Modified lysine-based polymers and compositions containing same

Abstract

The present invention relates to modified lysine-based polymers obtained or obtained from a process comprising Michael addition of at least a portion of the free amino groups in the lysine-based polymer with a Michael acceptor selected from at least one of unsaturated carboxylic acids and unsaturated carboxylic acid esters, and detergent compositions comprising the same. The present invention also relates to a method for storing the aqueous detergent composition comprising the modified lysine-based polymer, and a method for laundering fabrics or cleaning hard surfaces with the detergent composition comprising the modified lysine-based polymer.

Description

[Technical field]

[0001] The present invention relates to modified lysine-based polymers, detergent compositions containing same and the use of modified lysine-based polymers in detergent compositions, particularly as dispersing agents. [Background technology]

[0002] Nowadays, dispersants play an important role in various industrial and household formulations, for example in laundry detergent formulations to prevent fabric graying.With regard to the development of dispersants, the dispersing effect has always been pursued to avoid undesirable phenomena such as scaling or dirt deposition in the washing and cleaning process.

[0003] Most dispersants currently in use are petroleum-based rather than bio-based. In recent years, bio-based products and products containing bio-based ingredients have gained consumer interest due to the sustainability of biomass resources. With this trend, bio-based dispersants pose new challenges for manufacturers, especially in household cleaning applications.

[0004] WO2021228642A1 discloses the use of carboxymethylated polylysine as a dispersing agent. Carboxymethylated polylysine is produced from biodegradable polylysine, for example by modification with chloroacetate. Although carboxymethylated polylysine exhibits acceptable anti-graying performance, its production has the disadvantage that sodium chloroacetate is toxic and corrosive. The residue of the modifier chloroacetate in the final product must be severely limited due to its toxicity. Furthermore, chloroacetate is corrosive, so its handling requires containers made of special and expensive materials. Summary of the Invention

[0005] Therefore, there is a need to provide biodegradable chemicals as dispersants useful in industrial and household formulations. It would be even more desirable if the biodegradable dispersants could be made from less toxic and less corrosive materials, reducing costs.

[0006] It is an object of the present invention to provide a biodegradable chemical that can provide at least acceptable anti-graying performance and / or primary cleaning power in detergents, particularly laundry detergents, and that can be manufactured in a more cost-effective process.

[0007] It has now been found that the objects of the present invention can be achieved by a lysine-based polymer in which at least a portion of the free amino groups contained in the polymer are modified via Michael addition with an unsaturated carboxylic acid or an unsaturated carboxylic acid ester.

[0008] In one aspect, the present invention relates to modified lysine-based polymers obtained or obtained from a process comprising Michael addition of at least a portion of the free amino groups in the lysine-based polymer with a Michael acceptor selected from unsaturated carboxylic acids and unsaturated carboxylic acid esters.

[0009] In another aspect, the present invention relates to a detergent composition comprising the modified lysine-based polymer according to the first aspect.

[0010] In yet another aspect, the present invention relates to the use of the modified lysine-based polymer according to the first aspect in a detergent composition.

[0011] In a further aspect, the present invention relates to the use of the modified lysine-based polymer according to the first aspect as a dispersing agent.

[0012] It has been found that the modified lysine-based polymers according to the present invention, while being biodegradable, exhibit acceptable anti-graying performance and primary cleaning power compared to commercially available non-biodegradable chelating and dispersing agents. Furthermore, the unsaturated carboxylic acids and unsaturated carboxylic acid esters as modifiers are less toxic and less corrosive than chloroacetic acid and its salts used in the preparation of biodegradable carboxymethylated polylysine in WO2021228642A1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present invention will be described in detail below. It should be understood that the present invention can be embodied in many different ways and should not be construed as being limited to the embodiments shown in this specification. Unless otherwise specified, all technical and scientific terms used in this specification have the same meaning as commonly understood by those skilled in the art to which the present invention belongs.

[0014] As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0015] As used herein, the terms "comprise," "comprising," and the like are used interchangeably with "contain," "containing," and the like, and are to be interpreted in an open-ended manner. That is, for example, additional components or elements may be present. Expressions such as "consists of" or "consists essentially of" or synonymous terms may be subsumed within "comprise" or synonymous terms.

[0016] As used herein, the term "biodegradable" generally refers to a material that can be broken down from the action of naturally occurring microorganisms, such as bacteria, fungi, algae, environmental heat, moisture, or other environmental factors.

[0017] As used herein, the term "lysine-based polymer" is intended to denote a polymer in which lysine constitutes the major molar proportion, i.e., 50 mol % or more, of all monomers constituting the polymer, which may be a homopolymer of lysine in which lysine constitutes 100 mol % of the monomers constituting the polymer, or a copolymer of lysine and one or more comonomers.

[0018] As used herein, the term "free amino group" refers to an amino group -NH2 that has not been modified by condensation with a carboxyl group or by Michael addition.

[0019] As used herein, the term "modified lysine-based polymer" is intended to refer to a lysine-based polymer that includes amino groups that have been modified via Michael addition of free amino groups contained in the lysine-based polymer with an unsaturated carboxylic acid or an unsaturated carboxylic acid ester. It will be understood that the term "modified lysine-based polymer" is intended to encompass unneutralized, partially neutralized, and fully neutralized forms with respect to any carboxyl groups that may be present in the polymer.

[0020] As used herein, the term "structural unit" is intended to refer to the smallest molecular residue derived from a monomer after polymerization, i.e., polycondensation of the monomer. It will be understood that the term "structural unit" can also include moieties derived from a Michael acceptor when free amino groups are present after polycondensation of the monomer and the amino groups are modified via Michael addition.

[0021] Herein, the terms "structural unit from a lysine monomer" and "lysine structural unit" are used interchangeably. Similarly, the terms "structural unit from at least one dicarboxylic acid of formula (I)" and "dicarboxylic acid structural unit" are used interchangeably.

[0022] As used herein, the K value, when referring to a modified lysine-based polymer according to the invention, refers to the corresponding parameter of the lysine-based polymer before modification by Michael addition, unless the context clearly dictates otherwise.

[0023] <Modified lysine-based polymer> The modified lysine-based polymers according to the present invention can be modified homopolymers of lysine or modified copolymers having a major proportion (e.g., greater than 50 mol %) of lysine and a minor proportion (e.g., less than 50 mol %) of at least one other monomer.

[0024] Unsaturated carboxylic acids useful as Michael acceptors for modifying lysine-based polymers via Michael addition can be selected from the group consisting of α,β-ethylenically unsaturated monocarboxylic acids having 3 to 10 carbon atoms, α,β-ethylenically unsaturated dicarboxylic acids having 4 to 8 carbon atoms, α,β-ethylenically unsaturated tricarboxylic acids having 4 to 8 carbon atoms, and α,β-ethylenically unsaturated carboxylic acids with more carboxylic acid groups.

[0025] Preferably, the unsaturated carboxylic acid may be selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid and aconitic acid.

[0026] More preferably, the unsaturated carboxylic acid may be selected from the group consisting of acrylic acid, maleic acid and itaconic acid, with particular mention being made of acrylic acid.

[0027] The unsaturated carboxylic acid ester useful as Michael acceptor for modifying lysine-based polymer via Michael addition can be selected from any ester of unsaturated carboxylic acid as described herein above.Preferably, the unsaturated carboxylic acid ester can be selected from the polyalkylene oxide ester or the terminated polyalkylene oxide ester of the unsaturated carboxylic acid described herein, preferably the terminated polyethylene oxide ester, the terminated polypropylene oxide ester or the terminated polybutylene oxide ester of the unsaturated carboxylic acid described herein, or a combination thereof.More preferably, the terminated polyethylene oxide ester of the unsaturated carboxylic acid can be mentioned, such as acrylic acid, maleic acid or itaconic acid, especially the terminated polyethylene oxide ester of acrylic acid.

[0028] In the terminated polyalkylene oxide esters of unsaturated carboxylic acids, suitable terminating groups may be selected from C1-C4-alkyl or C1-C4-hydroxyalkyl, for example methyl, ethyl, propyl, isopropyl, butyl, hydroxymethyl, hydroxyethyl, hydroxypropyl or hydroxybutyl.

[0029] Examples of terminal polyalkylene oxide esters of unsaturated carboxylic acids include, but are not limited to, polyethylene oxide mono(C1-C4-alkyl) ether acrylate, polyethylene oxide mono(C1-C4-alkyl) ether maleate, polyethylene oxide mono(C1-C4-alkyl) ether itaconate, preferably polyethylene oxide monomethyl ether acrylate, polyethylene oxide monomethyl ether maleate, polyethylene oxide monomethyl ether itaconate, more preferably polyethylene oxide monomethyl ether acrylate.

[0030] The polyalkylene oxide ester of unsaturated carboxylic acid or the polyalkylene oxide portion in the terminal polyalkylene oxide ester may have a number average molecular weight of 100-2,000, preferably 200-1,200, and more preferably 400-800.

[0031] The unsaturated carboxylic acids and unsaturated carboxylic acid esters useful for modifying the lysine-based polymers in the present invention are also generally referred to herein as Michael acceptors.

[0032] As homopolymers of lysine (also called lysine homopolymers) to be modified, both linear polylysine and branched polylysine are useful. It is known that polylysine can have linear or branched structures depending on the manufacturing process. For example, ε-linear polylysine is generally prepared by a microbial fermentation process, as is well known in the art. Branched polylysine is generally produced by thermal polycondensation of lysine, since lysine has one reactive carboxyl group and two reactive amino groups (α-NH2 and ε-NH2) per molecule. For the purpose of the present invention, the type of polylysine structure (linear or branched), the arrangement of their structural units, and the degree of branching are all immaterial.

[0033] In some embodiments of the present invention, the modified lysine-based polymer may be a linear or branched lysine homopolymer modified with a Michael acceptor as described herein above. In particular, the lysine homopolymer may be an ε-linear polylysine or a branched polylysine.

[0034] As modified lysine copolymers (also called lysine copolymers), polymerization products of more than 50 mol% lysine and dicarboxylic acid or its amide-forming derivatives are useful. Thus, lysine copolymers contain amide moieties resulting from lysine and dicarboxylic acid or its amide-forming derivatives. The lysine copolymers can be prepared by thermal polycondensation of lysine and dicarboxylic acid, or any suitable polymerization reaction of lysine and dicarboxylic acid.

[0035] In some other embodiments of the present invention, the modified lysine-based polymer is a copolymer of lysine modified with a Michael acceptor as described herein, comprising greater than 50 mol % structural units from lysine monomers and less than 50 mol % structural units from at least one dicarboxylic acid or amide-forming derivative thereof.

[0036] In particular, copolymers of lysine (A) 60 to 99 mol % of structural units derived from lysine monomers; (B) 1 to 40 mol % of at least one dicarboxylic acid of formula (I) or an amide-forming derivative thereof HOOC-R1-COOH(I) (In the formula, R1 is a direct bond or an aliphatic linear hydrocarbylene, which is unsubstituted or substituted with at least one group selected from unsubstituted or substituted alkyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkylamino, di(alkyl)amino, alkylidene, hydroxyl, mercapto, amino, and halogen. Structural units from The polymer may be a polymer comprising:

[0037] The term "aliphatic linear hydrocarbylene" as used herein refers to a divalent group derived from an unsaturated or saturated acyclic hydrocarbon, which may or may not be interrupted by at least one heteroatom selected from O, S and N. Typically, the hydrocarbylene group herein has 1 to 24 carbon atoms (C1 to C 24 -hydrocarbylene), preferably having 1 to 18 carbon atoms (C 18 -hydrocarbylene), more preferably having 1 to 12 carbon atoms (C 12 -hydrocarbylene). Examples of aliphatic linear hydrocarbylene groups are especially alkylene and alkenylene.

[0038] The term "alkylene" as used herein refers to a saturated divalent group derived from a linear alkane, which may or may not be interrupted by at least one heteroatom selected from O, S, and N. Typically, an alkylene group herein is an alkylene group having 1 to 24 carbon atoms (C1 to C 24 -alkylene), preferably having 1 to 18 carbon atoms (C 18 -alkylene), more preferably 1 to 12 carbon atoms (C 12 -alkylene), such as C1-C4-alkylene and C1-C2-alkylene. Examples of alkylene groups are in particular methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, hexadecamethylene, octadecamethylene etc.

[0039] The term "alkenylene" as used herein refers to an unsaturated divalent group derived from a linear alkene in which any double bond is in an internal position. Typically, an alkenylene group herein is an alkyl group having 2 to 24 carbon atoms (C 24 -alkenylene), preferably having 2 to 18 carbon atoms (C 18 -alkenylene), more preferably having 2 to 12 carbon atoms (C 12 -alkenylene). Examples of alkenylene groups are in particular vinylene, 1,3-propenylene, 1,4-but-2-enylene, 1,5-pent-2-enylene, 1,6-hex-3-enylene, etc.

[0040] The term "alkyl" as used herein and in the alkyl moiety of alkoxy, alkylthio, alkylamino, dialkylamino, etc., generally refers to an alkyl group having 1 to 18 carbon atoms (C 18 -alkyl), preferably having 1 to 12 carbon atoms (C 12-alkyl), more preferably saturated linear or branched hydrocarbyl having 1 to 8 carbon atoms (C1-C8-alkyl) or 1 to 6 carbon atoms (C1-C6-alkyl), such as C1-C4-alkyl and C1-C2-alkyl. Examples of alkyl groups are in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 1-ethylpropyl, neopentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 1-ethylpentyl, 1-propylbutyl, 2-ethylpentyl, n-octyl, 1-methylheptyl, 2-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 1-propylpentyl, 2-propylpentyl, n-nonyl, etc.

[0041] The term "alkoxy," as used herein, refers to an alkyl attached through an oxygen atom and may be represented by --O-alkyl, where alkyl is as defined above.

[0042] The term "alkylthio" as used herein refers to an alkyl attached through a sulfur atom and may be represented by --S-alkyl, where alkyl is as defined above.

[0043] The terms "alkylamino" and "di(alkyl)amino" as used herein refer to an amino (-NH2) in which the hydrogen atom is replaced by one or two alkyl groups, respectively, where alkyl is defined above.

[0044] The term "alkylidene" as used herein refers to an unsaturated divalent group derived from an alkane having both valences on the same carbon atom, which is represented as follows: *=CR a R b where the asterisk (*) indicates the position at which the alkylidene group is attached to the residue, and R a and R beach represents H or alkyl. Typically, alkylidene groups herein have 1 to 6 carbon atoms (C1-C6-alkylidene), preferably 1 to 4 carbon atoms (C1-C4-alkylidene). Examples of alkylidene groups are especially methylidene, ethylidene, propylidene etc.

