WO2021209278A1

WO2021209278A1 - Method of imparting chlorine resistance effect to colored fabric

Info

Publication number: WO2021209278A1
Application number: PCT/EP2021/058853
Authority: WO
Inventors: Yan KANG; Shan Ling GE; Shu Shu DING; Jia Zhou; Yue Liu; Xiao Li ZHANG
Original assignee: Basf Se
Priority date: 2020-04-14
Filing date: 2021-04-06
Publication date: 2021-10-21

Abstract

The present invention relates to a method of imparting chlorine resistance effect to colored fabric in a washing process. The present invention further relates to a method for inhibiting or minimizing color fading or damage of a colored fabric to chlorinated water.

Description

METHOD OF IMPARTING CHLORINE RESISTANCE EFFECT TO COLORED FABRIC

Technical Field

The present invention relates to a method of imparting chlorine resistance effect to a colored fabric in a washing process. The present invention further relates to a method for inhibiting or minimizing color fading or damage of a colored fabric to chlorinated water.

Background Art

Colored fabrics are a sensitive class of fabrics warranting special care during the normal wash cycle. For instance, colored fabrics have a tendency to release dye into the wash solution which can cause fading. This released dye can also be transferred to other fabrics in the same wash solution or even to other differently-colored parts of the same fabric.

Chlorine is one of the most commonly used disinfectants for water disinfection, Chlorine can be applied for the deactivation of most microorganism and help protect water for disinfection purpose from picking up disease and microbes. To ensure that the city water is safe, a small residual amount, typically about 1 to 2 parts per million (ppm), of chlorine is left in the water. At lease about 10% of U.S. households has about 2 ppm or more of chlorine in its tap water at some time. Aside from being smelly, using chlorinated water for laundry through a wash and rinse cycle, can make colored fabrics be faded. It has been found that this small amount of chlorine in the tap water can contribute to fading or color changes of some fabric dyes. Both reactive dyes and direct dyes have the defect of being poor in the color fastness to chlorinated water, and there are many cases where cotton textiles dyed with reactive dyes are faded or discolored due to the presence of active chlorine in water such as tap water or pool water. Thus, chlorine-induced fading of fabric colors over time can result from the presence of residual chlorine in the wash or rinse water.

Some attempts have been made to solve the above-mentioned problem, for instance, U.S patent application US 5,767,052 discloses a laundry detergent composition comprises chlorine-scaven gers to eliminate or reduce the bleaching activity of the chlorine material, such chlorine-scavenger can be ammonium chloride. U.S patent application US 4,424,061 has disclosed a mixture com prising a diamine or a salt and a hydrolysable tannin, which is used in washing a colored fabric to improve the color fastness of dyed cotton textiles to chlorinated water. This is the reason one of the major challenges, when contacting a colored fabric with chlorinated water in laundry washing process or other process comprising use of chlorinated water, is to avoid color fading and improve color fastness.

The objective of the present invention is thus to provide a method of imparting chlorine resistance effect to a colored fabric in a washing process. Still another objective of the present invention is also to provide a method for inhibiting/minimizing color fading or damage of a colored fabric due to contacting with chlorinated water.

Summary of Invention

In one aspect, the present invention is directed to a method of imparting chlorine resistance effect to a colored fabric in a washing process, which comprises a step of contacting a colored fabric with a wash liquor which contains at least one hydrophobically modified polyalkyleneimine, wherein the colored fabric is contacted with chlorinated water during or after the washing process; wherein the hydrophobically modified polyalkyleneimine comprises a polyalkyleneimine back bone having a weight-average molecular weight greater than or equal to 200 g/mol and less than 2000 g/mol, and hydrophobic moieties which are covalently attached to the backbone of poly alkyleneimine.

Preferably, the unmodified polyalkyleneimine backbone can be polyethyleneimine, polypropyl- eneimine or polybutyleneimine. Preferably said unmodified polyalkyleneimine has a weight-aver age molecular weight greater than or equal to 300 g/mol and less than 1500 g/mol, more prefer ably greater than or equal to 500 g/mol and less than 1000 g/mol.

In another aspect, the present invention relates to a method for inhibiting/minimizing color dam age of a colored fabric, which comprises applying to the colored fabric a wash liquor comprising the hydrophobically modified polyalkyleneimine, wherein the color fading or damage of colored fabric is due to contacting with chlorinated water.

In still another aspect, the present invention is directed to use of hydrophobically modified poly alkyleneimine as chlorine resistant agent in a laundry washing process, wherein the colored fabric is contacted with chlorinated water during or after the washing process.

The present invention surprisingly and unexpectedly has found that use of hydrophobically mod ified polyethyleneimine as chlorine resistant agent in a laundry washing process, can effectively prevent or minimize color fading which is due to contacting colored fabric with chlorinated water. Detailed Description of The Invention

Throughout the description, including the claims, the term "comprising one" or “comprising a" should be understood as being synonymous with the term "comprising at least one", unless oth erwise specified, and "between" should be understood as being inclusive of the limits.

The terms “a”, “an” and “the” are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article.

The term “and/or” includes the meanings “and”, “or” and also all the other possible combinations of the elements connected to this term.

It should be noted that in specifying any range of concentration, weight ratio or amount, any par ticular upper concentration, weight ratio or amount can be associated with any particular lower concentration, weight ratio or amount, respectively.

As used herein, the term “laundry detergent” is meant a composition which is required to comprise one or more detersive surfactants.

As used herein, the term “washing process” means those steps of the process in which a wash liquor produced by dissolving or diluting a detergent in water is contacted with the fabric to be washed.

As used herein, all percentages are percent by weight unless otherwise indicated. All component or composition levels are in reference to the active level of that component or composition.

The term “wash liquor” used herein, means a water-based solution that includes a surfactant- based detergent.

