JP2023502217A - Fabric care composition containing hydrophobically modified polyalkyleneimine and biocide - Google Patents

Abstract

The present invention relates to fabric care compositions comprising at least one hydrophobically modified polyalkyleneimine as dye-fixing polymer and a biocide such as 4,4'-dichloro-2-hydroxydiphenyl ether. The present invention further relates to a method of providing improved color care benefits during washing or treating colored fabrics comprising the use of a hydrophobically modified polyalkyleneimine as a dye-fixing polymer. [Selection figure] None

Description

The present invention relates to hydrophobically modified polyalkyleneimines as dye-fixing polymers in combination with biocides in fabric care formulations. The present invention also relates to a method for color fixation effects when washing colored fabrics by using dye fixation polymers.

A known problem in cleaning and/or treating colored fabrics is the fading of the fabric's appearance, due at least in part to loss of color shade intensity, fidelity and color definition. Such color loss problems are exacerbated in the laundry process after several wash cycles, especially for dark colors such as black, red, blue and green.

If the color fixation of the colored fabric is poor, i.e. bleeds, during the washing process, not only does the colored fabric quickly fade, but as a result of the relatively high dye concentration in the washing liquor, the washing Dyeing of the colored or white fabric may also occur.

Several mechanisms of color loss have been postulated to solve the problem of color bleeding and fading, and various means have been proposed to prevent or reduce the extent of color loss or migration. . Dye fixatives and dye transfer inhibitors designed to improve the appearance of colored fabrics by minimizing dye loss and migration from the fabric due to washing or handling are well known. US Patent Application Publication No. 2010/0017973 discloses dye transfer inhibitors that can prevent color transfer during the laundering process. However, bleeding and fading of colored fabrics cannot be prevented. US Patent Application Publication No. 2007/0277327 discloses detergents and cleaning agents containing polyamines/polyimines or their derivatives as dye fixatives, which can be used in combination with soil release polymers. can. However, the use of most dye fixatives in liquid laundry detergent formulations actually suffers from the incompatibility of the anionic surfactant with the dye fixative compound causing flocculation, precipitation or phase separation of the compound. Due to the lack of , one is limited to formulations without any anionic surfactant or with a very low content of anionic surfactant.

In recent years there has been a continuing increase in demand for laundry formulations containing dye fixatives and biocides that can improve color retention and exhibit excellent compatibility with detersive surfactants.

It is therefore an object of the present invention to help effectively lock dyes through the laundry wash and/or treatment process while exhibiting better and broader compatibility with laundry formulations and providing antimicrobial efficacy. It is another object of the present invention to provide a dye-fixing polymer in combination with a biocide.

In one aspect, the present invention comprises, as component (a), a polyalkyleneimine backbone having a weight average molecular weight of 200 g/mol or more and less than 1000 g/mol and a hydrophobic moiety covalently bound to the polyalkyleneimine backbone. A fabric care composition comprising at least one hydrophobically modified polyalkyleneimine is of interest. component (b) is a biocide selected from the group consisting of 4,4'-dichloro-2-hydroxydiphenyl ether, 2-phenoxyethanol, glutaraldehyde, 2-bromo-2-nitropropane-1,3-diol; Especially the biocide 4,4'-dichloro-2-hydroxydiphenyl ether.

Preferably, the unmodified polyalkyleneimine backbone can be polyethyleneimine, polypropyleneimine or polybutyleneimine. Preferably, said unmodified polyalkyleneimine has a weight average molecular weight of 300 g/mol to less than 1000 g/mol, more preferably 500 g/mol to less than 1000 g/mol.

In a further aspect, the hydrophobically modified polyalkyleneimine is obtained by a process comprising reacting an unmodified polyalkyleneimine with a hydrophobicizing agent.

In a still further aspect, the invention provides a fabric care composition comprising a hydrophobically modified polyalkyleneimine (a), the biocide (b), and at least one nonionic, anionic and/or cationic surfactant. offer things.

In another aspect, the present invention provides a method of providing improved color care benefits during washing and/or treatment of colored fabrics comprising a wash solution containing a hydrophobically modified polyalkyleneimine and a biocide and a coloring agent. A method is provided that includes the step of contacting a fabric.

In yet another aspect, the present invention provides hydrophobically modified polyalkyleneimines such as 4,4'-dichloro-2-hydroxydiphenyl ether, 2-phenoxyethanol, glutaraldehyde, 2-bromo-2-nitropropane-1,3-diol. The use of a fabric care composition comprising in combination with a biocide selected from the group consisting of washing and/or treating colored fabrics, especially when containing 4,4'-dichloro-2-hydroxydiphenyl ether Use to enhance mid-color care benefits while also providing anti-microbial benefits to fabrics during and/or washed.

A further advantage is the good stabilization and Protection.

Unexpectedly, the combination of the present hydrophobically modified polyalkyleneimine and 4,4'-dichloro-2-hydroxydiphenyl ether according to the invention yields satisfactory color fastness effects when formulated into fabric care compositions. , exhibit good antimicrobial activity and excellent compatibility, thereby making it possible to achieve the objectives outlined above. Excellent compatibility with fabric care products is also observed when the hydrophobically modified polyalkyleneimines are combined with 2-phenoxyethanol, glutaraldehyde and/or 2-bromo-2-nitropropane-1,3-diol.

Throughout the specification, including the claims, the terms "comprising one" or "comprising a" are unspecified otherwise. To the extent that the term "comprising at least one" is to be understood synonymously, "between" is to be understood to include endpoints.

The terms "a", "an" and "the" refer to one (1) or two (2) or more of the articles (i.e. at least one (1) )) is used to refer to the grammatical object of

The term "and/or" includes the meaning of "and", "or" and also all other possible combinations of the elements connected to this term.

In specifying any range of concentrations, weight ratios or amounts, it should be noted that the upper limit of any particular concentration, weight ratio or amount can be associated with the lower limit of any particular concentration, weight ratio or amount, respectively. is.

As used herein, the term "fabric care" is the broadest term referring to compositions of the present invention that improve the appearance or wear properties of fabrics, especially garments. For the purposes of the present invention, fabric care compositions are divided into several categories, especially laundry detergent compositions, fabric appearance, each of which is typically characterized by the presence or absence of ingredients. For example, a "laundry detergent composition" should include one or more detersive surfactants, while a "fabric softener composition" should include one or more cationic quaternary ammonium compounds. is required. The term "fabric care" can refer to laundry detergent compositions and fabric conditioning compositions.

As used herein, the term "hydrophobic modified polyalkyleneimine" refers to polyalkyleneimine having hydrophobic groups chemically attached to the unmodified polyalkyleneimine backbone.

As used herein, the term "unmodified or unmodified" refers to polymeric substrates that have not been modified or functionalized.

As used herein, the term "hydrocarbon group" includes a carbon skeleton containing one or more hydrogen atoms, optionally substituted with one or more heteroatoms in or on the carbon skeleton. , refers to any linear, branched, cyclic, acyclic, heterocyclic, saturated or unsaturated chain.

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

As used herein, the term "alkyl" refers to a saturated hydrocarbon group which may be linear, branched or cyclic, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t -means butyl, pentyl, n-hexyl, cyclohexyl and the like.

As used herein, the term "hydroxyalkyl" means an alkyl group, more typically an alkyl group substituted with a hydroxyl group, such as hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxydecyl.

As used herein, the term "alkylene" includes, but is not limited to, methylene, polymethylene and alkyl-substituted polymethylene groups, divalent saturated acyclic hydrocarbon groups such as dimethylene, tetramethylene and 2-methyltrimethylene. and so on.

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

As used herein, the term "alkenylcarbonyl" refers to a -C(=O)R group, where R is optionally substituted alkenyl.

The present invention provides a polyalkyleneimine skeleton having a weight average molecular weight of 200 g/mol or more and less than 1000 g/mol, preferably 300 g/mol or more and less than 1000 g/mol, more preferably 500 g/mol or more and less than 1000 g/mol, and a polyalkyleneimine. Provided is a fabric care composition comprising at least one hydrophobically modified polyalkyleneimine comprising a hydrophobic moiety covalently attached to a backbone.

Hydrophobic modified polyalkyleneimines are those in which the hydrogen atoms of the primary and secondary amino groups are linear or branched aliphatic saturated or unsaturated hydrocarbon groups such as alkyls, alkenyls, alkadienyls or hydroxyalkyls. It should be understood to mean polyalkyleneimines which are partially or completely substituted by groups. Hydrocarbon groups generally have 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 8 to 16 carbon atoms.