[0045] As used herein, the term "halogen" refers to fluorine, bromine, chlorine and iodine.

[0046] In certain embodiments, the modified lysine-based polymer according to the invention is, for example, [ka] (In the formula, R2 and R3 are, independently of each other, H or R4, provided that at least one of R2 and R3 is R4; R4 represents a moiety derived from a Michael acceptor via Michael addition; and The structural units include those derived from lysine monomers represented by the symbols * (where * indicates the position at which the structural unit is attached to another structural unit by an amide bond).

[0047] In some embodiments, the modified lysine-based polymer according to the present invention is such that R4 in (Ua) and (Ub) is a group represented by formula (II): [ka] (In the formula, R5 and R6 are independently of one another H, C1-C6-alkyl, carboxyl (-COOH), -COOM, -(C1-C4-alkylene)-COOH or -(C1-C4-alkylene)-COOM, R7 is H, C1-C6-alkyl, -(CH2CH2O) n - R8 or M; R8 is C1-C4-alkyl; M is a cation selected from an alkali metal cation, an alkaline earth metal cation, an ammonium cation, and an amine cation; n is a number ranging from 2 to 40, and ** indicates the position where the moiety is attached to the N atom bearing R4), and includes at least one of the structural units (Ua) and (Ub) as described herein.

[0048] Preferably, the modified lysine-based polymer according to the present invention has R4 represented by formula (II) R5 and R6 are independently of one another H, C1-C4-alkyl, carboxyl (-COOH), -COOM, -(C1-C2-alkylene)-COOH or -(C1-C2-alkylene)-COOM, R7 is H, -(CH2CH2O) n - R8 or M; R8 is C1-C2-alkyl; M is a cation selected from an alkali metal cation, an alkaline earth metal cation, an ammonium cation, and an amine cation; n is a number ranging from 4 to 25, and ** denotes the position where the moiety is bonded to the N atom carrying R4) and / or structural unit (Ua) and / or structural unit (Ub) indicate a moiety represented by

[0049] More preferably, the modified lysine-based polymer according to the present invention has R4 represented by formula (II) R5 is H, methyl, carboxyl (-COOH) or -COOM; R6 is H, methyl, carboxyl (-COOH), -COOM, -(C1-C2-alkylene)-COOH or -(C1-C2-alkylene)-COOM, R7 is H, -(CH2CH2O) n - R8 or M; R8 is C1-C2-alkyl; M is a cation selected from an alkali metal cation, an alkaline earth metal cation, an ammonium cation, and an amine cation; n is a number ranging from 8 to 15, and ** denotes the position where the moiety is bonded to the N atom carrying R4) and / or structural unit (Ua) and / or structural unit (Ub) indicate a moiety represented by

[0050] Most preferably, the modified lysine-based polymer according to the present invention has R4 represented by formula (II), R5 is H, carboxyl (-COOH) or -COOM; R6 is H, carboxyl (-COOH), -COOM, -(C1-C2-alkylene)-COOH or -(C1-C2-alkylene)-COOM, R7 is H, -(CH2CH2O) n - R8 or M; R8 is methyl; M is a cation selected from an alkali metal cation, an alkaline earth metal cation, an ammonium cation, and an amine cation; n is a number ranging from 8 to 15, and ** denotes the position where the moiety is bonded to the N atom carrying R4) and / or structural unit (Ua) and / or structural unit (Ub) indicate a moiety represented by

[0051] In particular, the modified lysine-based polymer according to the present invention is one in which R4 is [ka] (In the formula, R7 is H, -(CH2CH2O) n - R8 or M; R8 is methyl; M is a cation selected from an alkali metal cation, an alkaline earth metal cation, an ammonium cation, and an amine cation; n is a number ranging from 8 to 15, and ** denotes the position where the moiety is bonded to the N atom carrying R4) and / or structural unit (Ua) and / or structural unit (Ub) indicate a moiety represented by

[0052] More specifically, R7 is H, -(CH2CH2O) in formula (II-1). n -R8 or M, which is H or M in formulas (II-2), (II-3) and (II-4), where R8, M and n are as described herein for formulas (II-1), (II-2), (II-3) and (II-4).

[0053] In each of formulas (II) and (II-1) to (II-4) described herein, M is preferably a cation selected from sodium, potassium, calcium, magnesium, ammonium or an amine cation.

[0054] Each lysine structural unit as above may be linked to the same or different lysine structural units to form an amide bond such as *-Ua-Ua-*, *-Ua-Ub-*, *-Ub-Ub-*, and any other possible bond. It will be understood that the modified lysine-based polymer may contain two or more of the above amide bonds. The lysine structural units as above may also be linked to dicarboxylic acid structural units in the case of a copolymer of lysine as described in the present invention.

[0055] The modified lysine-based polymer according to the present invention may, for example, be represented by the formula (III): [ka] (In the formula, R1 is as defined herein above with respect to formula (I), The structure may include dicarboxylic acid structural units represented by the symbol * (indicating the position at which the structural unit is attached to any other structural unit by an amide bond).

[0056] It will be understood that each structural unit of formula (III) as above may be linked to two lysine structural units in the same or different bonds.

[0057] It will also be understood that when R1 is a hydrocarbylene substituted with an amino group (NH2), the dicarboxylic acid structural unit constituted in the carboxyalkyl-modified lysine-based polymer according to the present invention may be in any other possible form. The amino substituent is reactive with the carboxyl group contained in the lysine monomer and the dicarboxylic acid to form the corresponding amide bond.

[0058] In a particular embodiment, the modified lysine-based polymer according to the invention comprises (B) a structural unit from at least one dicarboxylic acid or its amide-forming derivative of formula (I), wherein R1 is an unsubstituted or substituted C1-C 18 -alkyl, unsubstituted or substituted C1-C 18 -Alkoxy, unsubstituted or substituted C1-C 18 -alkylthio, unsubstituted or substituted C1-C 18 -Alkylamino, di(C1-C 18 -alkyl)amino, C1-C6-alkylidene, hydroxyl, mercapto, amino and halogen. 24 -hydrocarbylene.

[0059] In a preferred embodiment, the modified lysine-based polymer according to the invention comprises (B) a structural unit from at least one dicarboxylic acid or its amide-forming derivative of formula (I), wherein R1 is an unsubstituted or substituted C1-C 12 -alkyl, unsubstituted or substituted C1-C 12 -Alkoxy, unsubstituted or substituted C1-C 12 -alkylthio, unsubstituted or substituted C1-C 12 -Alkylamino, di(C1-C 12 -alkyl)amino, C1-C4-alkylidene, hydroxyl, mercapto, amino and halogen. 18 -hydrocarbylene.

[0060] In a more preferred embodiment, the modified lysine-based polymer according to the present invention comprises (B) structural units from at least one dicarboxylic acid of formula (I) or its amide-forming derivative, in which R1 is a direct bond or an aliphatic linear C1-C alkyl group, which is substituted by at least one group selected from unsubstituted or substituted C1-C8-alkyl, unsubstituted or substituted C1-C8-alkoxy, unsubstituted or substituted C1-C8-alkylthio, unsubstituted or substituted C1-C8-alkylamino, di(C1-C8-alkyl)amino, C1-C4-alkylidene, hydroxyl, mercapto, amino and halogen. 12 -hydrocarbylene.

[0061] In a further preferred embodiment, the modified lysine-based polymer according to the invention comprises (B) a structural unit from at least one dicarboxylic acid of formula (I) or an amide-forming derivative thereof, in which R1 is a direct bond, a C1-C4 alkyl group, which is substituted by at least one group selected from unsubstituted or substituted C1-C4 alkyl, unsubstituted or substituted C1-C4 alkoxy, unsubstituted or substituted C1-C4 alkylthio, unsubstituted or substituted C1-C4 alkylamino, di(C1-C4 alkyl)amino, C1-C4 alkylidene, hydroxyl, mercapto, amino and halogen. 12 Alkylene or C2-C 12 -alkenylene.

[0062] In a further preferred embodiment, the modified lysine-based polymer according to the invention comprises (B) structural units from at least one dicarboxylic acid of formula (I) or its amide-forming derivative, in which R1 is a direct bond, C1-C 12 Alkylene or C2-C 12 -alkenylene.

[0063] In a most preferred embodiment, the modified lysine-based polymer according to the present invention comprises (B) structural units from at least one dicarboxylic acid or its amide-forming derivative of formula (I), in which R1 is a direct bond, C1-C2 alkylene, hydroxyl and amino, which are substituted by at least one group selected from unsubstituted or substituted C1-C4 alkyl, C1-C2 alkylidene, hydroxyl and amino. 12 Alkylene or C2-C 12 -alkenylene.

[0064] In particular, the modified lysine-based polymer according to the present invention comprises structural units from (B) at least one of oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, tartaric acid, aspartic acid, glutaric acid, itaconic acid, glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid, more preferably at least one of succinic acid, tartaric acid, glutaric acid, adipic acid, most preferably tartaric acid or adipic acid.

[0065] Preferably, the modified lysine-based polymer according to the present invention comprises (A) 70 to 97 mol % of lysine structural units; and (B) 3 to 30 mol % of dicarboxylic acid structural units Includes.

[0066] More preferably, the modified lysine-based polymer according to the present invention is (A) 75 to 97 mol % of lysine structural units; and (B) 4 to 25 mol % of dicarboxylic acid structural units Includes.

[0067] Most preferably, the modified lysine-based polymer according to the present invention comprises: (A) 75 to 95 mol % of lysine structural units; and (B) 5 to 25 mol % of dicarboxylic acid structural units Includes.

[0068] Carboxymethylated lysine-based polymers according to the invention can be prepared from lysine-based polymers having a K value in the range of 8 to 20, more preferably 9 to 15, most preferably 9.5 to 13, determined according to DIN ISO 1628-1 using a 1 wt. % solution of the respective lysine-based polymer in water at 23° C. The K value, often called intrinsic viscosity, is an indirect measure of the molecular weight of the polymer.

[0069] The modified lysine-based polymer according to the present invention has a degree of modification (DM) by Michael addition of at least 10%, for example, 20%, 30%, 35%, 40%, 45%, 50%, 60%, 65%, 70%, 80% or more. For example, the DM can be in the range of 10-70%, preferably 20-50%.

[0070] Here, the degree of modification (DM) is theoretically defined according to the following formula:

number

[0071] DM was measured by hydrolyzing modified lysine-based polymers and 1 It can be carried out by determining the moles of the moiety derived from the Michael acceptor after Michael addition, the moles of the structural unit of lysine, and the moles of the dicarboxylic acid structural unit having an amino group, if present, according to the resonance signals assigned to each proton in the hydrolysis product measured by H NMR. It should be understood that due to the limitations of the measurement method, the measured DM value may not completely coincide with the theoretical value.

[0072] The modified lysine-based polymer according to the present invention has a weight average molecular weight (Mw) in the range of 600 to 20,000 g / mol, preferably 700 to 17,000 g / mol, more preferably 800 to 13,000 g / mol, and / or a number average molecular weight (Mn) in the range of 500 to 20,000 g / mol, preferably 600 to 15,000 g / mol, more preferably 700 to 12,000 g / mol. The number average molecular weight can be determined according to the method described below.

[0073] There is no particular limitation on the preparation process of the modified lysine-based polymer according to the present invention. In general, the modified lysine-based polymer according to the present invention can be prepared by a process comprising reacting a lysine-based polymer with a Michael acceptor as described herein under controlled conditions for the Michael addition between free amino groups and unsaturated carboxylic acid or unsaturated carboxylic acid ester as Michael acceptor. It can be considered that the modified lysine-based polymer can also be prepared by a process comprising reacting a lysine-based polymer with an unsaturated carboxylic acid as Michael acceptor and optionally esterifying it. The known conditions for the Michael addition between free amino groups and unsaturated carboxylic acid or unsaturated carboxylic acid ester can be applied without limitation.

[0074] The modified lysine-based polymers according to the present invention have been found to be useful as dispersing and / or chelating agents in detergent compositions.

[0075] <Detergent Composition> According to the present invention, the detergent composition may be any composition that comprises a surfactant or a mixture of surfactants to provide cleaning benefits. In particular, the detergent composition is a laundry detergent composition.

[0076] There is no limitation in the formulation of detergent compositions.The modified lysine-based polymer according to the present invention is useful in any conventional formulation of detergent compositions, such as laundry detergent compositions.It is understood that the modified lysine-based polymer according to the present invention can be used in detergent compositions in addition to or instead of dispersing agents and / or chelating agents that would be included in conventional formulations of detergent compositions.

[0077] In some embodiments of the present invention, the laundry detergent composition comprises the modified lysine-based polymer according to the present invention in an amount of 0.5 to 30 wt.%, preferably 1 to 25 wt.%, more preferably 1 to 15 wt.%, for example 1 to 10 wt.%, based on the total solids content of the detergent composition.

[0078] The essential components that provide cleaning benefits to the detergent composition may include at least one of cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants, depending on the particular application and desired performance of the detergent composition.

[0079] Nonionic Surfactants Useful nonionic surfactants may include, but are not limited to, (1) condensation products of alcohols with ethylene oxide, (2) condensation products of alcohols with ethylene oxide and additional alkylene oxides, (3) condensation products of polypropylene glycols with ethylene oxide, or (4) condensation products of ethylene oxide with the reaction product of ethylene diamine and propylene oxide, fatty acid amides, and semi-polar nonionic surfactants.

[0080] The condensation products of alcohols with ethylene oxide may be, for example, C8-C condensates which may be linear or branched, primary or secondary. 22 -Alkyl group, preferably C 10 ~C 18 The ethylene oxide is derived from an alcohol having a -alkyl group. The alcohol is condensed with about 1 to 25 moles, preferably about 3 to 18 moles, of ethylene oxide per mole of alcohol.

[0081] Condensation products of alcohols with ethylene oxide and further alkylene oxides can be prepared according to the scheme RO-EO-AO or RO-AO-EO, where R is a primary or secondary, branched or linear C-C 22 -Alkyl group, preferably C 10 ~C 18 -alkyl group, EO is ethylene oxide, and AO is an alkylene oxide, preferably including propylene oxide, butylene oxide or pentylene oxide).

[0082] The condensation product of polypropylene glycol and ethylene oxide preferably contains a hydrophobic portion having a molecular weight of about 1,500 to about 1,800. Addition of up to about 40 moles of ethylene oxide to this hydrophobic portion results in an amphiphilic compound.

