Use of carboxymethylated lysine polymer as a dispersant and composition containing the same

Abstract

The present invention relates to the use of carboxymethylated polylysine as a dispersant and / or chelating agent. The present invention also relates to a detergent composition and a peroxy bleach composition comprising carboxymethylated polylysine. The present invention further relates to a method for formulating a detergent composition or a peroxy bleach composition with carboxymethylated polylysine.

Description

Field of the Invention

[0001] The present invention relates to the use of carboxymethylated lysine polymers as dispersants, in particular as dispersants in a detergent composition or a bleaching composition. The present invention also relates to detergent compositions and peroxygen bleaching compositions comprising carboxymethylated lysine polymers. Background Art

[0002] Today, dispersants play an important role in various industrial and household formulations, for example, preventing graying of textiles in laundry detergent formulations and preventing scale formation on tableware in automatic dishwashing detergent formulations.

[0003] Chelating agents are also important additives in industrial and household formulations, for example, for washing, cleaning and bleaching processes, especially in hard water areas.

[0004] Most of the currently used dispersants and chelating agents are petroleum-based rather than bio-based. Recently, bio-based products and products containing bio-based components have attracted consumers' interest due to the sustainability of biomass resources. Along with such a trend, bio-based dispersants and chelating agents pose new challenges to manufacturers, especially in household detergent applications.

[0005] For applications that require both chelating and dispersing efficacy, such as in washing and cleaning processes, to avoid undesirable phenomena such as scale formation or dirt deposition, there is a trend to develop additives that have both chelating and dispersing capabilities, i.e., multifunctional additives, to reduce the total number of substances and / or the total amount of additives in a single formulation. As examples of existing multifunctional additives, phosphates and phosphonates are well-known for their excellent chelating and dispersing capabilities and have been widely used in the past. However, phosphate-free additives that are environmentally friendly are more attractive with the increasing public environmental awareness and more environmental regulatory requirements worldwide.

[0006] Therefore, for example, in detergent applications, there is a need to provide a bio-based chemical that can be used as an alternative to petroleum-based dispersants or chelating agents, especially a bio-based chemical that has both chelating and dispersing functions. Summary of the Invention

[0008] The object of the present invention is to provide a phosphate-free, bio-based and biodegradable additive that can be used especially in detergent compositions and bleaching compositions and can be used as a chelating and / or dispersing agent.

[0009] It has been found that the object of the present invention can be achieved by a bio-based polymer, namely a carboxymethylated lysine polymer.

[0010] The present invention in one aspect relates to the use of a carboxymethylated lysine polymer having a degree of modification (DM) of at least 50% as a dispersing and / or chelating agent.

[0011] The present invention relates, in another aspect, to the use of a carboxymethylated lysine polymer having a degree of modification (DM) of at least 50% in a detergent composition or a peroxygen bleaching composition.

[0012] The present invention relates, in yet another aspect, to a detergent composition or a peroxygen bleaching composition comprising a carboxymethylated lysine polymer having a degree of modification (DM) of at least 50%.

[0013] Surprisingly, it has been found that the carboxymethylated lysine polymer exhibits chelating and / or dispersing properties comparable to or even better than those of commercially available chelating or dispersing agents. It has also been found that the carboxymethylated lysine polymer can be used simultaneously as a chelating and a dispersing agent and particularly offers promising commercial opportunities in detergent and bleaching compositions. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present invention will now be described in detail hereinafter. It should be understood that the present invention can be embodied in many different ways and should not be construed as limited to the embodiments described herein. Unless otherwise mentioned, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains.

[0016] As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.

[0017] As used herein, the terms "comprising", "including", etc. can be used interchangeably with "containing", etc. and should be interpreted in a non-restrictive and open-ended manner. That is, for example, other components or elements may be present. The expressions "consisting of" or "consisting essentially of" or cognates can be included within "comprising" or cognates.

[0018] As used herein, the term "lysine polymer" is intended to refer to any polymer comprising repeating units obtained by the condensation of lysine molecules with each other and is intended to include linear and branched polymer structures. The term "lysine polymer" may be abbreviated as "polylysine", and the two terms may be used interchangeably hereinafter.

[0019] As used herein, the term "bio-based" is intended to mean that the specified material can be derived from biomass resources.

[0020] As used herein, "renewable additive" relates to an additive component derived from renewable raw materials and containing renewable carbon.

[0021] As used herein, "biodegradable" generally relates to a material that degrades due to the action of natural microorganisms, such as bacteria, fungi and algae; environmental heat; moisture; or other environmental factors.

[0022] As used herein, the term "carboxymethylated lysine polymer" is intended to mean a lysine polymer that has been modified by carboxymethylating the free amino groups present in the lysine polymer to introduce carboxyl groups into the polymer, which may be abbreviated hereinafter as "carboxymethylated polylysine". It is understood that the terms "carboxymethylated lysine polymer" and "carboxymethylated polylysine" are intended to include forms that are partially or fully neutralized with respect to the carboxyl groups.

[0023] As used herein, the K value when referring to the carboxymethylated polylysine of the present invention relates to the corresponding parameter of the polymer without carboxymethylation, unless the context clearly dictates otherwise.

[0024] <Carboxymethylated polylysine>

[0025] Carboxymethylated polylysine having a linear or branched structure and its derivatives have been known for several decades. For example, Kazuo Uehara et al. described the preparation of carboxymethylated polylysine and some of its physical properties in "Preparation and Properties of Poly(N ε ,N ε -dicarboxymethyl-L-lysine)", Polymer, 1979, Vol. 20, 670 - 674. DE 3701665 A describes a carboxymethylated polylysine and its use in forming polymer metal complexes that can be used as diagnostic and radiotherapeutic agents. WO2011 / 031284 A1 describes a polylysine modified with aminocarboxylate groups such as iminodiacetic acid and nitrilotriacetic acid. The resulting polymer can be used to promote the blood circulation of active agents. The applications of modified polylysine such as carboxymethylated polylysine have been studied especially in the medical and pharmaceutical fields. The application of carboxymethylated polylysine in detergent or bleaching compositions has never been mentioned in the prior art.

[0026] The carboxymethylated polylysine that can be used in the present invention can be prepared by carboxymethylating polylysine. Specifically, the carboxymethylation of polylysine occurs on the free amino groups remaining in the polylysine. This carboxymethylation can be carried out by any conventional method via a carboxymethylating amine to provide an aminocarboxylic acid. For example, polylysine can be simply carboxymethylated via a carboxymethylating agent such as iodoacetic acid as described in "Preparation and Properties of Poly(N ε ,N ε -dicarboxymethyl-L-lysine)", Kazuo Uehara et al., Polymer, 1979, Vol. 20, 670 - 674 or sodium chloroacetate as described in US 2,860,164A. Alternatively, polylysine can be carboxymethylated via the reaction of an amino group with formaldehyde and hydrogen cyanide or sodium cyanide under the corresponding conditions as described in US 2,860,164A. There is no particular limitation on the method for preparing carboxymethylated polylysine in the present invention.

[0027] The carboxymethylated polylysine that can be used in the present invention can be in a partially or fully neutralized form with respect to the carboxyl groups depending on the preparation method and conditions. In the case of the partially or fully neutralized form, the carboxyl groups can be in the form of ammonium salts or alkali metal salts such as sodium or potassium salts.

[0028] As the polylysine to be carboxymethylated, which is bio-based and biodegradable, both linear polylysine and branched polylysine (i.e., having a branched structure) are useful. It is known that polylysine can have a linear or branched structure depending on the production method. For example, ε-linear polylysine is usually prepared by the well-known microbial fermentation method in the art. Branched polylysine is usually obtained by the thermal polycondensation of lysine due to the fact that each molecule of lysine has one reactive carboxyl group and two reactive amino groups (α-NH2 and ε-NH2). For the purposes of the present invention, the type of polylysine structure (linear or branched), the arrangement of those structural units, and the degree of branching are all unimportant. Branched polylysine may only be preferred from a cost perspective.

[0029] In a particular embodiment of the present invention, the carboxymethylated polylysine is a carboxymethylated lysine homopolymer, also known as homopolylysine.