Hydrophobic modified polyalkyleneimine can be obtained by a method comprising reacting an unmodified polyalkyleneimine with a hydrophobizing agent. Depending on the hydrophobizing agent used in each case, the hydrocarbon group is attached directly to the nitrogen atom of the polyalkyleneimine or via a functional group, for example via a carbonyl group (*-C(=O)- ^# ), Via an oxycarbonyl group (*-OC(=O)- ^# ), via an aminocarbonyl group (*-NH-C(=O)- ^# ), a carbonyloxy hydroxylpropyl group (*-C(=O )-O-CH ₂ -CH(OH)-CH ₂ - ^# ), via a 2-oxycarbonylethylenecarbonyl group (*-CH(COOH)-CH ₂ -CO- ^# ) or formula *- may be linked through the group CH2- ₍ C=O)-CH-(C=O)- ^# (where * represents a bond to a hydrocarbon group and ^# represents a polyalkylene representing the bond to the nitrogen atom of the imine). The hydrocarbon group can also form an aldimine or ketimine group with the nitrogen of the polyalkyleneimine or be attached to the two nitrogen atoms of the polyalkyleneimine through the carbon atoms of the cyclic amidine group.

Preferably, the hydrophobically modified polyalkyleneimine has a hydrocarbon group attached directly or through a carbonyl group to one nitrogen atom of the polyalkyleneimine. The latter is particularly preferred. Preferably the hydrocarbon group is linear, more preferably the hydrocarbon group is saturated.

According to any one of the embodiments of the present invention, the hydrocarbon groups in the preferred hydrophobically modified polyalkyleneimines are C ₄ -C ₃₀ -alkyl, C ₄ -C ₃₀ -alkylcarbonyl, C ₄ -C ₃₀ - in the form of alkenyl, C ₄ -C ₃₀ -alkenylcarbonyl, C ₄ -C ₃₀ -alkadienyl, C ₄ -C ₃₀ -alkadienylcarbonyl and/or hydroxy-C ₄ -C ₃₀ -alkyl radicals, in particular C ₆ - C ₁₈ -alkyl, C ₆ -C ₁₈ -alkylcarbonyl, C ₆ -C ₁₈ -alkenyl, C ₆ -C ₁₈ -alkenylcarbonyl, C ₆ -C ₁₈ -alkadienyl, C ₆ -C ₁₈ -alkadienylcarbonyl and or in the form of hydroxy-C6 _{- C18} -alkyl groups, particularly preferably C8 _- C16-alkyl, C8- _C16 -alkylcarbonyl, C8 _{- C16 -} alkenyl, _{C8 - C16-} are present in the form of alkenylcarbonyl, C ₈ -C ₁₆ -alkadienyl, C ₈ -C ₁₆ -alkadienylcarbonyl and/or hydroxy-C ₈ -C ₁₆ -alkyl groups, the alkyl, hydroxy-alkyl, Alkenyl and alkadienyl groups are preferably linear.

In some preferred embodiments, the hydrocarbon group is in the form of a C ₄ -C ₃₀ -alkylcarbonyl or C ₄ -C ₃₀ -alkenylcarbonyl group, especially C ₆ -C ₁₈ -alkylcarbonyl or C ₆ -C ₁₈ - _In the form of alkenylcarbonyl groups, more particularly in the form of C8 _- C16-alkylcarbonyl or C8 _{- C16} -alkenylcarbonyl groups, the alkyl and alkenyl groups of said groups are preferably straight-chain. .

According to any one of the embodiments of the present invention about 2-25 mol %, especially 5-20 mol %, more especially 6-15 mol % of the nitrogen atoms of the hydrophobically modified polyalkyleneimine have hydrocarbon groups. Correspondingly, the fraction of hydrocarbon groups preferably constitutes 5-60% by weight, especially 10-50% by weight, especially 10-35% by weight, based on the total weight of the hydrophobically modified polyalkyleneimine. do.

The hydrophobically modified polyalkyleneimines used according to the invention can be linear or branched. In particular, branching of branched polyalkyleneimines can occur at the nitrogen portion thereof. Linear polyalkyleneimines are composed only of repeating units of formula A, and branched polyalkyleneimines are composed of repeating units of formula B in addition to linear repeating units:

(式中、QはC₂～C₈アルキレンであり、好ましくはエチレン、プロピレン又はブチレンである)
による第三級窒素原子を有する。

(Where Q is _C2 - _C8 alkylene, preferably ethylene, propylene or butylene)
with a tertiary nitrogen atom.

Branched, hydrophobically-modified polyalkyleneimines, especially branched, hydrophobically-modified polyethyleneimines, based on their underlying polyalkyleneimine, on average at least one per polyalkyleneimine molecule , preferably at least 5 or at least 10 branching points according to formula B are preferred. In particular, at least 5%, especially at least 10%, particularly preferably at least 15%, eg 5-40%, especially 15-35%, of the nitrogen atoms of the parent polyalkyleneimine are tertiary nitrogen atoms. Especially in the case of a high degree of branching, i.e. at least 10%, especially 15%, such as 10-40%, especially 15-35%, of the nitrogen atoms of the parent polyalkylimine are tertiary nitrogen atoms. Alkyleneimines have structures similar to core-shell structures, where the polyalkyleneimine moiety forms the core and the hydrophobic groups form the shell.

According to any one of the embodiments of the invention, the hydrophobically modified polyalkyleneimine may exist in uncrosslinked or crosslinked form. Preferably, the hydrophobically modified polyalkyleneimine is non-crosslinked. According to any one of the embodiments of the present invention, the hydrophobically modified polyalkyleneimine is in the range of 300g/mol to 5000g/mol, preferably 500 to 3000g/mol, more preferably 800g/mol to 2000g/mol. has a weight average molecular weight of

The hydrophobically modified polyalkyleneimines used according to the invention are partly known from the prior art or can be prepared in a manner analogous to the methods described below. Accordingly, one embodiment of the present invention is a method comprising reacting an unmodified polyalkyleneimine, particularly an unmodified branched polyalkyleneimine, particularly an unmodified branched polyethyleneimine, with a hydrophobizing agent. It relates to the use of hydrophobically modified polyalkyleneimines obtainable.

Examples of suitable hydrophobizing agents include, but are not limited to:
i) long-chain straight or branched carboxylic having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 8 to 16 carbon atoms in the alkyl or alkenyl group; Acids such as caprylic acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanic acid, arachidic 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 amide-forming derivatives thereof such as acid chlorides, esters or anhydrides of the carboxylic acids mentioned and mixtures thereof ,
ii) Natural oils, including vegetable, nut, seed, animal and marine oils, typically containing triglycerides, free fatty acids or combinations of triglycerides and free fatty acids. Examples of suitable natural vegetable oils are soybean oil, rapeseed oil, palm oil, corn oil, cottonseed oil, coconut oil, palm kernel oil and examples of suitable animal/marine oils are lard, fish oil, beef tallow oil, seal oil. and milk fats and those obtained by hydrogenation or transesterification of these oils and mixtures thereof,
iii) straight or branched chain having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 8 to 16 carbon atoms in the straight or branched alkyl group alkyl halides 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, more preferably 8 to 16 carbon atoms in the linear or branched alkyl group, such as hexade senyl 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, especially 8 to 16 carbon atoms in the linear or branched alkyl group, such as lauryl ketene, palmityl ketene, stearyl ketene and oleyl ketene dimers and mixtures thereof;
vi) cyclic dicarboxylic acid anhydrides having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, especially 8 to 16 carbon atoms in the linear or branched alkyl group, especially alkyl-substituted succinic anhydrides such as dodecenyl succinic anhydride, tetradecyl succinic anhydride, hexadecenyl succinic anhydride and mixtures thereof;
vii) alkyl isocyanates having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 8 to 16 carbon atoms in the linear or branched alkyl group, such as tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate and mixtures thereof,
viii) linear or branched alkanols or chloroformates of alkenols having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 8 to 16 carbon atoms and in total Dialkylketones having 4 to 30 carbon atoms, especially 6 to 18 carbon atoms, and mixtures thereof.
viii) a linear or branched aliphatic aldehyde having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, especially 8 to 16 carbon atoms and in total two alkyl groups Dialkyl ketones having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, especially 8 to 16 carbon atoms, and mixtures thereof.

According to any one of the embodiments of the present invention, the unmodified polyalkyleneimines forming the basis of the hydrophobically modified polyalkyleneimines are ethyleneimine (aziridine) and its higher homologues, propyleneimine (methylaziridine) and butylene. Homopolymers of imines (1,2-dimethylaziridine, 1,1-dimethylaziridine and 1-ethylaziridine), copolymers of ethyleneimine and its higher homologues and polyamidoamines or polyvinylamines with ethyleneimine and/or its higher homologues Including graft polymer with the body. Also suitable are the graft polymers of alkyleneimines described in WO 02/095122, eg graft polymers of ethyleneimine onto polyamidoamine or polyvinylamine. Such graft polymers generally have a weight fraction of alkyleneimine of at least 10% by weight, especially at least 30% by weight, such as 10 to 90% by weight, especially 10 to 85% by weight, based on the total weight of unmodified polyalkyleneimine. have. In some preferred embodiments, the unmodified polyalkyleneimine is a branched polyalkyleneimine, preferably a polyethyleneimine, particularly a branched polyethyleneimine, more particularly a homopolymer of ethyleneimine, even more particularly a branched ethyleneimine. It is a linear homopolymer.