[0083] The condensation product of ethylene oxide with the reaction product of ethylenediamine and propylene oxide contains a hydrophobic portion consisting of the reaction product of ethylenediamine and propylene oxide, and generally has a molecular weight of about 2,500 to about 3,000. Ethylene oxide is added so that the polyoxyethylene content is about 40% by weight to about 80% by weight and the molecular weight is about 5,000 to about 11,000, based on the hydrophobic unit.

[0084] The fatty acid amide has the following formula: [ka] (In the formula, R1 is an alkyl group having 7 to 21, preferably 9 to 17, carbon atoms; R2 are each independently hydrogen, C1-C4-alkyl, C1-C4-hydroxyalkyl or (C2H4O) x H, where x varies from 1 to 3).

[0085] C8-C such as monoethanolamide, diethanolamide, and diisopropanolamide 20 Fatty acid amides are preferred.

[0086] Semi-polar nonionic surfactants each have at least one C8-C 18 -Alkyl group, preferably C 10 ~C 14 Examples of the water-soluble amine oxides having a C-alkyl group include water-soluble phosphine oxides and water-soluble sulfoxides. 10 ~C 12 -Alkoxyethyl dihydroxyethylamine oxides are preferred.

[0087] Anionic Surfactants Useful anionic surfactants include, but are not limited to, alkenyl- or alkylbenzenesulfonates, alkane sulfonates, olefin sulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates, alkyl carboxylates (soaps). Counterions present are alkali metal cations, preferably sodium or potassium, alkaline earth metal cations, such as calcium or magnesium, as well as ammonium and substituted ammonium compounds, such as mono-, di- or triethanolammonium cations, and mixtures of the aforementioned cations.

[0088] The alkenyl- or alkylbenzene sulfonates are branched or linear, optionally hydroxyl-substituted alkenyl or alkyl groups, preferably linear C9-C 25 It may contain an alkyl group.

[0089] Alkanesulfonates are available on a large industrial scale in the form of secondary alkanesulfonates, in which the sulfo group is attached to a secondary carbon atom of the alkyl moiety. The alkyl can in principle be saturated, unsaturated, branched or linear, and can optionally be substituted with hydroxyl. Preferred secondary alkanesulfonates are linear C9-C 25 -Alkyl group, preferably C 10 ~C 20 -alkyl group, more preferably C12 ~C 18 -Contains an alkyl group.

[0090] Olefin sulfonates are C8-C 24 , preferably C 14 ~C 16 -Olefin sulfonates are obtained by sulfonating α-olefins with sulfur trioxide and then neutralizing. These olefin sulfonates may contain small amounts of hydroxyalkanesulfonates and alkanedisulfonates, depending on the production process.

[0091] Alkyl ester sulfonates are, for example, C8-C alkyl esters sulfonated with sulfur trioxide. 20 - carboxylic acids, i.e. linear esters of fatty acids, of the formula: [ka] (In the formula, R' is C8~C 20 -Alkyl group, preferably C 10 ~C 16 -alkyl and R″ is a C1-C6-alkyl group, preferably a methyl, ethyl or isopropyl group. 10 ~C 16 -alkyl methyl ester sulfonates are particularly preferred.

[0092] Alkyl sulfates are surfactants of the formula ROSO3M', where R is C 10 ~C 24 -alkyl, preferably C 12 ~C 18 -alkyl. M' is a counterion as described above for the anionic surfactants.

[0093] Alkyl ether sulfates have the general structure RO(A) m SO3M, where R is C 10 ~C 24 -alkyl, preferably C 12 ~C 18-alkyl group, A is an alkoxy unit, preferably ethoxy, m has a value of from about 0.5 to about 6, preferably from about 1 to about 3, and M is a cation, such as sodium, potassium, calcium, magnesium, ammonium or a substituted ammonium cation.

[0094] Alkyl carboxylates are commonly known by the term "soap". Soaps are saturated or unsaturated, preferably natural, linear C8-C 18 They can be made on the basis of fatty acids. Saturated fatty acid soaps include, for example, salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, as well as soap mixtures derived in particular from natural fatty acids, such as coconut fatty acid, palm kernel fatty acid or tallow fatty acid. Known alkenyl succinates can also be used together with the soap or as a substitute for soap.

[0095] Further anionic surfactants are salts of acylaminocarboxylic acids, acyl sarcosinates, fatty acid-protein condensation products obtained by reacting fatty acid chlorides with oligopeptides; salts of alkylsulfamidocarboxylic acids; salts of alkyl and alkylaryl ether carboxylic acids; sulfonated polycarboxylic acids, alkyl and alkenyl glycerol sulfates, such as oleyl glycerol sulfate, alkylphenol ether sulfates, alkyl phosphates, alkyl ether phosphates, isethionates, such as acyl isethionates, N-acyltaurides, alkyl succinates, sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C 12 ~C 18 Monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C 12 ~C 18 diesters), sulfates of alkyl polysaccharides, such as alkyl polyglycosides and sulfates of alkyl polysaccharides, such as alkyl polyglycosides and sulfates of alkyl polyethoxycarboxylates, such as those of the formula RO(CH2CH2) k CH2COOM (wherein R is C8-C 22-alkyl, k is a number from 0 to 10, and M is a cation.

[0096] Cationic Surfactants Useful cationic surfactants include R 1 N(CH3)3 + X - , R 1 R 2 N(CH3)2 + X - , R 1 R 2 R 3 N(CH3) + X - or R 1 R 2 R 3 R 4 N + X - (In the formula, R 1 , R 2 , R 3 and R 4 are, independently of each other, unsubstituted C8-C 24 -Alkyl, preferably C8-C 18 -Alkyl, hydroxyl alkyl having 1 to 4 carbon atoms, phenyl, C2 to C 18 -Alkenyl, C7-C 24 -Aralkyl, (C2H4O) x H, x is from about 1 to about 3, the alkyl group optionally contains one or more ester groups, and X is a suitable anion. Useful cationic surfactants can also be cyclic quaternary ammonium salts.

[0097] Amphoteric / Zwitterionic Surfactants Useful amphoteric surfactants may be aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, where the aliphatic group may be linear or branched, one of the aliphatic substituents contains at least about 8 carbon atoms, or from about 8 to about 18 carbon atoms, and at least one of the aliphatic substituents contains an anionic water-soluble group, such as carboxy, sulfonate, sulfate. Suitable amphoteric surfactants also include sarcosinates, glycinates, taurinates, and mixtures thereof. Examples of amphoteric surfactant species are known in the art, for example from WO2005095569A1.

[0098] Useful zwitterionic surfactants can be derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Suitable examples of zwitterionic surfactants include betaines, such as alkyl betaines and alkyl amido betaines, such as N-alkyl-N,N-dimethyl-N-carboxymethyl betaines, N-(alkylamidopropyl)-N,N-dimethyl-N-carboxymethyl betaines, alkyl dipolyethoxy betaines, alkyl amine oxides, and sulfo and hydroxy betaines, such as N-alkyl-N,N-dimethylamino-1-propanesulfonates, each of which is a linear or branched C8-C 22 -Alkyl, preferably C8-C 18 -alkyl group, more preferably C 12 ~C 18 Examples of the aryl group include, but are not limited to, those having -alkyl.

[0099] In an exemplary embodiment of the present invention, the laundry detergent composition may contain 0.1 to 80 wt. % of at least one surfactant selected from an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant, based on the total solids content of the detergent composition. Some preferred laundry detergent compositions of the present invention may contain at least one of an anionic surfactant or a nonionic surfactant.

[0100] Adjuvants The detergent composition may further include conventional adjuvants which serve to modify the performance characteristics of the detergent composition.

[0101] Suitable adjuvants for the detergent composition include, but are not limited to, builders such as complexing agents other than the modified lysine-based polymers according to the invention, ion exchange agents and precipitants, bleaching agents, bleach activators, corrosion inhibitors, foam boosters, defoamers, dyes, fillers, color care agents, optical brighteners, disinfectants, alkali agents, antioxidants, thickeners, fragrances, solvents, solubilizers, softeners and antistatic agents. By way of example, some adjuvants are described below.

[0102] In general, the detergent composition may comprise at least one builder selected from organic builders and inorganic builders.Examples of suitable inorganic builders are sodium sulfate or sodium carbonate, or sodium silicate, especially sodium disilicate and sodium metasilicate, zeolites, sheet silicates, especially those of formula α-Na2Si2O5, β-Na2Si2O5, and δ-Na2Si2O5.Examples of suitable organic builders are fatty acid sulfonates, α-hydroxypropionic acid, alkali metal malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, methylglycine diacetic acid and its alkali salts, especially Na salt, N,N-dicarboxymethylglutamic acid and its alkali salts, especially Na salt, citric acid and its Na salt, and polymeric builders, such as polycarboxylates and polyaspartic acid.

[0103] The detergent composition may comprise builders in a total amount of, for example, 10 to 70% by weight, preferably up to 50% by weight, based on the total solids content of the detergent composition. In the context of the present invention, the modified lysine-based polymers according to the invention are not counted as builders.

[0104] The detergent composition may contain at least one defoaming agent selected from, for example, silicone oil and paraffin oil, and the defoaming agent may be present in a total amount of 0.05 to 0.5% by weight based on the total solid content of the detergent composition.

[0105] The detergent composition may comprise at least one bleaching agent, which may be selected from chlorine bleaches and peroxide bleaches.

[0106] The peroxide bleaching agent may be selected from inorganic and organic peroxide bleaching agents. Preferred inorganic peroxide bleaching agents are selected from alkali metal percarbonates, alkali metal perborates and alkali metal persulfates. In solid detergent compositions for cleaning hard surfaces and solid laundry detergent compositions, alkali metal percarbonates, especially sodium percarbonate, are preferably used in coated form. Such coatings may be of organic or inorganic nature. Examples include glycerol, sodium sulfate, silicates, sodium carbonate, and any combination thereof, such as a combination of sodium carbonate and sodium sulfate. An example of an organic peroxide bleaching agent is percarboxylic acid.

[0107] Suitable chlorine-containing bleaches are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate. The laundry detergent composition may contain the chlorine-containing bleaches in a total amount of, for example, 3 to 10% by weight, based on the total solids content of the detergent composition.

[0108] The detergent composition may also include at least one bleach activator, such as N-methylmorpholinium-acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts, N-acylimides such as N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine ("DADHT") or nitrile quats (trimethylammonium acetonitrile salts). Further examples of bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.

[0109] The detergent composition may comprise at least one corrosion inhibitor. Examples of suitable corrosion inhibitors are triazoles, especially benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, phenol derivatives, such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol. The detergent composition may comprise a total amount of corrosion inhibitors of 0.1-1.5 wt. %, based on the total solid content of the detergent composition.

[0110] The detergent composition according to the invention further comprises at least one enzyme. Preferably, the at least one enzyme is a detergent enzyme.

[0111] Suitable enzymes may be classified as oxidoreductases (EC1), transferases (EC2), hydrolases (EC3), lyases (EC4), isomerases (EC5), or ligases (EC6) (EC numbering follows the Enzyme Nomenclature Recommendations of the Commission on Nomenclature of the International Union of Biochemistry and Molecular Biology (1992) including its supplements published in 1993-1999). Preferably, the enzyme is a hydrolase (EC3).

[0112] Preferably, the enzyme is a protease, amylase, lipase, cellulase, mannanase, hemicellulase, phospholipase, esterase, pectinase, lactase, peroxidase, xylanase, cutinase, pectate lyase, keratinase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, nuclease, DNase, phosphodiesterase, The enzyme is selected from the group consisting of phytase, carbohydrase, galactanase, xanthanase, xyloglucanase, oxidoreductase, perhydrolase, aminopeptidase, asparaginase, carbohydrase, carboxypeptidase, catalase, chitinase, cyclodextrin glycosyltransferase, α-galactosidase, β-galactosidase, glucoamylase, α-glucosidase, β-glucosidase, invertase, ribonuclease, transglutaminase, and dispersion, and any combination thereof. More preferably, the enzyme is selected from the group consisting of protease, amylase, lipase, cellulase, mannanase, xylanase, DNase, dispersion, pectinase, oxidoreductase, and cutinase, and any combination thereof. In particular, the enzyme is a protease, preferably a serine protease, more preferably a subtilisin protease.

[0113] Such enzymes may be incorporated into the composition at a level sufficient to provide an effective amount to achieve a beneficial effect, preferably a primary cleaning effect and / or a secondary cleaning effect, such as an anti-graying effect or an anti-pilling effect (e.g., in the case of cellulases). Preferably, the enzyme is present in the composition in an amount of from 0.00001% to 5%, preferably from 0.00001% to 2%, more preferably from 0.0001% to 1%, and even more preferably from 0.001% to 0.5% enzyme protein by weight of the composition.

[0114] Preferably, the detergent composition according to the present invention may further comprise an enzyme stabilizing system. Preferably, the composition according to the present invention comprises an enzyme stabilizing system in an amount of 0.001-10%, 0.005-8%, or 0.01-6% based on the total weight of the composition. The enzyme stabilizing system may be any stabilizing system compatible with enzymes.

[0115] Preferably, the enzyme stabilization system comprises at least one compound selected from the group consisting of polyols, such as 1,3-propanediol, ethylene glycol, glycerol, 1,2-propanediol or sorbitol, inorganic salts, such as CaCl2, MgCl2 or NaCl, short chain (preferably C1-C6) carboxylic acids and their salts, such as formic acid, formates (preferably sodium formate), acetic acid, acetate or lactate, borates, boric acid, boronic acids (preferably 4-formylphenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals and peptide aldehyde bisulfite adducts. Preferably, the enzyme stabilization system comprises a combination of at least two compounds selected from the group consisting of inorganic salts, polyols, and short chain carboxylic acids, and preferably one or more compounds selected from the group consisting of borates, boric acid, boronic acids (preferably 4-formylphenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts. In particular, when proteases are present in the composition, protease inhibitors may be added, which are preferably selected from borates, boric acid, boronic acids (preferably 4-FPBA), peptide aldehydes (preferably peptide aldehydes such as Z-VAL-H or Z-GAY-H), peptide acetals, and peptide aldehyde hydrosulfite adducts.

[0116] Detergent compositions comprising modified lysine-based polymers according to the present invention may also comprise at least one antimicrobial and / or preservative agent.