[0030] More specifically, the carboxymethylated polylysine is a linear or branched carboxymethylated homopolylysine.

[0031] In a preferred embodiment, the carboxymethylated polylysine is carboxymethylated ε-linear polylysine. ε-linear polylysine can be prepared by bioconversion or can be those commercially available.

[0032] In another preferred embodiment of the present invention, the carboxymethylated polylysine is a carboxymethylated branched homopolylysine obtained by the thermal polycondensation of lysine.

[0033] In a preferred embodiment of the present invention, the carboxymethylated polylysine has a degree of modification (DM) of at least 50%, preferably at least 70%, more preferably at least 80%, and up to 90% or even 100%. The degree of modification (DM) herein is determined according to the following equation:

[0034]

[0035] where the number of moles of carboxymethyl and the number of moles of lysine monomer units are determined according to the resonance signals of the corresponding protons attributed to 1 1H NMR measured in D2O.

[0036] Preferably, the carboxymethylated polylysine is prepared from a polylysine having a K value in the range of 8 - 25, more preferably 10 - 20, as determined according to DIN ISO 1628 - 1 at 23 °C in a 1 wt% solution of the corresponding polylysine in water. More specifically, the carboxymethylated polylysine is prepared from a branched homopolylysine having a K value in the range of 8 - 25, more preferably 10 - 14, or an ε-linear homopolylysine having a K value in the range of 10 - 25, more preferably 17 - 22.

[0037] The K value is commonly referred to as the intrinsic viscosity and is an indirect measure of the polymer molecular weight.

[0038] The carboxymethylated polylysine has a number average molecular weight (Mn) in the range of 800 - 17,000 g / mol, preferably 1,000 - 15,000 g / mol, and / or a weight average molecular weight (Mw) in the range of 900 - 18,000 g / mol, preferably 1,100 - 16,000 g / mol.

[0039] In particular, in the case of carboxymethylated branched homopolylysine, the carboxymethylated polylysine has a number average molecular weight (Mn) in the range of 800 - 7,000 g / mol, preferably 1,000 - 6,000 g / mol, and / or a weight average molecular weight (Mw) in the range of 900 - 11,000 g / mol, preferably 1,100 - 7,000 g / mol. In the case of carboxymethylated ε-linear homopolylysine, the carboxymethylated polylysine has a number average molecular weight (Mn) in the range of 5,000 - 17,000 g / mol, preferably 6,000 - 15,000 g / mol, and / or a weight average molecular weight (Mw) in the range of 5,500 - 18,000 g / mol, preferably 6,500 - 16,000 g / mol.

[0040] It has been found that carboxymethylated polylysine can be used to provide chelating and / or dispersing functions in detergent compositions and chelating functions in peroxy bleach compositions.

[0041] <Detergent and Bleach Compositions>

[0042] Detergent Composition

[0043] According to the present invention, the detergent composition can be any composition comprising a surfactant or mixture of surfactants to provide cleaning efficacy. Specifically, the detergent composition is a laundry detergent composition or a detergent composition for cleaners. The term "detergent composition for cleaners" includes compositions for household care as well as for industrial or institutional applications. Specifically, the detergent composition for cleaners includes compositions for dishwashing, especially hand dishwashing and automatic dishwashing as well as warewashing, compositions for hard surface cleaning such as but not limited to compositions for bathroom cleaning, kitchen cleaning, floor cleaning, pipe descaling, window cleaning, automotive cleaning including truck cleaning, and also open plant cleaning, in-situ cleaning, metal cleaning, disinfection cleaning, farm cleaning, high pressure cleaning, but not laundry detergent compositions.

[0044] There is no limitation on the formulation of the detergent composition. Carboxymethylated polylysine can be used in any conventional formulation of a detergent composition, such as a laundry detergent composition or a detergent composition for cleaners. It should be understood that carboxymethylated polylysine can be included in the detergent composition in addition to or in place of chelating agents and / or dispersants otherwise included in the conventional formulation of the detergent composition.

[0045] In some embodiments of the present invention, the laundry detergent composition comprises carboxymethylated polylysine in an amount of 0.5 - 30%, preferably 1 - 20%, more preferably 1 - 10% by weight based on the total solids content of the detergent composition.

[0046] In some other embodiments of the present invention, the detergent composition for cleaners comprises carboxymethylated polylysine in an amount of 0.5 - 30%, preferably 1 - 20%, more preferably 1 - 10% by weight based on the total solids content of the detergent composition.

[0047] As an essential component for providing cleaning efficacy to the detergent composition, at least one of cationic, anionic, nonionic, and amphoteric surfactants can be included depending on the specific application and desired properties of the detergent composition.

[0048] Nonionic surfactants

[0049] Useful nonionic surfactants can include but are not limited to (1) condensation products of alcohols with ethylene oxide, (2) alcohols with ethylene oxide and another alkylene oxide, (3) polypropylene glycol with ethylene oxide, or (4) reaction products of ethylene oxide with ethylenediamine and propylene oxide, fatty acid amides, and semi-polar nonionic surfactants.

[0050] Condensation products of alcohols with ethylene oxide are derived, for example, from primary or secondary C8 - C 22 alkyl groups, which can be linear or branched, preferably C 10-C 18 alcohols of alkyl groups. The alcohol is condensed with about 1-25 mol, preferably about 3-18 mol of ethylene oxide / mol of alcohol.

[0051] The condensation products of alcohols with ethylene oxide and another alkylene oxide can be constituted according to the scheme R-O-EO-AO or R-O-AO-EO, where R is a primary or secondary branched or linear C8-C 22 alkyl group, preferably C 10 -C 18 alkyl group, EO is ethylene oxide and AO contains an alkylene oxide, preferably propylene oxide, butylene oxide or pentylene oxide.

[0052] The condensation product of polypropylene glycol and ethylene oxide contains a hydrophobic structural part preferably having a molecular weight of about 1,500-1,800. Up to about 40 moles of ethylene oxide are added to this hydrophobic structural part to obtain an amphiphilic compound.

[0053] The condensation product of the reaction product of ethylene oxide with ethylenediamine and propylene oxide contains a hydrophobic structural part constituted by the reaction product of ethylenediamine and propylene oxide and generally having a molecular weight of about 2,500-3,000. Ethylene oxide is added based on this hydrophobic unit in a content of up to about 40-80 wt% of polyoxyethylene and a molecular weight of about 5,000-11,000.

[0054] Fatty acid amides can be those of the following formula:

[0055]

[0056] where

[0057] R 1 is an alkyl group having 7-21, preferably 9-17 carbon atoms, and

[0058] R 2 are independently of each other hydrogen, a C1-C4 alkyl group, a C1-C4 hydroxyalkyl group or (C2H4O) x H, where x varies within 1-3.

[0059] Preferably C8-C 20 fatty acid amides such as monoethanolamide, diethanolamide and diisopropanolamide.

[0060] As semi-polar nonionic surfactants, water-soluble amine oxides, water-soluble phosphine oxides and water-soluble sulfoxides can be mentioned, each of which has at least one C 8- C 18 alkyl group, preferably C 10- C 14 alkyl group. Preferably C 10 -C 12 alkoxyethyldi(hydroxyethyl)amine oxide.

[0061] In some embodiments, weakly foaming or low-foaming nonionic surfactants are preferred, for example in automatic dishwashing compositions. The following nonionic surfactants of the formulas (I), (II) and (III) may be mentioned in particular:

[0062] R 1 -O-(CH2CH2O) a -(CHR 2 CH2O)b-R 3 (I),

[0063] where

[0064] R 1 is a linear or branched C8-C 22 alkyl group,

[0065] R 2 and R 3 are independently of one another hydrogen or a linear or branched C1-C 10 alkyl group, where R 2 is preferably methyl, and

[0066] a and b are independently of one another 0 - 300;

[0067] R 4 -O-[CH2CH(CH3)O] c [CH2CH2O] d [CH2CH(CH3)O] e CH2CH(OH)R 5 (II),

[0068] where

[0069] R 4 is a linear or branched aliphatic C4-C 22 hydrocarbon group or a mixture thereof,

[0070] R 5 is a linear or branched C2-C 26 hydrocarbon group or a mixture thereof,

[0071] c and e are values from 0 - 40, and

[0072] d is a value of at least 15;

[0073] R 6 O-(CH2CHR 7 O) f (CH2CH2O) g (CH2CHR 8 O) h -CO-R 9 (III),

[0074] wherein

[0075] R 6 is a branched or unbranched C8-C 16 alkyl group,

[0076] R 7 、R 8 are independently of each other H or a branched or unbranched C1-C5 alkyl group, R 9 is an unbranched C5-C 17 alkyl group,

[0077] f and h are independently numbers from 1 to 5, and

[0078] g is a number from 13 to 35.