According to any one of the embodiments of the invention, the unmodified polyalkyleneimine has a weight average molecular weight _Mw of ≧200 g/mol and <1000 g/mol. Preferably, the unmodified polyalkyleneimine has a weight average molecular weight M _w of 300 g/mol or more and less than 1000 g/mol. More preferably, the unmodified polyalkyleneimine has a weight average molecular weight _Mw of 500 g/mol or more and less than 1000 g/mol. Molecular weights given herein refer to molecular weights determined using gel permeation chromatography and measured in dilute aqueous solutions at 25° C., which correspond to weight average molecular weights.

The present invention also relates to the reaction of unmodified polyalkyleneimines with at least one hydrophobizing agent, which can be carried out according to methods known in the prior art. Reaction conditions will, of course, depend on the type and functionality of the polyalkyleneimine and hydrophobizing agent. In some embodiments, reactions may be performed with or without a solvent or diluent. Examples of suitable solvents for the reaction include, but are not limited to, hydrocarbons, especially aromatic hydrocarbons such as alkylbenzenes such as xylene, toluene, cumene, tert-butylbenzene, and the like. In some embodiments, the reaction may be conducted as a solventless reaction, which comprises at least (a) heating a mixture of the polyalkyleneimine and the hydrophobizing agent to a molten state, (b) stirring the mixture, reacting the polyalkyleneimine with an amount of hydrophobizing agent, wherein the amount of hydrophobizing agent used is from about 2 mol% to 25 mol%, especially from about 5 to 20 mol% of the nitrogen atoms of the polyalkyleneimine; More particularly it is sufficient to derivatize 6-15 mol %. In some preferred embodiments, the reaction between the unmodified polyalkyleneimine and the natural oil as hydrophobizing agent is (a) heating the mixture of the polyalkyleneimine and the natural oil to a molten state, (b) comprising stirring the mixture and reacting the polyalkyleneimine with an amount of natural oil under a stream of nitrogen at a temperature of 80-120°C, wherein the amount of hydrophobizing agent used is equal to the number of nitrogen atoms of the polyalkyleneimine. It is sufficient to derivatize about 2 mol % to 25 mol %, especially about 5 to 20 mol %, more particularly 6 to 15 mol %. In some embodiments, the hydrophobizing agent is used in an amount corresponding to the desired functionality, and it is possible to use an excess of hydrophobizing agent.

In some embodiments, the reaction can also be carried out in the presence of a catalyst that improves the reactivity of the hydrophobizing agent towards the polyalkyleneimine. The type of catalyst depends in a manner known per se on the type and reactivity of the hydrophobizing agent. The catalyst is usually a Lewis or Bronsted acid.

In some embodiments, carboxylic acids and carboxylic acid derivatives are used as hydrophobizing agents to advantageously remove low molecular weight products formed during the reaction, such as water, alcohols or hydrogen chloride, from the reaction mixture. It turns out. For example, when using carboxylic acids, the water formed is preferably removed from the reaction mixture by an entrainer or vacuum. Typical entrainers are hydrocarbons, especially alkylaromatic compounds such as toluene or xylene.

The hydrophobically modified polyalkyleneimines are generally water-soluble or water-dispersible and can be used in solid and/or liquid fabric care compositions. The fabric care compositions comprising hydrophobically modified polyalkyleneimines find use in a variety of fabric care products including, but not limited to, laundry detergents, post-rinse conditioners, pre-treatments, tumble dryer sheets, post-wash sprays, and the like. can be done.

The hydrophobically modified polyalkyleneimines of the present invention are particularly compatible with conventional detergent ingredients, especially liquid detergent formulations comprising anionic surfactants, nonionic surfactants and optionally cationic surfactants. Characterized by high compatibility. Solid/liquid fabric care compositions comprising hydrophobically modified polyalkyleneimines can be prepared by methods known in the prior art, wherein the hydrophobically modified polyalkyleneimines are used in powder or granular form or in liquid form. can be used, preferably in liquid form, ie in dissolved or dispersed form.

In some embodiments, the hydrophobically modified polyalkyleneimines can be used in detergent formulations including, for example, detersive surfactant systems containing predominantly nonionic surfactants. Preferably, the concentration of nonionic surfactant is 10% to 100%, preferably 20% to 100%, more preferably 30% by weight, based on the total amount of surfactants in the fabric care composition. ~100% by weight. In still some embodiments, the hydrophobically modified polyalkyleneimines are particularly useful in detergent formulations, which may include relatively high levels of anionic surfactant in the detersive surfactant system. Preferably, the concentration of the anionic surfactant is 10-100% by weight, preferably 20%-100% by weight, more preferably 30-100% by weight, based on the total amount of surfactants in the fabric care composition. be.

The fabric care compositions according to the invention are (as component b) the group consisting of 4,4'-dichloro-2-hydroxydiphenyl ether, 2-phenoxyethanol, glutaraldehyde, 2-bromo-2-nitropropane-1,3-diol and more particularly the biocide 4,4'-dichloro-2-hydroxydiphenyl ether (CAS: 3380-30-1), which is 30 wt% in 1,2-propylene glycol It is commercially available as a solution of 4,4'-dichloro-2-hydroxydiphenyl ether under the tradename Tinosan® HP 100 (BASF, Germany). The fabric care composition preferably contains the biocide 4,4'-dichloro-2-hydroxydiphenyl ether at a concentration of 0.001-3%, preferably 0.001-1%, more preferably 0.002-0.6% by weight of the composition. and preferred amounts of 2-phenoxyethanol, glutaraldehyde, 2-bromo-2-nitropropane-1,3-diol are further indicated below.

The solid composition further comprises at least one nonionic, cationic and/or anionic surfactant (component c). The total concentration of surfactants in the composition can be from 0.5% to 60% by weight, preferably from 5% to 40% by weight. Typical amounts of hydrophobically modified polyalkyleneimine used in the compositions of the invention range from 0.01% to 30%, preferably from 0.01% to 15%, more preferably from 0.05% to 5% by weight of the composition. %.

The liquid composition further comprises at least one nonionic, anionic and/or cationic surfactant (component c). The total concentration of surfactants in the composition can be from 0.5% to 80% by weight, preferably from 5% to 70% by weight. Typical amounts of hydrophobically modified polyalkyleneimine used in compositions of the invention range from 0.01% to 30%, preferably from 0.01% to 15%, more preferably from 0.05% to 5% by weight of the formulation. %.

Accordingly, a typical composition of the present invention is each by weight of the composition
(i) 0.01-30% of component (a), 0.001-1% of component (b), and 5-69% of component (c);
(ii) 0.01-20% of component (a), 0.001-1% of component (b), and 5-79% of component (c);
(iii) 0.05-5% of component (a), 0.005-1% of component (b), 5-40% of component (c), and up to 100% water and further components.
(iv) 0.05-5% of component (a), 0.005-1% of component (b), 40-80% of component (c), and up to 100% water and further components
(v) 0.05-5% of component (a), 0.005-1% of component (b), 5-40% of component (c), and up to 100% solid builders, solid fillers and further components can include

Depending on their intended use, the compositions are adapted to the type of fabrics to be cleaned/treated.

Surfactants used can be anionic, nonionic, amphoteric and cationic. It is also possible to use mixtures of said surfactants. Preferred laundry detergent formulations contain anionic and/or nonionic surfactants and mixtures thereof with other surfactants.

Suitable anionic surfactants are sulfates, sulfonates, carboxylates, phosphates and mixtures thereof. Suitable cations here are alkali metals, such as sodium or potassium, or alkaline earth metals, such as calcium or magnesium, and ammonium, substituted ammonium compounds, such as mono-, di- or triethanolammonium cations, and also is a mixture of

The following types of anionic surfactants are particularly preferred:
Sulfates of (fatty)alcohols having 8 to 22, preferably 10 to 18 carbon atoms, especially C ₉ C ₁₁ -alcohol sulfates, C ₁₂ -C ₁₄ -alcohol sulfates, C ₁₂ -C ₁₈ -alcohols Sulfates, Lauryl Sulfates, Cetyl Sulfates, Myristyl Sulfates, Palmitylsulfates, Stearyl Sulfates and Tallow Fatty Alcohol Sulfates; Sulfated Alkoxylated C8 _- C22-Alcohols ₍ Alkyl Ether Sulfates): This Type are prepared, for example, by first alkoxylating a C ₈ -C ₂₂ -, preferably C ₁₀ -C ₁₈ -alcohol, such as a fatty alcohol, and then sulfating the alkoxylation product. For alkoxylation, ethylene oxide is preferably used; linear C ₈ -C ₂₀ alkylbenzene sulfonates (LAS), preferably linear C ₉ -C ₁₃ -alkylbenzene sulfonates and alkyltoluene sulfonates; alkanesulfonates, especially C ₈ - _C24- , preferably C10- _{C18 -} alkanesulfonates; olefin sulfonates; fatty acid and fatty acid ester sulfonates; soaps such as Na and K salts of C8 _{- C24} -carboxylic acids and mixtures thereof.