As used herein, the term “contacting” can be carried out, for example, immersing the fabrics in a wash liquor and agitating the fabrics. Contacting can also be accomplished by wiping, spraying, or padding a wash liquor onto the fabrics.

As used herein, the term “hydrophobically modified polyalkyleneimine” refers to polyalkyleneimine with hydrophobic groups chemically attached to unmodified polyalkyleneimine backbone.

As used herein, the term “unmodified or non-modified” refers to a polymer substrate that is not modified or functionalized. As used herein, the term “hydrocarbon radical” refers to any straight, branched, cyclic, acyclic, heterocyclic, saturated or unsaturated chain, which contains a carbon backbone comprising one or more hydrogen atoms, optionally substituted with one or more heteroatoms in or on the carbon backbone.

As used herein, the term “hydrophobic moiety” is a moiety which can be saturated or unsaturated, substituted or unsubstituted, straight or branched, cyclic or acyclic hydrocarbon group.

As used herein, the term "alkyl" means a saturated hydrocarbon radical, which may be straight, branched or cyclic, such as, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t- butyl, pentyl, n-hexyl, cyclohexyl.

As used herein, the term "hydroxyalkyl" means an alkyl radical, more typically an alkyl radical, that is substituted with a hydroxyl groups, such as for example, hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxydecyl.

As used herein, the term "alkylene" means a bivalent acyclic saturated hydrocarbon radical, in cluding but not limited to methylene, polymethylene, and alkyl substituted polymethylene radicals, such as, for example, dimethylene, tetramethylene, and 2-methyltrimethylene.

As used herein, the term "alkenyl" and “alkadienyl” refer to alkyl groups having, respectively, one or two carbon-carbon double bonds within the chain.

As used herein, the term “alkenylcarbonyl” refers to a group -C(=0)R, wherein R is alkenyl which can be optionally substituted.

The present invention is directed to a method of imparting chlorine resistance effect to a colored fabric in a washing process, which comprises a step of contacting a colored fabric with a wash liquor which contains at least one hydrophobically modified polyalkyleneimine, wherein the col ored fabric is contacted with chlorinated water during or after the washing process; wherein the hydrophobically modified polyalkyleneimine comprises a polyalkyleneimine backbone having a weight-average molecular weight greater than or equal to 200 g/mol and less than 2000 g/mol, and hydrophobic moieties which are covalently attached to the backbone of polyalkyleneimine.

Particularly, the method comprises i) forming a wash liquor comprising at least one hydrophobi cally modified polyalkyleneimine, ii) contacting the hydrophobically modified polyalkyleneimine with the fabric to provide chlorine resistance to the fabric, wherein the colored fabric is contacted with chlorinated water during or after the washing process.

Hvdrophobicallv Modified Polvalkyleneimines as Chlorine Resistant Agent

The hydrophobically modified polyalkyleneimines are to be understood as meaning polyalkylene- imines in which the hydrogen atoms of the primary and secondary amino groups are partially or completely replaced by linear or branched aliphatic, saturated or unsaturated hydrocarbon radi cals such as alkyl, alkenyl, alkadienyl or hydroxyalkyl radicals. The hydrocarbon radicals generally have 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms.

The hydrophobically modified polyalkyleneimines can be obtained by a process which comprises the reaction of an unmodified polyalkyleneimine with a hydrophobicizing agent. Depending on the hydrophobicizing agent used in each case, the hydrocarbon radicals can be linked to the nitrogen atom of the polyalkyleneimine directly or via a functional group, e.g. via a carbonyl group (*-C(=0)- ^#), via an oxycarbonyl group (*-0-C(=0)-^#), via an aminocarbonyl group (*-NH-C(=0)-^#), via a carbonyloxyhydroxylpropyl group (^*-C(=0)-0-CH₂-CH(0H)-CH₂-^#), via a 2-oxycarbonylethylene- carbonyl group (*-CH(COOH)-CH2-CO-^#), or via a radical of the formula *-CH₂-(C=0)-CH-(C=0)- ^# (in the formulae given above. Represents the linkage to the hydrocarbon radical and ^# represents the linkage to the nitrogen atom of the polyalkyleneimine). The hydrocarbon radical can also form an aldimine or ketimine group with the nitrogen of the polyalkyleneimine or be linked to 2 nitrogen atoms of the polyalkyleneimine via the carbon atom of a cyclic amidine group.

Preferably, the hydrophobically modified polyalkyleneimine has the hydrocarbon radical which is linked to one nitrogen atom of the polyalkyleneimine directly or via a carbonyl group. The latter being particularly preferred. Preferably, the hydrocarbon radicals are linear, more preferably, the hydrocarbon radicals are saturated.

According to any one of the invention embodiments, the hydrocarbon radicals in the preferred hydrophobically modified polyalkyleneimines are present in the form of C4-C3o-alkyl, C4-C3o-alkyl- carbonyl, C4-C3o-alkenyl, C4-C3o-alkenylcarbonyl, C4-C3o-alkadieny, C4-C3o-alkadienylcarbonyl and/or hydroxy-C4-C3o-alkyl groups, in particular in the form of C₆-Cis-alkyl, C₆-Cis-alkylcarbonyl, C₆-Cis-alkenyl, C₆-Ci₈-alkenylcarbonyl, C₆-Cis-alkadienyl, C₆-Ci₈-alkadienylcarbonyl and/or hy- droxy-C₆-Cis-alkyl groups, where the alkyl, hydroxy-alkyl, alkenyl, alkadienyl radicals of the afore mentioned groups are preferably linear.

In some preferred embodiment, the hydrocarbon radicals are present in the form of C4-C3o-alkyl- carbonyl or C4-C3o-alkenylcarbonyl group, particularly in the form of C₆-Cis-alkylcarbonyl or C₆- Cis-alkenylcarbonyl group, where the alkyl and alkenyl radicals of the aforementioned groups are preferably linear.

