Biodegradable cationic galactomannan

Abstract

The present invention generally relates to compositions having biodegradable cationic galactomannan.

Description

[Technical Field]

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 592,312, filed on 23 October 2023, the entire contents of which are incorporated herein by reference in their entirety for any purpose.

[0002] This invention generally relates to biodegradable cationic galactomannan. More specifically, this invention relates to a specific degree of cationic substitution (DS). cationic This invention relates to a biodegradable cationic galactomannan having a molecular weight (Mw) and an average molecular weight (Mw). The present invention also relates to a method for producing biodegradable cationic galactomannan, and to a composition containing biodegradable cationic galactomannan. [Background technology]

[0003] Galactomannan is a type of natural polymer formed from specific sugar residues. More specifically, galactomannan is a polysaccharide having β-(1,4)-linked D-mannopyranosyl residues that form the polymer's backbone (also called the backbone), along which α-(1,6)-linked D-galactopyranosyl residues are linked as side chains at varying degrees of substitution. The mannose-to-galactose ratio not only determines the physical properties of galactomannan but also the type of galactomannan. For example, fenugreek, a galactomannan, has a mannose-to-galactose ratio of approximately 1:1. Other galactomannans have different mannose-to-galactose ratios. Cod, carob, and cassia have mannose-to-galactose ratios of approximately 3:1, 4:1, and 5:1, respectively. On the other hand, natural guar or guar gum generally has a mannose-to-galactose ratio of approximately 2:1.

[0004] Naturally occurring galactomannan can be extracted from the endosperm of various seeds. While naturally occurring galactomannan can be used in its raw form for specific applications without functionalization or chemical modification, chemical modification can enhance its performance in many applications. For example, depending on the application, cationic galactomannan can be used as a conditioner, stabilizer, thickener, emulsifier, adhesion promoter, rheological modifier, and flocculant. In particular, each galactose and mannose unit in natural galactomannan contains a hydroxyl group, which can be chemically modified to functionalize the galactomannan. In this regard, galactomannan can be functionalized using a variety of reactive reagents. For example, one or more cationic reactive reagents, also called cationizing agents, can be used to introduce cationic groups into galactomannan. By adding cationic functional groups, cationic galactomannan not only possesses superior performance characteristics, but also offers significant advantages over petroleum-based or synthetic polymers, as it is extracted from natural, renewable raw materials.

[0005] However, while cationic galactomannan has a wide range of applications, and its starting material, unmodified galactomannan, is naturally occurring, it may not possess desirable biodegradability in the environment, especially under more stringent biodegradability guidelines and requirements in recent years. In other words, cationic galactomannan may not be considered inherently biodegradable, particularly under stricter biodegradability standards. In this regard, there is still a need in the field for cationic galactomannan that is not only sufficiently cationized to achieve the desired performance but also possesses sufficient biodegradability.

[0006] Furthermore, not only methods for producing biodegradable cationic galactomannan, but also compositions containing biodegradable cationic galactomannan remain in demand in this field. [Overview of the project]

[0007] The present invention generally relates to biodegradable cationic galactomannan. In this regard, one embodiment of the present invention has a galactose unit to mannose unit ratio of about 1:1, (a) DS less than 0.17, preferably 0.16 or less, more preferably 0.15 or less cationic and (b) Average molecular weight (Mw) less than 3,500,000 g / mol; This relates to biodegradable cationic galactomannan having the following properties.

[0008] One embodiment of the present invention has a ratio of galactose units to mannose units of approximately 1:1. (a) DS less than 0.17, preferably 0.16 or less, more preferably 0.15 or less cationic and (b) Average molecular weight (Mw) less than 3,500,000 g / mol; A biodegradable cationic galactomannan having, In another embodiment, the cationic galactomannan has a biodegradability of 60% or more within 28 days according to OECD 302B.

[0009] Another embodiment of the present invention is one in which the ratio of galactose units to mannose units is about 1:3 to about 1:5, preferably about 1:3 to about 1:4. (a) DS less than 0.20, preferably 0.18 or less, more preferably less than 0.18 cationic and (b) Average molecular weight (Mw) less than 2,500,000 g / mol; This relates to cationic galactomannans having the properties of [the specified characteristic].

[0010] One embodiment of the present invention has a galactose unit to mannose unit ratio of about 1:3 to about 1:5, preferably about 1:3 to about 1:4. (a) DS less than 0.20, preferably 0.18 or less, more preferably less than 0.18 cationicand (b) Average molecular weight (Mw) less than 2,500,000 g / mol; A biodegradable cationic galactomannan having, With regard to cationic galactomannan whose biodegradability according to OECD 302B is 60% or more within 28 days, in another embodiment, the cationic galactomannan has a biodegradability according to OECD 302B of 60% or more within 60 days.

[0011] In an additional embodiment, the present invention has a galactose unit to mannose unit ratio of about 1:5, (a) DS less than 0.24 cationic and (b) Average molecular weight (Mw) less than 1,000,000 g / mol; This relates to cationic galactomannans having the properties of [the specified characteristic].

[0012] One embodiment of the present invention has a ratio of galactose units to mannose units of approximately 1:5. (a) DS less than 0.24 cationic and (b) Average molecular weight (Mw) less than 1,000,000 g / mol; A biodegradable cationic galactomannan having, With regard to cationic galactomannan whose biodegradability according to OECD 302B is 60% or more within 28 days, in another embodiment, the cationic galactomannan has a biodegradability according to OECD 302B of 60% or more within 60 days.

[0013] Furthermore, in another embodiment, the cationic galactomannan comprises a cationic group selected from primary, secondary, or tertiary amino groups, quaternary ammonium groups, sulfonium groups, phosphinium groups, and combinations thereof, preferably the cationic group is selected from trialkylammonium groups such as trimethylammonium, triethylammonium, or tributylammonium groups, aryldialkylammonium groups such as benzyldimethylammonium groups, ammonium groups in which the nitrogen atom is a ring member of the ring structure, such as pyridinium and imidazoline groups, and combinations thereof. Embodiments of the present invention also include biodegradable cationic galactomannan cationized with at least one cationizing agent selected from 2,3-epoxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, and mixtures thereof.

[0014] In yet another embodiment, the present invention relates to a composition containing biodegradable cationic galactomannan. The present invention also relates to a method for producing biodegradable cationic galactomannan, which includes an embodiment in which non-cationic galactomannan is reacted with at least one cationizing agent. [Modes for carrying out the invention]

[0015] The terms and expressions used herein, “invention,” “present invention,” “instant invention,” and similar terms and expressions are non-limiting and are not intended to limit the subject matter of the invention to any single embodiment, but rather encompass all possible embodiments described herein.

[0016] Throughout the entire description, including the claims, the terms “one (a)” and “at least one” should be understood as synonymous, and similarly, unless otherwise specified, the terms “including one” or “including one” should be understood as synonymous with the term “including at least one.” Furthermore, “between” should be understood as including a limit. Furthermore, throughout the entire description, including the claims, the terms “including” and “having” should be understood as interchangeable and synonymous.

[0017] When specifying any range for concentration, weight ratio, or quantity, please note that any specific upper limit concentration, weight ratio, or quantity may be related to any specific lower limit concentration, weight ratio, or quantity.

[0018] Biodegradable cationic galactomannan Various types of galactomannan can be used in the present invention. As described above, galactomannan is a natural polymer formed from mannose units and galactose units, where the mannose units form the main chain or backbone of the polymer, while the galactose units are substituted along the main chain or backbone. In this regard, galactomannan with a mannose-to-galactose ratio of about 1:1 to about 5:1 can be used.

[0019] In certain embodiments, galactomannan may have a mannose-to-galactose ratio of approximately 1:1. Galactomannan with a mannose-to-galactose ratio of approximately 1:1 is commonly called fenugreek, but is also known as Trigonella foenum-graecum. In other embodiments, galactomannan may have a mannose-to-galactose ratio of approximately 3:1 to approximately 5:1. Such galactomannan are commonly known as tara (also called Tara spinosa), carob (also called Parkia biglobosa), and cassia (also called Cassia obtusifolia and Cassia tora), respectively. Cassia may also be called Senna obtusifolia and Senna tora.

[0020] For example, the galactomannan of the present invention is of the following formula (I): [ka] (In the formula, n can be between 0 and 5, preferably between 0 and 4, and m can be between 0 and 5, preferably between 0 and 4, provided that n + m is approximately 5 or less, preferably approximately 4 or less.) It may include having repeating residues (i.e., units) as shown. The value p in formula (I) is based on the total molecular weight (Mw) of the galactomannan, as will be described in detail below. In certain preferred embodiments, n+m may be about 0, 2, 3, 4, or 5, preferably n+m may be about 0, 2, 3, or 4. In certain embodiments, p may be up to about 35,000, up to about 30,000, up to about 25,000, and even up to about 20,000, and p may be at least about 10, at least about 100, and at least about 500. In other embodiments, p may be less than about 10 (including at least about 5) when n+m is about 5 or less, preferably n+m is about 4 or less, and in certain other preferred embodiments, when n+m is about 0, 2, 3, 4, or 5, preferably about 0, 2, 3, or 4, p may be at least about 5. For example, in a particular embodiment, p may be in the range of about 10 to about 35,000, such as about 100 to about 30,000. In a particular embodiment, p may be about 500 to about 10,000, especially when n+m is about 0; p may be about 2,500 to about 5,000, especially when n+m is about 2 to 4, especially when n+m is about 2 to 3; and p may be about 100 to about 1,200, especially when n+m is about 5, especially when n+m is about 4.

[0021] Galactomannan can be functionalized by chemical modification using various cationic reactive reagents, also known as cationizing agents. The cationizing agents can react with the available hydroxyl groups of galactomannan. In particular, depending on the galactomannan and the hydroxyl groups available for chemical modification, the cationizing agents can react with the available hydroxyl groups of the mannose backbone or skeleton, the available hydroxyl groups of substituted galactose units along the mannose backbone or skeleton, or both. Various cationizing agents can be used in this regard. Furthermore, cationic galactomannan can be formed by reacting at least one galactomannan according to the present invention with at least one cationizing agent.