Anionic surfactants are preferably added to the laundry formulation in salt form. Suitable salts here are, for example, alkali metal salts such as sodium, potassium and lithium salts and ammonium salts such as hydroxyethylammonium, di(hydroxyethyl)ammonium and tri(hydroxyethyl)ammonium salts.

Examples of suitable nonionic surfactants are the following compounds:
Alkoxylated C ₈ -C ₂₂ -alcohols such as fatty alcohol alkoxylates, oxoalcohol alkoxylates and Guerbet alcohol ethoxylates, alkoxylation can be carried out with ethylene oxide, propylene oxide and/or butylene oxide. Block copolymers of random copolymers may be present. Per mole of alcohol, they usually contain 2 to 50 mol, preferably 3 to 20 mol, of at least one alkylene oxide. A preferred alkylene oxide is ethylene oxide. The alcohol preferably has 10 to 18 carbon atoms; alkylphenol alkoxylates, especially alkylphenol ethoxylates, containing C ₆ to C ₁₄ -alkyl chains and 5 to 30 mol of alkylene oxide; C ₈ to C ₂₂ -, preferably C Alkyl polyglucosides containing ₁₀ -C ₁₈ -alkyl chains and generally 1 to 20, preferably 1.1 to 5 glucoside units; N-alkylglucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates, long-chain amine oxides , polyhydroxy(alkoxy) fatty acid amides, gemini surfactants and block copolymers of ethylene oxide, propylene oxide and/or butylene oxide; and mixtures thereof.

Examples of suitable cationic surfactants are the following compounds:
_{R1N ( CH3} ) ₃ ⁺ X- ^, _{R1R2N ( CH3} ) ⁺ _X- ^, _{R1R2R3N ( CH3} ^{) +} _X- ^or _{R1R2R3R4N +} Substituted or unsubstituted, linear or branched quaternary ammonium salts of the X ^-type . The R ₁ , R ₂ , R ₃ and R ₄ groups each independently preferably have a chain length of 8 to 24 carbon atoms, especially 10 to 18 carbon atoms, unsubstituted alkyl, about 1 to 4 hydroxy-alkyl, phenyl, _C2 - _C18 -alkeyl, C7 _{- C24} -aralkyl, _{( C2H4O} )xH, where _x is an integer from 1 to 3 ), alkyl groups containing one or more ester groups, or cyclic quaternary ammonium salts. X is a preferred anion.

Accordingly, the compositions of the present invention can be fabric softener compositions comprising one or more such cationic quaternary ammonium compounds as softening actives. Of particular interest are fabric-softening actives comprising ester-linked triethanolamine quaternary ammonium compounds, such as those described in EP-A-2838982. Commercially available examples of such actives are Stepantex™ UL85 from Stepan, Prapagen™ TQL from Clariant and Tetranyl™ AHT-1 from Kao, both diethanolammonium methylsulfate. -[hardened beef tallow ester]), AT-1 (di-[beef tallow ester] of triethanolammonium methyl sulfate) and L5/90 (di-[palm ester] of triethanolammonium methyl sulfate), both from Kao , and Rewoquat™ WE15 (a diester of triethanolammonium methylsulfate with fatty acyl residues derived from C10-C20 and C16-C18 unsaturated fatty acids) from Witco Corporation. Also, quaternary ammonium actives such as Stepantex VK90, Stepantex VT90, SP88 (from Stepan), Ceca Noramine, Prapagen TQ (from Clariant), Dehyquart AU-57 (from Cognis), Rewoquat WE18 (from Degussa), and Tetranyl L190 P, Tetranyl L190 SP and Tetranyl L190 S (all from Kao) are preferred. An aqueous softener composition comprising component (a), 4,4'-dichloro-2-hydroxydiphenyl ether as component (b), and 0.5 to 35% by weight of the total composition of the fabric softening active described above. is particularly preferred. Softener compositions typically contain 0.01 to 10% perfume by weight of the total composition.

Further preferred cationic surfactants are C7 _{- C25} -alkylamines; N,N-dimethyl-N-(hydroxy-C7 _{- C25} -alkyl)ammonium salts; mono- quaternized with alkylating agents; and di(C ₇ -C ₂₅ -alkyl)dimethylammonium compounds; ester quaternary ammonium salts, especially quaternary esterified mono-, di- and trialkanols esterified with C ₈ -C ₂₂ -carboxylic acids. amines; quaternary ammonium imidazolines and their derivatives.

Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates or amphoteric imidazolinium compounds. Among these preferred amphoteric surfactants are cocoamphocarboxypropionate, cocoamidocarboxylpropionic acid, cocoamphocarboxyglycinate (also called cocoamphodiacetate) and cocoamphoacetate. Further preferred amphoteric surfactants are alkyldimethylbetaines and alkyldipolyethoxybetaines in which the alkyl groups have from about 8 to about 22 carbon atoms, which may be linear or branched, preferably about It has 12 to about 18 carbon atoms.

Additional laundry ingredients that can be used in the present invention include inorganic and/or organic builders to reduce water hardness.

These builders can be present in fabric care formulations in weight percentages of from about 5% to about 80%. Inorganic builders are, for example, carbonates, sulfates and alumosilicates, including polyphosphates, pyrophosphates and glassy polymeric metaphosphates, phosphonates, silicates, bicarbonates and sesquicarbonates. alkali metal, ammonium and alkanolammonium salts of Examples of alumosilicate builders are crystalline and amorphous alumosilicates with ion-exchange properties, such as especially zeolites, various types of zeolites, especially zeolites A, X, B, P, MAP and HS. are preferred in their Na form or in forms in which Na is partially replaced by other cations such as Li, K, Ca, Mg or ammonium; examples of silicate builders are alkali metal silicates Salts, especially those having a _SiO2 : _Na2O ratio between 1.6:1 and 3.2:1 and phyllosilicates, amorphous silicates such as sodium metasilicate and amorphous disilicate. Examples of carbonate and bicarbonate builders are those that can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. A preferred example of a polyphosphate builder is pentasodium triphosphate. Organic builders are, for example, low molecular weight carboxylic acids such as citric acid, hydrophobically modified citric acids such as agaricic acid, malic acid, tartaric acid, gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid, oxydisuccinic acid, propane tricarboxylic acids, butanetetra-carboxylic acids, cyclopentanetetracarboxylic acids, alkyl- and alkenylsuccinic acids and aminopolycarboxylic acids such as nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, serine diacetic acid, isoserine diacetic acid, N -(2-Hydroxyethyl)iminoacetic acid, ethylenediaminedisuccinic acid and methyl- and ethylglycinediacetic acid or alkali metal salts thereof; oligomeric and polymeric carboxylic acids such as homopolymers of acrylic acid and aspartic acid, oligomaleic acid, maleic acid of acids with acrylic acid, methacrylic acid or C ₂ -C ₂₂ -olefins such as isobutene or long-chain α-olefins, vinyl C ₁ -C ₈ -alkyl ethers, vinyl acetate, vinyl propionate, C ₁ -C ₈ -alcohols Copolymers of (meth)acrylates and styrene; phosphonic acids such as 1-hydroxyethylene (1,1-diphosphonic acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid) and diethylenetriaminepenta(methylenephosphonic acid) ), etc., as well as their alkali metal salts.