According to any one of the invention embodiments, about from 2 to 25 mol%, in particular 5 to 20 mol%, in more particular from 6 to 15 mol% of the nitrogen atoms of the hydrophobically mod ified polyalkyleneimine carry a hydrocarbon radical. Correspondingly, the fraction of the hydro carbon radicals constitutes preferably 5 to 60% by weight, in particular 10 to 50% by weight and specifically 10 to 40% by weight, based on the total weight of the hydrophobically modified poly alkyleneimine.

The hydrophobically modified polyalkyleneimine used according to the present invention can be linear or branched. In particular, the branched polyalkyleneimine branching may occur at its ni trogen fractions. The linear polyalkyleneimines are composed exclusively of repeat units of for mula A; the branched polyalkyleneimines have, besides the linear repeat units, tertiary nitrogen atoms according to the formula B:

A B

In which Q is C2-C8 alkylene, preferably is ethylene, propylene or butylene.

Preference is given to those branched, hydrophobically modified polyalkyleneimines, in particular branched, hydrophobically modified polyethyleneimines, which, based on the polyalkyleneimine on which they are based, have, on average, per polyalkyleneimine molecule at least one, prefer ably at least 5 or at least 10, branching points according to formula B. In particular, at least 5%, in particular at least 10% and particularly preferably at least 15%, e.g. 5 to 40% and specifically 15 to 35%, of the nitrogen atoms of the parent polyalkyleneimine are tertiary nitrogen atoms. Particularly, in the case of high degrees of branching, i.e. if at least 10%, in particular 15%, e.g. 10 to 40%, in particular 15 to 35% of the nitrogen atoms of the parent polyalkylimine are tertiary nitrogen atoms, the hydrophobically modified polyalkyleneimines have a structure similar to a core-shell structure, where the polyalkyleneimine moieties form the core and the hydrophobic radicals form the shell.

According to any one of the invention embodiments, the hydrophobically modified polyalkylene- imines can be present in uncrosslinked or crosslinked form. Preferably, the hydrophobically modified polyalkyleneimines are uncrosslinked. According to any one of the invention embodi ments, the hydrophobically modified polyalkyleneimine has a weight-average molecular weight in the range of from 300 g/mol to 5000 g/mol, preferably from 500 to 3000 g/mol, more preferably from 800 g/mol to 2000 g/mol.

The hydrophobically modified polyalkyleneimines which are used according to the invention are in part known from the prior art or can be prepared analogously to the methods described here inafter. Accordingly, one embodiment of the present invention relates to the use of a hydrophobi cally modified polyalkyleneimine obtainably by a process which comprises the reaction of an un modified polyalkyleneimine, in particular, an unmodified branched polyalkyleneimine, and specif ically an unmodified branched polyethyleneimine, with a hydrophobicizing agent.

Examples of suitable hydrophobicizing agents include but not limit to: i) long chain, linear or branched carboxylic acids having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, in the alkyl or alkenyl radical, such as caprylic acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid and mixtures thereof, preferably lauric acid, stearic acid, palmitic acid and oleic acid, or their amide-forming derivatives, such as acid chlorides, esters or anhydrides of the specified carboxylic acids and mixtures thereof; ii) natural oils, including plant oils, nut oils, seed oils, animal oils and marine oils, which typically contain triglycerides, free fatty acids, or a combination of triglycerides and free fatty acids. Exam ple of suitable natural plant oils are soybean oil, rapeseed oil, palm oil, corn oil, cottonseed oil, coconut oil, palm kernel oil; Example of suitable animal/marine oils are lard, fish oil, beef tallow oil, seal oil and milk fat, and those obtained by hydrogenation or ester-exchange of these oil, and mixture thereof; iii) linear or branched alkyl halides having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, in the linear or branched alkyl radical such as octyl chloride, nonyl chloride, decyl chloride, dodecyl chloride, tetradecyl chloride, hexadecyl chloride, octadecyl chloride and mixtures thereof; iv) alkyl epoxides having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms in the linear or branched alkyl radical, such as hexadecenyl oxide, dodecenyl oxide and octadecenyl oxide and mixtures thereof; v) alkyl ketene dimers having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, in the linear or branched alkyl radical, such as lauryl ketene, palmityl ketene, stearyl ketene and oleyl ketene dimers and mixtures thereof; vi) cyclic dicarboxylic acid anhydrides, in particular alkyl-substituted succinic anhydrides having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms in the linear or branched alkyl radical, such as dodecenylsuccinic anhydride, tetradecylsuccinic anhydride, hexadecenylsuccinic anhydride and mixtures thereof; vii) alkyl isocyanates having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, in the linear or branched alkyl radical, such as tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocy anate and mixtures thereof; viii) chloroformic acid esters of linear or branched alkanols or alkenols having 4 to 30 carbon at oms, preferably 6 to 18 carbon atoms, and dialkyl ketones having in total 4 to 30 carbon atoms, in particular 6 to 18 carbon atoms and mixtures thereof. viiii) linear or branched aliphatic aldehydes having 4 to 30 carbon atoms, preferably 6 to 18 car bon atoms, and dialkyl ketones having in total 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, in the two alkyl groups and mixtures thereof.