[0079] The surfactants of formulas (I), (II) and (III) can be random copolymers or block copolymers as described in US9796951B2, preferably in the form of block copolymers, which patent is incorporated herein by reference.

[0080] Anionic surfactants

[0081] Useful anionic surfactants can include, but are not limited to, alkenyl- or alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates, alkyl carboxylates (soaps). The counterions present are alkali metal cations, preferably sodium or potassium, alkaline earth metal cations, such as calcium or magnesium, and also ammonium and substituted ammonium compounds, such as mono-, di- or triethanolammonium cations and mixtures of the above cations.

[0082] Alkenyl- or alkylbenzenesulfonates can contain branched or linear, optionally hydroxy-substituted alkenyl or alkyl groups, preferably linear C9-C 25 alkyl groups.

[0083] Alkanesulfonates are industrially available on a large scale in the form of secondary alkanesulfonates in which the sulfo group is attached to a secondary carbon atom of the alkyl structural moiety. The alkyl group can in principle be saturated, unsaturated, branched or linear and optionally substituted by hydroxy groups. Preferred secondary alkanesulfonates contain linear C9-C 25 alkyl groups, preferably C 10 -C 20 alkyl groups, more preferably C 12 -C 18 alkyl groups.

[0084] Olefinsulfonates are obtained by sulfonation of C8-C 24 , preferably C 14 -C 16-α-olefins and then neutralized. Due to their production method, these olefin sulfonates may contain small amounts of hydroxyalkane sulfonates and alkane disulfonates.

[0085] Alkyl ester sulfonates are derived, for example, from C8-C sulfonated with sulfur trioxide 20 carboxylic acids, i.e., linear esters of fatty acids. Compounds of the following formula are preferred:

[0086]

[0087] where

[0088] R 1 is a C8-C 20 alkyl group, preferably a C 10 -C 16 alkyl group and R is a C1-C6 alkyl group, preferably methyl, ethyl or isopropyl. Particular preference is given to methyl ester sulfonates in which R 1 is a C 10 -C 16 alkyl group.

[0089] Alkyl sulfates are surfactants of the formula ROSO3M, where R is a C 10 -C 24 alkyl group, preferably a C 12 -C 18 alkyl group. M is a counterion as described at the beginning for anionic surfactants.

[0090] Alkyl ether sulfates have the general structure RO(A) m SO3M, where R is a C 10 -C 24 alkyl group, preferably a C 12 -C 18 alkyl group, where A is an alkoxy unit, preferably ethoxy, m has a value of about 0.5-6, preferably about 1-3 and M is a cation such as sodium, potassium, calcium, magnesium, ammonium or a substituted ammonium cation.

[0091] Alkyl carboxylates are commonly known by the term "soap". Soaps can be based on saturated or unsaturated, preferably natural linear C8-C 18 fatty acids. Saturated fatty acid soaps include, for example, salts of lauric acid, myristic acid, palmitic acid, stearic acid, erucic acid and behenic acid, and especially soap mixtures derived from natural fatty acids such as coconut, palm kernel or tallow fatty acids. Known alkenyl succinates can also be used together with soaps or as a substitute for soaps.

[0092] Other anionic surfactants are salts of acylamino carboxylic acids, acylsarcosinates, fatty acid-protein condensation products obtained by the reaction of fatty acyl chlorides with oligopeptides; salts of alkylaminosulfonyl carboxylic 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, hydroxyethyl sulfonates such as acyl hydroxyethyl sulfonates, N-acyl taurates, alkyl succinates, sulfosuccinates, sulfosuccinic acid monoesters (especially saturated and unsaturated C 12 -C 18 monoesters) and sulfosuccinic acid diesters (especially saturated and unsaturated C 12 -C 18 diesters), sulfates of alkyl polysaccharides such as alkyl polyglycosides and sulfates of alkyl polysaccharides such as sulfates of alkyl polyglycosides and alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2) k CH2COOM, where R is a C8-C 22 alkyl, k is a number from 0 to 10 and M is a cation.

[0093] Cationic surfactants

[0094] Useful cationic surfactants can be R 1 N(CH3)3 + X - 、R 1 R 2 N(CH 3)2 + X - 、R 1 R 2 R 3 N(CH3) + X - or R 1 R 2 R 3 R 4 N + X - of substituted or unsubstituted straight-chain or branched quaternary ammonium salts, where R 1 、R 2 、R 3 and R 4 are independently of each other unsubstituted C8-C 24 alkyl, preferably C8-C 18 alkyl, hydroxyalkyl having 1 to 4 carbon atoms, phenyl, C2-C 18 alkenyl, C7-C 24 aralkyl, (C2H4O) xH, where x is about 1 - 3, the alkyl optionally contains one or more ester groups, and X is a suitable anion. Useful cationic surfactants can also be cyclic quaternary ammonium salts.

[0095] Amphoteric / zwitterionic surfactants

[0096] Useful amphoteric surfactants can be aliphatic derivatives of secondary or tertiary amines or aliphatic derivatives of heterocyclic secondary and tertiary amines, where the aliphatic group can be straight-chain or branched and where one of the aliphatic substituents contains at least about 8 carbon atoms or about 8 - 18 carbon atoms and at least one of the aliphatic substituents contains an anionic water-solubilizing group such as carboxyl, sulfonate, sulfate. Suitable amphoteric surfactants also include sarcosinates, glycinate, taurates and mixtures thereof. Examples of substances as amphoteric surfactants are known in the art, for example, known from WO 2005095569A1.

[0097] Useful zwitterionic surfactants can be derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary or tertiary sulfonium compounds. Suitable examples of zwitterionic surfactants include, but are not limited to, betaines such as alkyl betaines and alkylamide betaines, such as N-alkyl-N,N-dimethyl-N-carboxymethyl betaine, N-(alkylamidopropyl)-N,N-dimethyl-N-carboxymethyl betaine, alkyl dimethoxyethyl betaine, alkylamine oxides and sulfobetaines and hydroxysulfobetaines such as N-alkyl-N,N-dimethylamino-1-propane sulfonate, each having a linear or branched C8 - C 22 alkyl, preferably C8 - C 18 alkyl, more preferably C 12 -C 18 alkyl.

[0098] In an exemplary embodiment of the present invention, a laundry detergent composition can contain 0.1 - 80% by weight, based on the total solids content of the detergent composition, of at least one surfactant selected from anionic surfactants, amphoteric surfactants and nonionic surfactants. Some preferred laundry detergent compositions of the present invention can contain at least one anionic or nonionic surfactant.

[0099] In another exemplary embodiment of the present invention, a cleaning detergent composition can contain 0.1 - 80% by weight, based on the total solids content of the detergent composition, of at least one surfactant selected from anionic surfactants, amphoteric surfactants and nonionic surfactants. Some preferred cleaning detergent compositions of the present invention can contain at least one anionic or nonionic surfactant.

[0100] Builders

[0101] The detergent composition may further comprise conventional auxiliaries for modifying the performance characteristics of the detergent composition.

[0102] Auxiliaries suitable for detergent compositions may include, but are not limited to, builders such as complexing agents other than carboxymethylated polylysine, ion exchangers and precipitants, bleaches, bleach activators, corrosion inhibitors, foam boosters, defoamers, dyes, fillers, color fixatives, optical brighteners, disinfectants, alkalis, antioxidants, thickeners, fragrances, solvents, solubilizers, softeners and antistatic agents. Some auxiliaries are described by way of example below.

[0103] The detergent composition may generally comprise at least one builder selected from organic and inorganic builders. Examples of suitable inorganic builders are sodium sulfate or sodium carbonate or sodium silicate, especially disodium silicate and sodium metasilicate, zeolites, phyllosilicates, especially those of the 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 diacetates, tartaric acid monoacetates, oxidized starch, and polymeric builders such as polycarboxylates and polyaspartic acid.