Compositions of the present invention may also contain the following additional antimicrobial agents:
Benzylhemiformal Synonyms: (benzyloxy)methanol (CAS No. 14548-60-8),
(Ethylenedioxy)dimethanol Synonyms: Dascocide 9, (Ethylenedioxy)dimethanol (reaction product of ethylene glycol with paraformaldehyde (EGForm)) (CAS No. 3586-55-8),
α,α',α"-Trimethyl-1,3,5-triazine-1,3,5(2H,4H,6H)-triethanol Synonyms: tris(N-hydroxypropyl)hexahydrotriazine, hexahydro- 1,3-5-tris(2-hydroxypropyl)-s-triazine (HPT, CAS No. 25254-50-6),
2,2-dibromo-2-cyanoacetamide (DBNPA, CAS No. 10222-01-2),
2,2'-Dithiobis[N-methylbenzamide] (DTBMA, CAS No. 2527-58-4),
2-bromo-2-(bromomethyl)pentanedinitrile (DBDCB, CAS No. 35691-65-7),
2-Butanone, Peroxide Synonyms: 2-butanone-peroxide (CAS No. 1338-23-4),
2-Butyl-benzo[d]isothiazol-3-one (BBIT, CAS No. 4299-07-4),
2-methyl-2H-isothiazol-3-one (MIT, CAS No. 2682-20-4),
2-octyl-2H-isothiazol-3-one (OIT, CAS No. 26530-20-1),
5-chloro-2-methyl-2H-isothiazol-3-one (CIT, CMIT, CAS No. 26172-55-4),
of 5-chloro-2-methyl-2H-isothiazol-3-one (CMIT, EINECS 247-500-7) and 2-methyl-2H-isothiazol-3-one (MIT, EINECS 220-239-6) mixture (CMIT/MIT mixture, CAS number 55965-84-9),
1,2-benzisothiazol-3(2H)-one (BIT, CAS No. 2634-33-5),
3,3'-methylenebis[5-methyloxazolidine] (oxazolidine/MBO, CAS No. 66204-44-2),
4,4-dimethyloxazolidine (CAS No. 51200-87-4),
7a-ethyldihydro-1H,3H,5H-oxazolo[3,4-c]oxazole (EDHO, CAS No. 7747-35-5),
benzyl alcohol (CAS number 100-51-6),
biphenyl-2-ol (CAS number 90-43-7),
biphenyl-2-ol and its salts, o-phenylphenol, o-phenylphenol MEA, phenylphenol potassium, phenylphenol sodium,
2-biphenyl sodium (CAS No. 132-27-4),
cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantan chloride (cis CTAC, CAS No. 51229-78-8),
didecyldimethylammonium chloride (DDAC, CAS No. 68424-95-3 and CAS No. 7173-51-5),
dodecylguanidine monohydrochloride (CAS number 13590-97-1),
Ethanol (CAS No. 64-17-5),
n-propanol (1-propanol, CAS No. 71-23-8)
Hexa-2,4-dienoic acid (sorbic acid, CAS No. 110-44-1) and its salts such as calcium sorbate, sodium sorbate
(E,E)-potassium hexa-2,4-dienoate (potassium sorbate, CAS number 24634-61-5),
hydrogen peroxide (CAS number 7722-84-1),
lactic acid and its salts,
L-(+)-lactic acid (CAS number 79-33-4),
2-methyl-1,2-benzothiazol-3(2H)-one (MBIT, CAS No. 2527-66-4),
Methenamine 3-chloroallylochloride (CTAC, CAS No. 4080-31-3),
Monochloramine produced from ammonium carbamate and chlorine source
N,N'-methylenebismorpholine (MBM, CAS No. 5625-90-1),
N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine (diamine, CAS number 2372-82-9),
N-(trichloromethylthio)phthalimide (Folpet, CAS No. 133-07-3),
p-[(diiodomethyl)sulfonyl]toluene (CAS No. 20018-09-1),
peracetic acid (CAS number 79-21-0),
Polyhexamethylene biguanide hydrochloride (PHMB, CAS No. 1802181-67-4), Polyhexamethylene biguanide hydrochloride (PHMB, CAS No. 27083-27-8), such as poly(iminoimidocarbonyl) iminohexamethylene hydrochloride, poly (iminocarbonimidoyliminocarbonimidoylimino-1,6-hexanediyl), polyaminopropyl biguanide,
pyridine-2-thiol 1-oxide, sodium salt (pyrithione sodium, CAS No. 3811-73-2),
zinc pyrithione (zinc pyrithione, CAS No. 13463-41-7),
reaction mass of titanium dioxide and silver chloride, silver chloride (CAS No. 7783-90-6),
sodium azide (CAS No. 26628-22-8),
Tetrahydro-1,3,4,6-tetrakis(hydroxymethyl)imidazo[4,5-d]imidazole-2,5(1H,3H)-dione (TMAD, CAS No. 5395-50-6),
tetrakis(hydroxymethyl)phosphonium sulfate (2:1) (THPS, CAS No. 55566-30-8),
salts of benzoic acid, such as ammonium benzoate, calcium benzoate, magnesium benzoate, MEA benzoate, potassium benzoate,
esters of benzoic acid such as butyl benzoate, ethyl benzoate, isobutyl benzoate, isopropyl benzoate, methyl benzoate, phenyl benzoate, propyl benzoate,
benzoic acid and its sodium salt (CAS No. 65-85-0, CAS No. 532-32-1),
Propionic acid and its salts, such as ammonium propionate, calcium propionate, magnesium propionate, potassium propionate, sodium propionate,
Salicylic acid and its salts, such as calcium salicylate, magnesium salicylate, MEA salicylate, sodium salicylate, potassium salicylate, TEA salicylate,
inorganic sulfites and bisulfites such as sodium sulfite, ammonium sulfite, ammonium bisulfite, potassium sulfite, potassium bisulfite, sodium bisulfite, sodium metasulfite, potassium metasulfite, potassium metabisulfite,
Chlorobutanol (CAS No. 57-15-8),
butyl 4-hydroxybenzoate and salts thereof such as butylparaben, butylparaben sodium, butylparaben potassium,
propyl 4-hydroxybenzoate and its salts such as propylparaben, propylparaben sodium, propylparaben potassium,
isopropyl-4-hydroxybenzoic acid and its salts and esters,
isobutyl-4-hydroxybenzoic acid and its salts and esters,
benzyl-4-hydroxybenzoic acid and its salts and esters,
pentyl-4-hydroxybenzoic acid and its salts and esters,
4-hydroxybenzoic acid and its salts and esters, such as methylparaben, ethylparaben, ethylparaben potassium, paraben potassium, methylparaben potassium, methylparaben sodium, ethylparaben sodium, paraben sodium, paraben calcium, methylparaben calcium, ethylparaben calcium,
3-acetyl-6-methylpyran-2,4(3H)-dione and salts thereof such as dehydroacetic acid, sodium dehydroacetate (Cas Nos. 520-45-6, 4418-26-2, 16807-48-0),
3,3'-dibromo-4,4'-hexamethylenedioxydibenzamidine and its salts (including isethionate), such as dibromohexamidine isethionate (CAS No. 93856-83-8),
Thiomersal (CAS No. 54-64-8),
Phenylmercury salts (including borates) such as phenylmercuric acetate, phenylmercuric benzoate (CAS numbers 62-38-4 and 94-43-9),
Undec-10-enoic acid and salts thereof such as undecylenic acid, potassium undecylenate, sodium undecylenate, calcium undecylenate, MEA undecylenate, TEA undecylenate,
5-pyrimidineamines, 1,3-bis(2-ethylhexyl)hexahydro-5-methyl-, e.g. hexetidine (CAS No. 141-94-6),
1-(4-chlorophenyl)-3-(3,4-dichlorophenyl)ureas such as triclocarban (CAS No. 101-20-2),
chlorocresols, such as p-chloro-m-cresol (CAS No. 59-50-7),
Chloroxylenol (CAS No. 88-04-0, 1321-23-9),
N,N"-methylenebis[N'-[3-(hydroxymethyl)-2,5-dioxoimidazolidin-4-yl]urea] Synonyms: imidazolidinyl urea (CAS No. 39236-46-9),
Methenamine (CAS No. 100-97-0),
Methenamine 3-Chloroallylochloride Synonyms: Quaternium 15 (CAS No. 4080-31-3), 1-(4-Chlorophenoxy)-1-(imidazol-1-yl)-3,3-dimethylbutane-2 -On, Synonyms: Climbazole (CAS No. 38083-17-9),
1,3-bis(hydroxymethyl)-5,5-dimethylimidazolidine-2,4-dione Synonyms: DMDM Hydantoin (CAS No. 6440-58-0),
1-Hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2 pyridone and its monoethanolamine salts such as 1-hydroxy-4-methyl-6-(2,4,4-trimethylpentenyl )-2-pyridone, piroctone olamine (CAS numbers 50650-76-5, 68890-66-4),
2,2'-Methylenebis(6-bromo-4-chlorophenol) Synonyms: Bromochlorophene (CAS No. 15435-29-7),
4-Isopropyl-m-cresol Synonyms: o-cymen-5-ol (CAS No. 3228-02-2),
2-Benzyl-4-chlorophenol Synonyms: Chlorophane (CAS No. 120-32-1),
2-chloroacetamide (CAS No. 79-07-2),
N,N'-bis(4-chlorophenyl)-3,12-diimino-2,4,11,13-tetraazatetradecanediamidine and its digluconates, diacetates and dihydrochlorides, e.g. chlorhexidine, digluconic acid Chlorhexidine, Chlorhexidine diacetate, Chlorhexidine dihydrochloride (CAS Nos. 55-56-1, 56-95-1, 18472-51-0, 3697-42-5),
Alkyl (C12-C22) trimethylammonium bromides and chlorides such as behentrimonium chloride, cetrimonium bromide, cetrimonium chloride, laultrimonium bromide, laultrimonium chloride, steartrimonium bromide, steartrimonium chloride (CAS No. 17301- 53-0, 57-09-0, 112-02-7, 1119-94-4, 112-00-5, 1120-02-1, 112-03-8),
4,4-dimethyl-1,3-oxazolidine (CAS No. 51200-87-4),
N-(Hydroxymethyl)-N-(dihydroxymethyl-1,3-dioxo-2,5-imidazolidinyl-4)-N'-(hydroxymethyl)urea Synonyms: diazolidinyl urea (CAS No. 78491-02-8) ),
Benzenecarboximidamide, 4,4'-(1,6-hexanediylbis(oxy))bis- and its salts (including isethionate and p-hydroxybenzoate), e.g. hexamidine, hexamidine diisethionate, hexamidine midinparaben (CAS Nos. 3811-75-4, 659-40-5, 93841-83-9),
5-Ethyl-3,7-dioxa-1-azabicyclo[3.3.0]octane Synonyms: 7-ethylbicyclooxazolidine (CAS No. 7747-35-5),
3-(p-Chlorophenoxy)-propane-1,2-diol Synonyms: Chlorphenesin (CAS No. 104-29-0),
Sodium Hydroxymethylaminoacetate Synonyms: Sodium N-(Hydroxymethyl)glycinate, Sodium Hydroxymethylglycinate (CAS No. 70161-44-3),
Benzethonium, N,N-dimethyl-N-[2-[2-[4-(1,1,3,3,-tetramethylbutyl)phenoxy]ethoxy]ethyl]-, chloride Synonyms: benzethonium chloride CAS number 121-54-0),
Benzalkonium chloride, bromide and saccharin, such as benzalkonium chloride, benzalkonium bromide, benzalkonium saccharin (CAS No. 8001-54-5, 63449-41-2, 91080-29-4, 68989-01-5 , 68424-85-1, 68391-01-5, 61789-71-7, 85409-22-9),
Methanol, (Phenylmethoxy) Synonyms: Benzyl Hemiformal (CAS No. 14548-60-8),
3-Iodo-2-propynylbutylcarbamate (IPBC, CAS No. 55406-53-6)
Ethyl Lauroyl Arginine HCl (CAS No. 60372-77-2),
1,2,3-propanetricarboxylic acid, 2-hydroxy-, monohydrate and 1,2,3-propanetricarboxylic acid, 2-hydroxy-silver(1+) salt, monohydrate, INCI: citric acid (and) silver citrate,
Tetrahydro-3,5-dimethyl-1,3,5-thiadiazin-2-thione (alias: 3,5-dimethyl-1,3-5-thiadiazinane-2-thione, Protectol® DZ, Protectol ® DZ P, Dazomet, CAS No. 533-74-4),
2,4-dichlorobenzyl alcohol (CAS No. 1777-82-8, also known as dichlorobenzyl alcohol, 2,4-dichloro-benzenemethanol, (2,4-dichloro-phenyl)-methanol, DCBA, Protectol® DA),
1-propanol (CAS No. 71-23-8, also known as n-propanol, propan-1-ol, n-propyl alcohol, Protectol® NP S),
5-bromo-5-nitro-1,3-dioxane (CAS No. 30007-47-7, also known as 5-bromo-5-nitro-m-dioxane, Brondox®),
2-bromo-2-nitropropane-1,3-diol (CAS No. 52-51-7, also known as 2-bromo-2-nitro-1,3-propanediol, Bronopol®, Protectol® )BN, Myacide AS),
Glutaraldehyde (CAS No. 111-30-8, also known as 1-5-pentanedial, pentane-1,5-dial, glutaral, glutaredialdehyde, Protectol® GA, Protectol® GA 50, Myacide® GA),
Glyoxal (CAS No. 107-22-2, also known as ethanedial, oxalaldehyde, 1,2-ethanedial, Protectol® GL),
2,4,4'-trichloro-2'-hydroxydiphenyl ether (CAS No. 3380-34-5, also known as Triclosan, Irgasan® DP 300, Irgacare® MP, TCS),
2-phenoxyethanol (CAS No. 122-99-6, also known as phenoxyethanol, methylphenyl glycol, phenoxetol, ethylene glycol phenyl ether, ethylene glycol monophenyl ether, Protectol® PE),
Phenoxypropanol (CAS No. 770-35-4, CAS No. 4169-04-4, Propylene Glycol Phenyl Ether, Phenoxyisopropanol 1-phenoxy-2-propanol, 2-phenoxy-1-propanol),
Glucoprotamine (CAS No. 164907-72-6, chemical description: reaction product of glutamic acid and alkylpropylenediamine, also known as glucoprotamine 50),
Cyclohexyl hydroxyldiazenium-1-oxide, potassium salt (CAS No. 66603-10-9, also known as N-cyclohexyl-diazenium dioxide, potassium HDO, Xyligene, Protectol® KD),
Formic acid (CAS No. 64-18-6, also known as methanoic acid, Protectol® FM, Protectol® FM 75, Protectol® FM 85, Protectol® FM 99, Lutensol® )FM) and salts thereof such as sodium formate (CAS No. 141-53-7),
performic acid and its salts,
Inorganic silver complexes such as silver zeolites and silver glass compounds (e.g. Irgaguard® B5000, Irgaguard® B6000, Irgaguard® B7000) and others described in WO-A-99/18790, EP1041879B1 thing,
1,3,5-tris-(2-hydroxyethyl)-hexahydro-1,3,5-triazine (CAS No. 4719-04-4, also known as hexyhydrotriazine, tris(hydroethyl)-hexyhydrotriazine, hexyhydro-1,3-5-tris(2-hydroxyethyl)-s-triazine, 2,2',2"-(hexahydro-1,3,5-triazine-1,3,5-triyl)triethanol, Protectol® HT).