[0117] Antimicrobial agents are chemical compounds that kill or inhibit the growth or reproduction of microorganisms. The microorganisms may be bacteria, yeasts or molds.

[0118] Preservatives are antimicrobial agents that can be added to aqueous products and compositions to maintain the original performance, properties and integrity of the products and compositions by killing or inhibiting the growth of contaminating microorganisms. Examples of preservatives are as described in patent application WO 2021 / 115912 A1, pages 35 to 39.

[0119] Of particular interest are the following antimicrobial and / or antiseptic agents: · 4,4'-Dichloro-2-hydroxydiphenyl ether (synonyms: 5-chloro-2-(4-chlorophenoxy)phenol, diclosan, DCPP); · 2-Phenoxyethanol (synonyms: phenoxyethanol, methylphenyl glycol, phenoxetol, ethylene glycol phenyl ether, ethylene glycol monophenyl ether, 2-(phenoxy)ethanol, 2-phenoxy-1-ethanol); · 2-Bromo-2-nitropropane-1,3-diol (synonyms: 2-Bromo-2-nitro-1,3-propanediol, Bronopol); · Glutaraldehyde (synonyms: 1-5-pentanedial, pentane-1,5-dial, glutar, glutaric dialdehyde); · Glyoxal (synonyms: ethanedial, oxylaldehyde, 1,2-ethanedial); · 2-Butyl-benzo[d]isothiazol-3-one (BBIT); 2-Methyl-2H-isothiazol-3-one (MIT); · 2-Octyl-2H-isothiazol-3-one (OIT); 5-Chloro-2-methyl-2H-isothiazol-3-one (CIT or CMIT); Mixture of 5-chloro-2-methyl-2H-isothiazol-3-one (CMIT) and 2-methyl-2H-isothiazol-3-one (MIT) (CMIT / MIT mixture); 1,2-Benzisothiazol-3(2H)-one (BIT); Hexa-2,4-dienoic acid (commonly known as "sorbic acid") and its salts, such as calcium sorbate, sodium sorbate; potassium (E,E)-hexa-2,4-dienoate (potassium sorbate); Lactic acid and its salts; L-(+)-lactic acid; in particular sodium lactate; Benzoic acid and its salts, such as sodium benzoate, ammonium benzoate, calcium benzoate, magnesium benzoate, MEA-benzoate, potassium benzoate; Salicylic acid and its salts, such as calcium salicylate, magnesium salicylate, MEA salicylate, sodium salicylate, potassium salicylate, TEA salicylate; Benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate Didecyldimethylammonium chloride (DDAC); · N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine (diamine); Peracetic acid; and Hydrogen peroxide.

[0120] At least one antimicrobial agent or preservative may be added to the detergent composition in an amount of 0.0001 to 10%, based on the total weight of the composition.

[0121] Preferably, the detergent composition comprises 2-phenoxyethanol in an amount of from 2 ppm to 5%, preferably from 0.1 to 2%, or 4,4'-dichloro-2-hydroxydiphenyl ether (DCPP) in an amount of from 0.001 to 3%, preferably from 0.002 to 1%, more preferably from 0.01 to 0.6%, based on the total weight of the composition.

[0122] Suitable species and amounts of conventional adjuvants for detergent compositions, particularly laundry detergent compositions, are well known in the art and are described, for example, in WO2017174413A1 and WO2015187757A1.

[0123] Embodiment Various embodiments are listed below, and it will be understood that the embodiments listed below may be combined with all aspects and other embodiments in accordance with the scope of the present invention.

[0124] 1. A modified lysine-based polymer obtained or derived from a process comprising Michael addition of at least a portion of the free amino groups in the lysine-based polymer with a Michael acceptor selected from at least one of unsaturated carboxylic acids and unsaturated carboxylic acid esters.

[0125] 2. The modified lysine-based polymer according to embodiment 1, wherein the Michael acceptor is at least one selected from the group consisting of α,β-ethylenically unsaturated monocarboxylic acids having 3 to 10 carbon atoms, α,β-ethylenically unsaturated dicarboxylic acids having 4 to 8 carbon atoms, α,β-ethylenically unsaturated tricarboxylic acids having 4 to 8 carbon atoms, α,β-ethylenically unsaturated carboxylic acids having more carboxylic acid groups, and esters thereof.

[0126] 3. The modified lysine-based polymer according to embodiment 2, wherein the Michael acceptor is at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, and esters thereof.

[0127] 4. The modified lysine-based polymer according to embodiment 3, wherein the Michael acceptor is at least one selected from the group consisting of acrylic acid, maleic acid, itaconic acid, and esters thereof.

[0128] 5. The modified lysine-based polymer according to any of the previous embodiments, wherein the ester is selected from a polyalkylene oxide ester or a terminal polyalkylene oxide ester of an unsaturated carboxylic acid, preferably a terminal polyethylene oxide ester, a terminal polypropylene oxide ester or a terminal polybutylene oxide ester, or a combination thereof.

[0129] 6. The modified lysine-based polymer according to any of the preceding embodiments, wherein the terminated polyethylene oxide ester comprises a terminating group selected from C1-C4-alkyl or C1-C4-hydroxyalkyl.

[0130] 7. The modified lysine-based polymer according to embodiment 5 or 6, wherein the polyalkylene oxide or the terminal polyalkylene oxide moiety has a number average molecular weight of 100 to 2,000, preferably 200 to 1,200, and more preferably 400 to 800.

[0131] 8.The following formula [ka] (In the formula, R2 and R3 are, independently of each other, H or R4, provided that at least one of R2 and R3 is R4; * indicates the position where a structural unit is bonded to another structural unit by an amide bond; R4 is a group represented by the formula (II) [ka] is the portion represented by R5 and R6 are independently of one another H, C1-C6-alkyl, carboxyl (-COOH), -COOM, -(C1-C4-alkylene)-COOH or -(C1-C4-alkylene)-COOM, R7 is H, C1-C6-alkyl, -(CH2CH2O) n - R8 or M; R8 is C1-C4-alkyl; M is a cation selected from an alkali metal cation, an alkaline earth metal cation, an ammonium cation, and an amine cation; n is a number ranging from 2 to 40, and A modified lysine-based polymer comprising structural units from lysine monomers represented by: (** represents the site of attachment to the N atom bearing R4).

[0132] 9. R5 and R6 are independently of each other H, C1-C4-alkyl, carboxyl (-COOH), -COOM, -(C1-C2-alkylene)-COOH or -(C1-C2-alkylene)-COOM, R7 is H, -(CH2CH2O) n - R8 or M; R8 is C1-C2-alkyl, and The modified lysine-based polymer according to embodiment 8, wherein n is a number ranging from 4 to 25.

[0133] 10. R5 is H, methyl, carboxyl (-COOH), or -COOM; R6 is H, methyl, carboxyl (-COOH), -COOM, -(C1-C2-alkylene)-COOH or -(C1-C2-alkylene)-COOM, R7 is H, -(CH2CH2O) n - R8 or M; R8 is C1-C2-alkyl, and The modified lysine-based polymer according to embodiment 9, wherein n is a number ranging from 8 to 15.

[0134] 11. R5 is H, carboxyl (-COOH), or -COOM; R6 is H, carboxyl (-COOH), -COOM, -(C1-C2-alkylene)-COOH or -(C1-C2-alkylene)-COOM, R7 is H, -(CH2CH2O) n - R8 or M, and The modified lysine-based polymer of embodiment 10, wherein R8 is methyl.

[0135] 12. The modified lysine-based polymer of any of the preceding embodiments, which is a modified homopolymer of lysine.

[0136] 13. The modified lysine-based polymer according to any of the preceding embodiments 1 to 11, which is a modified copolymer of lysine comprising more than 50 mol % of structural units derived from lysine monomers and less than 50 mol % of structural units derived from at least one dicarboxylic acid or amide-forming derivative thereof.

[0137] 14. (A) 60 to 99 mol % of structural units derived from lysine monomers; (B) 1 to 40 mol % of at least one dicarboxylic acid of formula (I) or an amide-forming derivative thereof HOOC-R1-COOH (I) (In the formula, R1 is a direct bond or an aliphatic linear hydrocarbylene, which is unsubstituted or substituted with at least one group selected from unsubstituted or substituted alkyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkylamino, di(alkyl)amino, alkylidene, hydroxyl, mercapto, amino, and halogen. Structural units from 14. The modified lysine-based polymer of embodiment 13, comprising:

[0138] 15. (B) A compound comprising structural units from at least one dicarboxylic acid of formula (I) or its amide-forming derivative, wherein R1 is an unsubstituted or substituted C1-C 18 -alkyl, unsubstituted or substituted C1-C 18 -Alkoxy, unsubstituted or substituted C1-C 18 -alkylthio, unsubstituted or substituted C1-C 18 -Alkylamino, di(C1-C 18 -alkyl)amino, C1-C6-alkylidene, hydroxyl, mercapto, amino and halogen. 24 15. The modified lysine-based polymer according to embodiment 14, wherein the polymer is -hydrocarbylene.

[0139] 16. (B) A compound comprising structural units from at least one dicarboxylic acid of formula (I) or its amide-forming derivative, wherein R1 is an unsubstituted or substituted C1-C 12 -alkyl, unsubstituted or substituted C1-C 12 -Alkoxy, unsubstituted or substituted C1-C 12 -alkylthio, unsubstituted or substituted C1-C 12 -Alkylamino, di(C1-C 12 -alkyl)amino, C1-C4-alkylidene, hydroxyl, mercapto, amino and halogen. 18 16. The modified lysine-based polymer according to embodiment 15, wherein the polymer is -hydrocarbylene.

[0140] 17. (B) A compound comprising structural units from at least one dicarboxylic acid of formula (I) or its amide-forming derivative, in which R1 is a direct bond or an aliphatic linear C1-C alkyl group, which is substituted by at least one group selected from unsubstituted or substituted C1-C8 alkyl, unsubstituted or substituted C1-C8 alkoxy, unsubstituted or substituted C1-C8 alkylthio, unsubstituted or substituted C1-C8 alkylamino, di(C1-C8 alkyl)amino, C1-C4 alkylidene, hydroxyl, mercapto, amino and halogen. 12 17. The modified lysine-based polymer according to embodiment 16, wherein the polymer is -hydrocarbylene.

[0141] 18. (B) A compound comprising structural units from at least one dicarboxylic acid of formula (I) or its amide-forming derivative, in which R1 is a direct bond, C1-C4 alkyl, unsubstituted or substituted C1-C4 alkoxy, unsubstituted or substituted C1-C4 alkylthio, unsubstituted or substituted C1-C4 alkylamino, di(C1-C4 alkyl)amino, C1-C4 alkylidene, hydroxyl, mercapto, amino and halogen, which is substituted by at least one group selected from the group consisting of: 12 Alkylene or C2-C 12 18. The modified lysine-based polymer of embodiment 17, wherein the polymer is -alkenylene.

[0142] 19. (B) A compound comprising structural units from at least one dicarboxylic acid of formula (I) or its amide-forming derivative, in which R1 is a direct bond, C1-C4 alkyl, C1-C4 alkylidene, hydroxyl, mercapto and amino, which are substituted by at least one group selected from the group consisting of: 12 Alkylene or C2-C 12 19. The modified lysine-based polymer of embodiment 18, wherein the -alkenylene.

[0143] 20. (B) A compound comprising structural units from at least one dicarboxylic acid of formula (I) or its amide-forming derivative, in which R1 is a direct bond, C1-C4 alkyl, C1-C2 alkylidene, hydroxyl and amino, which is substituted by at least one group selected from the group consisting of: 12 Alkylene or C2-C 12 20. The modified lysine-based polymer according to embodiment 19, wherein the -alkenylene is preferably comprised of structural units from at least one of oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, tartaric acid, aspartic acid, glutaric acid, itaconic acid, glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid.

[0144] 21. (A) 70 to 97 mol % structural units from lysine monomers; and (B) 3 to 30 mol % of structural units from at least one dicarboxylic acid of formula (I) or its amide-forming derivative The modified lysine-based polymer according to any one of embodiments 14 to 20, comprising:

[0145] 22. (A) 75 to 97 mol % structural units derived from lysine monomers; and (B) 4 to 25 mol % of structural units from at least one dicarboxylic acid of formula (I) or its amide-forming derivative 22. The modified lysine-based polymer of embodiment 21, comprising:

[0146] 23. (A) 75 to 95 mol % of lysine structural units; and (B) 5 to 25 mol % of dicarboxylic acid structural units 23. The modified lysine-based polymer of embodiment 22, comprising:

[0147] 24. The modified lysine-based polymer according to any of the previous embodiments, having a degree of modification by Michael addition of at least 10%, such as at least 20%.

[0148] 25. The modified lysine-based polymer according to any of the preceding embodiments, having a weight average molecular weight (Mw) in the range of 600 to 20,000 g / mol, and / or having a number average molecular weight (Mn) in the range of 500 to 20,000 g / mol.

[0149] 26. A detergent composition, preferably a laundry detergent composition, comprising the modified lysine-based polymer of any of the preceding embodiments 1-25.

[0150] 27. The detergent composition according to embodiment 26, wherein the detergent composition comprises the modified lysine-based polymer in an amount of 0.5 to 30% by weight, preferably 1 to 25% by weight, more preferably 1 to 15% by weight, based on the total solids content of the detergent composition.

[0151] 28. The detergent composition according to embodiment 25 or 26, comprising 2-phenoxyethanol in an amount preferably from 2 ppm to 5 wt%, more preferably from 0.1 to 2 wt%, based on the total weight of the detergent composition.

[0152] 29. The detergent composition according to embodiment 25 or 26, comprising 4,4'-dichloro-2-hydroxydiphenyl ether in an amount of preferably 0.001 to 3% by weight, preferably 0.002 to 1% by weight, more preferably 0.01 to 0.6% by weight, based on the total weight of the detergent composition.

[0153] 30. The detergent composition of any of the previous embodiments 26-29, comprising at least one enzyme, preferably at least one enzyme selected from the group consisting of protease, amylase, lipase, cellulase, mannanase, xylanase, DNase, dispersant, pectinase, oxidoreductase, and cutinase.

[0154] 31. Use of a modified lysine-based polymer as defined in any of embodiments 1 to 25 in a detergent composition, in particular a laundry detergent composition.

[0155] 32. Use of a modified lysine-based polymer according to any one of embodiments 1 to 25 as a dispersing agent.

[0156] 33. A method of preserving an aqueous detergent composition comprising a modified lysine-based polymer according to any of the preceding embodiments 1-25 against microbial contamination or growth, comprising adding 2-phenoxyethanol to the detergent composition.