According to any one of the invention embodiments, the unmodified polyalkyleneimines which form the basis of the hydrophobically modified polyalkyleneimines comprise homopolymers of ethyleneimine (aziridine) and higher homologs thereof, propyleneimine (methylaziridine) and bu- tyleneimine (1,2-dimethylaziridine, 1,1-dimethylaziridine and 1-ethylaziridine), copolymers of eth yleneimine with its higher homologs, and the graft polymers of polyamidoamines or polyvinyla- mines with ethyleneimine and/or its higher homologs. Also suitable are the graft polymers of al- kyleneimines described in W002/095122, such as ethyleneimine onto polyamidoamines or onto polyvinylamines. Such graft polymers generally have a weight fraction of alkyleneimines of at least 10% by weight, in particular at least 30% by weight, e.g. 10 to 90% by weight in particular 10 to 85% by weight, based on the total weight of the unmodified polyalkyleneimne. In some preferred embodiments, the unmodified polyalkyleneimines are branched polyalkyleneimines, preferably polyethyleneimines, in particular branched polyethyleneimines, in more particular ho mopolymers of ethyleneimines, in still more particular branched homopolymers of ethyleneimines.

According to any one of the invention embodiments, the unmodified polyalkyleneimine has a weight-average molecular weight M_w of from greater than or equal to 200 g/mol to less than 2000 g/mol. Preferably, the unmodified polyalkyleneimine has a weight-average molecular weight M_w of from greater than or equal to 300 g/mol to less than 1500 g/mol. More preferably, the unmodi fied polyalkyleneimine has a weight-average molecular weight M_w of from greater than or equal to 500 g/mol to less than 1000 g/mol. The molecular weights given here refer to the molecular weights specified by means of gel permeation chromatography and measured on dilute aqueous solutions at 25°C, which correspond to the weight-average molecular weight.

The reaction of the unmodified polyalkyleneimine with at least one hydrophobicizing agent can take place according to the processes known in the prior art. The reaction conditions naturally depend on the type and functionality of the polyalkyleneimine and the hydrophobicizing agents. In some embodiments, the reaction may be performed with or without a solvent or diluent. Exam ples of suitable solvents for the reaction include but not limit to hydrocarbons, in particular aro matic hydrocarbons, e.g. alkylbenzenes such as xylenes, toluene, cumene, tert-butylbenzene and the like. In some embodiments, the reaction may take place as a solvent-free reaction, which at least comprises (a) heating the mixture of polyalkyleneimine and hydrophobicizing agent to melt state; (b) stirring the mixture and reacting the polyalkyleneimine with an amount of hydrophobi cizing agent, wherein the amount of the hydrophobicizing agent used is sufficient to derivatize about 2 mol% to 25 mol%, in particular about 5 to 20 mol%, in more particular 6 to 15 mol% of the nitrogen atoms of the polyalkyleneimine. In some preferred embodiment, the reaction taking place between the unmodified polyalkyleneimine and natural oils as the hydrophobicizing agent, comprises (a) heating the mixture of polyalkyleneimine and natural oil to melt state; (b) stirring the mixture and reacting the polyalkyleneimine under nitrogen flow with an amount of natural oil at a temperature of 80 to 120°C, wherein the amount of the hydrophobicizing agent used is suffi cient to derivatize about 2 mol% to 25 mol%, in particular about 5 to 20 mol%, in more particular 6 to 15 mol% of the nitrogen atoms of the polyalkyleneimine. In some embodiments, the hydro phobicizing agent will be used in an amount which corresponds to the desired functionality, it also being possible to use the hydrophobicizing agent in excess. The reaction may be also performed in the presence of catalysts which improve the reactivity of the hydrophobicizing agent toward the polyalkyleneimine. The type of catalyst depends in a manner known per se on the type and reac tivity of the hydrophobicizing agent. The catalysts are usually Lewis acids or Bronsted acids.

In some embodiments, the carboxylic acids and carboxylic acid derivatives are used as the hy drophobicizing agent, it has proven advantageous to remove the low molecular weight products, such as water, alcohols or hydrogen chloride which form during the reaction from the reaction mixture. For example, when using carboxylic acids, the water formed will preferably be removed from the reaction mixture via an entrainer or vacuum. Typical entrainers are hydrocarbons, in particular alkyl aromatics such as toluene or xylenes. Laundry Detergent Composition Comprising Hydrophobically Modified Polyalkyleneimine as

Chlorine Resistant Agent

According to any one of the invention embodiments, the hydrophobically modified polyalkylene imine are generally water-soluble or water-dispersible and can be used in combination with at least one surfactant in a solid and/or liquid laundry detergent composition. The wash liquor is prepared from laundry detergent composition comprising the hydrophobically modified poly alkyleneimine upon dissolution by water or aqueous solution.

According to any one of the invention embodiments, the hydrophobically modified polyalkylene imine is present in a laundry detergent composition in an amount of 0.01 to 30 wt.%, preferably 0.05 to 20 wt.%, more preferably 0.1 to 15 wt.%, still more preferably 0.2 to 10 wt. % by weight of total composition.

Further, the hydrophobically modified polyalkyleneimine can be employed in combination with at least one surfactant in a laundry detergent composition. The surfactants suitable for the present invention include but are not limited to anionic surfactant, nonionic surfactant, cationic surfactant and/or amphoteric surfactant.

Useful anionic surfactants may be selected from alkyl benzenesulfonates, alkanesulfonates, ole- finsulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates, alkyl carboxylates (soap) and alkyl phosphates. The counter-ions present are alkali metal cations, preferably sodium or potassium, alkaline earth metal cations, for example calcium or magnesium, and also ammonium and substituted ammonium compounds, for example mono-, di- or triethanol ammonium cations and mixtures of the aforementioned cations therefrom.

Alkenyl- or alkyl benzenesulfonates may comprise a branched or linear, optionally hydroxyl- sub stituted alkenyl or alkyl group. Preferably they comprise linear alkyl chains having 9 to 25 carbon atoms and more preferably having 10 to about 13 carbon atoms.