[0022] As used herein, the terms “cationic” and “cationization” mean at least partially cationic. Therefore, “cationizing agent,” “cationic group,” “cationic site,” or their plural forms include, for example, positively charged ammonium and primary, secondary, and tertiary amines and their precursors that can become or produce positively charged compounds.

[0023] Since cationizing agents can react with available hydroxyl groups of galactomannan to produce cationic galactomannan, cationizing agents may have at least one functional group (or moiety) that can react with hydroxyl groups. Such functional groups include, but are not limited to, at least one epoxy group, halide group, ester group, anhydride group, ethylenically unsaturated group, or combinations thereof, as well as salts and radicals thereof. In one embodiment, the cationizing agent may have a divalent linking group, such as an alkylene group or oxyalkylene group, between or linking the cationic group or moiety and the functional group or reactive group or moiety of the cationizing agent. For example, cationic groups or moieties include, but are not limited to, amino groups (primary, secondary and / or tertiary amino groups, etc.), quaternary ammonium groups, sulfonium groups, phosphonium groups, and combinations thereof.

[0024] In one embodiment, the cationizing agent may have a cationic group or moiety comprising a cationic nitrogen group, more typically a quaternary ammonium group. Typical quaternary ammonium groups include, but are not limited to, trialkylammonium groups (such as trimethylammonium group, triethylammonium group, tributylammonium group), aryldialkylammonium groups (such as benzyldimethylammonium group), and ammonium groups in which the nitrogen atom is a ring member of a ring structure (such as pyridinium group and imidazolinium group), each of which is combined with a counter ion, typically a counter ion that is chloride, bromide, iodide or acetate. In one embodiment, the cationic substituent is linked to the reactive functional group of the cationizing agent by a linking group that is an alkylene or oxyalkylene.

[0025] In certain embodiments, the cationic group or moiety is of Formula (II): -N + R 2 R 3 R 4 X - (II) (wherein, for the amine salt group, R 2 , R 3 and R 4 are each independently an organic group or H, at least one of R for the amine salt group 2 , R 3 and R 4 is H, and for the quaternary ammonium group, R 2 , R 3 and R 4 are each independently an organic group, or any two of R 2 , R 3 and R 4 may be fused with the nitrogen atom to which they are attached to form a heterocyclic group, and X - is an anion)

[0026] ​In another embodiment, the cationizing agent may be a cationic epoxide, for example, a cationic nitrogen compound having an epoxy functional group and a cationic nitrogen compound having a chlorohydrin functional group, a cationic ethylenically unsaturated monomer or its precursor, or a combination thereof. For example, the cationic epoxides of the present invention include, but are not limited to, 2,3-epoxypropyltrimethylammonium chloride, 2,3-epoxypropyltrimethylammonium bromide, 2,3-epoxypropyltrimethylammonium iodide, and mixtures thereof. The cationic nitrogen compound having a chlorohydrin functional group includes, but is not limited to, 3-halogeno-2-hydroxypropyltrimethylammonium chloride, for example, 3-chloro-2-hydroxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyldodecyldimethylammonium chloride, 3-chloro-2-hydroxypropyllauryldimethylammonium chloride, 3-chloro-2-hydroxypropylcocoalkyldimethylammonium chloride, 3-chloro- Examples include 2-hydroxypropylstearyldimethylammonium chloride and mixtures thereof. Cationic ethylene unsaturated monomers or their precursors include, but are not limited to, trimethylammoniumpropyl methacrylamide chloride, methacrylamidepropyltrimethylammonium chloride (MAPTAC), trimethylammoniumpropyl methacrylamide methyl sulfate, diallyldimethylammonium chloride, vinylbenzyltrimethylammonium chloride, dimethylaminopropyl methacrylamide (tertiary amine), precursors of cationic monomers, such as N-vinylformamide and N-vinylacetamide (those that can be hydrolyzed after polymerization or graft polymerized onto vinylamine units), and combinations thereof.

[0027] In certain preferred embodiments, the cationizing agent may be selected from 2,3-epoxypropyltrimethylammonium chloride, 2,3-epoxypropyltrimethylammonium bromide, 2,3-epoxypropyltrimethylammonium iodide, 3-halogeno-2-hydroxypropyltrimethylammonium chloride (e.g., 3-chloro-2-hydroxypropyltrimethylammonium chloride) and combinations thereof.

[0028] For example, the cationic galactomannan of the present invention is of the following formula (III): [ka] (In the formula, R 1 The formula is: R 5 N + R 2 R 3 R 4 X - (IV) It may have, R for the group of amine salts 2 , R 3 and R 4 Each of these is independently an organic group or H, preferably each independently C1-C 32 Alkyl alkyl groups or H, more preferably each independently C1-C 18 The alkyl group is H, and in certain preferred embodiments, R 2 , R 3 and R 4 These are, independently, C1~C 10 The alkyl group or H (each independently being a C1-C5 alkyl group or H) and the R group of the amine salt 2 , R 3 and R 4 At least one of them is H, and R for the quaternary ammonium group 2 , R 3 and R 4 Each of these is an organic group, preferably each is independently C1-C 32They are alkyl groups, more preferably each independently C1-C 18 It is an alkyl group, and in certain preferred embodiments, R 2 , R 3 and R 4 These are, independently, C1~C 10 Alkyl alkyl groups (including those that are independently C1-C5 alkyl groups), or R 2 , R 3 and R 4 Any two of them can condense with the nitrogen atom to which they are bonded to form a heterocyclic group, X - is an anion, preferably Cl-, Br-, I or a mixture thereof, more preferably Cl-. R 5 is a C1-C5 hydrocarbon group optionally substituted with at least one group selected from (-OH), (=O), (-NH3), or a mixture thereof, preferably a C1-C5 alkyl group optionally substituted with at least one group selected from (-OH), (=O), (-NH3), or a mixture thereof. R 10 This can be selected from -OH, an alkoxyquaternary ammonium group, or a combination thereof, preferably R 10 is at least one R 10 Assuming that is an alkoxy quaternary ammonium group, -OH, -OR 1 Or a combination of these may be selected, preferably -OR 1 And, n can be 0 to 5, preferably 0 to 4, and m can be 0 to 5, preferably 0 to 4, provided that n+m is about 5 or less, preferably about 4 or less, preferably n+m can be about 0, 2, 3, 4 or 5, preferably n+m can be about 0, 2, 3 or 4. Examples include those having repeating residues (i.e., units) as shown by . The value p in formula (III) is based on the total molecular weight (Mw) of the galactomannan, as will be described in detail below. Furthermore, in certain embodiments, p may be up to about 35,000, up to about 30,000, up to about 25,000, and even up to about 20,000, and p may be at least about 10, at least about 100, and at least about 500. In other embodiments, p may be less than about 10 (including at least about 5) when n+m is about 5 or less, preferably when n+m is about 4 or less, and in certain preferred other embodiments, when n+m is about 0, 2, 3, 4 or 5, preferably when n+m is about 0, 2, 3 or 4, p may be at least about 5. In certain embodiments, p may be in the range of about 10 to about 35,000, such as about 100 to about 30,000. In certain embodiments, p can be about 500 to about 10,000, especially when n+m is about 0; about 2,500 to about 5,000, when n+m is about 2 to 4, especially 2 to 3; and about 100 to about 1,200, when n+m is about 5, especially 4.

[0029] In certain embodiments, the cationic galactomannan of the present invention is defined by the following formula (V): [ka] (In the formula, R 1 The formula is: R 5 N + R 2 R 3 R 4 X - (VI) It may have, R for the group of amine salts 2 , R 3 and R 4 Each of these is independently an organic group or H, preferably each independently C1~ 32 The alkyl group or H, more preferably each independently C1~ 18 The alkyl group is H, and in certain preferred embodiments, R 2, R 3 and R 4 each independently represent C1~ 10 alkyl group or H (including the case where each independently represents a C1-5 alkyl group or H), and for the groups of the amine salt, R 2 , R 3 and R 4 at least one of is H; for the quaternary ammonium group, R 2 , R 3 and R 4 each independently represent an organic group, preferably each independently represent C1~ 32 alkyl group, more preferably each independently represent C1~ 18 alkyl group; in certain preferred embodiments, R 2 , R 3 and R 4 each independently represent C1~ 10 alkyl group (including the case where each independently represents a C1-5 alkyl group), or any two of R 2 , R 3 and R 4 may be condensed with the nitrogen atom to which they are bonded to form a heterocyclic group; X - represents an anion, preferably Cl⁻, Br⁻, I⁻ or a mixture thereof, more preferably Cl⁻, R 5 represents a C1-C5 hydrocarbon group optionally substituted with at least one group selected from (-OH), (=O), (-NH₃) or a mixture thereof, preferably a C1-C5 alkyl group optionally substituted with at least one group selected from (-OH), (=O), (-NH₃) or a mixture thereof, R 10 may be selected from -OH, alkoxy quaternary ammonium groups or combinations thereof, preferably, R 10 may be selected from -OH, -OR 1 or combinations thereof, n can be 0 to 5, preferably 0 to 4, and m can be 0 to 5, preferably 0 to 4, provided that n+m is about 5 or less, preferably about 4 or less, preferably n+m can be about 0, 2, 3, 4 or 5, preferably n+m can be about 0, 2, 3 or 4. Examples include those having repeating residues (i.e., units) as shown by . The value p in formula (V) is based on the total molecular weight (Mw) of the galactomannan, as will be described in detail below. Furthermore, in certain embodiments, p may be up to about 35,000, up to about 30,000, up to about 25,000, and even up to about 20,000, and p may be at least about 10, at least about 100, and at least about 500. In other embodiments, p may be less than about 10 (including at least about 5) when n+m is about 5 or less, preferably when n+m is about 4 or less, and in certain preferred other embodiments, when n+m is about 0, 2, 3, 4 or 5, preferably when n+m is about 0, 2, 3 or 4, p may be at least about 5. In certain embodiments, p may be in the range of about 10 to about 35,000, such as about 100 to about 30,000. In certain embodiments, p can be about 500 to about 10,000, especially when n+m is about 0; about 2,500 to about 5,000, when n+m is about 2 to 4, especially 2 to 3; and about 100 to about 1,200, when n+m is about 5, especially 4.

