopropanol.

[0114] In specific embodiments of the invention, at least one enzyme is selected from galactosidase, preferably α-galactosidase, and even more preferably α-galactosidase (glycoside hydrolase 27) of the CAZy family GH27, which can be obtained from, for example, guar bean seeds and Aspergillus niger. Typically, GH27 α-galactosidase is an "endonuclease" capable of random cleavage.

[0115] Without being bound by any theory, it is assumed that the properties of α-galactosidases (GH27 or GH36) influence the final galactose / mannose distribution in modified guar gum. Specifically, GH27 α-galactosidase can promote random cleavage, while GH36 α-galactosidase can only cleave the galactose units at the ends of the polymer chains.

[0116] By means of the method according to the present invention, the mannose / galactose ratio in the modified galactomannan can be accurately controlled, and the molecular weight (Mw) and cationicity (DS) targets of the cationic galactomannan as described above can ultimately be appropriately achieved.

[0117] Subsequently, in the second step, the modified galactomannan is reacted with at least one cationic agent to produce the cationic galactomannan as described above.

[0118] Using methods generally known in the art, cationization of galactomannans can be readily performed by those skilled in the art. Various methods for providing galactomannans with cationic functionality are known in the art, for example, as disclosed in U.S. Patent Publication No. 2008 / 0112907. Various methods for crosslinking galactomannans (both with and without cationic modification) are also known, see, for example, U.S. Patent Nos. 5,532,350, 5,801,116, and 5,473,059.

[0119] According to the present invention, a modified galactomannan with a controlled mannose / galactose ratio obtained by enzymatic treatment of guar gum is derivatized or modified to contain cationic groups. The resulting compound is the cationic galactomannan of the present invention.

[0120] The cationic galactomannan of the present invention can be used in household and personal applications, such as as a conditioning agent, stabilizer, thickener, emulsifier, deposition aid, rheology modifier, and flocculant.

[0121] Home and personal care compositions containing various types of conditioning agents, such as conditioning shampoos, shower gels, and fabric care compositions, have been previously disclosed and are well known to those skilled in the art to allow for the cleaning and conditioning of hair, skin, and fabrics, the repair of damaged hair, and the styling of hair.

[0122] Personal care compositions refer to any substance that is personal in nature. This can include compositions for bathing and showering, including, in particular, bed-baths, lotions, and creams for skin care, oral hygiene, cosmetics, and hair care. Specifically, the compositions of the present invention can be skin care compositions such as shower gels, soaps, hydrogels, creams, lotions, or balms, or hair care compositions such as shampoos, rinse-out conditioners, leave-in conditioners, gels, hair creams, or cuticle coats.

[0123] Home care compositions should include general household cleaning products such as toilet cleaners, laundry detergents, fabric softeners, dishwashing liquids, bathroom cleaners, and surface cleaners.

[0124] These compositions may also include aesthetic modifiers, film-forming agents, chelating agents, emulsifiers, humectants, emollients, surfactants (such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants, or combinations thereof), propellants, stabilizers, preservatives, detergents and suspending / gelling agents, and active ingredients.

[0125] It is noteworthy that these compositions of the present invention, preferably personal care compositions, comprise one or more "beneficial agents," i.e., materials that provide care benefits (such as moisturizing or conditioning), such as emollients, oils, humectants, moisturizers, conditioning agents, polymers, vitamins, abrasives, UV absorbers, antimicrobial agents, anti-dandruff agents, fragrances, and / or appearance-modifying additives, such as coloring particles or reflective particles, which may be in solid, liquid, or gaseous form and may be insoluble or only partially soluble in the composition. Mixtures of beneficial agents may be used.

[0126] Throughout the specification (including the claims), all process terms shall be understood to be synonymous with the term method.

[0127] The following examples are included to illustrate embodiments of the invention, but are not limited to the examples described. Example

[0128] All materials are commercially available.