[0157] 34. A method of laundering fabrics or cleaning hard surfaces comprising antimicrobially treating the fabrics or hard surfaces with a detergent composition comprising the modified lysine-based polymer of any of the preceding embodiments 1-25 and 4,4'-dichloro-2-hydroxydiphenyl ether.

[0158] The following examples are provided to illustrate the invention, but are not intended to limit it. EXAMPLES

[0159] Description of materials used in the examples

[0160] [Table 1]

[0161] Molecular weight determination The number average molecular weight (Mn) and weight average molecular weight (Mw) of the modified lysine-based polymers prepared in the following examples were determined by measuring the unmodified lysine-based polymers by gel permeation chromatography (GPC) and converting the measured values ​​to the molecular weight of the modified polymers based on the corresponding degree of modification (DM). The definition and determination of the DM of the modified lysine-based polymers by Michael addition are as described above in this specification. The DM of the carboxymethylated lysine-based polymers is defined according to the following formula and is determined according to the same procedure as that of the modified lysine-based polymers by Michael addition.

number

[0162] The native lysine-based polymers were analyzed using a cascade of columns (i.e., TSKgel G4000, G3000, G3000, 300 x 7.8 mm) at 35 °C and a flow rate of 0.8 ml / min in an aqueous eluent containing 0.1 M NaCl and 0.1 wt% trifluoroacetic acid. For analysis, the native polymers were dissolved in the eluent at a concentration of 1.5 mg / ml at room temperature and filtered through a 0.22 μm membrane 2 h before injecting 100 μL on an Agilent 1100 chromatography system. The relative molecular weights ranged from 6.2 to 1.06 million g / mol and were characterized by refractive index detection against a calibration curve obtained with polyvinylpyrrolidone standards.

[0163] Identification of polymer composition All polymer compositions are 1 This was confirmed by H-NMR spectroscopy.

[0164] Preparation Example Example 1: Modified lysine homopolymer by Michael addition of acrylic acid A 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet, a vacuum connection condenser and a receiver was charged with 350 g of an aqueous solution of L-lysine (71% by weight). The mixture was heated to an internal temperature of 160° C. with stirring, and water was continuously separated. After a reaction time of 3 hours, further water was distilled off under reduced pressure (670 mbar). Finally, 103 g of water fraction was collected and the highly viscous polymer was discharged as quickly as possible while still hot and fluid into a silicon container. The k value of the lysine homopolymer was 10.1.

[0165] 50 g of lysine homopolymer, 64.74 g of acrylic acid, and 114.74 g of DI water were charged into a 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser. The pH of the mixture was approximately 3, and was adjusted to exactly 3 by adding a small amount of HCl (1 mol / L) solution or NaOH (1 mol / L) solution. The mixture was then heated to an internal temperature of 70° C. for 24 hours while stirring. After the reaction mixture was cooled to 25° C., the modified polymer was precipitated with excess acetone (weight ratio 1:10). After repeating the precipitation three times, the supernatant was colorless and transparent, and the precipitate was dried in a vacuum oven at 40° C. for 48 hours to obtain the final product. 1 The solids content was 100% and the active content was 99.1% by weight as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer determined by H NMR was 35% and the determined molecular weights were Mn=718 g / mol and Mw=883 g / mol.

[0166] Example 2: Modified lysine homopolymer by Michael addition of acrylic acid A 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet, a vacuum connection condenser and a receiver was charged with 350 g of an aqueous solution of L-lysine (71% by weight). The mixture was heated to an internal temperature of 160° C. with stirring, and water was continuously separated. After a reaction time of 3.5 hours, further water was distilled off under reduced pressure (670 mbar). Finally, 102 g of water fraction was collected and the highly viscous polymer was discharged as quickly as possible while still hot and fluid into a silicon container. The k value of the lysine homopolymer was 10.1.

[0167] 15 g of lysine homopolymer, 19.42 g of acrylic acid, and 34.42 g of DI water were charged into a 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser. The pH of the mixture was approximately 3, and was adjusted to exactly 3 by adding a small amount of HCl (1 mol / L) solution or NaOH (1 mol / L) solution. The mixture was then heated to an internal temperature of 70° C. for 24 hours while stirring. After the reaction mixture was cooled to 25° C., the modified polymer was precipitated with excess acetone (weight ratio 1:10). After repeating the precipitation three times, the supernatant was colorless and transparent, and the precipitate was dried in a vacuum oven at 40° C. for 48 hours to obtain the final product. 1 The solids content was 100% and the active content was 99.1% by weight as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer as determined by H NMR was 52%, and the determined molecular weights were Mn=817 g / mol and Mw=1,005 g / mol.

[0168] Example 3: Modified lysine homopolymer by Michael addition of acrylic acid A 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet, a vacuum connection condenser and a receiver was charged with 350 g of an aqueous solution of L-lysine (71% by weight). The mixture was heated to an internal temperature of 160° C. with stirring, and water was continuously separated. After a reaction time of 3.5 hours, further water was distilled off under reduced pressure (670 mbar). Finally, 102 g of water fraction was collected and the highly viscous polymer was discharged as quickly as possible while still hot and fluid into a silicon container. The k value of the lysine homopolymer was 10.1.

[0169] A 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser was charged with 30 g of lysine homopolymer, 38.85 g of acrylic acid, and 68.84 g of DI water. The pH of the mixture was approximately 3, and was adjusted to exactly 3 by adding a small amount of HCl (1 mol / L) solution or NaOH (1 mol / L) solution. The mixture was then heated to an internal temperature of 70° C. for 24 hours while stirring. After the reaction mixture was cooled to 25° C., the modified polymer was precipitated with excess acetone (weight ratio 1:10). After repeating the precipitation three times, the supernatant was colorless and transparent, and the precipitate was dried in a vacuum oven at 40° C. for 48 hours to obtain the final product. 1 The solids content was 100% and the actives content was 96.0% by weight as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer as determined by H NMR was 68%, and the determined molecular weights were Mn=911 g / mol and Mw=1,120 g / mol.

[0170] Example 4: Modified lysine homopolymer by Michael addition of acrylic acid A 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet, a vacuum connection condenser and a receiver was charged with 350 g of an aqueous solution of L-lysine (71% by weight). The mixture was heated to an internal temperature of 160° C. with stirring, and water was continuously separated. After a reaction time of 3 hours, further water was distilled off under reduced pressure (670 mbar). Finally, 103 g of water fraction was collected and the highly viscous polymer was discharged as quickly as possible while still hot and fluid into a silicon container. The k value of the lysine homopolymer was 10.1.

[0171] 25 g of lysine homopolymer, 32 g of acrylic acid, and 57 g of DI water were charged into a 250 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser. The pH of the mixture was approximately 3, and was adjusted to exactly 3 by adding a small amount of HCl (1 mol / L) solution or NaOH (1 mol / L) solution. The mixture was then heated to an internal temperature of 70° C. for 24 hours while stirring. After the reaction mixture was cooled to 25° C., the modified polymer was precipitated with excess acetone (weight ratio 1:10). After repeating the precipitation three times, the supernatant was colorless and transparent, and the precipitate was dried in a vacuum oven at 40° C. for 48 hours to obtain the final product. 1 The solids content was 100% and the active content was 99.5% by weight as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer as determined by H NMR was 98% and the determined molecular weights were Mn=1,086 g / mol and Mw=1,336 g / mol.

[0172] Example 5: Modified lysine homopolymer by Michael addition of acrylic acid A 1000 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet, a vacuum connection condenser and a Dean-Stark receiver was charged with 500 g of an aqueous solution of L-lysine (50% by weight). The mixture was heated to an internal temperature of 160° C. with stirring, and water was continuously separated. After a reaction time of 4.5 hours, further water was distilled off under reduced pressure (670 mbar). Finally, 272 g of water fraction was collected and the highly viscous polymer was discharged as quickly as possible while still hot and fluid into a silicon container. The k value of the lysine homopolymer was 12.5.

[0173] 25 g of lysine homopolymer, 16 g of acrylic acid, and 57 g of DI water were charged into a 250 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser. The pH of the mixture was approximately 3, and was adjusted to exactly 3 by adding a small amount of HCl (1 mol / L) solution or NaOH (1 mol / L) solution. The mixture was then heated to an internal temperature of 70° C. for 24 hours while stirring. After the reaction mixture was cooled to 25° C., the modified polymer was precipitated with excess acetone (weight ratio 1:10). After repeating the precipitation three times, the supernatant was colorless and transparent, and the precipitate was dried in a vacuum oven at 40° C. for 48 hours to obtain the final product. 1 The solids content was 100% and the active content was 99.0% by weight as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer as determined by H NMR was 30% and the determined molecular weights were Mn=1,936 g / mol and Mw=3,595 g / mol.

[0174] Example 6: Modified poly(lysine-co-tartaric acid) with a molar ratio of lysine to tartaric acid of 90:10 by Michael addition of acrylic acid A 1000 ml four-neck flask equipped with a stirrer, internal thermometer, gas inlet, vacuum condenser and receiver was charged with 400 g lysine, 46 g tartaric acid and 190 g DI water. The mixture was heated to an internal temperature of 160° C. with stirring. After a reaction time of 2 hours and 25 minutes, further water was distilled off under reduced pressure (670 mbar). Finally, 221 g of water was collected and the highly viscous polymer was discharged as quickly as possible while still hot and fluid into a silicon container. The k value of the lysine copolymer was 11.9.

[0175] A 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser was charged with 80 g of lysine copolymer, 37.17 g of acrylic acid, and 117 g of DI water. The pH of the mixture was approximately 3, and was adjusted to exactly 3 by adding a small amount of HCl (1 mol / L) solution or NaOH (1 mol / L) solution. The mixture was then heated to an internal temperature of 70° C. for 24 hours while stirring. After the reaction mixture was cooled to 25° C., the modified polymer was precipitated with excess acetone (weight ratio 1:10). After repeating the precipitation three times, the supernatant was colorless and transparent, and the precipitate was dried in a vacuum oven at 40° C. for 48 hours to obtain the final product. 1 The solids content was 100% and the active content was 98.4% by weight as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer as determined by H NMR was 22% and the determined molecular weights were Mn=1,253 g / mol and Mw=2,605 g / mol.

[0176] Example 7: Modified poly(lysine-co-tartaric acid) with a molar ratio of lysine to tartaric acid of 80:20 by Michael addition of acrylic acid A 500 ml four-neck flask equipped with a stirrer, internal thermometer, gas inlet, vacuum connection condenser and receiver was charged with 200 g lysine, 22.82 g tartaric acid and 108 g DI water. The mixture was heated with stirring to an internal temperature of 160° C. for 2 h 50 min, with continuous separation of water. When 108 g distilled water had been collected, another 28.52 g tartaric acid was introduced into the reactor. After a total reaction time of 3 h 50 min, further water was distilled off under reduced pressure (900 mbar). Finally, 132 g of water fraction was collected and the high-viscosity polymer was discharged as quickly as possible into a silicon container while still hot and fluid. The k value of lysine was 12.3.

[0177] A 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser was charged with 60 g of lysine copolymer, 30.88 g of acrylic acid, and 120 g of DI water. The pH of the mixture was approximately 3, and was adjusted to exactly 3 by adding a small amount of HCl (1 mol / L) solution or NaOH (1 mol / L) solution. The mixture was then heated to an internal temperature of 70° C. for 24 hours while stirring. After the reaction mixture was cooled to 25° C., the modified polymer was precipitated with excess acetone (weight ratio 1:10). After repeating the precipitation three times, the supernatant was colorless and transparent, and the precipitate was dried in a vacuum oven at 40° C. for 48 hours to obtain the final product. 1 The solids content was 100% and the actives content was 93.28% by weight as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer as determined by H NMR was 37%, and the determined molecular weights were Mn=1,021 g / mol and Mw=1,799 g / mol.

[0178] Example 8: Modified poly(lysine-co-adipic acid) with a molar ratio of lysine to adipic acid of 80:20 by Michael addition of acrylic acid A 500 ml four-neck flask equipped with stirrer, internal thermometer, gas inlet, vacuum connection condenser and receiver was charged with 200 g lysine, 22.21 g adipic acid and 100 g DI water. The mixture was heated with stirring to an internal temperature of 160° C. for 2 h 50 min, with continuous separation of water. Then, another 27.77 g adipic acid was introduced into the reactor. After a total reaction time of 3 h 50 min, further water was distilled off under reduced pressure (900 mbar). Finally, 117 g of water fraction was collected and the highly viscous polymer was discharged as quickly as possible while still hot and fluid into a silicon container. The k value of the lysine copolymer was 11.2.

[0179] A 250 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser was charged with 36.94 g of lysine copolymer, 19.12 g of acrylic acid, and 60 g of DI water. The pH of the mixture was approximately 3, and was adjusted to exactly 3 by adding a small amount of HCl (1 mol / L) solution or NaOH (1 mol / L) solution. The mixture was then heated to an internal temperature of 70° C. for 24 hours while stirring. After the reaction mixture was cooled to 25° C., the modified polymer was precipitated with excess acetone (weight ratio 1:10). After repeating the precipitation three times, the supernatant was colorless and transparent, and the precipitate was dried in a vacuum oven at 40° C. for 48 hours to obtain the final product. 1 The solids content was 100% and the actives content was 96.9% by weight as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer as determined by H NMR was 38.24%, and the determined molecular weights were Mn=934 g / mol and Mw=1,705 g / mol.

[0180] Example 9: Modified lysine homopolymer by Michael addition of itaconic acid A 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet, a vacuum connection condenser and a receiver was charged with 350 g of an aqueous solution of L-lysine (71% by weight). The mixture was heated to an internal temperature of 160° C. with stirring, and water was continuously separated. After a reaction time of 3 hours, further water was distilled off under reduced pressure (670 mbar). Finally, 104 g of water fraction was collected and the highly viscous polymer was discharged as quickly as possible while still hot and fluid into a silicon container. The k value of the lysine homopolymer was 10.2.

[0181] 20 g of lysine homopolymer, 46.75 g of itaconic acid, and 66.75 g of DI water were charged into a 250 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser. The pH of the mixture was approximately 4, and was adjusted to exactly 4 by adding a small amount of HCl (1 mol / L) solution or NaOH (1 mol / L) solution. The mixture was then heated to an internal temperature of 70° C. for 24 hours while stirring. After the reaction mixture was cooled to 25° C., the modified polymer was precipitated with excess acetone (weight ratio 1:10). After repeating the precipitation three times, the supernatant was colorless and transparent, and the precipitate was dried in a vacuum oven at 40° C. for 48 hours to obtain the final product. 1 The final product was 100% solids and 67.4% actives by weight as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer determined by H NMR was 22% and the determined molecular weights were Mn=740 g / mol and Mw=911 g / mol.