[0030] When galactomannan reacts with at least one cationizing agent to form the cationic galactomannan of the present invention, the cationic galactomannan has a degree of substitution (DS) relative to the cationic group bonded to the galactomannan. cationic ) has. Specifically, DS cationicThis refers to the average number of cationic groups or sites attached per monomer unit (i.e., each sugar unit) of galactomannan. To clarify, the cationic galactomannan of the present invention has a certain degree of cationic substitution. That is, the cationic galactomannan of the present invention must not have zero or no cationic substitution. In this regard, DS specifies only an upper limit, such as less than 0.24, less than 0.23, less than 0.22, less than 0.21, less than 0.20, less than 0.19, less than 0.18, less than 0.17, less than 0.16, less than 0.15 and similarly 0.24 or less, 0.23 or less, 0.22 or less, 0.21 or less, 0.20 or less, 0.19 or less, 0.18 or less, 0.17 or less, 0.16 or less, 0.15 or similar ranges. cationic For the range, the lower limit of the range is greater than zero (>0). In such embodiments, the lower limit of the range may be 0.000001, 0.00001, 0.0001, 0.001, 0.01, or 0.10.

[0031] Depending on the type of galactomannan and its average molecular weight (Mw), in certain embodiments, the cationic galactomannan of the present invention typically has a DS of up to approximately 0.30. cationic It can have the following characteristics. However, in one aspect of the present invention, surprisingly and unexpectedly, it was found that cationic galactomannans with a low average molecular weight can have a higher degree of cationic substitution while maintaining sufficient biodegradability, while cationic galactomannans with a high molecular weight usually have a lower degree of cationic substitution to obtain sufficient biodegradability. In another aspect of the present invention, surprisingly and unexpectedly, the type of galactomannan, i.e., the ratio of galactose units to mannose units, can also be DS cationic It was found that this, along with the average molecular weight (Mw), can affect biodegradability.

[0032] Therefore, in certain embodiments of cationic galactomannan where the ratio of galactose units to mannose units is approximately 1:1 (commonly referred to as fenugreek), cationic galactomannan typically has a DS of less than 0.17 (including 0.16 or less) or less than 0.15. cationic It can have a DS of less than 0.17. For example, in a particular embodiment in which the ratio of galactose units to mannose units of the cationic galactomannan is about 1:1, the cationic galactomannan has a DS of less than 0.17. cationic It can have. In an additional embodiment, if the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:1, the cationic galactomannan has a DS of 0.15 or less, preferably 0.14 or less. cationic It can have. In this regard, DS cationic The DS may be in the range of 0.001-0.16, 0.01-0.16, 0.10-0.16, and 0.001-0.15, 0.01-0.15, 0.10-0.15, and even 0.001-0.14, 0.01-0.14, and 0.10-0.14. In a further embodiment in which the ratio of galactose units to mannose units of the cationic galactomannan is about 1:1, the cationic galactomannan has a DS in the range of 0.05-0.16, preferably 0.08-0.16, more preferably 0.10-0.16. cationic It can have the following characteristics. Similarly, in another embodiment in which the ratio of galactose units to mannose units of the cationic galactomannan is about 1:1, the cationic galactomannan has a DS in the range of 0.05 to less than 0.17, preferably 0.08 to less than 0.17, more preferably 0.10 to less than 0.17. cationic Cationic galactomannan, which may also have a galactose unit to mannose unit ratio of approximately 1:1, may further have a DS in the range of 0.10-0.16, 0.12-0.16, more preferably 0.14-0.16. cationic It can have a DS of 0.16 or less. In certain embodiments, when the ratio of galactose units to mannose units is about 1:1, the cationic galactomannan has a DS of 0.16 or less. cationicCationic galactomannan can have biodegradability according to OECD 302B, modified and described below, of 60% or more within 60 days, preferably within 28 days.

[0033] In another embodiment, the cationic galactomannan has a galactose-to-mannose unit ratio of about 1:3 to about 1:5 (commonly known as cod, carob, or cassia) and an average molecular weight of less than 2,500,000 g / mol, in which case the cationic galactomannan has a DS of typically less than 0.20, preferably 0.18 or less, and more preferably less than 0.18. cationic It can have the following characteristics. In certain preferred embodiments, the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:3 to about 1:4, preferably about 1:3 or about 1:4. In additional embodiments, if the galactose unit to mannose unit ratio of the cationic galactomannan is about 1:3 to about 1:5, preferably about 1:3 to about 1:4, more preferably about 1:3 or about 1:4, and the average molecular weight is less than 2,500,000 g / mol, the cationic galactomannan has a DS of 0.19 or less, preferably 0.18 or less. cationic In another embodiment, if the ratio of galactose units to mannose units of the cationic galactomannan is about 1:3 to about 1:5, preferably about 1:3 to about 1:4 (including about 1:3 or about 1:4) and the average molecular weight is less than 2,500,000 g / mol, then the cationic galactomannan has a DS of less than 0.20, preferably 0.18 or less, more preferably less than 0.18. cationic While it may have a DS of 0.17 or less, preferably less than 0.17, more preferably 0.16 or less, in another embodiment, the cationic galactomannan has a DS of 0.17 or less. cationic It can have. In this regard, DS cationicThis can be in the range of 0.001 to less than 0.20 (including 0.001 to 0.18), 0.01 to less than 0.20 (including 0.01 to 0.18), and 0.10 to less than 0.20 (including 0.10 to 0.18), as well as 0.001 to less than 0.18, 0.01 to less than 0.18, and 0.10 to less than 0.18, and furthermore, 0.001 to 0.17 or less, 0.01 to 0.17 or less, and 0.10 to 0.17 or less. DS when the ratio of galactose units to mannose units of cationic galactomannan is about 1:3 to about 1:5, preferably about 1:3 to about 1:4 (including about 1:3 or about 1:4). cationic The range may be 0.001 to 0.16, 0.01 to 0.16, and 0.10 to 0.16. In a further embodiment in which the galactose unit to mannose unit ratio of the cationic galactomannan is about 1:3 to about 1:5, preferably about 1:3 to about 1:4 (including about 1:3 or about 1:4) and the average molecular weight is less than 2,500,000 g / mol, the cationic galactomannan has a DS in the range of 0.05 to 0.20, preferably 0.08 to 0.20, more preferably 0.10 to 0.20. cationic It can have a DS in the range of 0.10 to 0.20, preferably 0.12 to 0.20, more preferably 0.14 to 0.20. cationic In another embodiment, the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:3 to about 1:5, preferably about 1:3 to about 1:4 (including about 1:3 or about 1:4) and an average molecular weight of less than 2,500,000 g / mol, the cationic galactomannan has a DS in the range of preferably 0.05 to 0.18, preferably 0.08 to 0.18, more preferably 0.10 to 0.18. cationic In yet another embodiment, the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:3 to about 1:5, preferably about 1:3 to about 1:4 (including about 1:3 or about 1:4) and an average molecular weight of less than 2,500,000 g / mol, and the cationic galactomannan has a DS in the range of 0.05 to 0.16, preferably 0.08 to 0.16, more preferably 0.10 to 0.16.cationic It may have the following: In certain embodiments where the ratio of galactose units to mannose units of the cationic galactomannan is about 1:3 to about 1:5, preferably about 1:3 to about 1:4 (including about 1:3 or about 1:4), the cationic galactomannan has a DS of less than 0.20, preferably 0.18 or less (including less than 0.18), more preferably less than 0.16. cationic Cationic galactomannan can have biodegradability according to OECD 302B, modified and described below, of 60% or more within 60 days, preferably within 28 days.

[0034] In addition, in certain embodiments where the ratio of galactose units to mannose units of the cationic galactomannan is about 1:3, the cationic galactomannan has a DS of less than 0.20, preferably 0.18 or less (including less than 0.18), and more preferably 0.17 or less. cationic It can have. Furthermore, in certain embodiments where the ratio of galactose units to mannose units of the cationic galactomannan is about 1:4, the cationic galactomannan has a DS of less than 0.20, preferably 0.18 or less (including less than 0.18), more preferably 0.17 or less. cationic It can have.

[0035] In another embodiment, the cationic galactomannan has a galactose-to-mannose unit ratio of 1:5 (commonly called cassia) and an average molecular weight of less than 1,000,000 g / mol, in which case the cationic galactomannan has a DS of typically less than 0.24, preferably 0.22 or less. cationic It can have the following: In an additional embodiment in which the ratio of galactose units to mannose units of the cationic galactomannan is 1:5 and the average molecular weight is less than 1,000,000 g / mol, the cationic galactomannan has a DS of 0.21 or less, preferably 0.20 or less. cationicIt can have the following characteristics. In a particular embodiment in which the ratio of galactose units to mannose units of the cationic galactomannan is 1:5 and the average molecular weight is less than 1,000,000 g / mol, the cationic galactomannan has a DS of typically 0.18 or less (including less than 0.18), preferably 0.17 or less. cationic It can have. In this regard, DS cationic This can be in the range of 0.001 to less than 0.24, 0.01 to less than 0.24, 0.10 to less than 0.24, and 0.001 to 0.22, 0.01 to 0.22, 0.10 to 0.22, and further 0.001 to 0.21, 0.01 to 0.21, 0.10 to 0.21 (including 0.001 to 0.20, 0.01 to 0.20, and 0.10 to 0.20). In another embodiment, DS cationic The DS can be in the range of 0.001~0.18, 0.01~0.18, 0.10~0.18, and further in the range of 0.001~0.16, 0.01~0.16, and 0.10~0.16. In yet another embodiment in which the galactose unit to mannose unit ratio of the cationic galactomannan is 1:5 and the average molecular weight is less than 1,000,000 g / mol, the cationic galactomannan has a DS in the range of 0.05~0.16 (including less than 0.05~0.16), preferably 0.08~0.16 (including less than 0.08~0.16), and more preferably 0.10~0.16 (including less than 0.10~0.16). cationic It can have. Also, if cationic galactomannan has a galactose unit to mannose unit ratio of about 1:5, DS cationic The DS can also be in the range of 0.10 to less than 0.18, preferably 0.12 to less than 0.18. In a further embodiment in which the galactose unit to mannose unit ratio of the cationic galactomannan is 1:5 and the average molecular weight is less than 1,000,000 g / mol, the cationic galactomannan has a DS in the range of 0.05 to less than 0.24, preferably 0.08 to 0.22, more preferably 0.10 to 0.20. cationicIn another embodiment, the cationic galactomannan may have a galactose unit to mannose unit ratio of 1:5 and an average molecular weight of less than 1,000,000 g / mol, and the cationic galactomannan may have a DS in the range of 0.10 to less than 0.24, preferably 0.14 to 0.22, more preferably 0.14 to 0.20. cationic It can have.