[0129] The enzyme α-galactosidase GH27 (glycoside hydrolase 27), purified from guar bean seeds (product code E-AGLGU), was obtained from MEGAZYME.

[0130] Guar gum: Jaguar from Solvay ® S.

[0131] Sodium acetate buffer solution (pH 5.2 ± 0.1 at 25°C, for molecular biology, 3 M, 0.2 μm filtered) was obtained from Sigma-Aldrich (product code S7899-500ML).

[0132] Test methods :

[0133] Galactose / mannose molar ratio

[0134] As described above, after acidic hydrolysis (solvent: TFA-d + D2O) at 90°C for 2 hours, through... 1 The galactose:mannose molar ratio of a modified galactomannan or cationic galactomannan was measured by 1H NMR spectroscopy.

[0135] molecular weight

[0136] As described above, the average molecular weight of modified galactomannan or cationic galactomannan was measured using SEC-MALS (size exclusion chromatography with multi-angle light scattering detection) with three Shodex Pack OH Pak LB-806 M columns.

[0137] Degree of cation substitution

[0138] As described above, after acidic hydrolysis (solvent: TFA-d + D2O) at 90°C for 2 hours, through... 1 H NMR was used to measure the degree of cationic substitution of cationic galactomannan.

[0139] Biodegradability

[0140] The biodegradability of cationic galactomannan was measured according to OECD 302B (modified as discussed above), a method modified for the percentage of biodegradation (i.e., at least 60%) of the tested sample and the sensor used to determine biodegradation. Biodegradability was assessed on a 28-day and 60-day basis. The OxiTop®-IDS sensor, available from Xylem Analytical Instruments, was used to determine biodegradation. The inoculum was not pre-adapted.

[0141] According to the present invention, a series of enzymatic reactions were carried out at the same temperature but with different amounts of enzyme added in the reaction medium (U / g guar gum, i.e., enzyme activity per gram of guar gum) and different guar gum concentrations. The modified galactomannans (MG4 to MG7) obtained are summarized in Table 1.

[0142] To compare the enzymatic reactions, comparative examples were conducted and the resulting comparative modified galactomannans (CMG1 to CMG3) are summarized in Table 1.

[0143] Part I: Synthesis of Modified Galactomannan

[0144] Comparative Example 1: Synthesis of Modified Galactomannan

[0145] In step b, 150 g of ultrapure water, 0.50 mL of sodium acetate buffer solution (3 M, pH 5.2 ± 0.1 at 25°C), and 29 µL of the enzyme α-galactosidase (2.9 U enzyme / g guar gum) are introduced into a 500 mL round-bottom flask equipped with a magnetic stirrer and a condenser. 5 g of guar gum is added to the enzyme-catalyzed solution. The resulting paste is mixed with a spatula for 5 minutes every 2 hours over the first 8 hours. The reaction medium is heated at 40°C for 24 hours. After 24 hours, the reaction medium is heated at 80°C for 30 minutes to denature the enzyme. After cooling to room temperature, 200 mL of isopropanol is added to the flask to reduce viscosity and obtain a reaction medium containing the enzymatically reacted guar gum.

[0146] In step c, the reaction medium was filtered under vacuum and washed four times with a solution (200 mL) of isopropanol and water. A white gel was obtained and dried in an oven at 50°C under atmospheric pressure for 16 hours to obtain a crude fragmented galactomannan solid. The crude fragmented galactomannan solid was ground into a fine powder to produce a comparatively modified galactomannan.

[0147] The resulting modified galactomannan CMG1 showed a mannose / galactose molar ratio of 1.88:1.

[0148] Comparative Example 2: Synthesis of Modified Galactomannan

[0149] In step a, 5 g of guar gum and 5 g of ultrapure water are introduced into a mortar. The mixture is then ground with a pestle to obtain swollen guar gum powder.