[0104] The detergent composition may comprise the builder in a total amount of, for example, 10 - 70% by weight, preferably at most 50% by weight, based on the total solids content of the detergent composition. In the context of the present invention, carboxymethylated polylysine is not counted as a builder.

[0105] The detergent composition may comprise at least one defoamer selected, for example, from silicone oil and paraffin oil. The total amount of defoamer may be 0.05 - 0.5% by weight based on the total solids content of the detergent composition.

[0106] The detergent composition may comprise at least one bleach. The bleach may be selected from chlorine-containing bleaches and peroxide bleaches.

[0107] Peroxide bleaches may be selected from inorganic peroxide bleaches and organic peroxide bleaches. Preferred inorganic peroxide bleaches are selected from alkali metal percarbonates, alkali metal perborates and alkali metal persulfates. In solid detergent compositions for hard surface cleaning 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 are glycerol, sodium sulfate, silicates, sodium carbonate and combinations thereof, such as a combination of sodium carbonate and sodium sulfate. Examples of organic peroxide bleaches are percarboxylic acids.

[0108] Suitable chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfonamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate. The laundry detergent composition and the cleaning detergent composition may contain the chlorine-containing bleaching agent in a total amount of, for example, 3-10% by weight based on the total solid content of the detergent composition.

[0109] The detergent composition may also contain at least one bleaching activator, such as N-methylmorpholine acetonitrile salt (“MMA salt”), trimethylammonium acetonitrile salt, N-acylimide, such as N-nonanoyl succinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine (“DADHT”) or nitrile quaternary compound (trimethylammonium acetonitrile salt). Other examples of bleaching activators are tetraacetylethylenediamine (TAED) and tetraacetylhexanediamine.

[0110] The detergent composition may contain at least one corrosion inhibitor. Examples of suitable corrosion inhibitors are triazoles, especially benzotriazoles, dibenzotriazoles, aminotriazoles, alkylaminotriazoles, phenol derivatives such as hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol. The detergent composition may contain the corrosion inhibitor in a total amount of 0.1-1.5% by weight based on the total solid content of the detergent composition.

[0111] The detergent composition may also contain at least one enzyme. Examples of enzymes are lipase, hydrolase, amylase, protease, cellulase, esterase, pectinase, lactase and peroxidase. The enzyme may be contained in the detergent composition, especially the laundry detergent composition and the cleaning detergent composition, in an amount of up to 5% by weight, preferably 0.1-3% by weight, based on the total solid content of the detergent composition. The enzyme may be stabilized, for example, with at least one sodium salt of a C1-C3 carboxylic acid or a C4-C 10 dicarboxylic acid.

[0112] Suitable types and dosages of conventional auxiliaries for detergent compositions, especially laundry detergent compositions and cleaning detergent compositions, are well known in the art and can be found, for example, in WO 2017174413A1, WO2015187757A1, US9796951B2 and US 20190136152A1.

[0113] <Peroxy bleaching composition>

[0114] Peroxy bleaching agents are widely used in various processes such as textile whitening, cellulose fiber pulp whitening, hair bleaching, and surface disinfection due to the strong oxidizing ability of peroxides. It is known that peroxides are generally sensitive to heavy metal ions such as Fe, Cu, Mn, Ni, Co, Zn, Pb, and Cd ions because heavy metal ions may catalyze the decomposition of peroxides. Even a small amount of heavy metal ions may inevitably have an adverse effect on the bleaching effect.

[0115] As a conventional measure to stabilize peroxides such as hydrogen peroxide against heavy metal ions, additives (such as EDTA, DTPA, NTA) that can chelate or coordinate heavy metal ions are usually used in peroxy bleaching compositions containing hydrogen peroxide or hydrogen peroxide precursors that can generate hydrogen peroxide during the bleaching process.

[0116] It has been found that carboxymethylated polylysine can be used as a stabilizer for peroxy bleaching agents. Specifically, the peroxy bleaching agent can be those commonly used for bleaching cellulose fiber materials such as wood, cotton, linen, jute, and other cellulosic materials, as well as for bleaching synthetic textiles including polyamides, viscose, rayon, and polyester. The cellulose fiber materials can be in the form of single fibers (such as wood pulp or cotton fibers) and yarns, tows, meshes, fabrics (woven or non-woven fabrics), and other aggregates of such fibers.

[0117] In one embodiment of the present invention, carboxymethylated polylysine is included as a stabilizer in a peroxy bleaching composition for bleaching cellulose fiber pulp. Cellulose fiber pulp usually contains a certain amount of heavy metal ions such as Fe, Cu, and Mn ions, and the latter need to be shielded so that the bleaching effect is not adversely affected.

[0118] In a specific embodiment, the peroxy bleaching composition for bleaching cellulose fiber pulp is in the form of an aqueous hydrogen peroxide solution. This aqueous hydrogen peroxide solution usually contains inorganic alkali metal alkaline materials such as sodium hydroxide, sodium carbonate, sodium silicate, and mixtures thereof. Using this inorganic alkali metal alkaline material gives the aqueous hydrogen peroxide solution an ideal pH in the range of 7.5 - 12.5. Carboxymethylated polylysine can be included in the solution in an amount of 0.01 - 3 wt%, preferably 0.1 - 1 wt%, based on the total weight of the aqueous hydrogen peroxide solution.

[0119] In another specific embodiment, the carboxymethylated polylysine and the peroxide component are separately included in the peroxy bleaching composition for bleaching cellulose fiber pulp. In this embodiment, the carboxymethylated polylysine and hydrogen peroxide are not mixed until the two are incorporated into the cellulose fiber pulp to be bleached. The carboxymethylated polylysine can be incorporated into the cellulose fiber pulp at a dosage of 0.01 - 3% by weight, preferably 0.1 - 1% by weight, more preferably 0.2 - 0.8% by weight based on the weight of the cellulose fiber pulp. The specific dosage of the carboxymethylated polylysine can vary depending on the heavy metal content of the pulp, the hydrogen peroxide dosage, the bleaching method, etc. It is also desirable to use inorganic alkali metal alkaline materials, such as sodium hydroxide, sodium carbonate, sodium silicate, and mixtures thereof, so that bleaching is carried out at a pH in the range of 7.5 - 12.5.

[0120] The following examples are provided to illustrate the invention, but are not intended to limit the invention. Examples

[0121] Description of materials used in the examples

[0122] Polymer PA-1: Aqueous solution of sodium polyacrylate, pH 8 (10%), solid content 40% by weight, Mw 4000 g / mol, purchased from BASF

[0123] Polymer PA-2: Aqueous solution of sodium polyacrylate, pH 8 (10%), solid content 45% by weight, Mw 1200 g / mol, purchased from BASF

[0124] Polymer PAA: Sodium salt particles of acrylic acid / 2-acrylamido-2-methylpropanesulfonic acid copolymer, solid content 92% by weight, purchased from BASF

[0125] EDTA liquid: Tetrasodium ethylenediaminetetraacetate (EDTA-Na4), active ingredient content 40% by weight, purchased from BASF

[0126] MGDA liquid: Trisodium methylglycine diacetate (MGDA-Na3), aqueous solution, active ingredient content 40%, purchased from BASF

[0127] MGDA particles: Trisodium methylglycine diacetate (MGDA-Na3), particles, active ingredient content 85%, purchased from BASF

[0128] Modified PEI: Carboxymethylated polyethyleneimine, aqueous solution, solid content 40%, purchased from BASF

[0129] Anionic surfactant AES: Sodium lauryl ether sulfate, purchased from BASF

[0130] Anionic surfactant DBS: Linear C 10 -C13 Alkylbenzene sulfonate, purchased from BASF

[0131] Nonionic surfactant AEO-1: Ethoxylated C 13 -C 15 Oxo alcohol (7EO), purchased from BASF

[0132] Nonionic surfactant AEO-2: Ethoxylated C 12 -C 14 Fatty alcohol (7EO), purchased from BASF