Alkane sulfonates are available on a large industrial scale in the form of secondary alkanesul fonates wherein the sulfo group is attached to a secondary carbon atom of the alkyl moiety. The alkyl group can in principle be saturated, unsaturated, branched or linear and optionally hydroxyl substituted. Preferred secondary alkane sulfonates comprise linear Cg to C25-alkyl radicals, pref erably Cio to C2o-alkyl radicals and more preferably C12 to Cis-alkyl radicals. Olefin sulfonates are obtained by sulfonation of Cs to C₂₄ and preferably CM to Ci₆-n-olefins with sulfur trioxide and subsequent neutralization. Owing to their production process, these olefinsul- fonates may comprise minor amounts of hydroxy alkanesulfonates and alkanedisulfonates.

Alkyl ester sulfonates derive for example from linear ester of Cs to C₂o-carboxylic acids, i.e. , fatty acids, which are sulfonated with sulfur trioxide. Compounds of following formula are preferred

wherein

R¹ is a Cs to C₂o-alkyl radical, preferably C₁₀ to Ci₆-alkyl and R is a Ci to C₆-alkyl radical, preferably a methyl, ethyl or isopropyl group. Particular preference is given to methyl ester sulfonates where R¹ is C₁₀ to Ci₆-alkyl.

Alkyl sulfates are surfactants of the formula ROSO₃M, where R is C₁₀ to C₂₄-alkyl and preferably C₁₂ to Ci₈-alkyl. M is a counter-ion as described at the beginning for anionic surfactants.

Alkyl ether sulfates have the general structure R0(A)_mS0₃M, where R is a C₁₀ to C₂₄-alkyl and preferably C₁₂ to Cis-alkyl radical, wherein A is an alkoxy unit, preferably ethoxy and m is a value from about 0.5 to about 6, preferably between about 1 and about 3, and M is a cation, for example sodium, potassium, calcium, magnesium, ammonium or a substituted ammonium cation.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof, as are obtained during production by esterification of a mono glycerol with 1 to 3 mol of fatty acid or on transesterification of triglycerides with 0.3 to 2 mol of glycerol.

Alkyl carboxylates are generally known by the term “soap”. Soap can be manufactured on the basis of saturated or unsaturated, preferably native, linear Cs to Cis-fatty acid. Saturated fatty acid soaps include for example the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydro genated erucic acid and behenic acid and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. Known alkenylsuccinic acid salts may also be used together with soap or as substitutes for soap.

Further anionic surfactant are salts of acylamino carboxylic acids, acyl sarcosinates, fatty acid- protein condensation products obtained by reaction of fatty acid chlorides with oligopeptides; salts of alkylsulfamido carboxylic acids; salts of alkyl and alkylary ether carboxylic acids; sulfonated polycarboxylic acids, alkyl and alkenyl glycerol sulfates, such as oleyl glycerol sulfates, alkylphenol ether sulfates, alkyl phosphates, alkyl ether phosphates, isethionates, such as acyl isethionates, N-acyltaurides, alkyl succinates, sulfosuccinates, monoesters of sulfosuccinates (particularly saturated and unsaturated C12 to Cis-monoesters) and diesters of sulfosuccinates (particularly saturated and unsaturated C12 to Cis-diesters), sulfates of alkylpolysaccharides such as sulfates of alkylpolyglycosides and alkypolysaccharides such as sulfates of alkylpolyglycosides and alkyl polyethoxy carboxylates such as those of the formula RO(CH₂CH2)_kCH2COO M⁺, where R is Cs to C22-alkyl, k is a number from 0 to 10 and M is a cation.

The anionic surfactant can be present in a laundry detergent composition ranging from 1 to 70 wt.%, more preferably from 2 to 60 wt.%, and most preferably from 5 to 40 wt.% of the laundry detergent composition.

Suitable nonionic surfactant can also be employed in combination with the hydrophobically mod ified polyalkyleneimine. Useful nonionic surfactants include, but are not limited to condensation products of (1) alcohols with ethylene oxide, (2) alcohols with ethylene oxide and a further al- kylene oxide, (3) polypropylene glycol with ethylene oxide or (4) ethylene oxide with a reaction product of ethylenediamine and propylene oxide, fatty acid amides, and semipolar nonionic sur factants.

Condensation product of alcohols with ethylene oxide derive for example from alcohols have a Cs to C₂2-alkyl group, preferably a C10 to Ci e-alkyl group, which may be linear or branched, primary or secondary. The alcohols are condensed with about 1 mol to about 25 mol and preferably with about 3 mol to about 18 mol of ethylene oxide per mole of alcohol.

Condensation products of alcohols with ethylene oxide and a further alkylene oxide may be con structed according to the scheme R-O-EO-AO or R-O-AO-EO, where R is a primary or secondary, branched or linear Cs to C₂2-alkyl group, preferably a C10 to Cis-alkyl group, EO is ethylene oxide and AO comprises an alkylene oxide, preferably propylene oxide, butylene oxide or pentylene oxide.

Condensation products of polypropylene glycol with ethylene oxide comprises a hydrophobic moi ety preferably having a molecular weight of from about 1,500 to about 1,800. The addition of up to about 40 mole of ethylene oxide onto this hydrophobic moiety leads to amphiphilic compounds.

Condensation products of ethylene oxide with a reaction product of ethylenediamine and propyl ene oxide comprises a hydrophobic moiety consisting of the reaction product of ethylenediamine and propylene oxide and generally having a molecular weight of from about 2,500 to about 3,000. Ethylene oxide is added up to a content, based on the hydrophobic unit, of about 40% to about 80% by weight of polyoxyethylene and a molecular weight of from about 5,000 to about 11 ,000.

Fatty Acid Amides may be those of following formula

wherein R is an alkyl radical having 7 to 21 and preferably 9 to 17 carbon atoms, and

R¹, independently from each other, is hydrogen, Ci to C4-alkyl, Ci to C4-hydroxyalkyl or (CaFUC _xH where x varies from 1 to 3. Preference is given to Cs to C2o-fatty acid amides such as monoeth- anolamides, diethanolamides and diisopropanolamides.