[0036] In another embodiment, the cationic galactomannan has a galactose unit to mannose unit ratio of 1:5 (commonly called cassia) and an average molecular weight of less than 1,000,000 g / mol, in which case the cationic galactomannan has a DS of typically 0.18 or less (including less than 0.18), preferably 0.16 or less. cationic In an additional embodiment, if the cationic galactomannan has a galactose unit to mannose unit ratio of 1:5 and an average molecular weight of less than 1,000,000 g / mol, the cationic galactomannan has a DS of 0.15 or less and 0.14 or less. cationic It can have the following: In a particular embodiment in which the galactose unit to mannose unit ratio of the cationic galactomannan is 1:5 and the average molecular weight is less than 1,000,000 g / mol, the cationic galactomannan has a DS of typically less than 0.18 (including 0.17 or less). cationic It can have. In this regard, DS cationic This can take the range of 0.001 to less than 0.18, 0.01 to less than 0.18, and 0.10 to less than 0.18, as well as 0.001 to 0.17 or less, 0.01 to 0.17 or less, and 0.10 to 0.17 or less, and furthermore, 0.001 to 0.16 or less, 0.01 to 0.16 or less, and 0.10 to 0.16 or less (including 0.001 to 0.15 or less, 0.01 to 0.15 or less, and 0.10 to 0.15 or less). In another embodiment, DS cationicThe DS can be in the range of 0.001~0.18, 0.01~0.18, 0.10~0.18, and further in the range of 0.001~0.16, 0.01~0.16, and 0.10~0.16. In yet another embodiment in which the galactose unit to mannose unit ratio of the cationic galactomannan is 1:5 and the average molecular weight is less than 1,000,000 g / mol, the cationic galactomannan has a DS in the range of 0.05~0.16 (including 0.05 to less than 0.16), preferably 0.08~0.16 (including 0.08 to less than 0.16), and more preferably 0.10~0.16 (including 0.10 to less than 0.16). cationic It can have. When cationic galactomannan has a galactose unit to mannose unit ratio of 1:5, DS cationic The DS can also be 0.10 to less than 0.18, preferably 0.12 to less than 0.18. In a further embodiment in which the galactose unit to mannose unit ratio of the cationic galactomannan is 1:5 and the average molecular weight is less than 1,000,000 g / mol, the cationic galactomannan has a DS in the range of 0.05 to less than 0.24, preferably 0.08 to 0.22, more preferably 0.10 to 0.20. cationic In another embodiment, the cationic galactomannan may have a galactose unit to mannose unit ratio of 1:5 and an average molecular weight of less than 1,000,000 g / mol, in which case the cationic galactomannan has a DS in the range of 0.10 to less than 0.24, preferably 0.14 to 0.22, more preferably 0.14 to 0.20. cationic It can have. In a particular embodiment where the ratio of galactose units to mannose units of the cationic galactomannan is 1:5, the cationic galactomannan has a DS of less than 0.24. cationic Cationic galactomannan can have biodegradability according to OECD 302B, modified and described below, of 60% or more within 60 days, preferably within 28 days.

[0037] Typically, the degree of cationic substitution of the cationic galactomannan in the present invention can be determined before or after the extraction step. In certain embodiments, the extraction step is carried out by an acidic methanol extraction step. The methanol to acid (preferably about 37% by volume of concentrated HCl) ratio may be about 25:1 to 100:1, preferably about 50:1. Furthermore, in certain embodiments, the acidic methanol extraction step can be considered a washing step that can remove other quaternary ammonium compounds that may be present at the end of the cationization reaction (but not limited to residual cationizing agents, by-products of unreacted cationizing agents, or mixtures thereof).

[0038] The terms "catenic substitution degree" and "DS" as used herein cationic The term "cation substitution" is interchangeable and synonymous, referring to the degree of cation substitution measured after the acidic methanol extraction step. Furthermore, DS cationic This refers to the average number of moles of cationic groups or molars per mole of sugar unit, and this means that 1 It can be measured by 1H-NMR (solvent: D2O). 1 After obtaining the 1H NMR spectrum, the integral values ​​of the multiline peaks corresponding to all anomeric protons of the galactomannan units, usually around 3.5–5.5 ppm, are normalized to 1. The peak of interest, corresponding to the methyl proton of the quaternary ammonium group of the galactomannan unit, is centered around 3–3.5 ppm. Considering the presence of three methyl groups on the ammonium functional group, this peak is integrated over nine protons. Therefore, as an example, in the case of the cationizing agent 2,3-epoxypropyltrimethylammonium chloride (DS) cationic The calculation for ) is as follows:

number

[0039] The extraction process can be carried out in various ways. As mentioned above, in certain embodiments, the extraction process involves acidic methanol (50:1, MeOH / HCl concentrated37% This can be carried out in ,v / v). Furthermore, cationic galactomannan may be added to acidic methanol at a concentration of about 1% under stirring. After adding acidic methanol to cationic galactomannan, the mixture can be brought to reflux temperature and held at reflux temperature for about 45 minutes. At the end of this extraction step, the acidic methanol can be decanted, and this process can be repeated. In certain embodiments, the extraction step comprises 1 to 3 (preferably 3) consecutive steps of adding acidic methanol to cationic galactomannan and refluxing the mixture for a predetermined time, after which the acidic methanol is removed and replaced with fresh acidic methanol. After the extraction step is completely finished, the cationic galactomannan may be filtered and washed with pure methanol, ethanol or another suitable solvent. The thus purified non-cellulosic polysaccharide derivative is then, 1 It is dried and ground before 1H-NMR analysis.

[0040] In another embodiment, the cationization of galactomannan can also be expressed in terms of charge density. As used herein, the term “charge density” means the ratio of the positive charge on the monomer units constituting galactomannan to the molecular weight of the monomer units. The value obtained by multiplying the charge density by the molecular weight of the polymer determines the number of positively charged sites on a given polymer chain. The degree of cationic substitution can be converted to charge density by several methods. In certain embodiments, the method for calculating the charge density of cationic galactomannan uses a method that specifically quantifies the equivalent amount of cationic groups or sites on the galactomannan, preferably quaternary ammonium groups. In a non-limiting example, for cationic galactomannan 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.

number

[0041] In certain embodiments, the galactomannan has a charge density after the acidic methanol extraction step of about 1.0 to about 2 meq / g, preferably about 1.1 to about 1.8 meq / g, and more preferably 1.2 to 1.5 meq / g.

[0042] Regarding the average molecular weight (Mw) of the cationic galactomannan of the present invention, the cationic galactomannan typically has an average molecular weight (Mw) of at least about 3,500 g / mol (including at least about 5,000 g / mol), and in certain embodiments, at least about 10,000 g / mol. The cationic galactomannan of the present invention also typically has an average molecular weight (Mw) of up to about 10,000,000 g / mol, and up to about 7,500,000 g / mol (including up to about 5,000,000 g / mol). In certain embodiments, the cationic galactomannan typically has an average molecular weight (Mw) in the range of 20,000 g / mol to 10,000,000 g / mol, preferably 50,000 g / mol to 7,500,000 g / mol, and more preferably 100,000 g / mol to 5,000,000 g / mol. In certain embodiments (commonly referred to as fenugreek) in which the ratio of galactose units to mannose units of cationic galactomannan is about 1:1, the cationic galactomannan may typically have an average molecular weight (Mw) of less than 3,500,000 g / mol (including less than or equal to 3,000,000 g / mol). In other embodiments, when the ratio of galactose units to mannose units of cationic galactomannan is about 1:1, the cationic galactomannan may have an average molecular weight (Mw) in the range of 200,000 g / mol to 3,000,000 g / mol, more preferably 250,000 g / mol to 2,500,000 g / mol, and even more preferably 500,000 g / mol to 2,500,000 g / mol.

[0043] In further embodiments (commonly referred to as cod, carob, or cassia) in which the galactose unit-to-mannose unit ratio of cationic galactomannan is about 1:3 to about 1:5, the cationic galactomannan may typically have an average molecular weight (Mw) of less than 2,500,000 g / mol. In certain preferred embodiments, the cationic galactomannan may have a galactose unit-to-mannose unit ratio of about 1:3 to about 1:4 (including about 1:3 or about 1:4) and have an average molecular weight (Mw) of less than 2,500,000 g / mol. In yet another embodiment, where the ratio of galactose units to mannose units of the cationic galactomannan is about 1:3 to about 1:5, the cationic galactomannan may have an average molecular weight (Mw) in the range of 200,000 g / mol to 2,000,000 g / mol, more preferably 250,000 g / mol to 2,000,000 g / mol, and even more preferably 300,000 g / mol to 2,000,000 g / mol.

[0044] In addition, in another embodiment (commonly called cassia as described above) in which the ratio of galactose units to mannose units of cationic galactomannan is about 1:5, the cationic galactomannan may typically have an average molecular weight (Mw) of less than 1,000,000 g / mol. Furthermore, when the ratio of galactose units to mannose units of cationic galactomannan is about 1:5, the cationic galactomannan may typically have an average molecular weight (Mw) in the range of 900,000 g / mol or less, preferably about 100,000 g / mol to 900,000 g / mol, more preferably about 150,000 g / mol to 800,000 g / mol (even more preferably including about 150,000 g / mol to 750,000 g / mol).