[0133] K12-18: Cocoa fatty acid, purchased from Henkel

[0134] NCD732: Diethylenetriamine penta(methylenephosphonic acid) (DTPMPA), active substance content 32.5%, purchased from Zschimmer & Schwarz GmbH

[0135] Protease: 150T, purchased from Novozymes

[0136] Amylase: Plus 12L, purchased from Novozymes

[0137] White polyester / cotton fabric: wfk 20A, purchased from wfk Testgewebe GmbH, Brüggen, Germany

[0138] White polyester fabric: wfk 30A, purchased from wfk Testgewebe GmbH, Brüggen, Germany

[0139] White polyamide fabric: EMPA 406, purchased from Swissatest Testmaterialien AG, Sankt Gallen, Switzerland

[0140] Soiled fabrics: EMPA 117 (polyester / cotton soiled with blood / milk / ink) purchased from Swissatest Testmaterialien AG, Sankt Gallen, Switzerland and wfk 10J (cotton soiled with tea) purchased from wfk Testgewebe GmbH, Brüggen, Germany

[0141] Determination of molecular weight

[0142] The number-average (Mn) and weight-average (Mw) molecular weights of the modified polymers prepared in the following examples were determined by measuring the unmodified polylysine by gel permeation chromatography (GPC) method and then converting the measured values to the molecular weights of the modified polymers based on the corresponding degree of modification (DM). The unmodified polymer was analyzed in an aqueous eluent containing 0.1 M NaCl and 0.1 wt% trifluoroacetic acid at 35 °C and a flow rate of 0.8 ml / min through a column cascade (i.e., TSKgel G4000, G3000, G3000, 300×7.8 mm). For this analysis, the unmodified polymer was dissolved in the eluent at a concentration of 1.5 mg / ml at room temperature and filtered through a 0.22 μm membrane, and 100 μl was injected into an Agilent 1100 chromatographic system after 2 hours. The relative molecular weights were characterized by refractive index detection against a calibration curve obtained with polyvinylpyrrolidone standards in the range of 620 - 1,060,000 g / mol.

[0143] Preparation Example

[0144] Example 1: Carboxymethylated polylysine homopolymer (Polymer 1)

[0145] 100 g of an aqueous L-lysine solution (50 wt%) was added to a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a pressure-reducing connection and a Dean-Stark receiver. The mixture was heated to an internal temperature of 160 °C with stirring. When the internal temperature reached 100 °C, 400 g of an aqueous L-lysine solution (50 wt%) was continuously fed in over 3.5 hours while continuously separating water. After a reaction time of 1 hour, water was further distilled off under reduced pressure (670 mbar). Finally, 264 g of water distillate was collected and the highly viscous polymer was discharged into a silica gel container as soon as it was still hot and flowable. The K value was determined to be 10.5 at 23 °C using a 1 wt% aqueous solution of polylysine in water according to DIN ISO 1628-1.

[0146] 7.86 g of sodium chloroacetate, 18.75 g of polylysine and 56.25 g of deionized water were added to a 250 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube and a condenser. The solution was then heated to 70 °C and maintained for 5 hours. 31.44 g of sodium chloroacetate and 27 g of sodium hydroxide (50 wt%) were added to the flask in 3 portions every 0.5 hour during the first 1.5 hours. After cooling the reaction mixture to 30 °C, the polymer was precipitated with an excess of methanol (1:10 weight) and filtered. After three consecutive precipitation steps, the product was dried in a vacuum oven at 40 °C for 16 hours to obtain a solid content of 100% and an active ingredient content of 1The end product was determined by ¹H NMR to be 94 wt%. The degree of modification (DM) of the polymer was determined by 1 ¹H NMR to be 89% and the measured molecular weight was M n = 2112 g / mol and M w = 2560 g / mol.

[0147] Example 2: Carboxymethylated polylysine homopolymer (Polymer 2)

[0148] 2.62 g of sodium chloroacetate, 6.25 g of ε-linear polylysine (from Yiming Biological Products Co., Ltd., Jiangsu, China, K value 19.6) and 18.75 g of deionized water were added to a 250 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube and a condenser. The solution was then heated to 70 °C and maintained for 5 hours. 10.48 g of sodium chloroacetate and 9.0 g of sodium hydroxide (50 wt%) were added to the flask in 3 portions every 0.5 hour within the first 1.5 hours. The reaction mixture was treated and the product was purified in the same manner as described in Example 1 to obtain an end product with a solids content of 100% and an active ingredient content of 96 wt%. The degree of modification (DM) was determined by 1 ¹H NMR to be 90% and the measured molecular weight was M n = 11358 g / mol and M w = 11902 g / mol.

[0149] Example 3: Carboxymethylated polylysine homopolymer (Polymer 3)

[0150] 100 g of an aqueous L-lysine solution (50 wt%) was added to a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a vacuum connection and a Dean-Stark receiver. The mixture was heated with stirring to an internal temperature of 160 °C and maintained for 45 minutes. Then 400 g of an aqueous L-lysine solution (50 wt%) was continuously fed in over 3.5 hours while continuously separating water. After a reaction time of 1 hour, water was further distilled off under reduced pressure (670 mbar). Finally, 276 g of water distillate was collected and the highly viscous polymer was discharged into a silica gel container as soon as it was still hot and flowable. The measured K value was 13.1.

[0151] 7.86 g of sodium chloroacetate, 18.75 g of polylysine and 56.25 g of deionized water were added to a 250 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube and a condenser. Then the solution was heated to 70 °C and maintained for 5 hours. 31.44 g of sodium chloroacetate and 27 g of sodium hydroxide (50 wt%) were added to the flask in 3 portions every 0.5 hour during the initial 1.5 hours. The reaction mixture was treated and the product was purified in the same manner as described in Example 1 to obtain a final product with a solid content of 100% and an active ingredient content of 98 wt%. The degree of modification (DM) was determined by 1 1H NMR to be 80% and the measured molecular weight was M n = 3265 g / mol and M w = 6976 g / mol.

[0152] Example 4: Carboxymethylated polylysine homopolymer (Polymer 4)

[0153] 7.86 g of sodium chloroacetate, 37.50 g of ε-linear polylysine (from Yiming Biological Products Co., Ltd., Jiangsu, China, K value 19.6) and 112.50 g of deionized water were added to a 250 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube and a condenser. Then the solution was heated to 70 °C and maintained for 5 hours. 31.44 g of sodium chloroacetate and 27.0 g of sodium hydroxide (50 wt%) were added to the flask in 3 portions every 0.5 hour during the initial 1.5 hours. The reaction mixture was treated and the product was purified in the same manner as described in Example 1 to obtain a final product with a solid content of 100% and an active ingredient content of 95 wt%. The degree of modification (DM) was determined by 1 1H NMR to be 53% and the measured molecular weight was M n = 7976 g / mol and M w = 8358 g / mol.

[0154] Example 5: Carboxymethylated polylysine homopolymer (Polymer 5)

[0155] Into a 250 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser, add 61.09 g of sodium chloroacetate, 38.91 g of ε-linear polylysine (from Yiming Biological Products Co., Ltd., Jiangsu, China, K value 19.6), and 100.00 g of deionized water. Then heat the solution to 70 °C and hold for 16 hours while maintaining the pH at 10 by feeding 53.25 g of NaOH over 2.0 hours. Treat the reaction mixture and purify the product in the same manner as described in Example 1 to obtain a final product with a solids content of 100% and an active ingredient content of 95 wt%. The degree of modification (DM) was determined by 1 1H NMR to be 70% and the measured molecular weight was M n = 10167 g / mol and M w = 10654 g / mol.

[0156] Example 6: Carboxymethylated polylysine homopolymer (Polymer 6)

[0157] Into a 2000 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser, add 104.80 g of sodium chloroacetate, 250.00 g of ε-linear polylysine (from Yiming Biological Products Co., Ltd., Jiangsu, China, K value 19.6), and 750.00 g of deionized water. Then heat the solution to 70 °C and hold for 5 hours. Add 419.20 g of sodium chloroacetate and 360.00 g of sodium hydroxide (50 wt%) in 3 portions every 0.5 hour to the flask during the first 1.5 hours. Treat the reaction mixture and purify the product in the same manner as described in Example 1 to obtain a final product with a solids content of 100% and an active ingredient content of 93 wt%. The degree of modification (DM) was determined by 1 1H NMR to be 75% and the measured molecular weight was M n = 10523 g / mol and M w = 11027 g / mol.