[0150] In step b, 145 g of ultrapure water, 0.50 mL of sodium acetate buffer solution (3 M, pH 5.2 ± 0.1 at 25°C), and 29 µL of the enzyme α-galactosidase (2.9 U enzyme / g guar gum) were introduced into a 500 mL round-bottom flask equipped with a magnetic stirrer and a condenser. The swollen guar gum was added partically to the enzyme solution while stirring (200 rpm). After addition, the reaction medium was heated at 40°C for 24 hours. After 24 hours, the reaction medium was heated at 80°C for 30 minutes to denature the enzyme. After cooling to room temperature, 200 mL of isopropanol was added to the flask to reduce the viscosity and obtain a reaction medium containing the enzymatically reacted guar gum.

[0151] In step c, the reaction medium was filtered under vacuum and washed four times with a solution (200 mL) of isopropanol and water. A white gel was obtained and dried in an oven at 50°C under atmospheric pressure for 16 hours to obtain a crude fragmented galactomannan solid. The crude fragmented galactomannan solid was ground into a fine powder to produce a comparatively modified galactomannan.

[0152] The resulting modified galactomannan CMG2 showed a mannose / galactose molar ratio of 2.3:1.

[0153] Comparative Example 3: Synthesis of Modified Galactomannan

[0154] In step b, 150 g of ultrapure water, 0.50 mL of sodium acetate buffer solution (3 M, pH 5.2 ± 0.1 at 25°C), and 29 µL of the enzyme α-galactosidase (2.9 U enzyme / g guar gum) are introduced into a 500 mL round-bottom flask equipped with a magnetic stirrer and a condenser. 5 g of guar gum is added to the enzyme-catalyzed solution. The resulting paste is mixed with a spatula for 5 minutes every 2 hours over the first 8 hours. The reaction medium is heated at 40°C for 24 hours. After 24 hours, the reaction medium is heated at 80°C for 30 minutes to denature the enzyme. After cooling to room temperature, 200 mL of isopropanol is added to the flask to reduce viscosity and obtain a reaction medium containing the enzymatically reacted guar gum.

[0155] In step c, the reaction medium was filtered under vacuum and washed four times with a solution (200 mL) of isopropanol and water. A white gel was obtained and dried in an oven at 50°C under atmospheric pressure for 16 hours to obtain crude cleaved galactomannan solids.

[0156] In step d, the crude cleaved galactomannan solid is ground into a fine powder and further washed four times with a solution of isopropanol and water (200 mL) to obtain comparative modified galactomannan.

[0157] The resulting modified galactomannan CMG3 showed a mannose / galactose molar ratio of 1.95:1.

[0158] Example 4: Synthesis of Modified Galactomannan

[0159] In step a, 15 g of guar gum and 15 g of ultrapure water are introduced into a mortar. The mixture is then ground with a pestle to obtain swollen guar gum powder.

[0160] In step b, 435 g of ultrapure water, 1.50 mL of sodium acetate buffer solution (3 M, pH 5.2 ± 0.1 at 25°C), and 78 µL of the enzyme α-galactosidase (2.60 U enzyme / g guar gum) were introduced into a 1 L round-bottom flask equipped with a magnetic stirrer and a condenser. The swollen guar gum was added partically to the enzyme solution while stirring (200 rpm). After addition, the reaction medium was heated at 40°C for 24 hours. After 24 hours, the reaction medium was heated at 80°C for 30 minutes to denature the enzyme. After cooling to room temperature, 200 mL of isopropanol was added to the flask to reduce the viscosity and obtain a reaction medium containing the enzymatically reacted guar gum.

[0161] In step c, the reaction medium was filtered under vacuum and washed four times with a solution (200 mL) of isopropanol and water. A white gel was obtained and dried in an oven at 50°C under atmospheric pressure for 16 hours to obtain crude cleaved galactomannan solids.

[0162] In step d, the crude broken galactomannan solid is ground into a fine powder and further washed four times with a solution of isopropanol and water (200 mL) to obtain modified galactomannan.