[0045] As used herein, the terms “average molecular weight,” “molecular weight,” and “(Mw)” are interchangeable and synonymous, all meaning the same as weight-average molecular weight. Average molecular weight is measured by SEC-MALS (size exclusion chromatography with multi-angle light scattering detection) with a Shodex Pack SB-806M HQ column. A value of 0.140 for dn / dc is used for molecular weight measurement. The Agilent refractive index detector and WYATT miniDawn are calibrated using a 22.5 kDa polyethylene glycol standard. All calculations of molecular weight distribution are performed using Wyatt's ASTRA software. Samples are prepared as a 0.05% solution in a mobile phase (100 mM Na2NO3, 200 ppm NaN3, 20 ppm pDADMAC, 100 ppm sodium azide) and filtered through a 0.45 μm PVDF filter before analysis. Average molecular weight is expressed by weight.

[0046] As described above, the cationic galactomannan of the present invention is biodegradable. In this regard, unexpectedly, certain DS cationicIt has also been found that cationic galactomannans possessing both a specific value and a particular average molecular weight (Mw) can exhibit sufficient biodegradability. In this regard, the cationic galactomannans of the present invention are considered biodegradable under OECD 302, and are considered biodegradable under OECD 302B, which is particularly modified and described therein. Specifically, OECD 302B provides test guidelines for determining whether a chemical substance is biodegradable (including whether it is intrinsically biodegradable). Test Method OECD 302B means, and is referred to herein, this method without prior inoculum adaptation (i.e., intrinsically complete biodegradability without prior inoculum adaptation), which is modified in the following respects: (i) with respect to the biodegradability (%) of the test sample, if at least 60% of the test sample is biodegradable within the test period, the sample is considered biodegradable; and ii) for determining biodegradability, an OxiTop®-IDS sensor available from Xylem Analytics was used. Therefore, if, for example, at least 60% of the material is biodegradable within a test period of 60 days, as described above and as used herein, the material is considered biodegradable under OECD 302B. In this specification, the inoculum used in OECD 302B as modified and described above means that the inoculum is taken from the environment and has not been cultured to specifically enhance the biodegradability of cationic galactomannan (i.e., the inoculum was not pre-adapted). In certain embodiments, the cationic galactomannan is biodegradable by 60% or more, preferably 70% or more, within 60 days, preferably 28 days, according to OECD 302B. In further embodiments, the cationic galactomannan is biodegradable by 75% or more, within 60 days, preferably 28 days, according to OECD 302B. In certain preferred embodiments, the cationic galactomannan of the present invention not only is biodegradable but also provides conditioning properties, particularly with respect to home care and personal care compositions, preferably hair care compositions.

[0047] Cationic galactomannans can be produced by various methods. First, unmodified natural (or gummatic) galactomannans used in the production of chemically modified and functionalized cationic galactomannans can be obtained from their respective seeds. For example, galactomannans can be extracted from the endosperm of seeds. Subsequently, galactomannans can be functionalized to be cationic by reacting them with at least one cationizing agent.

[0048] Typically, the cationic galactomannan of the present invention can be produced by reacting a non-cationic galactomannan with at least one cationizing agent. Examples of non-cationic galactomannan include galactomannan in its natural form and galactomannan that may have undergone chemical pretreatment. In certain embodiments, the cationic galactomannan of the present invention can be produced by reacting an unmodified galactomannan with at least one cationizing agent. In such embodiments, the galactomannan may be in its natural form (i.e., gum form). As a non-limiting example, galactomannan having the repeating residue of formula (I) shown above can be used to produce a cationic galactomannan having the repeating residue of formula (III), formula (V), or a combination thereof shown above. In another embodiment, the cationic galactomannan may be produced by reacting a non-cationic galactomannan with at least one cationizing agent, in which case the non-cationic galactomannan is optionally chemically modified before cationization.

[0049] Typically, the cationization process can be carried out in a reaction medium comprising an aqueous solution, at least one cationizing agent, galactomannan, and at least one base. Preferred bases include, but are not limited to, alkali metal hydroxides such as sodium hydroxide, ammonium hydroxide, and combinations thereof. The base may be present in excess and may catalyze the reaction. In certain embodiments, the base may be present in about 0.01 to about 25% by weight, more preferably about 0.05 to about 20% by weight, based on the weight percent of galactomannan in the reaction system.

[0050] The aqueous solution may contain at least one solvent, such as at least one water-miscible organic solvent. The water-miscible organic solvent may be selected from alkanols, glycols, cyclic and acyclic alkyl ethers, alkanones, dialkylformamides, and mixtures thereof. Non-limiting water-miscible organic solvents include methanol, ethanol, propanol (including isopropanol), butanol, pentanol (including secondary pentanol), ethylene glycol, acetone, methyl ethyl ketone, diethyl ketone, tetrahydrofuran, dioxane, dimethylformamide, and mixtures thereof. In certain embodiments, the amount of water-miscible organic solvent may be about 1 to about 20% by weight, preferably about 1 to about 10% by weight. In another embodiment, the weight ratio of water-miscible organic solvent to galactomannan is about 10:1, preferably about 5:1.

[0051] The cationization process may be carried out at a temperature range of about 10°C to about 100°C, preferably about 20°C to about 80°C. The reaction time may be in the range of about 1 to about 8 hours, preferably about 1 to about 6 hours. The cationization process may be carried out in batch or continuous operation in various apparatuses and vessels, such as open or closed tanks or reactors equipped with a stirrer.

[0052] Furthermore, after functionalizing galactomannan by reacting unmodified natural galactomannan (i.e., galactomannan gum) with at least one cationizing agent, the cationic galactomannan may undergo at least one chemical post-treatment step. In certain embodiments, after the cationization process, the cationic galactomannan may undergo chemical post-treatment to remove and / or neutralize unreacted reactants (including unreacted or partially reacted cationizing agents) and to remove water-miscible solvents. Non-limiting examples of chemical post-treatment include at least one washing step (with water), crosslinking with borate, at least one alkali treatment step, at least one acid addition step, and combinations thereof. For example, after functionalizing galactomannan by reacting unmodified natural galactomannan with at least one cationizing agent, the cationic galactomannan may be chemically post-treated with borate, washed with water, or both. In another embodiment, the cationic galactomannan may be chemically post-treated with an alkali treatment step, washed with water, or both. In embodiments using the alkaline treatment step, alkali metal hydroxides such as sodium hydroxide, ammonium hydroxide, and combinations thereof can be used. Furthermore, in embodiments using the alkaline treatment step, the pH can be adjusted to a neutral or acidic pH as needed using at least one acid (including at least one inorganic acid, at least one organic acid, and mixtures thereof). Non-limiting acids include, but are not limited to, hydrochloric acid, sulfuric acid, acetic acid, lactic acid, citric acid, carbon dioxide, fumaric acid, and mixtures thereof.

[0053] After obtaining cationic galactomannan from a cationization process (including chemical post-treatment steps), the cationic galactomannan can be dried and then subjected to additional mechanical treatments such as grinding.

[0054] The biodegradable cationic galactomannan of the present invention can be used in a variety of compositions and applications. For example, biodegradable cationic galactomannan can be used as a conditioning agent, suspending agent, thickener, or rheology modifier, film-forming agent, or a combination thereof. In certain embodiments, biodegradable cationic galactomannan can be used in home care and personal care compositions, as well as cleaning and disinfecting compositions. In certain embodiments, cationic galactomannan can be used in hair care compositions, skin care compositions, and cosmetic compositions, including, but not limited to, shampoos, hair conditioners, body washes, soaps, facial cleansers, makeup products, lotions, skin creams, skin conditioners, balms, hair gels, sunscreen compositions, and similar compositions. In another embodiment, biodegradable cationic galactomannan can be used in laundry or fabric detergents, fabric softeners, and conditioners, as well as hard surface cleaning compositions such as sprays, wipes, aerosols, gels, bars, and similar compositions.

[0055] Depending on the composition and application, the composition may include, in addition to biodegradable cationic galactomannan, various other conventional components and additives known in their respective art. For example, a composition containing biodegradable cationic galactomannan may include at least one surfactant, emulsifier, emollient, moisturizer, hair conditioner, hair fixative, film-forming agent, skin protectant, binder, chelating agent, disinfectant, insecticide, fungicide, deodorant, insect repellent, fragrance, antibacterial agent, antifungal agent, antibiotic, anti-dandruff agent, abrasive, adhesive, absorbent, colorant, deodorant, antiperspirant, water-retaining agent, oil (mineral oil, vegetable oil, animal oil, synthetic oil, silicone oil and... These may further include (mixtures thereof), opacifiers and pearlescent agents, antioxidants, preservatives, propellants, spreaders, exfoliants, keratolytic agents, blood coagulants, vitamins, sunscreens, artificial tanning accelerators, UV absorbers, pH adjusters, plant components, hair dyes, dyes, preservatives, inorganic particles, buffers, preservatives, oxidizing agents, reducing agents, rheology adjusters, skin bleaching agents, pigments, anti-inflammatory agents, thickeners, local anesthetics, fragrances, fragrance solubilizers, fine particles, fine abrasives, and combinations thereof. [Examples]

[0056] The following examples illustrate preferred embodiments of cationic galactomannan and methods for producing the same, and are not intended to limit them. All compositional percentages are based on totals equal to 100% by weight unless otherwise specified.

[0057] Test method molecular weight The average molecular weight of cationic galactomannan was measured by SEC-MALS (size exclusion chromatography by multi-angle light scattering detection) using a Shodex Pack SB-806M HQ column, as described above. The measurement was performed at ambient temperature with a run time of 50 minutes and a flow rate of 1.0 mL / min.

[0058] Degree of cation substitution The degree of cationic substitution of cationic galactomannan is as described above. 1 The results were measured by 1H-NMR (solvent: D2O).

[0059] biodegradable The biodegradability of cationic galactomannan was measured according to OECD 302B (modified as described above). This was modified regarding the percentage biodegradability of the test sample (i.e., at least 60%) and the sensor used to determine biodegradability. Biodegradability was evaluated based on 28 and 60 days. The OxiTop®-IDS sensor, available from Xylem Analytics, was used to determine biodegradability. No prior adaptation was performed on the inoculum.