[0182] Example 10: Modified lysine homopolymer by Michael addition of maleic acid A 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet, a vacuum connection condenser and a receiver was charged with 350 g of an aqueous solution of L-lysine (71% by weight). The mixture was heated to an internal temperature of 160° C. with stirring, and water was continuously separated. After a reaction time of 3 hours, further water was distilled off under reduced pressure (670 mbar). Finally, 104 g of water fraction was collected and the highly viscous polymer was discharged as quickly as possible while still hot and fluid into a silicon container. The k value of the lysine homopolymer was 10.2.

[0183] A 250 ml four-neck flask equipped with a stirrer, internal thermometer, gas inlet, and condenser was charged with 25 g of lysine homopolymer, 52 g of maleic acid, and 77 g of DI water. The pH of the mixture was adjusted to 10 by adding 29 g of solid NaOH. The mixture was then heated to an internal temperature of 95° C. with stirring for 24 hours. After cooling the reaction mixture to 25° C., the unreacted maleic acid was precipitated by adding aqueous HCl (36 wt %) to adjust the pH to 3.2. The filtrate was collected and lyophilized to give a filtrate of 10. The pH of the mixture was adjusted to 10 by adding 29 g of solid NaOH. The pH of the mixture was adjusted to 10 by adding 29 g of solid NaOH. The mixture was then heated to an internal temperature of 95° C. with stirring for 24 hours. After cooling the reaction mixture to 25° C., the unreacted maleic acid was precipitated by adding aqueous HCl (36 wt %) to adjust the pH to 3.2. The filtrate was collected and lyophilized to give a filtrate of 10. The filtrate was then ... 1The final product was obtained with 100% solids and 92.1% actives by weight as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer as determined by H NMR was 73%, and the determined molecular weights were Mn=1,186 g / mol and Mw=1,459 g / mol.

[0184] Example 11: Modified ε-polylysine by Michael addition of itaconic acid 20 g of ε-polylysine, 46.75 g of itaconic acid, and 66.75 g of DI water were charged into a 250 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser. The pH of the mixture was approximately 4, and was adjusted to exactly 4 by adding a small amount of HCl (1 mol / L) solution or NaOH (1 mol / L) solution. The mixture was then heated to an internal temperature of 70° C. for 24 hours while stirring. After the reaction mixture was cooled to 25° C., the modified polymer was precipitated with excess acetone (weight ratio 1:10). 1 The final product was 100% solids and 74.78% actives by weight as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer as determined by H NMR was 33% and the determined molecular weights were Mn=10,091 g / mol and Mw=10,574 g / mol.

[0185] Example 12: Modified ε-polylysine by Michael addition of maleic acid 25 g of ε-polylysine, 52.14 g of maleic acid, and 77.14 g of DI water were charged into a 250 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser. The pH of the mixture was adjusted to 1.4 by adding an HCl solution (36 wt%). The mixture was then heated to an internal temperature of 95° C. for 24 hours while stirring. After the reaction mixture was cooled to 25° C., the modified polymer was precipitated with excess acetone (weight ratio 1:10). After repeating the precipitation three times, the supernatant was colorless and transparent, and the precipitate was dried in a vacuum oven at 40° C. for 48 hours to obtain the final product. 1 The final product was 100% solids and 68.77% actives by weight as determined by 1 H NMR. 1The degree of modification (DM) of the polymer as determined by H NMR was 37% and the determined molecular weights were Mn=10,089 g / mol and Mw=10,572 g / mol.

[0186] Example 13: Modified ε-polylysine by Michael addition of acrylic acid 30 g of ε-polylysine, 38.84 g of acrylic acid, and 68.84 g of DI water were charged into a 250 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser. The pH of the mixture was approximately 3, and was adjusted to exactly 3 by adding a small amount of HCl (1 mol / L) solution or NaOH (1 mol / L) solution. The mixture was then heated to an internal temperature of 70° C. for 24 hours while stirring. After the reaction mixture was cooled to 25° C., the modified polymer was precipitated with excess acetone (weight ratio 1:10). After repeating the precipitation three times, the supernatant was colorless and transparent, and the precipitate was dried in a vacuum oven at 40° C. for 48 hours to obtain the final product. 1 The final product was 100% solids and 95.86% actives by weight as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer as determined by H NMR was 65% and the determined molecular weights were Mn=10,553 g / mol and Mw=11,058 g / mol.

[0187] Example 14: Modified lysine homopolymer by Michael addition of mPEG-acrylate A 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet, a vacuum connection condenser and a receiver was charged with 350 g of an aqueous solution of L-lysine (71% by weight). The mixture was heated to an internal temperature of 160° C. with stirring, and water was continuously separated. After a reaction time of 3 hours, further water was distilled off under reduced pressure (670 mbar). Finally, 106 g of water fraction was collected and the highly viscous polymer was discharged as quickly as possible while still hot and fluid into a silicon container. The k value of the lysine homopolymer was 10.6.

[0188] A 250 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser was charged with 8.54 g of lysine homopolymer, 32.03 g of mPEGA480 (poly(ethylene glycol) methyl ether acrylate (mPEG-acrylate, Mn=480), and 121.7 g of glycerol. The mixture was heated to an internal temperature of 70° C. for 4 hours with stirring. After the reaction mixture was cooled to 25° C., 1 A solution of 23.23% solids and 23.23% actives by weight was recovered as the final product as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer as determined by H NMR was 26%, and the determined molecular weights were Mn=2,233 g / mol and Mw=3,388 g / mol.

[0189] Example 15: Modified lysine homopolymer by Michael addition of mPEG-acrylate A 1000 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet, a vacuum connection condenser and a Dean-Stark receiver was charged with 500 g of an aqueous solution of L-lysine (50% by weight). The mixture was heated to an internal temperature of 160° C. with stirring, and water was continuously separated. After a reaction time of 4 hours, further water was distilled off under reduced pressure (670 mbar). Finally, 264 g of water fraction was collected and the highly viscous polymer was discharged as quickly as possible while still hot and fluid into a silicon container. The k value of the lysine homopolymer was 11.2.

[0190] A 250 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser was charged with 8.54 g of lysine homopolymer and 102.5 g of water. The pH of the solution was adjusted to 6 by adding an HCl (1 mol / L) solution. Then, 25.62 g of mPEGA480 was added, and the mixture was heated to an internal temperature of 60° C. for 8 hours with stirring. After cooling the reaction mixture to 25° C., 1 A solution of 50.8% solids and 37.6% actives by weight was recovered as the final product as determined by 1 H NMR. 1The degree of modification (DM) of the polymer as determined by H NMR was 24% and the determined molecular weights were Mn=2,693 g / mol and Mw=3,884 g / mol.

[0191] Example 16: Modified ε-polylysine by Michael addition with mPEG-acrylate A 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a cooling tube was charged with 8.54 g of linear ε-polylysine and 179.3 g of water. The pH of the solution was adjusted to 6 by adding an HCl (1 mol / L) solution. Next, 51.23 g of mPEGA480 was added, and the mixture was heated to an internal temperature of 60° C. for 8 hours while stirring. After cooling the reaction mixture to 25° C., 1 A solution of 49.4% solids and 27.1 wt % actives was recovered as the final product as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer as determined by H NMR was 39% and the determined molecular weights were Mn=23,749 g / mol and Mw=24,885 g / mol.

[0192] Example 17: Modified poly(lysine-co-tartaric acid) with a molar ratio of lysine to tartaric acid of 80:20 by Michael addition of mPEG-acrylate A 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet, a vacuum connection condenser and a Dean-Stark receiver was charged with 165 g of an aqueous solution of L-lysine (50% by weight) and 9.4 g of tartaric acid suspended in 9.5 g of water. The mixture was heated to an internal temperature of 160° C. for 2 hours and 25 minutes with stirring, continuously separating water. Then, another 11.8 g of tartaric acid was introduced into the reactor. Finally, 94 g of water fraction was collected and the highly viscous polymer was discharged as quickly as possible while still hot and fluid into a silicon container. The k value of the lysine homopolymer was 11.5.

[0193] A 250 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser was charged with 8.54 g of lysine copolymer and 71.73 g of water. The pH of the solution was adjusted to 6 by adding HCl (1 mol / L) solution. Then, 15.37 g of mPEGA480 was added, and the mixture was heated to an internal temperature of 60° C. for 8 hours with stirring. After cooling the reaction mixture to 25° C., 1 A solution of 47.0% solids and 35.7% actives by weight as determined by 1 H NMR was recovered as the final product. 1 The degree of modification (DM) of the polymer as determined by H NMR was 17%, and the determined molecular weights were Mn=1,295 g / mol and Mw=1,709 g / mol.

[0194] Application Examples I. Anti-graying performance Test I.1 According to GBT 13174-2008, a Terg-o-meter (RHLG-IV, Shanghai Bank Equipment Co. Ltd, China) containing 12 barrels with respective rotor blades as the washing unit was used to simulate the washing process in the laboratory.

[0195] Prior to washing, all fabrics used were pretreated with fabric softener. 7 g of the fabric softener formulation shown in Table 1 was diluted in 10 L of tap water (25°C) and transferred to a small washing machine (Hair MW-PQ28SW). 300 g of fabrics to be used were placed in the washing machine and agitated for 3 minutes. The treated fabrics were then transferred to another washing machine of the same type without performing a rinse, tumble dried for 1 minute, and then dried at 40°C for 1 hour.

[0196] The washing units were operated at an agitation speed of 120 revolutions per minute (rpm) and each contained 1 L of hard water (100 ppm Ca:Mg = 3:2). Three white test cloths of each type (15 in total) were washed in the same barrel at 30°C together with 10 g of red clay and oil mixture in a wash liquor containing 0.93 g of detergent with the formula shown in Table 2. After washing, the cloths were removed from the washing unit, drained, and rinsed twice with 10 L of tap water for 30 seconds. The wash cycle was repeated two more times with fresh red clay and oil mixture and fresh wash liquor. After rinsing in the third wash cycle, the test cloths were instead dried in air. The details of the wash cycle are summarized in Table 3.

[0197] The anti-graying performance was measured on the fabrics using a Datacolor spectrophotometer Elrepho 2000 at 457 nm and was calculated as the remission (R before ) and Remission after 3 cycles of washing (R after ) difference.

[0198] The difference in remission (ΔR) is calculated according to the following formula: ΔR=R before -R after

[0199] The smaller the ΔR value, the better the performance.

[0200] The results are summarized in Table 5.

[0201] [Table 2]

[0202] [Table 3]

[0203] [Table 4]

[0204] [Table 5]

[0205] [Table 6]

[0206] Test I.2 According to GBT 13174-2008, a Terg-o-meter (RHLG-IV, Shanghai Bank Equipment Co. Ltd, China) containing 12 barrels with respective rotor blades was used as the washing unit to simulate the washing process in the laboratory. The washing units were operated at the same agitation speed of 120 revolutions per minute (rpm) and each contained 1 L of water. The white test cloth was washed in the same barrel at 30°C together with 10 g of red clay and oil mixture in a washing liquid containing detergent with the formulation shown in Table 6. After washing, the cloth was removed from the washing unit, drained, and rinsed twice with 10 L of tap water for 30 seconds. The washing cycle was repeated twice with new red clay and oil mixture and new washing liquid. After rinsing in the third washing cycle, the test cloth was dried in air instead. The washing cycle details are summarized in Table 7.

[0207] The anti-graying performance was measured using a Datacolor spectrophotometer Elrepho 2000 at 457 nm and was calculated as the remission (R before ) and Remission after 3 cycles of washing (R after ) difference.

[0208] The difference in remission (ΔR) is calculated according to the following formula: ΔR=R before -R after

[0209] The smaller the ΔR value, the better the performance.

[0210] [Table 7]

[0211] [Table 8]

[0212] [Table 9]

[0213] II. Primary cleaning power of liquid select formulations Test II.1 The liquid laundry formulations shown in Table 9 were measured for primary cleaning power at full scale in a domestic washing machine according to the protocol set forth in Table 10. A soil monitor was used to evaluate cleaning power against bleachable stains.

[0214] [Table 10]

[0215] [Table 11]

[0216] The primary cleaning power is characterized in accordance with DIN EN ISO 11664-4 (June 2012) by the ΔE value, which is calculated according to the following formula: ΔE = (ΔL *2 +Δa *2 +Δb *2 ) 1 / 2 (In the formula, ΔL * =L * washed -L * initial ;Δa * =a * washed -a * initial ; and Δb * =b *washed -b * initial (It is.)

[0217] L * , a * , b * The values ​​were measured on the soiled fabrics before and after washing using a Color Consult spectrophotometer MACH5 provided by CFT, NL-Vlaardingen. The higher the ΔE value, the better the performance. The results are summarized in Table 11.

[0218] [Table 12]

[0219] Test II.2 The liquid laundry formulations shown in Table 12 were measured for primary cleaning power at full scale in a domestic washing machine according to the protocol set forth in Table 13. A soil monitor was used to evaluate cleaning power against bleachable stains.

[0220] [Table 13]

[0221] [Table 14]

[0222] The primary cleaning power was characterized according to the protocol described in test II.1. The results are summarized in Table 14.

[0223] [Table 15]

[0224] III. Compatibility with Biocides in Liquid Laundry Products Liquid laundry detergent formulations were prepared containing 1 wt.% of the inventive polymer of the examples shown in Table 15 and / or 0.3 wt.% of the biocide Tinosan® HP100 (BASF) and / or 1 wt.% of phenoxyethanol (Protectol® PE, BASF). The formulations were prepared by first preparing a premix containing the surfactants, solvents, fatty acids, citric acid and NaOH shown in Table 15, and water up to 90%. The premix was prepared by adding all ingredients to the appropriate amount of water and stirring at room temperature. The pH was then set to pH=8.5 using NaOH. The final formulations were then prepared by adding 90% of the premix, the appropriate concentration of polymer and / or Tinosan® HP100 (a commercial product from BASF SE containing 30% of the antimicrobially active 4,4′-dichloro 2-hydroxydiphenyl ether) and / or 2-phenoxyethanol, and water up to 100% and stirring at room temperature. For comparison purposes, a standard liquid detergent formulation was prepared containing neither the polymer of the present invention nor a biocide.