The composition may comprise at least one antimicrobial agent from the list above and/or combinations thereof.

This additional antimicrobial agent is added to the composition at a concentration of 0.001-10% relative to the total weight of the composition.

Preferably, the composition contains 2-phenoxyethanol at a concentration of 0.1-2% and/or bronopol at a concentration of 20 ppm-1000 ppm and/or glutaraldehyde at a concentration of 10 ppm-2000 ppm and/or formic acid (as acid or its salt). ) at a concentration of 0.05-0.50% (relative to the total weight of the composition in all cases).

In a preferred embodiment, the composition is an aqueous composition comprising 2-phenoxyethanol, bronopol, glutaraldehyde and/or formic acid (as acid or salt thereof), especially in the amounts indicated above. The invention therefore further provides a method of protecting an aqueous composition according to the invention against contamination or growth of microorganisms, comprising: 2-phenoxyethanol, glutaraldehyde, 2-bromo-2-nitropropane-1,3-diol and formic acid in acid form or as a salt thereof.

Fabric care compositions according to the present invention further comprise conventional adjuvants or other materials that serve to enhance the cleaning action, treat or care for the fabric material to be washed, or to modify the performance characteristics of the fabric care formulation. obtain.

Examples of suitable auxiliaries are the substances indicated in U.S. Pat. No. 3,936,537, such as enzymes, especially proteases, lipases, cellulases and amylases, mannanases; graying inhibitors, especially carboxymethylcellulose and grafting of vinyl acetate onto polyethylene glycol. polymers; bleaching agents, especially adducts of hydrogen peroxide to inorganic salts such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium carbonate perhydrate and percarboxylic acids such as phthalimidopercaproic acid; bleach activators, especially N,N,N',N'-tetraacetylethylenediamine, sodium p-nonanoyloxybenzenesulfonate and N-methylmorpholinium acetonitrile methylsulfate.

Other suitable auxiliaries are in particular enzyme stabilizers, foam boosters, foam limiters, anti-tarnish and/or corrosion inhibitors, suspending agents, dyes, fillers, optical brighteners, Further disinfectants, alkalis, hydrotropic compounds, antioxidants, perfumes, solvents, solubilizers, antiredeposition agents, dispersants, processing aids, softeners, antistatic aids and soil release polymers.

The fabric care composition according to the invention may further comprise a dye transfer inhibitor. Examples of these dye transfer inhibitors are polyamine N-oxides such as poly-(4-vinylpyridine N-oxide), copolymers of N-vinylpyrrolidone with N-vinylimidazole and optionally other monomers, chloroacetic acid Homopolymers and copolymers of 4-vinylpyridine reacted with A significant drawback of dye transfer inhibitors is that they not only strip from the fabric and bind to any dye present in the wash liquor, but also remove the dye from the fabric, thereby potentially accelerating the fading of colored fabrics being washed. There is also

Detergent ingredients are otherwise generally known. A detailed description can be found, for example, in WO-A-99/06524 and 99/04313, Liquid Detergents, Kuo-Yann Lai, ed., Surfactant Sci. Ser., Vol. 67, Marcel Decker, New York, 1997, pages 272-304 be able to.