[0060] Example 1 - Biodegradable cationic fenugreek In a 1-liter stirred reactor, 280.0 g of isopropanol solvent mixed with 110.0 g of deionized water was introduced at room temperature under an inert nitrogen gas atmosphere. Then, 125.0 g of fenugreek powder was added while vigorously stirring at room temperature. After stirring for several minutes to homogenize, 47.1 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat 188, 65% aqueous solution) was added. This reagent was mixed with the fenugreek dispersion at room temperature for 30 minutes, after which 18.0 g of sodium hydroxide (50% aqueous solution) was slowly added. This reagent was mixed with the fenugreek dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and held at this temperature for 60 minutes, after which the temperature was reduced to at least 50°C to initiate the washing procedure.

[0061] The reaction mixture obtained as described in the paragraph above was dispersed with 158.0 g of 99% isopropanol and 44.0 g of water while stirring. The pH was adjusted to approximately 9-10 using 1.4 g of glacial acetic acid. The mixture was then stirred for 30 minutes, and after standing, it was removed from the reactor. The dispersion was then vacuum filtered through qualitative filter paper. This washing and filtering procedure was repeated for 30 minutes using 356 g of 99% isopropanol and 145 g of water. The resulting solid was then dried overnight in a 60°C oven for 6 hours.

[0062] Degree of cation substitution (DS) cationic The molecular weight (Mw) was 0.12, and the average molecular weight (Mw) was 1,626,000 g / mol. When cationic fenugreek was tested for biodegradability, it was demonstrated to be intrinsically biodegradable (i.e., pass) within 28 days and 60 days.

[0063] Example 2 - Biodegradable cationic fenugreek In a 1-liter stirred reactor, 196.7 g of isopropanol solvent mixed with 75.2 g of deionized water was introduced at room temperature under an inert nitrogen gas atmosphere. Then, 87.5 g of fenugreek powder was added while vigorously stirring at room temperature. After stirring for several minutes to homogenize, 45.0 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat 188, 65% aqueous solution) was added. This reagent was mixed with the fenugreek dispersion at room temperature for 30 minutes, after which 15.4 g of sodium hydroxide (50% aqueous solution) was slowly added. This reagent was mixed with the fenugreek dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and held at this temperature for 60 minutes, after which the temperature was reduced to at least 50°C to initiate the washing procedure.

[0064] The reaction mixture obtained as described in the paragraph above was dispersed with 112.0 g of 99% isopropanol and 23.0 g of water while stirring. The pH was adjusted to approximately 9-10 using 4.1 g of glacial acetic acid. The mixture was then stirred for 30 minutes, and after standing, it was removed from the reactor. The dispersion was then vacuum filtered through qualitative filter paper. This washing and filtering procedure was repeated for 30 minutes using 250 g of 99% isopropanol and 100 g of water. The resulting solid was then dried overnight in a 60°C oven for 6 hours.

[0065] Degree of cation substitution (DS) cationicThe molecular weight (Mw) was 0.13, and the average molecular weight (Mw) was 2,020,000 g / mol. When cationic fenugreek was tested for biodegradability, it was demonstrated to be intrinsically biodegradable (i.e., pass) within 60 days.

[0066] Example 3 - Biodegradable cationic fenugreek In a 1-liter stirred reactor, 195.5 g of isopropanol solvent mixed with 74.8 g of deionized water was introduced at room temperature under an inert nitrogen gas atmosphere. Then, 87.8 g of fenugreek powder was added while vigorously stirring at room temperature. After stirring for several minutes to homogenize, 45.0 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat 188, 65% aqueous solution) was added. This reagent was mixed with the fenugreek dispersion at room temperature for 30 minutes, after which 15.4 g of sodium hydroxide (50% aqueous solution) was slowly added. This reagent was mixed with the fenugreek dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and held at this temperature for 60 minutes, after which the temperature was reduced to at least 50°C to initiate the washing procedure.

[0067] The reaction mixture obtained as described in the paragraph above was dispersed with 110.5 g of 99% isopropanol and 22.9 g of water while stirring. The pH was adjusted to approximately 9-10 using 4.1 g of glacial acetic acid. The mixture was then stirred for 30 minutes, and after standing, it was removed from the reactor. The dispersion was then vacuum filtered through qualitative filter paper. This washing and filtering procedure was repeated for 30 minutes using 250 g of 99% isopropanol and 100 g of water. The resulting solid was then dried overnight in a 60°C oven for 6 hours.

[0068] Degree of cation substitution (DS) cationic The molecular weight (Mw) was 0.15, and the average molecular weight (Mw) was 1,384,000 g / mol. When cationic fenugreek was tested for biodegradability, it was demonstrated to be intrinsically biodegradable (i.e., pass) within 60 days.

[0069] Comparative Example 1 - Non-biodegradable cationic fenugreek In a 1-liter stirred reactor, 195.5 g of isopropanol solvent mixed with 74.8 g of deionized water was introduced at room temperature under an inert nitrogen gas atmosphere. Then, 87.8 g of fenugreek powder was added while vigorously stirring at room temperature. After stirring for several minutes to homogenize, 45.0 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat 188, 65% aqueous solution) was added. This reagent was mixed with the fenugreek dispersion at room temperature for 30 minutes, after which 17.0 g of sodium hydroxide (50% aqueous solution) was slowly added. This reagent was mixed with the fenugreek dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and held at this temperature for 60 minutes, after which the temperature was reduced to at least 50°C to initiate the washing procedure.

[0070] The reaction mixture obtained as described in the paragraph above was dispersed with 110.5 g of 99% isopropanol and 22.7 g of water while stirring. The pH was adjusted to approximately 9-10 using 2.0 g of glacial acetic acid. The mixture was then stirred for 30 minutes, and after standing, it was removed from the reactor. The dispersion was then vacuum filtered through qualitative filter paper. This washing and filtering procedure was repeated for 30 minutes using 250 g of 99% isopropanol and 100 g of water. The resulting solid was then dried overnight in a 60°C oven for 6 hours.

[0071] Degree of cation substitution (DS) cationic The molecular weight (Mw) was 0.17, and the average molecular weight (Mw) was 1,696,000 g / mol. Cationic fenugreek was tested for biodegradability and demonstrated to be intrinsically non-biodegradable (i.e., unsuccessful) within 60 days.

[0072] Comparative Example 2 - Non-biodegradable cationic fenugreek In a 1-liter stirred reactor, 280.2 g of isopropanol solvent mixed with 112.0 g of deionized water was introduced at room temperature under an inert nitrogen gas atmosphere. Then, 125.2 g of fenugreek powder was added while vigorously stirring at room temperature. After stirring for several minutes to homogenize, 74.2 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat 188, 65% aqueous solution) was added. This reagent was mixed with the fenugreek dispersion at room temperature for 30 minutes, after which 28.3 g of sodium hydroxide (50% aqueous solution) was slowly added. This reagent was mixed with the fenugreek dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and held at this temperature for 60 minutes, after which the temperature was reduced to at least 50°C to initiate the washing procedure.

[0073] The reaction mixture obtained as described in the paragraph above was dispersed with 158.5 g of 99% isopropanol and 36.2 g of water while stirring. The pH was adjusted to approximately 9-10 using 2.0 g of glacial acetic acid. The mixture was then stirred for 30 minutes, and after standing, it was removed from the reactor. The dispersion was then vacuum filtered through qualitative filter paper. This washing and filtering procedure was repeated for 30 minutes using 357 g of 99% isopropanol and 146 g of water. The resulting solid was then dried overnight in a 60°C oven for 6 hours.

[0074] Degree of cation substitution (DS) cationic The 0.20 ratio and the average molecular weight (Mw) were 1,819,000 g / mol. When cationic fenugreek was tested for biodegradability, it was shown to be essentially non-biodegradable (i.e., unsuitable) within 60 days.

[0075] The results for Examples 1-3 and Comparative Examples 1 and 2 are shown in Table 1 below.

[0076] [Table 1]

[0077] As shown in Table 1 above, cationic fenugreek with a degree of cationic substitution of less than 0.17 exhibits superior biodegradability compared to cationic fenugreek with a degree of cationic substitution of 0.17 or greater.

[0078] Example 4 - Biodegradable cationic cod In a 1-liter stirred reactor, 98.7 g of isopropanol solvent mixed with 37.4 g of deionized water was introduced at room temperature under an inert nitrogen gas atmosphere. Then, 43.8 g of tara gum powder was added while vigorously stirring at room temperature. After stirring for several minutes to homogenize, 18.5 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat 188, 65% aqueous solution) was added. This reagent was mixed with the tara gum dispersion at room temperature for 30 minutes, after which 7.1 g of sodium hydroxide (50% aqueous solution) was slowly added. This reagent was mixed with the tara gum dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and held at this temperature for 60 minutes, after which the temperature was reduced to at least 50°C to initiate the washing procedure.

[0079] The reaction mixture obtained as described in the paragraph above was dispersed with 55.2 g of 99% isopropanol and 12.0 g of water while stirring. The pH was adjusted to approximately 9-10 using 1.0 g of glacial acetic acid. The mixture was then stirred for 30 minutes, and after standing, it was removed from the reactor. The dispersion was then vacuum filtered through qualitative filter paper. This washing and filtering procedure was repeated for 30 minutes using 125 g of 99% isopropanol and 50 g of water. The resulting solid was then dried overnight in a 60°C oven for 6 hours.

[0080] Degree of cation substitution (DS) cationic The molecular weight (Mw) was 0.14, and the average molecular weight (Mw) was 1,167,000 g / mol. When the cationic cod was tested for biodegradability, it was demonstrated to be intrinsically biodegradable (i.e., pass) within 28 days and 60 days.

[0081] Example 5 - Biodegradable cationic cod In a 1-liter stirred reactor, 195.9 g of isopropanol solvent mixed with 74.8 g of deionized water was introduced at room temperature under an inert nitrogen gas atmosphere. Then, 87.6 g of tara gum powder was added while vigorously stirring at room temperature. After stirring for several minutes to homogenize, 45.3 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat 188, 65% aqueous solution) was added. This reagent was mixed with the tara gum dispersion at room temperature for 30 minutes, after which 16.2 g of sodium hydroxide (50% aqueous solution) was slowly added. This reagent was mixed with the tara gum dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and held at this temperature for 60 minutes, after which the temperature was reduced to at least 50°C to initiate the washing procedure.