[0225] All amounts shown in Table 15 are provided as the active ingredient.

[0226] [Table 16]

[0227] As is evident from the above table, the polymers according to the invention can be combined with the biocides Tinosan® HP100 (4,4′-dichloro-2-hydroxydiphenyl ether) or Protectol® PE (2-phenoxyethanol) without causing instability or cloudiness in liquid laundry formulations.

[0228] III. Biodegradability of modified lysine-based polymers Biodegradation of polymers in wastewater was tested in triplicate using the OECD 301F manometric respirometry method. 30 mg / mL of the test substance is inoculated into wastewater taken from the Mannheim Wastewater Treatment Plant and incubated in closed flasks at 25°C for 28 days. Oxygen consumption during this time is measured as the change in pressure inside the flask using an OxiTop C (WTW). The evolved CO2 is absorbed using a NaOH solution. The amount of oxygen consumed by the microbial population during the biodegradation of the test substance is expressed as % of ThOD (theoretical oxygen demand) after correction using blanks.

[0229] [Table 17]

[0230] The test results show that the carboxymethylated lysine-based polymers according to the present invention exhibit acceptable biodegradability.

[0231] Example 18 82.5 g of L-lysine, 9.4 g of tartaric acid and 90 g of water were charged into a 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet, a vacuum connection condenser and a Dean-Stark receiver. The mixture was heated to an internal temperature of 160° C. with stirring. After a reaction time of 2 hours and 25 minutes, further water was distilled off under reduced pressure (670 mbar). Finally, 94 g of water was collected and the highly viscous polymer was discharged as quickly as possible while still hot and fluid into a silicon container. The K value was 11.6. The molar ratio of lysine structural units to tartaric acid structural units was: 1 The ratio was determined to be 95:05 by 1 H NMR.

[0232] A 250 ml four-neck flask equipped with a stirrer, internal thermometer, gas inlet, and condenser was charged with 50 g of polylysine copolymer, 29.0 g of acrylic acid, and 80 g of DI water. The pH of the mixture was approximately 3. A slight pH adjustment to exactly 3 could be achieved by adding a small amount of HCl (1 mol / L) or NaOH solution (1 mol / L). The mixture was then heated to an internal temperature of 70° C. with stirring for 24 hours. After the reaction mixture was cooled to 25° C., the modified polymer was precipitated with excess acetone (weight ratio 1:10). After repeating the precipitation three times, the supernatant was colorless and transparent, and the precipitate was dried in a vacuum oven at 40° C. for 48 hours to obtain the final product. 1 The solids content was 100% and the actives content was 96.4% by weight as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer as determined by H NMR was 29%, and the determined molecular weights were Mn=1,047 g / mol and Mw=1,590 g / mol.

[0233] Example 19 250 g of L-lysine, 30 g of tartaric acid and 120 g of water were charged into a 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet, a vacuum connection condenser and a Dean-Stark receiver. The mixture was heated to an internal temperature of 160° C. with stirring. After a reaction time of 2 hours and 25 minutes, further water was distilled off under reduced pressure (670 mbar). Finally, 127 g of water fraction was collected and the highly viscous polymer was discharged as quickly as possible while still hot and fluid into a silicon container. The K value was 10.9. The molar ratio of lysine structural units to tartaric acid structural units was: 1 The ratio was determined to be 95:05 by 1 H NMR.

[0234] A 250 ml four-neck flask equipped with a stirrer, internal thermometer, gas inlet, and condenser was charged with 50 g of polylysine copolymer, 29.0 g of acrylic acid, and 80 g of DI water. The pH of the mixture was approximately 3. A slight pH adjustment to exactly 3 could be achieved by adding a small amount of HCl (1 mol / L) or NaOH solution (1 mol / L). The mixture was then heated to an internal temperature of 70° C. with stirring for 24 hours. After the reaction mixture was cooled to 25° C., the modified polymer was precipitated with excess acetone (weight ratio 1:10). After repeating the precipitation three times, the supernatant was colorless and transparent, and the precipitate was dried in a vacuum oven at 40° C. for 48 hours to obtain the final product. 1 The solids content was 100% and the actives content was 96.1% by weight as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer as determined by H NMR was 33%, and the determined molecular weights were Mn=995 g / mol and Mw=1,425 g / mol.

[0235] Example 20 250 g of L-lysine, 30 g of tartaric acid, and 120 g of water were charged into a 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a vacuum connection condenser, and a Dean-Stark receiver. The mixture was heated to an internal temperature of 160° C. while stirring. Finally, 125 g of water fraction was collected, and the high-viscosity polymer was discharged into a silicon container as quickly as possible while still hot and fluid. The K value was 10.3. The molar ratio of lysine structural units to tartaric acid structural units was: 1 The ratio was determined to be 92:08 by 1 H NMR.

[0236] A 500 ml four-neck flask equipped with a stirrer, internal thermometer, gas inlet, and condenser was charged with 80 g of polylysine copolymer, 56.7 g of acrylic acid, and 135 g of DI water. The pH of the mixture was approximately 3. A slight pH adjustment to exactly 3 could be achieved by adding a small amount of HCl (1 mol / L) or NaOH solution (1 mol / L). The mixture was then heated to an internal temperature of 70° C. with stirring for 24 hours. After the reaction mixture was cooled to 25° C., the modified polymer was precipitated with excess acetone (weight ratio 1:10). After repeating the precipitation three times, the supernatant was colorless and transparent, and the precipitate was dried in a vacuum oven at 40° C. for 48 hours to obtain the final product. 1 The solids content was 100% and the active content was 99.3% by weight as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer as determined by H NMR was 51%, and the determined molecular weights were Mn=1,060 g / mol and Mw=1,481 g / mol.

[0237] Comparative Example 1 200 g of lysine, 22.82 g of tartaric acid and 108 g of DI water were charged to a 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet, a vacuum connection condenser and a receiver. The mixture was heated to an internal temperature of 160° C. with stirring for 2 hours and 50 minutes, with continuous separation of water. When 108 g of distilled water had been collected, another 28.52 g of tartaric acid was introduced into the reactor. After a total reaction time of 3 hours and 50 minutes, further water was distilled off under reduced pressure (900 mbar). Finally, 131 g of water fraction was collected and the highly viscous polymer was discharged as quickly as possible while still hot and fluid into a silicon container. The k value of lysine was 12.1. The molar ratio of lysine structural units to tartaric acid structural units was: 1 The ratio was determined to be 83:17 by 1 H NMR.

[0238] A 2000 ml four-neck flask equipped with a stirrer, internal thermometer, gas inlet, and condenser was charged with 145.6 g of sodium chloroacetate, 175 g of polylysine copolymer, and 480 g of DI water. The solution was then heated to 70° C. for 5 hours, during which the pH was maintained at 10 by controlled addition of 48 wt % NaOH aqueous solution using the control unit of a Systag FlexyPat automated lab reactor equipped with a membrane pump and a pH probe with a high temperature electrolyte. After cooling the reaction mixture to 30° C., the modified polymer was precipitated with excess methanol (1:10 by weight) and filtered. After repeating the precipitation three times, the product was dried in a vacuum oven at 40° C. for 16 hours to obtain the final product. 1 The solids content was 100% and the actives content was 96.8% by weight as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer as determined by H NMR was 45% and the determined molecular weights were Mn=1,045 g / mol and Mw=1,820 g / mol.

[0239] Comparative Example 2 82.5 g of L-lysine, 9.4 g of tartaric acid and 90 g of water were charged into a 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet, a vacuum connection condenser and a Dean-Stark receiver. The mixture was heated to an internal temperature of 160° C. with stirring. After a reaction time of 2 hours and 25 minutes, further water was distilled off under reduced pressure (670 mbar). Finally, 94 g of water was collected and the highly viscous polymer was discharged as quickly as possible while still hot and fluid into a silicon container. The K value was 11.6. The molar ratio of lysine structural units to tartaric acid structural units was: 1 The ratio was determined to be 91:9 by 1 H NMR.

[0240] A 250 ml four-neck flask equipped with a stirrer, internal thermometer, gas inlet, and condenser was charged with 18.08 g sodium chloroacetate, 27.5 g lysine copolymer, and 70 g DI water. The solution was then heated to 70° C. for 5 hours, during which the pH was maintained at 10 by controlled addition of 48 wt % NaOH aqueous solution using the control unit of a Systag FlexyPat automated lab reactor equipped with a peristaltic pump and a pH probe with a hot electrolyte. After cooling the reaction mixture to 30° C., the modified polymer was precipitated with excess methanol (1:10 wt ratio) and filtered. After precipitation was repeated three times, the product was dried in a vacuum oven at 40° C. for 16 hours to obtain the final product. The solids content was 100% and the actives content was 97.6 wt %. 1 The degree of modification (DM) of the polymer as determined by H NMR was 32% and the determined molecular weights were Mn=1,018 g / mol and Mw=1,547 g / mol.

[0241] Comparative Example 3 A 500 ml four-neck flask equipped with a stirrer, an internal thermometer, a gas inlet, a vacuum connection condenser and a Dean-Stark receiver was charged with 100 g of an aqueous solution of L-lysine (50% by weight). The mixture was heated with stirring to an internal temperature of 160° C. for 45 minutes. Then, 400 g of an aqueous solution of L-lysine (50% by weight) was continuously charged over a period of 3.5 hours with continuous water separation. After 1 hour of reaction time, further water was distilled off under reduced pressure (670 mbar). Finally, 259 g of water vapor was collected and the highly viscous polymer was discharged as quickly as possible into a silicon container while still hot and fluid. The k value of the lysine homopolymer was 10.6.

[0242] A 250 ml four-neck flask equipped with a stirrer, internal thermometer, gas inlet, and condenser was charged with 3.93 g sodium chloroacetate, 18.75 g lysine homopolymer, and 56.25 g DI water. The solution was then heated to 70° C. for 5 hours. During the first 1.5 hours, 15.72 g sodium chloroacetate and 13.5 g sodium hydroxide (50 wt%) were added to the flask in three portions every 0.5 hours. After cooling the reaction mixture to 30° C., the modified polymer was precipitated with excess methanol (1:10 wt. ratio) and filtered. After repeating the precipitation three times, the product was dried in a vacuum oven at 40° C. for 16 hours to obtain the final product. 1 The solids content was 100% and the actives was 94% by weight as determined by 1 H NMR. 1 The degree of modification (DM) of the polymer as determined by H NMR was 45% and the determined molecular weights were Mn=1,067 g / mol and Mw=1,619 g / mol.

[0243] Comparative Example 4 A 1000 ml four-neck flask equipped with a stirrer, internal thermometer, gas inlet, and condenser was charged with 104.65 g sodium chloroacetate, 50 g linear ε-polylysine, and 154.65 g DI water. The solution was then heated to 70° C. for 5 h. During this time, the pH was maintained at 10 by controlled addition of 48 wt % NaOH aqueous solution using the control unit of a Systag FlexyCube automated lab reactor equipped with a peristaltic pump and a pH probe with a hot electrolyte. After cooling the reaction mixture to 30° C., the pH of the solution was adjusted to 4 using aqueous HCl. The modified polymer was then precipitated with excess methanol (1:10 by weight) and filtered. After precipitation was repeated three times, the product was dried in a vacuum oven at 40° C. for 16 h to obtain the final product. The solid content was 100% and the active content was 84 wt %. 1 The degree of modification (DM) of the polymer as determined by H NMR was 86% and the determined molecular weights were Mn=10,864 g / mol and Mw=11,384 g / mol.

[0244] Application Test IV. Anti-graying test Test 1: According to GBT 13174-2008, a Terg-o-meter (RHLG-IV, Shanghai Bank Equipment Co. Ltd, China) containing 12 barrels with respective rotor blades was used as the washing unit to simulate the washing process in the laboratory. The washing units were operated at the same agitation speed of 120 revolutions per minute (rpm) and each contained 1 L of washing liquor. The white test cloth was washed in the same barrel at 30°C together with 10 g of yellow clay and oil mixture in the washing liquor containing the detergent formulation shown in Table 17. After washing, the cloth was removed from the washing unit, drained, rinsed twice with 10 L of tap water for 30 seconds, and dried in air. The details of the washing cycle are summarized in Table 18.

[0245] The anti-graying performance was measured using a Datacolor spectrophotometer Elrepho 2000 at 457 nm and was calculated as the remission (R before ) and Remission after washing (R after ) difference.

[0246] The difference in remission (ΔR) is calculated according to the following formula: ΔR=R before -R after

[0247] The smaller the ΔR value, the better the performance.

[0248] [Table 18]

[0249] [Table 19]

[0250] [Table 20]

[0251] Test 2: The laundering process was simulated in the laboratory using a Terg-o-meter (Testfabrics, Inc., West Pittston, Pennsylvania, USA) conforming to ASTM D4008-16. Several white test cloths were washed at 30°C in a wash solution containing the liquid detergent formulation detailed in Table 20 with selected polymers along with 0.5 g Georgia Red Clay (solid particulates). After washing, the test cloths were rinsed and hand dried. This wash cycle was repeated three times (four times in total) with fresh Georgia Red Clay and fresh wash solution. After the fourth wash, the test cloths were rinsed, spun dry in a wringer, and dried in a machine dryer at a medium heat setting for 30 minutes. The wash cycle details are summarized in Table 21.

[0252] The anti-deposition performance is determined by measuring the L, a and b values ​​of a white test cloth before and after washing with a Konica Minolta spectrophotometer. The ΔE value is then calculated from the resulting values ​​according to the following formula: ΔE = (ΔL *2 +Δa *2 +Δb *2 ) 1 / 2 (In the formula, ΔL * =L * washed -L * initial ;Δa * =a * washed -a * initial ; and Δb * =b * washed -b * initial (It is.)

[0253] The smaller the ΔE value, the better the performance.

[0254] [Table 21]

[0255] [Table 22]

[0256] [Table 23]

[0257] Test 3: A Launder-o-meter (LP2 Type, SDL Atlas Inc., USA) was used to simulate the washing process. The details of the washing cycle are summarized in Table 23. The white test cloth was washed in the same beaker at 30°C in the washing liquid containing detergent with the formulation shown in Table 24 together with 2.5g EMPA101 and 2.5g SBL2004, and 20 steel balls, then rinsed and spun dry to complete the washing cycle. The washing cycle was repeated twice using a new clay dispersion and a new washing liquid. After rinsing in the third washing cycle, the test cloth was dried in air instead.