[0158] Example 7: Carboxymethylated polylysine homopolymer (Polymer 7)

[0159] 100 g of an aqueous L-lysine solution (50 wt%) was added to a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a pressure reducing connection and a Dean-Stark receiver. The mixture was heated to an internal temperature of 160 °C with stirring. When the internal temperature reached 100 °C, 400 g of an aqueous L-lysine solution (50 wt%) was continuously fed in over 3.5 hours while continuously separating water. After a reaction time of 1 hour, water was further distilled off under reduced pressure (670 mbar). Finally, 269 g of a water distillate was collected and the highly viscous polymer was discharged into a silica gel container as soon as it was still hot and flowable. The K value was measured to be 12.2.

[0160] 104.80 g of sodium chloroacetate, 250.00 g of polylysine and 750.00 g of deionized water were added to a 2000 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube and a condenser. The solution was then heated to 70 °C and maintained for 5 hours. 419.20 g of sodium chloroacetate and 360.00 g of sodium hydroxide (50 wt%) were added to the flask in 3 portions every 0.5 hour during the first 1.5 hours. The reaction mixture was treated and the product was purified in the same manner as described in Example 1 to obtain a final product with a solids content of 100% and an active ingredient content of 98 wt%. The degree of modification (DM) was determined by 1 1H NMR to be 70% and the measured molecular weights were M n = 2429 g / mol and M w = 3825 g / mol.

[0161] Example 8: Carboxymethylated polylysine homopolymer (Polymer 8)

[0162] 100 g of an aqueous L-lysine solution (50 wt%) was added to a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a pressure reducing connection and a Dean-Stark receiver. The mixture was heated to an internal temperature of 160 °C with stirring. When the internal temperature reached 100 °C, 400 g of an aqueous L-lysine solution (50 wt%) was continuously fed in over 3.5 hours while continuously separating water. After a reaction time of 1 hour, water was further distilled off under reduced pressure (670 mbar). Finally, 264 g of a water distillate was collected and the highly viscous polymer was discharged into a silica gel container as soon as it was still hot and flowable. The K value was measured to be 11.0.

[0163] 104.80 g of sodium chloroacetate, 190.80 g of polylysine and 750.00 g of deionized water were added to a 2000 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube and a condenser. Then the solution was heated to 70 °C and maintained for 5 hours. 419.20 g of sodium chloroacetate and 360.00 g of sodium hydroxide (50 wt%) were added to the flask in 3 portions every 0.5 hour within the first 1.5 hours. The reaction mixture was treated and the product was purified in the same manner as described in Example 1 to obtain a final product with a solids content of 100% and an active content of 89 wt%. The degree of modification (DM) determined by 1 1H NMR was 78% and the determined molecular weights were M n = 1345 g / mol and M w = 1986 g / mol.

[0164] Working Example

[0165] The chelating and dispersing properties of carboxymethylated polylysine were studied by the following methods:

[0166] Chelating properties:

[0167] - CaCO3 dissolution (CCD)

[0168] - Hydrogen peroxide stability (HPS)

[0169] Dispersing properties:

[0170] - CaCO3 dispersing ability (CCDC)

[0171] - CaCO3 dispersibility (CCDA)

[0172] - CaCO3 inhibition (CCI)

[0173] CaCO3 dissolution (CCD)

[0174] 100 ml of a CaCO3 dispersion (0.005 mol / L) was titrated with a 2.5 wt% polymer additive solution at room temperature without stirring. The transmittance was recorded until 14 ml of the additive solution was added. The transmittance measurement was carried out using a Metrohm photometer 662 including a photometric electrode and a Metrohm Titrino 716 DMS at pH 11 (the pH was adjusted to 11 and controlled by additional pH measurement with a Metrohm 654). 100% transmittance means that the CaCO3 in the system was completely dissolved. The test results are summarized in Table 1.

[0175] Table 1. CaCO3 dissolution (CCD)

[0176] Additive Chemical Transmittance (%) Modified PEI Carboxymethylated polyethyleneimine 82 Polymer 1 Carboxymethylated branched polylysine 84 Polymer 2 Carboxymethylated ε-polylysine 89 Polymer 3 Carboxymethylated branched polylysine 79

[0177] Hydrogen peroxide stability

[0178] Prepare 100 mL of an aqueous solution containing metal ions and additives. Then add 6.67 g of a 30 wt% H2O2 solution to obtain a solution containing 2 wt% H2O2. Adjust the pH to a constant value with NaOH or HCl. After stirring for a certain time, determine the remaining H2O2 content by iodometric titration. The test results are summarized in Tables 2 and 3.

[0179] Table 2. H2O2 stabilization in the presence of Fe 3+ (120 ppm) at pH 10

[0180] Additive Chemical Dosage <![CDATA[H2O2 (%) remaining after 30 minutes]]> None - - 4 EDTA liquid <![CDATA[EDTA-Na4]]> <![CDATA[0.6g a) > 78 MGDA liquid <![CDATA[MGDA-Na4]]> <![CDATA[0.6g a) > 31 Polymer 1 Carboxymethylated branched polylysine <![CDATA[0.6g b) > 38 Polymer 2 Carboxymethylated ε-polylysine <![CDATA[0.6g b) > 69 Polymer 3 Carboxymethylated branched polylysine <![CDATA[0.6g b) > 24

[0181] a) Based on active substance content, b) Based on solid content

[0182] Table 3. H2O2 stabilization in the presence of Mn 2+ (60 ppm) at pH 9

[0183] Additive Chemical Dosage <![CDATA[H2O2 remaining (%) after 60 minutes]]> None - - 0 EDTA liquid <![CDATA[EDTA-Na4]]> <![CDATA[0.6g a) > 84 MGDA liquid <![CDATA[MGDA-Na4]]> <![CDATA[0.6g a) > 34 Polymer 1 Carboxymethylated branched polylysine <![CDATA[0.6g b) > 68 Polymer 2 Carboxymethylated ε-polylysine <![CDATA[0.6g b) > 56 Polymer 3 Carboxymethylated branched polylysine <![CDATA[0.6g b) > 66

[0184] a) Based on active substance content, b) Based on solid content

[0185] CaCO3 dispersibility (CCDA)

[0186] Titrate CaCl2 in a Na2CO3 solution using a commercial titration system from Metrohm. The setup consists of a titration device (Titrando 905) operating two dosing units (Dosino 807). Monitor the turbidity using an optrode (Metrohm, No. 6.1115.000). Pour 60 ml of an aqueous solution containing 400 ppm Ca 2+ as fast as possible with stirring into 60 ml of an aqueous solution containing 600 ppm CO3 2- and an additive at 200 ppm based on active substance content. Record the turbidity of the mixture at pH 11 and 25 °C within 30 minutes. The test results are summarized in Table 4.

[0187] Table 4. CaCO3 dispersibility (CCDA)

[0188]

[0189] CaCO3 dispersing capacity (CCDC)

[0190] The calcium carbonate dispersing capacity (CCDC) allows quantification of the ability of a polymer dispersant to inhibit the precipitation of calcium carbonate in an aqueous medium.

[0191] Dissolve the polymer additive based on 1.0 g of solid content in 100 ml of water. Then add 10 ml of 10 wt% sodium carbonate solution. Adjust the pH value of the test solution to pH 11 with 1N NaOH. Titrate the test solution with 0.25M calcium acetate solution until it starts to become turbid. Keep the pH constant during titration by adjusting with 1N NaOH or 1N HCl. The test results are summarized in Table 5.

[0192] Table 5. CaCO3 dispersion ability (CCDC)

[0193] Additive Chemical <![CDATA[CCDC (mg CaCO3 / g additive)]]> Polymer PA-1 Sodium polyacrylate 120 Polymer 1 Carboxymethylated branched polylysine, DM 89% 195 Polymer 2 Carboxymethylated ε-polylysine, DM 90% 165 Polymer 3 Carboxymethylated branched polylysine, DM 80% 160 Polymer 4 Carboxymethylated ε-polylysine, DM 53% 60 Polymer 5 Carboxymethylated ε-polylysine, DM 70% 77

[0194] Calcium carbonate inhibition (CCI)

[0195] Calcium carbonate inhibition (CCI) is a measure of the ability of a polymer additive to inhibit or retard the precipitation of sparingly soluble calcium salts (such as CaCO3) during application.