The present invention also relates to a method of preparing a fabric care composition with improved color care properties comprising adding a hydrophobically modified polyalkyleneimine into the composition. Specifically, the present invention is a method of providing improved color care benefits during cleaning and/or treatment of colored fabrics comprising a cleaning solution containing a hydrophobically modified polyalkyleneimine and the biocide and a coloring agent. A method comprising contacting a fabric. More specifically, the improved color care effect is attributed to the color fixation effect.

Materials Polyethylenimine (Lupasol® FG marketed by BASF)
Palm kernel oil sold by Shanghai Jinyang Co., Ltd.
Tinosan® HP 100: 30 wt% solution of 4,4'-dichloro-2-hydroxydiphenyl ether (CAS: 3380-30-1) in 1,2-propylene glycol
EMPA 130: CI Direct Red 83.1 on cotton (commercially available from Swissastest, Swisstest Testmaterialien AG, Switzerland)
EMPA 133: CI Direct Blue 71 on cotton (commercially available from Switzerlandstest, Swissstest Testmaterialien AG, Switzerland)
Dyeing fabric:
JB 01: Mineral Oil with Carbon Black on Cotton, Chinese Standard for Detergency Test
JB 03: Sebum containing pigments on cotton, Chinese standard for detergency test Test white fabric:
WFK 10A: standard cotton (commercially available from wfk testgewebe GmbH, Germany),
WFK 20A: polyester/cotton (65%/35%) (commercially available from wfk testgewebe GmbH, Germany)
WFK 80A: cotton knit (commercially available from wfk testgewebe GmbH, Germany)
WFK Clay-Oil: Prepared using 20% WFK clay (code 05203, commercially available from wfk testgewebe GmbH, Germany) in water with 1.25% mineral oil and 3.75% peanut oil.

Determination of molecular weight The weight average molecular weight (M _w ) was determined on a gel using a TSKgel GMPW _XL column, an aqueous solution containing 1.8% acetic acid and 0.3 mol/L sodium acetate as the eluent, and polyethylene glycol salts as standards. It can be measured by permeation chromatography (GPC). Values outside this elution range are extrapolated.

EXAMPLES Unless otherwise specified, all percentages given are by weight of the total composition.

Preparation of hydrophobically modified polyethyleneimine of the invention (unmodified polyethyleneimine has M _w =800 g/mol)
Polymer 1: 120 g polyethyleneimine (M _w =800 g/mol) and 20.3 g hexanoic acid were mixed and purged with a stream of nitrogen. The mixture was heated to 150° C. and stirred. The reaction was carried out for 6 hours and the product was obtained as a yellow liquid. The fraction of hydrocarbon groups is 14.4% based on the weight of polyethyleneimine.

Polymer 2: 120 g polyethyleneimine (M _w =800 g/mol) and 25.1 g octanoic acid were mixed and purged with a stream of nitrogen. The mixture was heated to 150° C. and stirred. The reaction was carried out for 6 hours and the product was obtained as a yellow liquid. The fraction of hydrocarbon groups is 18.5% based on the weight of polyethyleneimine.

Polymer 3: 60 g polyethyleneimine (M _w =800 g/mol) and 17.5 g lauric acid were mixed and purged with a stream of nitrogen. The mixture was heated to 150° C. and stirred. The reaction was carried out for 6 hours and the product was obtained as a yellow liquid. The fraction of hydrocarbon groups is 26.6% 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 a stream of nitrogen. The mixture was heated to 90° C. and stirred. The reaction was carried out for 6 hours and the product was obtained as a yellow liquid. The fraction of hydrocarbon groups is 28.7% based on the weight of polyethyleneimine.

Polymer 5: 90 g polyethyleneimine (M _w =800 g/mol) and 29.9 g myristic acid were mixed and purged with a stream of nitrogen. The mixture was heated to 150° C. and stirred. The reaction was carried out for 6 hours and the product was obtained as a yellow liquid. The fraction of hydrocarbon groups is 30.7% based on the weight of polyethyleneimine.

Polymer 6: 90 g of polyethyleneimine (M _w =800 g/mol) and 33.5 g of palmitic acid were mixed and purged with a stream of nitrogen. The mixture was heated to 150° C. and stirred. The reaction was carried out for 6 hours and the product was obtained as a yellow paste. The fraction of hydrocarbon groups is 34.8% based on the weight of polyethyleneimine.

Polymer 7: 80 g polyethyleneimine (M _w =800 g/mol) and 33.1 g stearic acid were mixed and purged with a stream of nitrogen. The mixture was heated to 150° C. and stirred. The reaction was carried out for 6 hours and the product was obtained as a yellowish paste. The fraction of hydrocarbon groups is 38.9% based on the weight of polyethyleneimine.

Preparation of comparative hydrophobically modified polyethyleneimines (unmodified polyethyleneimines have M _w between 1300 and 5000 g/mol)
Comparative polymer 1 was obtained by reacting polyethyleneimine (M _w =2000 g/mol) and lauric acid under the conditions described in US 2010/0017973. The fraction of hydrocarbon groups is 25.6% based on the weight of polyethyleneimine.

Comparative polymer 2 was obtained by reacting polyethyleneimine (M _w =1300 g/mol) and lauric acid under the conditions described in US 2010/0017973. The fraction of hydrocarbon groups is 25.6% based on the weight of polyethyleneimine.

Comparative polymer 3 was obtained by reacting polyethyleneimine (M _w =5000 g/mol) and lauric acid under the conditions described in US 2010/0017973. The fraction of hydrocarbon groups is 28.0% based on the weight of polyethyleneimine.

Comparative polymer 4 was obtained by reacting polyethyleneimine (M _w =5000 g/mol) and palmitic acid under the conditions described in US 2010/0017973. The fraction of hydrocarbon groups is 36.5% based on the weight of polyethyleneimine.

Comparative polymer 5 was obtained by reacting polyethyleneimine (M _w =5000 g/mol) and palmitic acid under the conditions described in US 2010/0017973. The fraction of hydrocarbon groups is 115.8% based on the weight of polyethyleneimine.

Color Fixation Performance Test Selected colored fabrics (EMPA 130 and EMPA 133) were treated with a liquid detergent composition (the detergent formulation was prepared at a pH between 7.0 and 9.0) in the presence of a white cotton test fabric and are shown in Table 2) at 40°C and 60°C with the dye-fixing polymer of the present invention added and washed. After the wash cycle, the fabric is rinsed, dewatered and dried. To determine the color care effect, the fabrics are instrumentally evaluated using a Datacolor reflectance spectrometer model type ELREPHO before and after washing. L*, a*, b*, Y are obtained from the reflectance data readings and expressed as ΔE and ΔY values.

For the color fixation effect, ΔY is taken to characterize, which is calculated from the Y value of lightness according to the CIE 1931 XYZ color space according to the following formula:
ΔY=Y _washed - Y _initial

For the dye transfer inhibition effect, ΔE conventionally used in this technical field is adopted. ΔE is the following formula:
ΔE=(ΔL* ² +Δa* ² +Δb* ² ) ^1/2
(In the formula,
ΔL*=L* _washed- L* _initial ,
Δa*=a* _washed- a* _initial and Δb*=b* _washed- b* _initial )
Calculated as CIE 1976 color difference according to DIN EN ISO 11664-4 (June 2012).

The L* _initial , a* _initial and b* _initial values are measured on the test white fabric before washing. The L* _washed , a* _washed and b* _washed values are measured on the test white fabric after washing. L*, a* and b* values are obtained using standard colorimetric measurements.

The higher the absolute value of ΔY observed for the bleed fabric compared to the initial lightness before testing, the more bleed and less color fastness is observed.

The higher the ΔE value observed for the test white fabric compared to the initial whiteness before the test, the higher the dye transfer.

Any of the well-known methods of preparing detergent compositions can be used to make the detergent compositions of the present invention. Table 1 shows the washing conditions. Table 2 shows the detergent composition used. Tables 3 and 4 list the test results for color fastness and dye inhibition.

As demonstrated in Table 3, formulations containing the polymers of the invention unexpectedly show absolute _ΔY values of Lower, showing improved color fastness and less fading effect.

As shown in Table 4, formulations containing the polymers of the present invention have lower ΔE values compared to formulations without dye-fixing polymers, allowing good dye inhibition effects to be obtained. .

Further liquid detergent formulations were prepared by varying the concentration of inventive polymer 4 according to the composition in Table 2 and replacing 0.2% propylene glycol with 0.2% biocide Tinosan® HP 100 in some of the samples. to prepare. The color-fastening and dye-retaining efficacy of the formulations are tested under the same wash conditions listed in Table 1. Table 5 shows the results.