[0163] The resulting modified galactomannan MG4 exhibited a mannose / galactose molar ratio of 2.82:1 and an average molar mass of Mw = 1782 kDa.

[0164] Example 5: Synthesis of Modified Galactomannan

[0165] In step a, 15 g of guar gum and 15 g of ultrapure water are introduced into a mortar. The mixture is then ground with a pestle to obtain swollen guar gum powder.

[0166] In step b, 435 g of ultrapure water, 1.50 mL of sodium acetate buffer solution (3 M, pH 5.2 ± 0.1 at 25°C), and 82 µL of the enzyme α-galactosidase (2.70 U enzyme / g guar gum) were introduced into a 1 L round-bottom flask equipped with a magnetic stirrer and a condenser. The swollen guar gum was added partically to the enzyme solution while stirring (200 rpm). After addition, the reaction medium was heated at 40°C for 24 hours. After 24 hours, the reaction medium was heated at 80°C for 30 minutes to denature the enzyme. After cooling to room temperature, 200 mL of isopropanol was added to the flask to reduce the viscosity and obtain a reaction medium containing the enzymatically reacted guar gum.

[0167] In step c, the reaction medium was filtered under vacuum and washed four times with a solution (200 mL) of isopropanol and water. A white gel was obtained and dried in an oven at 50°C under atmospheric pressure for 16 hours to obtain crude cleaved galactomannan solids.

[0168] In step d, the crude broken galactomannan solid is ground into a fine powder and further washed four times with a solution of isopropanol and water (200 mL) to obtain modified galactomannan.

[0169] The resulting modified galactomannan MG5 exhibited a mannose / galactose molar ratio of 2.98:1 and an average molar mass of Mw = 1853 kDa.

[0170] Example 6: Synthesis of Modified Galactomannan

[0171] In step a, 15 g of guar gum and 15 g of ultrapure water are placed in a mortar. The mixture is then ground with a pestle to obtain swollen guar gum powder.

[0172] In step b, 435 g of ultrapure water, 1.50 mL of sodium acetate buffer solution (3 M, pH 5.2 ± 0.1 at 25°C), and 87 µL of the enzyme α-galactosidase (2.90 U enzyme / g guar gum) were introduced into a 1 L round-bottom flask equipped with a magnetic stirrer and a condenser. The swollen guar gum was added partically to the enzyme solution while stirring (200 rpm). After addition, the reaction medium was heated at 40°C for 24 hours. After 24 hours, the reaction medium was heated at 80°C for 30 minutes to denature the enzyme. After cooling to room temperature, 200 mL of isopropanol was added to the flask to reduce the viscosity and obtain a reaction medium containing the enzymatically reacted guar gum.

[0173] In step c, the reaction medium was filtered under vacuum and washed four times with a solution (200 mL) of isopropanol and water. A white gel was obtained and dried in an oven at 50°C under atmospheric pressure for 16 hours to obtain crude cleaved galactomannan solids.

[0174] In step d, the crude broken galactomannan is ground into a fine powder and further washed four times with a solution of isopropanol and water (200 mL) to obtain modified galactomannan.

[0175] The resulting modified galactomannan MG6 exhibited a mannose / galactose molar ratio of 3.06:1 and an average molar mass of Mw = 1698 kDa.

[0176] Example 7: Synthesis of Modified Galactomannan

[0177] In step a, 17 g of guar gum and 17 g of ultrapure water are introduced into a mortar. The mixture is then ground with a pestle to obtain swollen guar gum powder.

[0178] In step b, 133 g of ultrapure water, 0.50 mL of sodium acetate buffer solution (3 M, pH 5.2 ± 0.1 at 25°C), and 99 µL of the enzyme α-galactosidase (2.90 U enzyme / g guar gum) were introduced into a 1 L round-bottom flask equipped with a magnetic stirrer and a condenser. The swollen guar gum was added partically to the enzyme solution while stirring (200 rpm). After addition, the reaction medium was heated at 40°C for 24 hours. After 24 hours, the reaction medium was heated at 80°C for 30 minutes to denature the enzyme. After cooling to room temperature, 200 mL of isopropanol was added to the flask to reduce the viscosity and obtain a reaction medium containing the enzymatically reacted guar gum.