[0196] Place a beaker containing a solution with 215 mg / l Ca 2+ , 43 mg / l Mg 2+ , 1220 mg / l HCO3 – , 460 mg / l Na + , 380 mg / l Cl – , 170 mg / l SO4 2– and 3 or 5 ppm of the additive (based on the active content for non-polymer additives or on the solid content for polymer additives) - with a pH of about 8.0 - 8.3 - in a shaking water bath and keep for 2 hours. After filtering the warm solution, determine the Ca 2+ concentration of the filtrate by titration with 0.01M EDTA-Na4 and calculate the degree of inhibition. The test results are summarized in Table 6.

[0197] Table 6. CaCO3 inhibition (CCI)

[0198]

[0199] It can be seen that the carboxymethylated polylysine of the present invention exhibits acceptable or desirable dispersion and chelating abilities required for detergent compositions. In addition, the carboxymethylated polylysine of the present invention exhibits an ideal ability to stabilize hydrogen peroxide against heavy metal ions.

[0200] Application examples

[0201] Study the performance of carboxymethylated polylysine in detergent applications and pulp bleaching applications.

[0202] Compatibility in liquid laundry formulations

[0203] Study the compatibility of polylysine with a liquid laundry formulation of the concentrated detergent formulation shown in Table 7. Visually observe the stability of the formulation containing 1% additive and adjusted to pH 8.5 after 1 week. The test results are summarized in Table 8.

[0204] Table 7

[0205]

[0206]

[0207] a) Based on the active ingredient content for non-polymer components and on the solid content for polymer components

[0208] Table 8

[0209] Additive Chemical 1.0%, 7 days Blank - Clear Polymer PA-1 Sodium polyacrylate Phase separation Polymer 1 Carboxymethylated branched polylysine Clear Polymer 2 Carboxymethylated ε-polylysine Clear Polymer 3 Carboxymethylated branched polylysine Clear

[0210] It can be seen that carboxymethylated polylysine shows good compatibility in the concentrated liquid detergent formulation at high pH.

[0211] Anti-greying performance of the liquid laundry formulation

[0212] Use the detergent formulation shown in Table 9 to evaluate the anti-greying performance.

[0213] Table 9

[0214]

[0215] a) Based on the active ingredient content for non-polymer components and on the solid content for polymer components, simulate the laundry process using a bottle-type detergency tester (LP2 Typ, SDL Atlas Inc., USA).

[0216] Wash a white test fabric together with 2.5 g of clay dispersion and 20 steel balls in a washing liquor containing the detergent of formulation 02 at 40 °C in the same beaker, then rinse and spin-dry to complete the washing cycle. Repeat the washing cycle twice with a new clay dispersion and a new washing liquor. After rinsing in the third washing cycle, dry the test fabric in air. The details of the washing cycle are summarized in Table 10.

[0217] The anti-greying performance is characterized by the ΔR value of lightening of the soiled fabric before and after washing, the latter being determined by measuring the fabric at 460 nm using a spectrophotometer Elrepho 2000 from Datacolor. The higher the ΔR value of lightening, the better the performance. The results are summarized in Table 11.

[0218] Table 10

[0219]

[0220] Table 11

[0221]

[0222] It can be seen that carboxymethylated polylysine shows acceptable anti-greying performance, which is even comparable to that of commercially available polymer additives.

[0223] Detergency performance of liquid laundry formulations

[0224] The detergency performance was evaluated using the detergent formulations shown in Table 12.

[0225] Table 12

[0226]

[0227]

[0228] a) For non-polymer components based on the active substance content and for polymer components based on the solid content

[0229] The laundering process was simulated in the laboratory using a bottle-type detergency tester (LP2 Typ, SDL Atlas Inc., USA).

[0230] Several soiled test fabrics were washed together with cotton ballast and 20 steel balls at 25 °C in a washing liquor containing the detergent of the specified formulation. After washing, the fabrics were rinsed, spun dry and air dried. The details of the washing cycle are summarized in Table 13.

[0231] The detergency performance was characterized by the ΔE value calculated according to DIN EN ISO 11664-4 (June 2012) using the following equation:

[0232] ΔE = (ΔL *2 + Δa *2 + Δb *2 ) 1 / 2 ,

[0233] where

[0234] ΔL* = L* 洗涤后 - L* 初始 ;

[0235] Δa * = a* 洗涤后 - a* 初始 ; and

[0236] Δb * = b* 洗涤后 - b* 初始 .

[0237] Measure the L, a, b values of the soiled fabric using a Datacolor spectrophotometer Elrepho 2000 before and after washing. The higher the ΔE value, the better the performance. The results are summarized in Tables 14 - 15. * a * b * value. The higher the ΔE value, the better the performance. The results are summarized in Tables 14 - 15.

[0238] Table 13

[0239]

[0240]

[0241] Table 14. Test results of washing EMPA 117 with the detergent of formulation 03 at a detergent dosage of 2 g / L

[0242]

[0243] Table 15. Test results of washing Wfk 10J with the detergent of formulation 04 at a detergent dosage of 4 g / L

[0244] Without DTPMPA With DTPMPA Blank 6.3 7.2 Modified PEI 7.2 7.6 Polymer 6 7.2 7.7 Polymer 7 7.0 7.5 Polymer 8 7.4 7.2

[0245] The test results show that the carboxymethylated polylysine exhibits a comparable or even better detergency effect than the commercially available polymer additives.

[0246] Anti - filming performance of automatic dishwashing formulations

[0247] Carry out the accumulation test according to the general procedure detailed in Table 16.

[0248] Table 16

[0249]

[0250]

[0251] Composition of ballast dirt

[0252] Starch 0.5% potato starch, 2.5% gravy Fat 10.2% margarine Protein 5.1% egg yolk, 5.1% milk Others 2.5% tomato ketchup, 2.5% mustard, 0.1% benzoic acid, 71.4% water

[0253] After 30 cycles, visually evaluate the tableware in a dark room under the light behind the aperture diaphragm using a scoring scale of 10 (very good) to 1 (very poor). Give a score of 1 - 10 for filming (1 = very severe filming, 10 = no filming).

[0254] Carry out the accumulation test with the tablet formulation without HEDP and with citrate as shown in Table 17. The test results of filming evaluation are summarized in Table 18.

[0255] Table 17

[0256]

[0257] a) For non-polymeric components, based on the active substance content, and for polymeric components, based on the solid content

[0258] Table 18

[0259] Table knife Glass Plastic Porcelain Total Blank 3.0 2.0 3.7 3.7 12.4 Polymer PA-1 6.0 5.0 6.3 6.7 24.0 Modified PEI 4.7 4.0 5.7 5.7 20.1 Polymer PAA 5.3 5.0 6.0 6.0 22.3 Polymer 7 5.0 4.3 5.3 5.3 19.9

[0260] Accumulation tests were carried out with tablet formulations having HEDP and citrate as shown in Table 19. The test results of the film formation evaluation are summarized in Table 20.

[0261] Table 19

[0262]

[0263] a) For non-polymeric components, based on the active substance content, and for polymeric components, based on the solid content

[0264] Table 20

[0265] Table knife Glass Plastic Porcelain Total Blank 5.0 4.3 6.7 6.7 22.7 Polymer 7 6.0 5.0 7.3 6.3 24.6 Polymer PA-1 4.0 4.0 5.0 5.0 18.0 Polymer PAA 6.3 5.0 6.7 6.7 24.7

[0266] The test results show that the carboxymethylated polylysine exhibits a film-forming resistance equivalent to or even better than that of commercially available polymer additives.