[0258] Anti-graying performance was characterized by the Remission R value of the stained fabric before and after washing, determined by measuring the fabric at 460 nm using a Datacolor Elrepho 2000 spectrophotometer. The higher the Remission R value, the better the performance. The results are summarized in Table 25.

[0259] [Table 24]

[0260] [Table 25]

[0261] [Table 26]

[0262] Detergent performance Test 1: Primary wash performance against protease-associated stains was determined as follows. A Terg-o-meter (Testfabrics, Inc., West Pittston, Pennsylvania, USA) was used to simulate the laundering process in the laboratory. A mixture of fabrics stained with standard stains was washed together with 30 g of unstained ballast fabric at 30° C. in a wash liquor containing the liquid detergent formulations of Table 26, with or without the presence of enzymes. After the wash cycle, the test fabrics and ballast were rinsed and spun dry in a wringer. The stained fabrics were then separated from the ballast fabrics and line-dried in the dark. Details of the laundering process are summarized in Table 27.

[0263] Primary detergency is determined by measuring the L, a and b values ​​of the soiled test cloth before and after washing using a Mach5+ Colour Consult spectrophotometer from the Center for Test materials. The ΔE value is then calculated from the resulting pre- and post-wash values ​​according to the following formula: ΔE = (ΔL *2 +Δa *2 +Δb *2 ) 1 / 2 (In the formula, ΔL * =L * washed -L * initial ;Δa * =a * washed -a * initial ; and Δb * =b * washed -b * initial (It is.)

[0264] The higher the ΔE value, the better the performance.Table 28 shows the cleaning performance of various polymer additives in the absence and presence of laundry proteases.

[0265] [Table 27]

[0266] [Table 28]

[0267] [Table 29]

[0268] Test 2: A Launder-o-meter (LP2 Type, SDL Atlas Inc., USA) was used to simulate the laundry process using the liquid laundry formulations in Table 29 and following the protocol described in Table 30. A soil monitor was used to evaluate the cleaning power for outdoor and fatty stains.

[0269] [Table 30]

[0270] [Table 31]

[0271] The primary cleaning power is characterized in accordance with DIN EN ISO 11664-4 (June 2012) by the ΔE value, which is calculated according to the following formula: ΔE = (ΔL *2 +Δa *2 +Δb *2 ) 1 / 2 (In the formula, ΔL * =L * washed -L * initial ;Δa * =a * washed -a * initial ; and Δb * =b * washed -b *initial (It is.)

[0272] L * , a * , b * The values ​​were measured on the stained fabrics before and after washing using a Colour Consult spectrophotometer MACH5 provided by CFT, NL-Vlaardingen. The higher the ΔE value, the better the performance.

[0273] The ΔE characteristic evaluation was performed twice, and the average was used as the test result. The higher the ΔE value, the better the performance. The test results are summarized in Table 31.

[0274] [Table 32]

[0275] V. Biodegradable Biodegradability was measured by the method described above, and the results are shown in Table 32.

[0276] [Table 33]

Claims

1. A modified lysine-based polymer obtained by a process comprising Michael addition of at least some of the free amino groups in a lysine-based polymer by a Michael acceptor selected from at least one of unsaturated carboxylic acids and unsaturated carboxylic acid esters.

2. The modified lysine-based polymer according to claim 1, wherein the Michael acceptor is at least one selected from the group consisting of α,β-ethylenically unsaturated monocarboxylic acids having 3 to 10 carbon atoms, α,β-ethylenically unsaturated dicarboxylic acids having 4 to 8 carbon atoms, α,β-ethylenically unsaturated tricarboxylic acids having 4 to 8 carbon atoms, α,β-ethylenically unsaturated carboxylic acids having more carboxylic acid groups, and esters thereof.

3. The modified lysine-based polymer according to claim 2, wherein the Michael acceptor is at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, and esters thereof.

4. The modified lysine-based polymer according to claim 3, wherein the Michael acceptor is at least one selected from the group consisting of acrylic acid, maleic acid, itaconic acid, and esters thereof.

5. The modified lysine-based polymer according to claim 1, wherein the ester is selected from polyalkylene oxide esters or terminal polyalkylene oxide esters of unsaturated carboxylic acids, preferably terminal polyethylene oxide esters, terminal polypropylene oxide esters, or terminal polybutylene oxide esters, or a combination thereof.

6. The aforementioned terminalized polyethylene oxide ester is C １ ~C ４ - Alkyl or C １ ~C ４ - A modified lysine-based polymer according to claim 1, comprising a terminal group selected from hydroxyalkyl groups.

7. The modified lysine-based polymer according to claim 5, wherein the polyalkylene oxide or terminal polyalkylene oxide portion has a number average molecular weight of 100 to 2,000, preferably 200 to 1,200, and more preferably 400 to 800.

8. The following formula 【Chemistry 1】 (In the formula, R ２ and R ３ are, independently of each other, H or R ４ however, provided that R ２ and R ３ at least one of which is R ４ and * indicates the position where a structural unit is bonded to another structural unit by an amide bond. R ４ Equation (II) 【Chemistry 2】 This is the part represented by, R ５ and R ６ H and C are independent of each other. １ ~C ６ -Alkyl, carboxyl (-COOH), -COOM, -(C １ ~C ４ -alkylene)-COOH or -(C １ ~C ４ -Alkilen)-COOM, R ７ H, C １ ~C ６ -Alkyl, -(CH ２ CH ２ O) ｎ -R ８ Or it is M, R ８ C １ ~C ４ -It is alkyl, M is a cation selected from alkali metal cations, alkaline earth metal cations, ammonium cations, and amine cations. n is a number in the range of 2 to 40, and ** is the part mentioned above, R ４ A modified lysine-based polymer containing structural units from lysine monomers, represented by (the position of bonding to the N atom supporting the polymer).

9. R ５ and R ６ H and C are independent of each other. １ ~C ４ -Alkyl, carboxyl (-COOH), -COOM, -(C １ ~C ２ -alkylene)-COOH or -(C １ ~C ２ -Alkilen)-COOM, R ７ H, -(CH ２ CH ２ O) ｎ -R ８ Or it is M, R ８ C １ ~C ２ - Alkyl, and The modified lysine-based polymer according to claim 8, wherein n is a number in the range of 4 to 25.

10. R ５ is H, methyl, carboxyl (-COOH), or -COOM, R ６ H, methyl, carboxyl (-COOH), -COOM, -(C １ ~C ２ -alkylene)-COOH, or -(C １ ~C ２ -Alkilen)-COOM, R ７ H, -(CH ２ CH ２ O) ｎ -R ８ Or it is M, R ８ C １ ~C ２ - Alkyl, and The modified lysine-based polymer according to claim 9, wherein n is a number in the range of 8 to 15.

11. R ５ is H, carboxyl (-COOH), or -COOM, R ６ H, carboxyl (-COOH), -COOM, -(C １ ~C ２ -alkylene)-COOH, or -(C １ ~C ２ -Alkilen)-COOM, R ７ H, -(CH ２ CH ２ O) ｎ -R ８ or M and R ８ The modified lysine-based polymer according to claim 10, wherein is methyl.

12. The modified lysine-based polymer according to claim 1, which is a modified homopolymer of lysine.

13. The modified lysine-based polymer according to claim 1, comprising a lysine-modified copolymer containing more than 50 mol% of structural units derived from lysine monomers and less than 50 mol% of structural units derived from at least one dicarboxylic acid or its amide-forming derivative.

14. (A) Structural units from lysine monomers in an amount of 60-99 mol%, (B) 1 to 40 mol% of at least one dicarboxylic acid of formula (I) or its amide-forming derivative. HOOC-R １ -COOH(I) (In the formula, R １ (This is a directly linked or aliphatic linear hydrocarbylene, which is unsubstituted or substituted with at least one group selected from unsubstituted or substituted alkyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkylamino, di(alkyl)amino, alkylidene, hydroxyl, mercapto, amino, and halogen.) Structural units from and A modified lysine-based polymer according to claim 13, comprising:

15. (B) comprising a structural unit from at least one dicarboxylic acid of formula (I) or its amide-forming derivative, wherein R １ C is either non-substituted or substituted. １ ~C １８ - Alkyl, unsubstituted, or substituted C １ ~C １８ - alkoxy, unsubstituted or substituted C １ ~C １８ - Alkylthio, unsubstituted, or substituted C １ ~C １８ - Alkylamino, di(C) １ ~C １８ -Alkyl)amino, C １ ~C ６ - Directly bonded or aliphatic linear C, substituted with at least one group selected from alkylidene, hydroxyl, mercapto, amino, and halogen. １ ~C ２４ - A modified lysine-based polymer according to claim 14, wherein the polymer is hydrocarbylene.

16. (B) a structural unit derived from at least one dicarboxylic acid of formula (I) or an amide-forming derivative thereof, wherein R １ is an unsubstituted or substituted C １ to C １２ -alkyl, an unsubstituted or substituted C １ to C １２ -alkoxy, an unsubstituted or substituted C １ to C １２ -alkylthio, an unsubstituted or substituted C １ to C １２ -alkylamino, di(C １ to C １２ -alkyl)amino, C １ to C ４ -alkylidene, hydroxyl, mercapto, amino and halogen, and is a direct bond or an aliphatic straight-chain C １ to C １８ -hydrocarbylene, the modified lysine-based polymer according to claim 15.

17. (B) comprising a structural unit from at least one dicarboxylic acid of formula (I) or its amide-forming derivative, wherein R １ C is either non-substituted or substituted. １ ~C ８ - Alkyl, unsubstituted, or substituted C １ ~C ８ - alkoxy, unsubstituted or substituted C １ ~C ８ - Alkylthio, unsubstituted, or substituted C １ ~C ８ - Alkylamino, di(C) １ ~C ８ -Alkyl)amino, C １ ~C ４ - Directly bonded or aliphatic linear C, substituted with at least one group selected from alkylidene, hydroxyl, mercapto, amino, and halogen. １ ~C １２ - A modified lysine-based polymer according to claim 16, wherein the polymer is hydrocarbylene.

18. (B) comprising a structural unit from at least one dicarboxylic acid of formula (I) or its amide-forming derivative, wherein R １ C is either non-substituted or substituted. １ ~C ４ - Alkyl, unsubstituted, or substituted C １ ~C ４ - alkoxy, unsubstituted or substituted C １ ~C ４ - Alkylthio, unsubstituted, or substituted C １ ~C ４ - Alkylamino, di(C) １ ~C ４ -Alkyl)amino, C １ ~C ４ - Directly bonded, C, substituted with at least one group selected from alkylidene, hydroxyl, mercapto, amino, and halogen. １ ~C １２ Alkylene or C ２ ~C １２ - The modified lysine-based polymer according to claim 17, which is an alkenylene.

19. (B) comprising a structural unit from at least one dicarboxylic acid of formula (I) or its amide-forming derivative, wherein R １ C is either non-substituted or substituted. １ ~C ４ - Alkyl, C １ ~C ４ - Directly bonded, C, substituted with at least one group selected from alkylidene, hydroxyl, mercapto, and amino. １ ~C １２ Alkylene, or C ２ ~C １２ - The modified lysine-based polymer according to claim 18, which is an alkenylene.

20. (B) comprising a structural unit from at least one dicarboxylic acid of formula (I) or its amide-forming derivative, wherein R １ C is either non-substituted or substituted. １ ~C ４ - Alkyl, C １ ~C ２ - Directly bonded, C, substituted with at least one group selected from alkylidene, hydroxyl, and amino. １ ~C １２ Alkylene, or C ２ ~C １２ - The modified lysine-based polymer according to claim 19, which is an alkenylene and preferably comprises structural units from (B) at least one of oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, tartaric acid, aspartic acid, glutaric acid, itaconic acid, glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid and dodecanediic acid.

21. (A) The structural units from 70 to 97 mol% of lysine monomer; and (B) The structural units from at least one dicarboxylic acid of formula (I) or its amide-forming derivative in an amount of 3 to 30 mol% A modified lysine-based polymer according to claim 14, comprising:

22. (A) the structural units from 75 to 97 mol% of lysine monomer; and (B) The structural units from at least one dicarboxylic acid of formula (I) or its amide-forming derivative in an amount of 4 to 25 mol% A modified lysine-based polymer according to claim 21, comprising:

23. (A) 75 to 95 mol% of the lysine structural units; and (B) 5 to 25 mol% of the dicarboxylic acid structural units A modified lysine-based polymer according to claim 22, comprising:

24. The modified lysine-based polymer according to claim 1, having a degree of modification of at least 10%, for example, at least 20%, by Michael addition.

25. The modified lysine-based polymer according to claim 1, having a weight-average molecular weight (Mw) in the range of 600 to 20,000 g / mol and / or a number-average molecular weight (Mn) in the range of 500 to 20,000 g / mol.

26. A detergent composition, preferably a laundry detergent composition, comprising a modified lysine-based polymer according to any one of claims 1 to 25.

27. The detergent composition according to claim 26, comprising 0.5 to 30% by weight, preferably 1 to 25% by weight, and more preferably 1 to 15% by weight of the modified lysine-based polymer, based on the total solids content of the detergent composition.

28. The detergent composition according to claim 26, which preferably contains 2 ppm to 5% by weight, more preferably 0.1 to 2% by weight, of 2-phenoxyethanol based on the total weight of the detergent composition.

29. The detergent composition according to claim 26, comprising, based on the total weight of the detergent composition, preferably 0.001 to 3% by weight, preferably 0.002 to 1% by weight, and more preferably 0.01 to 0.6% by weight of 4,4'-dichloro-2-hydroxydiphenyl ether.

30. The detergent composition according to claim 26, comprising at least one enzyme, preferably selected from the group consisting of protease, amylase, lipase, cellulase, mannanase, xylanase, DNase, dispersion, pectinase, oxidoreductase, and cutinase.

31. Use of a modified lysine-based polymer according to any one of claims 1 to 25 in a detergent composition, particularly a laundry detergent composition.

32. Use of a modified lysine-based polymer according to any one of claims 1 to 25 as a dispersant.

33. A method for preserving an aqueous detergent composition containing a modified lysine-based polymer according to any one of claims 1 to 25 against microbial contamination or growth, comprising adding 2-phenoxyethanol to the detergent composition.

34. A method for washing fabric or cleaning a hard surface, comprising antimicrobial treatment of the fabric or hard surface with a detergent composition comprising a modified lysine-based polymer and 4,4'-dichloro-2-hydroxydiphenyl ether as described in any one of claims 1 to 25.

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