[0179] In step c, the reaction medium was filtered under vacuum and washed four times with a solution (200 mL) of isopropanol and water. A white gel was obtained and dried in an oven at 50°C under atmospheric pressure for 16 hours to obtain crude cleaved galactomannan solids.

[0180] In step d, the crude broken galactomannan is ground into a fine powder and further washed four times with a solution of isopropanol and water (200 mL) to obtain modified galactomannan.

[0181] The resulting modified galactomannan MG7 exhibited a mannose / galactose molar ratio of 2.53:1 and an average molar mass of Mw = 1652 kDa.

[0182] Table 1: Modified galactomannan obtained from the enzymatic reaction of guar gum.

[0183]

[0184] As shown in Table 1, comparative examples CMG1 to CMG3 not only demonstrate the importance of proper enzymatic cleavage but also the importance of complete removal of galactose residues cleaved from guar gum. All examples of the present invention, MG4 to MG7, show precise control of the mannose / galactose molar ratio, similar to the average mannose / galactose molar ratio of galactomannan derived from tara gum.

[0185] Part II: Synthesis of Cationic Galactomannan

[0186] Example 8: Synthesis of cationic galactomannan

[0187] In a 100 mL round-bottom flask, under an inert nitrogen atmosphere, 11.2 g of isopropanol solvent, mixed with 4.3 g of deionized water, was introduced at room temperature. Then, 5.01 g of modified galactomannan powder with a mannose / galactose ratio of 2.82:1 was loaded at room temperature with vigorous stirring. After stirring for several minutes to allow homogenization, 2.15 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat188, 65% in water) was added. This reagent was allowed to mix with the modified galactomannan dispersion at room temperature for 30 minutes, followed by the slow addition of 0.82 g of sodium hydroxide (50% in water). This reagent was allowed to mix with the modified galactomannan dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and maintained at that temperature for 60 minutes, after which the temperature was lowered to at least 50°C to begin the washing procedure.

[0188] The reaction mixture obtained as described above was dispersed with 6.3 g isopropanol (99%) and 1.3 g water under stirring. The pH was adjusted to approximately 9–10 using glacial acetic acid. The mixture was then allowed to stand with stirring for 30 minutes. The dispersion was then filtered under vacuum. This washing and filtration process was repeated twice more with 14.4 g isopropanol (99%) and 5.8 g water, each time for 30 minutes. The resulting solid was then dried overnight in an oven at 60°C for 6 hours.

[0189] Degree of cation substitution (DS) 阳离子 The value is 0.17 and (DS) 阳离子 ) 萃取 The value was 0.14. The average molecular weight (Mw) was 1037 kDa. Cationic galactomannan was evaluated according to the OECD 302B procedure. After 28 days, the indicated biodegradation was 64%. Cationic galactomannan is considered inherently and ultimately biodegradable.

[0190] Example 9: Synthesis of cationic galactomannan

[0191] In a 100 mL round-bottom flask, under an inert nitrogen atmosphere, 22.5 g of isopropanol solvent, mixed with 8.6 g of deionized water, was introduced at room temperature. Then, 10.05 g of modified galactomannan powder with a mannose / galactose ratio of 2.53:1 was loaded at room temperature with vigorous stirring. After stirring for several minutes to allow homogenization, 4.29 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat188, 65% in water) was added. This reagent was allowed to mix with the modified galactomannan dispersion at room temperature for 30 minutes, followed by the slow addition of 1.74 g of sodium hydroxide (50% in water). This reagent was allowed to mix with the modified galactomannan dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and maintained at that temperature for 60 minutes, after which the temperature was lowered to at least 50°C to begin the washing procedure.