[0267] Pulp bleaching application

[0268] An aqueous suspension containing 4.0 wt% groundwood cellulose fibers, 1.5 wt% hydrogen peroxide (10%) relative to the amount of cellulose fibers, 0.2 wt% additive, 0.75 wt% sodium hydroxide, and 2.0 wt% sodium silicate was heated to 70 °C. After 1.5 hours, the fibers were filtered, and then the filter cake was pressed and dried into a sheet of paper. The Tappi whiteness of the dried paper sheet was measured by Datacolor DC 400 from Datacolor. The test results are summarized in Table 21.

[0269] Table 21

[0270] Additive Blank EDTA liquid Polymer 6 Polymer 7 Polymer 8 Dosage - <![CDATA[0.2% a) > <![CDATA[0.2% b) > <![CDATA[0.2% b) > <![CDATA[0.2% b) > Tappi whiteness 60.1 63.3 63.8 64.0 63.6

[0271] a) Based on the active substance content, b) Based on the solid content

[0272] The test results show that carboxymethylated polylysine can stabilize hydrogen peroxide to an equivalent or even better extent than conventional chelating agents.

Claims

1. Use of carboxymethylated polylysine with a degree of modification (DM) of at least 50% as a dispersant and / or chelating agent, wherein the degree of modification (DM) is determined according to the following equation:

2. Use according to claim 1, wherein the degree of modification (DM) is at least 70%.

3. Use according to claim 1, wherein the degree of modification (DM) is at least 80%.

4. Use according to claim 1, wherein the degree of modification (DM) is at most 90%.

5. Use according to claim 1, wherein the degree of modification (DM) is at most 100%.

6. Use according to claim 1, wherein the carboxymethylated polylysine is prepared from polylysine with a K value in the range of 8 - 25; or wherein the carboxymethylated polylysine has a number-average molecular weight (Mn) in the range of 800 - 17,000 g / mol and / or a weight-average molecular weight (Mw) in the range of 900 - 18,000 g / mol, where the K value is called the intrinsic viscosity.

7. Use according to claim 6, wherein the carboxymethylated polylysine is prepared from polylysine with a K value in the range of 10 - 20.

8. Use according to claim 6, wherein the carboxymethylated polylysine has a number-average molecular weight (Mn) in the range of 1000 - 15,000 g / mol.

9. Use according to claim 6, wherein the carboxymethylated polylysine has a weight-average molecular weight (Mw) in the range of 1100 - 16,000 g / mol.

10. Use according to any one of claims 1 - 9, wherein the carboxymethylated polylysine is linear or branched carboxymethylated polylysine.

11. Use according to claim 10, wherein the carboxymethylated polylysine is linear or branched carboxymethylated homopolylysine.

12. Use according to any one of claims 1 - 9 and 11, wherein the carboxymethylated polylysine is carboxymethylated ε-linear polylysine.

13. A detergent composition or a peroxy bleach composition comprising carboxymethylated polylysine with a degree of modification (DM) of at least 50%, wherein the degree of modification (DM) is determined according to the following equation:

14. Composition according to claim 13, wherein the degree of modification (DM) is at least 70%.

15. Composition according to claim 13, wherein the degree of modification (DM) is at least 80%.

16. Composition according to claim 13, wherein the degree of modification (DM) is at most 90%.

17. Composition according to claim 13, wherein the degree of modification (DM) is at most 100%.

18. Composition according to claim 13, wherein the carboxymethylated polylysine is prepared from polylysine with a K value in the range of 8 - 25; or wherein the carboxymethylated polylysine has a number-average molecular weight (Mn) in the range of 800 - 17,000 g / mol and / or a weight-average molecular weight (Mw) in the range of 900 - 18,000 g / mol, where the K value is called the intrinsic viscosity.

19. The composition according to claim 18, wherein the carboxymethylated polylysine is prepared from polylysine having a K value in the range of 10 - 20.

20. The composition according to claim 18, wherein the carboxymethylated polylysine has a number average molecular weight (Mn) in the range of 1000 - 15,000 g / mol.

21. The composition according to claim 18, wherein the carboxymethylated polylysine has a weight average molecular weight (Mw) in the range of 1100 - 16,000 g / mol.

22. The composition according to any one of claims 13 - 21, wherein the carboxymethylated polylysine is linear or branched carboxymethylated polylysine.

23. The composition according to claim 22, wherein the carboxymethylated polylysine is linear or branched carboxymethylated homopolylysine.

24. The composition according to any one of claims 13 - 21 and 23, wherein the carboxymethylated polylysine is carboxymethylated ε - linear polylysine.

25. The composition according to any one of claims 13 - 21 and 23, which is a laundry detergent composition or a cleaning agent detergent composition.

26. The composition according to claim 25, which is an automatic dishwashing detergent composition.

27. The composition according to any one of claims 13 - 21, 23 and 26, wherein the detergent composition comprises 0.1 - 80% by weight, based on the total solids content of the detergent composition, of at least one surfactant selected from anionic surfactants, amphoteric surfactants and non - ionic surfactants.

28. The composition according to claim 27, wherein the surfactant is an anionic surfactant.

29. The composition according to any one of claims 13 - 21, 23, 26 and 28, wherein the detergent composition comprises the carboxymethylated polylysine in an amount of 0.5 - 30% by weight, based on the total solids content of the detergent composition.

30. The composition according to claim 29, wherein the detergent composition comprises the carboxymethylated polylysine in an amount of 1 - 20% by weight, based on the total solids content of the detergent composition.

31. The composition according to claim 29, wherein the detergent composition comprises the carboxymethylated polylysine in an amount of 1 - 10% by weight, based on the total solids content of the detergent composition.

32. The composition according to any one of claims 13 - 21 and 23, which is a peroxygen bleaching composition for bleaching cellulose fiber materials selected from wood, cotton, linen, jute and for bleaching synthetic textiles selected from polyamide, viscose, rayon and polyester, the cellulose fiber materials being in the form of single fibers and yarns, tows, meshes, fabrics of such fibers.

33. The composition according to claim 32, which is a peroxygen bleaching composition for bleaching cellulose fiber pulp.

34. The composition according to any one of claims 13 - 21 and 33, wherein the peroxygen bleaching composition comprises hydrogen peroxide or a hydrogen peroxide precursor.

35. The composition according to claim 32, wherein the peroxygen bleaching composition comprises hydrogen peroxide or a hydrogen peroxide precursor.

36. The composition according to claim 34, wherein the peroxy bleaching composition is in the form of an aqueous hydrogen peroxide solution.

37. The composition according to claim 36, wherein the aqueous solution contains the carboxymethylated polylysine in an amount of 0.01 - 3% by weight based on the total weight of the solution.

38. The composition according to claim 36, wherein the aqueous solution contains the carboxymethylated polylysine in an amount of 0.1 - 1% by weight based on the total weight of the solution.

39. The composition according to claim 35, wherein the peroxy bleaching composition is in the form of an aqueous hydrogen peroxide solution.

40. The composition according to claim 39, wherein the aqueous solution contains the carboxymethylated polylysine in an amount of 0.01 - 3% by weight based on the total weight of the solution.

41. The composition according to claim 39, wherein the aqueous solution contains the carboxymethylated polylysine in an amount of 0.1 - 1% by weight based on the total weight of the solution.

42. Use of the carboxymethylated polylysine as defined in any one of claims 1 - 12 or claims 13 - 24 in a detergent composition or a peroxy bleaching composition.

43. A method for bleaching cellulose fiber pulp with a peroxy bleach, wherein the carboxymethylated polylysine as defined in any one of claims 1 - 12 or claims 13 - 24 is used as a stabilizer for the peroxy bleach.

44. The method according to claim 43, wherein the carboxymethylated polylysine is incorporated into the cellulose fiber pulp in a dose of 0.01 - 3% by weight based on the weight of the cellulose fiber pulp.

45. The method according to claim 44, wherein the carboxymethylated polylysine is incorporated into the cellulose fiber pulp in a dose of 0.1 - 1% by weight based on the weight of the cellulose fiber pulp.

46. The method according to claim 44, wherein the carboxymethylated polylysine is incorporated into the cellulose fiber pulp in a dose of 0.2 - 0.8% by weight based on the weight of the cellulose fiber pulp.

47. A method for formulating a detergent composition or a peroxy bleaching composition with the carboxymethylated polylysine as defined in any one of claims 1 - 12 or claims 13 - 24.

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