As the semipolar nonionic surfactants, water-soluble amine oxides, water-soluble phosphine ox ides and water-soluble sulfoxides each having at least one Cs to Cis-alkyl radical, preferably a Cioto Ci4-alkyl may be mentioned. Preference is given to Cio-Ci2-alkoxyethyldihydroxyethylamine oxides.

Useful nonionic surfactants may further include alkyl and alkenyl oligoglycosides and also fatty acid polyglycol esters or fatty amine polyglycol esters each having 8 to 20 and preferably 12 to 18 carbon atoms in the fatty alkyl moiety, and fatty acid N-alkylglucamides.

Nonionic surfactant is conventionally present in a laundry detergent formulation ranging from 5 to 70 wt.%, more preferably from 10 to 50 wt.% and most preferably from 15 to 40 wt.% of the laundry detergent composition.

In some embodiments, cationic surfactants can be employed in combination with the hydropho- bically modified polyalkyleneimine in a laundry detergent composition. Useful cationic surfactants may be substituted or unsubstituted straight chain or branched quaternary ammonium salts of RIN(CH₃)³⁺X , RIR₂N(CH₃)²⁺X-, RIR₂R3N(CH₃)⁺X- or R₁R₂R₃R₄N⁺X-, wherein Ri, R₂, R₃ and R₄ independently from each other are unsubstituted C₈ to C24-alkyl and preferably Cs to Cis-alkyl, hydroxylalkyl having 1 to 4 carbon atoms, phenyl, C₂ to Cis-alkenyl, Cy to C24-aralkyl, (C₂H₄0)_XH where x is from about 1 to about 3, the alkyl radical optionally comprising one or more ester groups, and X is a suitable anion. Useful cationic surfactants may also be cyclic quaternary am monium salts. In some embodiments, suitable amphoteric surfactants to be used with the hydrophobically mod ified polyalkyleneimine may be aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, in which the aliphatic radical may be straight or branched-chain and where 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 substit uents contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. Suitable am photeric surfactants also include sarcosinates, glycinates, taurinates, and mixtures thereof. Ex amples of the species as the amphoteric surfactants are known in the art, for example from W02005095569A1. Suitable zwitterionic surfactants may 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, but are not limited to, betaines such as alkylbetaines and alkyla- mide betaines, such as N-alkyl-N,N-dimethyl-N-carboxymethylbetaines, N-(alkylamidopropyl)- N,N-dimethyl-N-carboxymethylbetaines, alkyldipolyethoxybetains, alkylamine oxides, and sulfo and hydroxy betaines such as N-alkyl-N,N-dimethylammino-1-propane sulfonate, each having a linear or branched Cs to C22-alkyl, preferably Cs to Cis-alkyl radical and more preferably C12 to Ci₈-alkyl.

In some embodiments, the laundry detergent composition comprising the hydrophobically modi fied polyalkyleneimine, may further comprise the customary assistants which serve to recondition the fabrics to be washed, or modify the performance characteristics of the laundry detergent com position. Suitable auxiliaries include for example chelating agent, bleaching agent, foam boosters, foam retarders, anticorrosion suspendants, dyes, fillers, optical brighteners, disinfectants, alkalis, hydrotropic compounds, antioxidants, enzyme stabilizer, thickener, perfumes, solvents, solubil izers, softener and antistats.

The laundry detergent composition comprising the hydrophobically modified polyalkyleneimine, is generally prepared by conventional methods such as those known in the art of making laundry detergent compositions. Such method typically involves mixing the essential and optional ingre dients in any desired order to a relatively uniform state, with or without heating, cooling, applica tion of vacuum, and the like.

Chlorine Resistance Effect

The present invention has surprisingly found that use of the hydrophobically modified poly alkyleneimine in a washing process can provide chlorine resistance effect to a colored fabric. Color fading due to the presence of active chlorine in water such as tap water or pool water can be thus inhibited or minimized. The active chlorine includes chlorine releasing substance suitable to liberate oxidizing active chlorine such as CI2, -OCI , HCIO, CIO2. The chlorinated water can comprise for example alkali metal or alkaline earth metal hypochlorite, such as sodium hypo chlorite, lithium hypochlorite and calcium hypochlorite. The chlorinated water usually comprises active chlorine in an amount of 1 to 10 ppm or 1 to 5 ppm.

The present invention provides a method of imparting chlorine resistance effect to a colored fabric in a washing process, which comprises a step of contacting the colored fabric with a wash liquor which contains the hydrophobically modified polyalkyleneimine, wherein the colored fabric is con tacted with chlorinated water during or after the washing process.

Particularly, the method comprises i) forming a wash liquor comprising the hydrophobically mod ified polyalkyleneimine, ii) contacting the hydrophobically modified polyalkyleneimine with the fab ric to provide chlorine resistance to the fabric, wherein the colored fabric is contacted with chlo rinated water during or after the washing process.

In some embodiments, the chlorinated water is used in washing or rinsing step in contact with the colored fabric during the washing process. In some embodiments, the colored fabric is washed or treated with a wash liquor comprising the hydrophobically modified polyalkyleneimine, such washing or treating step can provide chlorine resistance effect to the colored fabric, so the colored fabric is chlorine resistant when being contacted with chlorinated water after the washing process and color fading can be inhibited. For instance, the colored fabric after being washed or treated with wash liquor comprising the hydrophobically modified polyalkyleneimine, can be resistant to chlorinated water in an after-washing process, like soaking, disinfecting, with the presence of active chlorine in water.