[0192] The reaction mixture obtained as described above was dispersed with 13.0 g isopropanol (99%) and 2.9 g water under stirring. The pH was adjusted to approximately 9–10 using glacial acetic acid. The mixture was then allowed to stand with stirring for 30 minutes. The dispersion was then filtered under vacuum. This washing and filtration process was repeated twice more with 28.6 g isopropanol (99%) and 11.4 g water, each time for 30 minutes. The resulting solid was then dried overnight in an oven at 60°C for 6 hours.

[0193] Degree of cation substitution (DS) 阳离子 The value is 0.19 and (DS) 阳离子 ) 萃取 The value was 0.16. The average molecular weight (Mw) was 1336 kDa. Cationic galactomannan was evaluated according to the OECD 302B procedure. After 41 days, the indicated biodegradation was 65%. Cationic galactomannan is considered inherently and ultimately biodegradable.

[0194] Part III: Conditioning Properties

[0195] In the following study, we compared standard shampoo formulations containing cationic galactomannan with those containing Jaguar. ® C17 (a commercial product from Solvay) is a standard shampoo formulation. Conditioning performance is evaluated through a combing process.

[0196] Example 10 - Adjustment - Streamlining and Improving the Test Plan

[0197] To evaluate the conditioning and dry appearance properties of the shampoo via wet combing, a flat, calibrated bleached Caucasian hair bundle weighing approximately 4.0 grams was used. The hair bundle was purchased from SP Equation, Quartier Fariguriere, 138 rue Marius Bourrelly, 83470 Pourcieux, France. Prior to actual shampooing, the hair bundle was first cleaned with a 14% active sodium lauryl ether sulfate (SLES) solution. For this cleaning step, the hair bundle was wetted with running water at 30°C for 60 seconds, washed with 2.0 mL of SLES solution for 60 seconds, and then rinsed under running water at 30°C for 60 seconds. This process was repeated a second time.

[0198] Then, gently comb the hair strands by hand to remove major tangles, and then comb ten times at 300 mm / min using an MTT 175 Miniature Tensile Tester (Dia-Stron Ltd.) equipped with an ACE hard rubber fine-tooth comb. Immerse the hair in water and squeeze it between your index and middle fingers to keep it moist between each combing cycle. Hang the hair strands upright and store them overnight in a climate chamber at approximately 21°C ±5°C and approximately 50% relative humidity.

[0199] In the second step, wet each of the aforementioned hair strands again under running water for 60 seconds, and apply 0.2 grams of shampoo per gram of hair along the length of the hair. Knead the hair strands for 45 seconds, and then rinse them under running water at 30°C for 30 seconds, and then squeeze them between your index and middle fingers. Repeat this second step again.

[0200] Then, gently comb the washed hair strands (while still wet) by hand to remove major tangles, and then comb ten times at 300 mm / min using an MTT 175 miniature tensile testing machine (Dia-Stron Ltd.) equipped with an ACE hard rubber fine-tooth comb. Between each combing cycle, the hair was re-wetted with water to keep it moist. A curve of combing force versus displacement was obtained during this process. The total combing work (corresponding to the integral of this signal) was extracted. The average wet combing work per hair strand was calculated from the data of 10 combing cycles. For each formulation, at least three hair strands were assigned and used to determine the average total combing work of the formulation. The lower the total work, the higher the wet conditioning efficiency of the formulation. Using the total combing work of each hair strand before and after shampoo application as described in the steps above, the percentage of combing improvement was calculated and reported in Table 2.

[0201] Table 2. Cationic galactomannan and Jaguar ® Improvements to C17.

[0202]

[0203] As shown in Table 2, the cationic galactomannan of the present invention can significantly reduce combing force, which is comparable to that of commercial cationic guar gum.

[0204] Therefore, a method has been demonstrated for developing cationic galactomannans starting from guar gum, which not only have a controlled mannose / galactose molar ratio similar to that of natural tara gum, but also have a controlled molecular weight and cationicity, with the added advantage of being biodegradable.