[0082] The reaction mixture obtained as described in the paragraph above was dispersed with 119.0 g of 99% isopropanol and 23.0 g of water while stirring. The pH was adjusted to approximately 9-10 using 4.1 g of glacial acetic acid. The mixture was then stirred for 30 minutes, and after standing, it was removed from the reactor. The dispersion was then vacuum filtered through qualitative filter paper. This washing and filtering procedure was repeated for 30 minutes using 250 g of 99% isopropanol and 100 g of water. The resulting solid was then dried overnight in a 60°C oven for 6 hours.

[0083] Degree of cation substitution (DS) cationic The molecular weight (Mw) was 0.17, and the average molecular weight (Mw) was 1,057,000 g / mol. When the cationic cod was tested for biodegradability, it was demonstrated to be intrinsically biodegradable (i.e., pass) within 60 days.

[0084] Example 6 - Biodegradable cationic cod In a 1-liter stirred reactor, 196.0 g of isopropanol solvent mixed with 74.6 g of deionized water was introduced at room temperature under an inert nitrogen gas atmosphere. Then, 87.8 g of tara gum powder was added while vigorously stirring at room temperature. After stirring for several minutes to homogenize, 45.0 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat 188, 65% aqueous solution) was added. This reagent was mixed with the tara gum dispersion at room temperature for 30 minutes, after which 16.3 g of sodium hydroxide (50% aqueous solution) was slowly added. This reagent was mixed with the tara gum dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and held at this temperature for 60 minutes, after which the temperature was reduced to at least 50°C to initiate the washing procedure.

[0085] The reaction mixture obtained as described in the paragraph above was dispersed with 113.0 g of 99% isopropanol and 24.0 g of water while stirring. The pH was adjusted to approximately 9-10 using 1.6 g of glacial acetic acid. The mixture was then stirred for 30 minutes and then removed from the reactor. The dispersion was then vacuum filtered through qualitative filter paper. This washing and filtering procedure was repeated for 30 minutes using 250 g of 99% isopropanol and 100 g of water. The resulting solid was then dried overnight in a 60°C oven for 6 hours.

[0086] Degree of cation substitution (DS) cationic The molecular weight (Mw) was 0.18, and the average molecular weight (Mw) was 1,387,000 g / mol. When the cationic cod was tested for biodegradability, it was demonstrated to be intrinsically biodegradable (i.e., pass) within 60 days.

[0087] Comparative Example 3 - Non-biodegradable cationic cod In a 1-liter stirred reactor, 97.4 g of isopropanol solvent mixed with 39.0 g of deionized water was introduced at room temperature under an inert nitrogen gas atmosphere. Then, 43.8 g of tara gum powder was added while vigorously stirring at room temperature. After stirring for several minutes to homogenize, 27.8 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat 188, 65% aqueous solution) was added. This reagent was mixed with the tara gum dispersion at room temperature for 30 minutes, after which 11.0 g of sodium hydroxide (50% aqueous solution) was slowly added. This reagent was mixed with the tara gum dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and held at this temperature for 60 minutes, after which the temperature was reduced to at least 50°C to initiate the washing procedure.

[0088] The reaction mixture obtained as described in the paragraph above was dispersed with 110.0 g of 99% isopropanol and 23.0 g of water while stirring. The pH was adjusted to approximately 9-10 using 1.6 g of glacial acetic acid. The mixture was then stirred for 30 minutes, and after standing, it was removed from the reactor. The dispersion was then vacuum filtered through qualitative filter paper. This washing and filtering procedure was repeated for 30 minutes using 250 g of 99% isopropanol and 100 g of water. The resulting solid was then dried overnight in a 60°C oven for 6 hours.

[0089] Degree of cation substitution (DS) cationic The molecular weight (Mw) was 0.20, and the average molecular weight (Mw) was 1,020,000 g / mol. When the cationic cod was tested for biodegradability, it was shown to be intrinsically non-biodegradable (i.e., unsuccessful) within 60 days.

[0090] Comparative Example 4 - Non-biodegradable cationic cod In a 1-liter stirred reactor, 140.1 g of isopropanol solvent mixed with 55.2 g of deionized water was introduced at room temperature under an inert nitrogen gas atmosphere. Then, 63.0 g of tara gum powder was added while vigorously stirring at room temperature. After stirring for several minutes to homogenize, 32.5 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat 188, 65% aqueous solution) was added. This reagent was mixed with the tara gum dispersion at room temperature for 30 minutes, after which 12.5 g of sodium hydroxide (50% aqueous solution) was slowly added. This reagent was mixed with the tara gum dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and held at this temperature for 60 minutes, after which the temperature was reduced to at least 50°C to initiate the washing procedure.

[0091] The reaction mixture obtained as described in the paragraph above was dispersed with 79.8 g of 99% isopropanol and 16.8 g of water while stirring. The pH was adjusted to approximately 9-10 using 1.9 g of glacial acetic acid. The mixture was then stirred for 30 minutes, and after standing, it was removed from the reactor. The dispersion was then vacuum filtered through qualitative filter paper. This washing and filtering procedure was repeated for 30 minutes using 180 g of 99% isopropanol and 72 g of water. The resulting solid was then dried overnight in a 60°C oven for 6 hours.

[0092] Degree of cation substitution (DS) cationic The molecular weight (Mw) was 0.20, and the average molecular weight (Mw) was 1,368,000 g / mol. When the cationic cod was tested for biodegradability, it was shown to be intrinsically non-biodegradable (i.e., unsuccessful) within 60 days.

[0093] Comparative Example 5 - Non-biodegradable cationic cod In a 1-liter stirred reactor, 195.9 g of isopropanol solvent mixed with 74.8 g of deionized water was introduced at room temperature under an inert nitrogen gas atmosphere. Then, 87.8 g of tara gum powder was added while vigorously stirring at room temperature. After stirring for several minutes to homogenize, 65.8 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat 188, 65% aqueous solution) was added. This reagent was mixed with the tara gum dispersion at room temperature for 30 minutes, after which 23.5 g of sodium hydroxide (50% aqueous solution) was slowly added. This reagent was mixed with the tara gum dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and held at this temperature for 60 minutes, after which the temperature was reduced to at least 50°C to initiate the washing procedure.

[0094] The reaction mixture obtained as described in the paragraph above was dispersed with 110.0 g of 99% isopropanol and 23.0 g of water while stirring. The pH was adjusted to approximately 9-10 using 2.5 g of glacial acetic acid. The mixture was then stirred for 30 minutes and then removed from the reactor. The dispersion was then vacuum filtered through qualitative filter paper. This washing and filtering procedure was repeated for 30 minutes using 250 g of 99% isopropanol and 100 g of water. The resulting solid was then dried overnight in a 60°C oven for 6 hours.

[0095] Degree of cation substitution (DS) cationic The molecular weight (Mw) was 0.25, and the average molecular weight (Mw) was 1,195,000 g / mol. When the cationic cod was tested for biodegradability, it was shown to be intrinsically non-biodegradable (i.e., unsuccessful) within 60 days.

[0096] Comparative Example 6 - Non-biodegradable cationic cod In a 1-liter stirred reactor, 97.8 g of isopropanol solvent mixed with 37.3 g of deionized water was introduced at room temperature under an inert nitrogen gas atmosphere. Then, 43.4 g of tara gum powder was added while vigorously stirring at room temperature. After stirring for several minutes to homogenize, 45.1 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat 188, 65% aqueous solution) was added. This reagent was mixed with the tara gum dispersion at room temperature for 30 minutes, after which 11.1 g of sodium hydroxide (50% aqueous solution) was slowly added. This reagent was mixed with the tara gum dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and held at this temperature for 60 minutes, after which the temperature was reduced to at least 50°C to initiate the washing procedure.

[0097] The reaction mixture obtained as described in the paragraph above was dispersed with 110.0 g of 99% isopropanol and 23.0 g of water while stirring. The pH was adjusted to approximately 9-10 using 1.0 g of glacial acetic acid. The mixture was then stirred for 30 minutes, and after standing, it was removed from the reactor. The dispersion was then vacuum filtered through qualitative filter paper. This washing and filtering procedure was repeated for 30 minutes using 250 g of 99% isopropanol and 100 g of water. The resulting solid was then dried overnight in a 60°C oven for 6 hours.

[0098] Degree of cation substitution (DS) cationic The value was 0.29. When cationic cod was tested for biodegradability, it was shown to be intrinsically non-biodegradable (i.e., unsuccessful) within 60 days.

[0099] The results for Examples 4-6 and Comparative Examples 3-6 are shown in Table 2 below.

[0100] [Table 2]

[0101] As shown in Table 2 above, cationic cod with a cationic substitution degree of less than 0.20 exhibits superior biodegradability compared to cationic fenugreek with a cationic substitution degree of 0.20 or greater.

[0102] Example 7 - Biodegradable cationic cassia In a 1-liter stirred reactor, 195.1 g of isopropanol solvent mixed with 74.0 g of deionized water was introduced at room temperature under an inert nitrogen gas atmosphere. Then, 87.6 g of cassia powder was added while vigorously stirring at room temperature. After stirring for several minutes to homogenize, 28.1 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat 188, 65% aqueous solution) was added. This reagent was mixed with the cassia dispersion at room temperature for 30 minutes, after which 15.1 g of sodium hydroxide (50% aqueous solution) was slowly added. This reagent was mixed with the cassia dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and held at this temperature for 60 minutes, after which the temperature was reduced to at least 50°C to initiate the washing procedure.

[0103] The reaction mixture obtained as described in the paragraph above was dispersed with 110.0 g of 99% isopropanol and 23.0 g of water while stirring. The pH was adjusted to approximately 9-10 using 3.9 g of glacial acetic acid. The mixture was then stirred for 30 minutes, and after standing, it was removed from the reactor. The dispersion was then vacuum filtered through qualitative filter paper. This washing and filtering procedure was repeated for 30 minutes using 250 g of 99% isopropanol and 100 g of water. The resulting solid was then dried overnight in a 60°C oven for 6 hours.