Particularly, the colored fabric can be non-synthetic or synthetic fibers or mixtures thereof. Non synthetic fibers include, for example cellulosic (e.g. cotton) or proteinaceous (e.g. wool or silk) fibers. Synthetic fibers include, for example, nylons and polyesters. Preferably, the suitable col ored fabric in the present invention is non-synthetic fibers, more preferable cotton.

The present invention further provides a method for inhibiting/minimizing color fading or damage of a colored fabric, which comprises applying to the colored fabric a wash liquor comprising the hydrophobically modified polyalkyleneimine, wherein the color fading or damage of colored fabric is due to contacting with chlorinated water.

The present invention will now be described with reference to examples and comparative exam ples, which are not intended to limit the present invention. Examples:

Materials

EM PA 132: Direct black 22 on cotton (commercially available from Swissatest, Swissatest Test- materialien AG, Switzerland)

EM PA 133: C.l. Direct Blue 71 on cotton (commercially available from Swissatest, Swissatest Testmaterialien AG, Switzerland)

EMPA 134: Direct orange 39 on cotton (commercially available from Swissatest, Swissatest Test materialien AG, Switzerland)

Polyethyleneimine (PEI Mw = 800 g/mol): Sold by BASF Polyethyleneimine (PEI Mw= 1300 g/mol), Sold by BASF Palm kernel oil sold from Shanghai Jinyang Co., Ltd

Preparation of hvdrophobicallv modified polvethyleneimines (Chlorine resistance polymers)

Polymer 1: 120 g of polyethyleneimine (Mw=800 g/mol) and 20.3 g of hexanoic acid were mixed and purged with nitrogen flow. The mixture was heated to 150°C and stirred at 150 rpm. The reaction was performed for 6h and the product was obtained as a yellow liquid. The fraction of hydrocarbon radicals is 14.4% based on the weight of polyethyleneimine.

Polymer 2: 90 g of polyethyleneimine (Mw=800 g/mol) and 29.9 g of myristic acid were mixed and purged with nitrogen flow. The mixture was heated to 150°C and stirred at 150 rpm. The reaction was performed for 6h and the product was obtained as a yellow liquid. The fraction of hydrocarbon radicals is 30.7% based on the weight of polyethyleneimine.

Polymer 3: 80 g of polyethyleneimine (Mw=800 g/mol) and 33.1 g of stearic acid were mixed and purged with nitrogen flow. The mixture was heated to 150°C and stirred at 150 rpm. The reaction was performed for 6h and the product was obtained as a yellowish paste. The fraction of hydro carbon radicals is 38.9% based on the weight of polyethyleneimine. Polymer 4: 900 g of polyethyleneimine (M_w=800 g/mol) and 297 g of palm kernel oil were mixed and purged with nitrogen flow. The mixture was heated to 90°C and stirred at 150 rpm. The reac tion was performed for 6h and the product was obtained as a yellow liquid. The fraction of hydro carbon radicals is 28.7% based on the weight of polyethyleneimine.

Polymer 5: 75 g of polyethyleneimine (Mw = 1300 g/mol) and 20.96 g of lauric acid were mixed and purged with nitrogen flow. The mixture was heated to 150 °C under stirring at 150 rpm. The reaction was performed for 6h and the product was obtained as yellow liquid. The fraction of hydrocarbon radicals is 25.6% based on the weight of polyethyleneimine.

Test of chlorine resistance performance during washing

The detergent formulations A & B (Table 1) were prepared by first preparing a premix under stir ring at 40 °C, containing surfactants, solvents, fatty acid, citric acid and NaOH and water up to 90%. Subsequently the pH was adjusted to pH=8.5 using NaOH. The final formulations were then prepared by mixing 90% of the pre-mix, 0.5 wt.% of the chlorine resistance polymer and water to 100 % at room temperature under stirring.

Table 1: The liquid detergent formulation

AEO: Ethoxylated C12/C14 fatty alcohol (7EO), sold by BASF AES: Sodium C12/C14 ether sulfate + 2 EO, sold by BASF LAS: Sodium-n-alkyl-(C10-C13) benzene sulfonate, sold by BASF Soap: Distilled Coconut Fatty Acid (DC-1218), Wilmar Oleo (Lianyungang) Co., Ltd Test method:

Selected colored fabric (50 g fabric) was washed using the detergent formulations A & B at 25°C or 40°C respectively. The washing liquor (1 kg water) contains 3 mg/L of sodium hypochlorite. The washing process was repeated for 3 times; each washing cycle includes 1 main wash phase and 2 rinse phases. After the washing cycle, the fabric was rinsed, spun and dried. The chlorine re sistance effect was tested and measured after one cycle or three cycles. The washing conditions are given in Table 2. The test results for chlorine resistance effect are listed in Table 3, Table 4 and Table 5.

Table 2: Washing conditions

Evaluation method

In order to determine the chlorine resistance effect, the fabrics were instrumentally assessed with a Datacolor reflection spectrometer Model Type ELREPHO before and after washing. From the reflection data reading L*, a*, b*, Y were derived and further expressed in DE value. For testing the variation in color, DE is adopted as conventionally used in the art. DE is calculated as CIE 1976 color difference according to DIN EN ISO 11664-4 (June 2012) in accordance with following equation: DE = (AL*²+Aa*²+Ab*²)^1/2 in which

DI- — L washed ^— I— *initial ,

D3 — 3 washed ^— 3*initial, and Ab — b washed ^— b*initial

The values L^* initial, a* mtiai, and b* mtiai were measured on the test fabric before washing. The values L^* _washed, a^* _washed, and b^* _washed were measured on the test fabric after washing. Standard colorimet ric measurement was used to obtain L*, a*, and b* values.

The higher absolute values DE are observed for the color fading fabrics in comparison to the initial lightness before the test, the higher color loss is found.