Claims

1. A cationic galactomannan comprising a mannose / galactose molar ratio in the range of 2.5:1 and 5:

1. The cationic galactomannan is derived from guar gum. The cationic galactomannan exhibits a (DS) content in the range of 0.01 to 1.0, preferably 0.01 to 0.4, and more preferably 0.05 to 0.2 for cationic substituents. 阳离子 ) 萃取 .

2. The cationic galactomannan according to claim 1, wherein, The average mannose / galactose ratio is 3:

1.

3. The cationic galactomannan according to any one of claims 1 to 3, wherein, This cationic galactomannan has a molecular weight distribution ranging from 600 kDa to 1900 kDa.

4. The cationic galactomannan according to any one of the preceding claims, wherein, This cationic galactomannan is cationicized by at least one cationic agent selected from 2,3-epoxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, and mixtures thereof.

5. The cationic galactomannan according to any one of the preceding claims, wherein, This cationic galactomannan contains cationic groups selected from the following: amino groups selected from primary amino, secondary amino, tertiary amino and combinations thereof; quaternary ammonium groups; sulfonium groups; phosphonium groups; and combinations thereof.

6. The cationic galactomannan according to any one of the preceding claims, wherein, The cationic group is selected from trialkylammonium groups, such as trimethylammonium, triethylammonium, or tributylammonium; aryldialkylammonium groups, such as benzyldimethylammonium; ammonium groups in which the nitrogen atom is a member of a ring structure, such as pyridinium and imidazoline; and combinations thereof.

7. The cationic galactomannan according to any one of the preceding claims, wherein, The cationic galactomannan may optionally further comprise at least one nonionic group selected from hydroxyalkyl, preferably hydroxypropyl.

8. The cationic galactomannan according to any one of the preceding claims, wherein, This cationic galactomannan is biodegradable.

9. A method for preparing cationic galactomannan according to any one of claims 1 to 8, the method being carried out by reacting a modified galactomannan derived from guar gum and comprising a mannose / galactose molar ratio in the range of 2.5:1 and 5:1 with at least one cationic agent.

10. The method according to claim 9, wherein, In a first step, guar gum is subjected to a reaction with at least one enzyme to obtain a modified galactomannan containing a mannose / galactose molar ratio in the range of 2.5:1 and 5:1, and in a second step, the modified galactomannan is reacted with at least one cationic agent, wherein in the first step: a. Soak the guar gum in water until it swells; b. Contact the obtained swollen guar gum with an enzyme solution containing at least one enzyme and a buffer, and heat the resulting mixture at a temperature of 30°C to 80°C for 5 to 30 hours to obtain enzymatically reacted guar gum; c. Wash the enzymatically reacted guar gum at least four times with a mixture of alcohol and water to obtain crude broken galactomannan. d. After the crude broken galactomannan is completely dried, it is ground into a fine powder and washed at least four times with a mixture of alcohol and water to obtain the modified galactomannan. The modified galactomannan contains mannose / galactose molar ratios in the range of 2.5:1 and 5:

1.

11. The method according to claim 10, wherein, The alcohol:water mixture contains a volume ratio of 1:1 to 10:5 based on the total volume of the mixture.

12. The method according to claim 10 or 11, wherein, The alcohol is selected from isopropanol, methanol, and ethanol.

13. The method according to any one of claims 10 to 12, wherein, At least one enzyme is selected from galactosidase, preferably α-galactosidase.

14. Use of cationic galactomannan according to any one of claims 1 to 8 as a conditioning agent, stabilizer, thickener, emulsifier, deposition aid, rheology modifier, hair repair agent, hair straightening formulation component, hair split end repair agent, and flocculant.

15. A composition comprising at least one cationic galactomannan according to any one of claims 1 to 8.

16. The composition according to claim 15, wherein, This composition is a home and personal care composition.

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