[0104] Degree of cation substitution (DS) cationic The molecular weight (Mw) was 0.13, and the average molecular weight (Mw) was 563,000 g / mol. When cationic cassia was tested for biodegradability, it was demonstrated to be intrinsically biodegradable (i.e., pass) within 28 days and 60 days.

[0105] Example 8 - Biodegradable cationic cassia In a 1-liter stirred reactor, 144.0 g of isopropanol solvent mixed with 55.0 g of deionized water was introduced at room temperature under an inert nitrogen gas atmosphere. Then, 62.5 g of cassia powder was added while vigorously stirring at room temperature. After stirring for several minutes to homogenize, 32.0 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat 188, 65% aqueous solution) was added. This reagent was mixed with the cassia dispersion at room temperature for 30 minutes, after which 11.8 g of sodium hydroxide (50% aqueous solution) was slowly added. This reagent was mixed with the cassia dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and held at this temperature for 60 minutes, after which the temperature was reduced to at least 50°C to initiate the washing procedure.

[0106] The reaction mixture obtained as described in the paragraph above was dispersed with 90.0 g of isopropanol (99%) and 15.0 g of water while stirring. The pH was adjusted to approximately 9-10 using 3.9 g of glacial acetic acid. The mixture was then stirred for 30 minutes, and after standing, it was removed from the reactor. The dispersion was then vacuum filtered through qualitative filter paper. This washing and filtering procedure was repeated for 30 minutes using 180 g of isopropanol (99%) and 70 g of water. The resulting solid was then dried overnight in a 60°C oven for 6 hours.

[0107] Degree of cation substitution (DS) cationic The molecular weight (Mw) was 0.18, and the average molecular weight (Mw) was 743,000 g / mol. When cationic cassia was tested for biodegradability, it was demonstrated to be intrinsically biodegradable (i.e., pass) within 28 days and 60 days.

[0108] Comparative Example 7 - Non-biodegradable cationic cassia In a 1-liter stirred reactor, 195.6 g of isopropanol solvent mixed with 74.9 g of deionized water was introduced at room temperature under an inert nitrogen gas atmosphere. Then, 87.7 g of cassia powder was added while vigorously stirring at room temperature. After stirring for several minutes to homogenize, 65.0 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat 188, 65% aqueous solution) was added. This reagent was mixed with the cassia dispersion at room temperature for 30 minutes, after which 12.6 g of sodium hydroxide (50% aqueous solution) was slowly added. This reagent was mixed with the cassia dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and held at this temperature for 60 minutes, after which the temperature was reduced to at least 50°C to initiate the washing procedure.

[0109] The reaction mixture obtained as described in the paragraph above was dispersed with 100.0 g of 99% isopropanol and 25.0 g of water while stirring. The pH was adjusted to approximately 9-10 using 2.0 g of glacial acetic acid. The mixture was then stirred for 30 minutes, and after standing, it was removed from the reactor. The dispersion was then vacuum filtered through qualitative filter paper. This washing and filtering procedure was repeated for 30 minutes using 250 g of 99% isopropanol and 100 g of water. The resulting solid was then dried overnight in a 60°C oven for 6 hours.

[0110] Degree of cation substitution (DS) cationic The molecular weight (Mw) was 0.24, and the average molecular weight (Mw) was 757,000 g / mol. When cationic cassia was tested for biodegradability, it was shown to be intrinsically non-biodegradable (i.e., unsuccessful) within 60 days.

[0111] The results for Examples 7-8 and Comparative Example 7 are shown in Table 3 below.

[0112] [Table 3]

[0113] As shown in Table 3 above, cationic cassia with a degree of cationic substitution of less than 0.24 exhibits superior biodegradability compared to cationic cassia with a degree of cationic substitution of 0.24 or more.

[0114] While the subject matter of the present invention has been described above, it will be apparent that it can be modified or altered in numerous ways. Such modifications and variations should not be considered to deviate from the spirit and scope of the subject matter of the present invention, and all such modifications and variations are intended to be included within the scope of the claims.

Claims

1. The ratio of galactose units to mannose units is approximately 1:

1. (a) DS less than 0.17, preferably 0.16 or less, more preferably 0.15 or less ｃａｔｉｏｎｉｃ and (b) Average molecular weight (Mw) less than 3,500,000 g / mol; A biodegradable cationic galactomannan having, A biodegradable cationic galactomannan that exhibits biodegradability of 60% or more within 60 days, preferably within 28 days, according to OECD 302B.

2. A biodegradable cationic galactomannan according to claim 1, comprising cationic fenugreek (Trigonnella foenum-graecum).

3. Said DS ｃａｔｉｏｎｉｃ The biodegradable cationic galactomannan according to claim 1 or 2, wherein the ratio is in the range of 0.10 to 0.16, preferably 0.12 to 0.16, and more preferably 0.14 to 0.

16.

4. The biodegradable cationic galactomannan according to any one of claims 1 to 3, wherein the Mw is 3,000,000 g / mol or less, preferably in the range of 200,000 g / mol to 3,000,000 g / mol, more preferably in the range of 250,000 g / mol to 2,500,000 g / mol, and even more preferably in the range of 500,000 g / mol to 2,500,000 g / mol.

5. The ratio of galactose units to mannose units is approximately 1:3 to approximately 1:5, preferably approximately 1:3 to approximately 1:

4. (a) DS less than 0.20, preferably 0.18 or less, more preferably less than 0.18 ｃａｔｉｏｎｉｃ and (b) Average molecular weight (Mw) less than 2,500,000 g / mol; A biodegradable cationic galactomannan having, A biodegradable cationic galactomannan that exhibits biodegradability of 60% or more within 60 days, preferably within 28 days, according to OECD 302B.

6. The biodegradable cationic galactomannan according to claim 5, comprising cationic cod (Tara spinosa), cationic carob (Parkia biglobosa), or a combination thereof.

7. The ratio of galactose units to mannose units is approximately 1:4, and the DS is 0.18 or less, preferably less than 0.18, more preferably 0.17 or less. ｃａｔｉｏｎｉｃ The biodegradable cationic galactomannan according to claim 5, having the characteristics described herein.

8. The ratio of galactose units to mannose units is approximately 1:3, and the DS is 0.18 or less, preferably less than 0.18, more preferably 0.17 or less. ｃａｔｉｏｎｉｃ The biodegradable cationic galactomannan according to claim 5, having the characteristics described herein.

9. Said DS ｃａｔｉｏｎｉｃ The biodegradable cationic galactomannan according to claim 5 or 6, wherein the ratio is in the range of 0.10 to 0.20, preferably 0.12 to 0.20, and more preferably 0.14 to 0.

20.

10. The biodegradable cationic galactomannan according to any one of claims 5 to 9, wherein the Mw is 2,000,000 g / mol or less, preferably in the range of 200,000 g / mol to 2,000,000 g / mol, more preferably in the range of 250,000 g / mol to 2,000,000 g / mol, and even more preferably in the range of 300,000 g / mol to 2,000,000 g / mol.

11. The ratio of galactose units to mannose units is approximately 1:

5. (a) DS less than 0.24 ｃａｔｉｏｎｉｃ and (b) Average molecular weight (Mw) less than 1,000,000 g / mol; A biodegradable cationic galactomannan having, A biodegradable cationic galactomannan that exhibits biodegradability of 60% or more within 60 days, preferably within 28 days, according to OECD 302B.

12. The biodegradable cationic galactomannan according to claim 11, comprising cationic cassia (Senna tora / Senna obtusifolia).

13. Said DS ｃａｔｉｏｎｉｃ The biodegradable cationic galactomannan according to claim 11 or 12, wherein the ratio is in the range of 0.10 to less than 0.24, preferably 0.14 to 0.22, and more preferably 0.14 to 0.

20.

14. A biodegradable cationic galactomannan according to any one of claims 11 to 13, having an Mw of 900,000 g / mol or less, preferably about 100,000 g / mol to 900,000 g / mol, and more preferably about 150,000 g / mol to 750,000 g / mol.

15. The biodegradable cationic galactomannan according to any one of claims 1 to 14, wherein the cationic galactomannan is cationized with at least one cationizing agent selected from 2,3-epoxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, and mixtures thereof.

16. The cationic galactomannan according to any one of claims 1 to 15, comprising an amino group selected from primary, secondary, and tertiary amino groups and combinations thereof, a quaternary ammonium group, a sulfonium group, a phosphinium group, and a cationic group selected from combinations thereof.

17. The cationic group is selected from trialkylammonium groups, such as trimethylammonium, triethylammonium, or tributylammonium groups; aryldialkylammonium groups, such as benzyldimethylammonium groups; ammonium groups in which the nitrogen atom is a ring member of a ring structure, such as pyridinium and imidazoline groups; and combinations thereof, according to any one of claims 1 to 16.

18. A biodegradable cationic galactomannan according to any one of claims 1 to 17, having 70% or more biodegradability within 28 days in accordance with OECD 302B.

19. A composition containing biodegradable cationic galactomannan as described in any one of claims 1 to 18.

20. At least one surfactant, emulsifier, emollient, moisturizer, hair conditioner, hair fixative, film-forming agent, skin protectant, binder, chelating agent, disinfectant, insecticide, fungicide, deodorant, insect repellent, fragrance, antibacterial agent, antifungal agent, antibiotic, anti-dandruff agent, abrasive, adhesive, absorbent, colorant, deodorant, antiperspirant, water-retaining agent, oil (mineral oil, vegetable oil, animal oil, synthetic oil, silicone oil and mixtures thereof, etc.), opacifier, and pearlescent agent. The composition according to claim 19, further comprising antioxidants, preservatives, propellants, spreaders, exfoliants, keratolytics, blood coagulants, vitamins, sunscreens, artificial tanning accelerators, UV absorbers, pH adjusters, plant components, hair dyes, dyes, preservatives, inorganic particles, buffers, preservatives, oxidizing agents, reducing agents, rheology adjusters, skin bleaching agents, pigments, anti-inflammatory agents, thickeners, local anesthetics, fragrances, fragrance solubilizers, fine particles, fine abrasives, polishing agents, and combinations thereof.

21. A method for producing biodegradable cationic galactomannan according to any one of claims 1 to 20, comprising reacting a noncationic galactomannan with at least one cationizing agent.

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