Table 3: Test Results with formulation A (after one washing cycle)

*Blank: The detergent formulation without chlorine resistance polymer *Colored fabric was washed at 25°C.

Table 4: Test Results with formulation A (after three washing cycle)

*Blank: The detergent formulation without chlorine resistance polymer

Colored fabric EM PA 132 was washed at 40°C; Colored fabric EM PA 133 was washed at 25°C. Table 5: Test results with formulation B

*Blank: The detergent formulation without chlorine resistance polymer

Colored fabric was washed at 25°C The test results shown in Table 3, 4 & 5 illustrate that use of the hydrophobically modified poly- alkyleneimine (Polymers 1 to 5) in washing process can make colored fabric be resistant to chlo rinated water, so that the color fading was inhibited.

Test of chlorine resistance performance after washing

Selected colored fabric (50g fabric) was washed (1kg water) using a liquid detergent formulation A (shown in Table 1) at 25°C or 40°C with the addition of the chlorine resistance polymer. After the washing cycle, the fabrics were rinsed, spun and dried. The washed/treated fabric then was soaked into water containing 3 mg/L of sodium hypochlorite for 30 min. These above washing- soaking cycles were repeated for 3-5 cycles. The chlorine resistance effect was tested and meas ured after 3 cycles and 5 cycles.

The washing conditions are given in Table 6. The test results for chlorine resistance effect are listed in Table 7 & Table 8.

Table 6

Table 7: Test Results with formulation A

*Blank: The detergent formulation without chlorine resistance po ymer

*Colored fabric EM PA 132 was washed at 40°C; Colored fabric EM PA 133 &134 were washed at 25°C.

Table 8: Test result with formulation A

*Blank: The detergent formulation without chlorine resistance polymer *Colored fabric was washed at 25°C. The test results shown in Table 7 & 8 illustrate that use of the hydrophobically modified poly- alkyleneimine (Polymers 1 to 4) in washing process can provide chlorine resistance effect to col ored fabric, so that the color fading was inhibited when the washed colored fabric is contacted with chlorinated water after the washing process.

Claims

1. A method of imparting chlorine resistance effect to a colored fabric in a washing process, which comprises a step of contacting a colored fabric with a wash liquor which contains at least one hydrophobically modified polyalkyleneimine; wherein the colored fabric is contacted with chlorinated water during or after the washing process; wherein the hydrophobically modified polyalkyleneimine comprises a polyalkyleneimine backbone having a weight-average molecular weight greater than or equal to 200 g/mol and less than 2000 g/mol, preferably greater than or equal to 300 g/mol and less than 1500 g/mol, more preferably greater than or equal to 500 g/mol and less than 1000 g/mol; and hydrophobic moieties which are covalently attached to the backbone of polyalkyleneimine.

2. The method according to claim 1, wherein the fraction of hydrophobic moieties, based on the total weight of the hydrophobically modified polyalkyleneimine, constitutes 5 to 60 %, preferably 10 to 50%, more preferably 10 to 40% by weight.

3. The method according to claim 1 or 2, wherein from 2 to 25 mol %, preferably from 5 to 20 mol% of the nitrogen atoms of the polyalkyleneimine carry an aliphatic, saturated or unsaturated hydro- phobic moiety.

4. The method according to claims 1 to 3, wherein the hydrophobic moieties are present in the form of C4-C30 alkyl, C4-C30 alkyl carbonyl, C4-C30 alkenyl, C4-C30 alkenyl carbonyl, C4-C30 alkadienyl, C4-C30 alkadienyl carbonyl and/or hydroxy-C4-C3o alkyl groups, preferably in the form of C6-C18 alkyl, C6-C18 alkyl carbonyl, C6-C18 alkenyl, C6-C18 alkenyl carbonyl, C6-C18 alkadienyl, C6-C18 alkadienyl carbonyl and/or hydroxy-C6-Cis alkyl groups.

5. The method according to claims 1 to 4, wherein the hydrophobically modified polyalkyleneimine has a weight-average molecular weight in the range of from 300 to 5000 g/mol, preferably 500 to 3000 g/mol, more preferably 800 to 2000 g/mol.

6. The method according to claims 1 to 5, wherein the hydrophobically modified polyalkyleneimine in the polyalkyleneimine backbone is branched.

7. The method according to claims 1 to 6, wherein the hydrophobically modified polyalkyleneimines are obtained by a process which comprises the reaction of an unmodified polyalkyleneimine with a hydrophobicizing agent.

8. The method according to claims 1 to 7, wherein the hydrophobicizing agent is selected from the group consisting of linear or branched carboxylic acids having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms; natural oils, linear or branched alkyl halides having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms; alkyl epoxides having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms; alkyl ketene dimers having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms; cyclic dicarboxylic acid anhydrides having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms; alkyl isocyanates having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms; chloroformic acid esters of linear or branched alkanols or alkenols having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms; and linear or branched aliphatic aldehydes having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms.

9. The method according to claims 1 to 8, wherein the hydrophobically modified polyalkyleneimine is hydrophobically modified polyethyleneimine, hydrophobically modified polypropyleneimine or hydrophobically modified polybutyleneimine.

10. The method according to claims 1 to 9, wherein the colored fabric is non-synthetic fabric, more preferably cotton.

11. The method according to claim 1 to 10, wherein the chlorinated water comprises alkali metal or alkaline earth metal hypochlorite.

12. A method for inhibiting or minimizing color fading or damage of a colored fabric, which com prises applying to the colored fabric a wash liquor comprising the hydrophobically modified poly alkyleneimine as defined according to claims 1 to 9, wherein the color fading or damage of colored fabric is due to contacting with chlorinated water.

13. Use of hydrophobically modified polyalkyleneimine as defined according to claims 1 to 9 as chlorine resistant agent in a laundry washing process.