Formulations containing varying concentrations of the hydrophobically modified polyalkyleneimines of the present invention, with or without biocides, can provide satisfactory color fastness and dye transfer inhibition benefits.

Formulation compatibility test
A) 0.2% by weight of Inventive Polymer 4 and Comparative Polymer 5 were added to each aqueous surfactant solution or each formulation, respectively, during the conventional compounding process. Each formulation contained a total surfactant concentration of 30% by weight, but differed in the anionic/nonionic surfactant ratio. Each sample containing the polymer was held for one week and visually checked for its appearance. Results are listed in Table 6a.

Compatibility studies were conducted using formulations containing various surfactants, particularly Formulation A and Formulation C, which contained anionic surfactant as the major component in the surfactant blend.

As shown in Table 6a, formulations containing polymer 4 useful in the compositions of the invention have improved compatibility compared to formulations containing comparative polymer 5 (M _w >1000 g/mol), It makes it possible to obtain a stable and clear solution.

B) A liquid laundry detergent formulation is prepared containing 0.5% by weight of the polymer 4 of the invention and/or 0.3% of the biocide Tinosan® HP 100. Formulations are prepared by first preparing a premix containing surfactants, solvents, fatty acids, citric acid and NaOH and up to 90% water as shown in Table 6b. This premix is prepared by adding all components to the appropriate amount of water and stirring at room temperature. The pH is then set to pH=8.5 using NaOH. The final formulation is then prepared by stirring the following at room temperature: 90% of this premix, appropriate concentration of this polymer and/or Tinosan® HP 100 and water to 100%. For comparison purposes, a standard liquid detergent formulation is prepared containing neither the polymer of the present invention nor the biocide. For density determination, weigh 1.00 ml of Formulation D (taken with a calibrated Eppendorf pipette) on an analytical balance.

Absorbance is measured at room temperature using a Hach-Lange DR3900 spectrometer with a 1 inch glass cuvette. Deionized water is collected to measure baseline. Compositions and results are shown in Table 6b.

From the above table it is clear that the present hydrophobically modified polyalkyleneimine and Tinosan HP 100 can be combined without any instability or turbidity in liquid laundry formulations, with very low absorbance at 600 and 860 nm. , indicating that the formulation is not cloudy.

Formulation D of the invention shows good antimicrobial activity.

Detergency Test Detergent formulations containing polymers 3 and 4 of the invention are used to test detergency. Washing conditions are listed in Table 7. A detergent formulation is prepared according to the composition listed in Table 8.

Whiteness Test Method The whiteness of the test fabric is used to determine the stain. Differences in whiteness are determined by reflectance photometry using an Elrepho 2000 photometer (Datacolor) at a wavelength of 457 nm.

The higher the whiteness loss value observed for the white test fabric compared to the initial brightness prior to testing, the higher redeposition of soil to the fabric is observed.

Table 9 shows the results of the whiteness test.

A formulation containing the present hydrophobically modified polyalkyleneimine and the biocide 4,4'-dichloro-2-hydroxydiphenyl ether cleans/washes the dirt removed from fabrics by laundry detergents during the wash cycle. It can prevent redeposition on the washed fabric and provide a good antimicrobial effect.

Liquid Laundry Detergent Formulations The following formulations are prepared (all concentrations are given in % by weight of the formulation):

Formulations 1-4 shown above provide good detergency and antimicrobial activity on fabrics.

Solid Laundry Detergent Formulations The following formulations are prepared (all concentrations are given in % by weight of the formulation):

Formulations 5-7 shown above provide good detergency and antimicrobial activity on fabrics.

Claims (18)

a) at least one hydrophobically modified polyalkyleneimine comprising a polyalkyleneimine backbone having a weight average molecular weight of 200 g/mol or more and less than 1000 g/mol and a hydrophobic moiety covalently attached to the backbone of the polyalkyleneimine;
b) a fabric care composition comprising a biocide selected from the group consisting of 4,4'-dichloro-2-hydroxydiphenyl ether, 2-phenoxyethanol, glutaraldehyde, 2-bromo-2-nitropropane-1,3-diol thing. 2 to 25 mol%, preferably 5 to 20 mol% of the nitrogen atoms of the polyalkyleneimine have aliphatic saturated or unsaturated hydrophobic moieties,
Said hydrophobic moieties are preferably C ₄ -C ₃₀ alkyl, C ₄ -C ₃₀ alkylcarbonyl, C ₄ -C ₃₀ alkenyl, C ₄ -C ₃₀ alkenylcarbonyl, C ₄ -C ₃₀ alkadienyl, C ₄ -C ₃₀ alka from the group consisting of dienylcarbonyl, hydroxy- _C4 - _C30 alkyl, more preferably C6 _{- C18} alkyl, C6 _{- C18} alkylcarbonyl, C6 _{- C18} alkenyl, C6 _{- C18} alkenylcarbonyl, from the group consisting of C6 _{- C18} alkadienyl, C6 _{- C18} alkadienylcarbonyl, hydroxy-C6 _{- C18} alkyl, most preferably C8 _{- C16} alkyl, C8 _{- C16} alkylcarbonyl, _{C8 -C16} alkenyl, C8 _- C16 _{alkenylcarbonyl} , C8 _- C16 _alkadienyl , C8 _- C16 _{alkadienylcarbonyl} , hydroxy-C8 _{- C16} alkyl,
Fabric care composition according to claim 1. Claim 1 or 2, wherein the fraction of hydrophobic moieties constitutes 5-60% by weight, preferably 10-50% by weight, more preferably 10-30% by weight, based on the total weight of the hydrophobically modified polyalkyleneimine. The fabric care composition according to . 4,4'-dichloro-2-hydroxydiphenyl ether and, as a preservative, a further biocide selected from the group consisting of 2-phenoxyethanol, glutaraldehyde, 2-bromo-2-nitropropane-1,3-diol. , preferably comprising said further biocide in an amount ranging from 10 ppm to 2% by weight of the composition, more preferably from 0.1% to 2% of 2-phenoxyethanol and from 20 ppm to 1000 ppm of 2-phenoxyethanol, respectively, by weight of the composition. -bromo-2-nitropropane-1,3-diol and/or 10 ppm to 2000 ppm of glutaraldehyde. 5. Any one of claims 1 to 4, wherein the hydrophobically modified polyalkyleneimine has a weight average molecular weight in the range 300-5000 g/mol, preferably 500-3000 g/mol, more preferably 800-2000 g/mol. A fabric care composition as described. 6. Any one of claims 1 to 5, wherein the hydrophobically modified polyalkyleneimine has a polyalkyleneimine skeleton and has a weight average molecular weight of 300 g/mol or more and less than 1000 g/mol, more preferably 500 g/mol or more and less than 1000 g/mol. A fabric care composition according to claim 1. 7. A fabric care composition according to any one of claims 1 to 6, wherein the polyalkyleneimine backbone in the hydrophobically modified polyalkyleneimine is branched. 4,4'-dichloro-2-hydroxydiphenyl ether as biocide (b), each at a concentration of 0.001-3%, preferably 0.002-1%, more preferably 0.01-0.6% by weight of the composition 8. The fabric care composition according to any one of claims 1-7. The hydrophobically modified polyalkyleneimine is obtained by a process comprising reacting an unmodified polyalkyleneimine with a hydrophobizing agent, the hydrophobizing agent preferably being a linear or branched carboxylic acid, a natural oil, a linear or Branched alkyl halides, alkyl epoxides, alkyl ketene dimers, cyclic dicarboxylic acid anhydrides, alkyl isocyanates, linear or branched alkanols or chloroformates of alkenols and linear or branched fatty acids is selected from the group consisting of group aldehydes, further characterized in that the hydrophobizing agent has 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 8 to 16 carbon atoms, 9. A fabric care composition according to any one of claims 1-8. 10. A fabric care composition according to any one of the preceding claims, wherein the hydrophobically modified polyalkyleneimine is a hydrophobically modified polyethyleneimine, a hydrophobically modified polypropyleneimine or a hydrophobically modified polybutyleneimine. 11. A fabric care composition according to any one of the preceding claims, further comprising at least one nonionic, anionic and/or cationic surfactant. A fabric care composition according to any one of the preceding claims, wherein the hydrophobically modified polyalkyleneimine is used in a concentration of 0.01-30% by weight of the composition. 12. A fabric care composition according to claim 11, wherein the surfactant is 0.5-80% by weight, based on the total weight of the composition. 14. A fabric care composition according to any one of claims 1 to 13, for providing an antimicrobial effect on fabrics during washing and/or an improved color care effect during washing and/or treatment of fabrics. A method comprising contacting the fabric with a cleaning solution containing at least one hydrophobically modified polyalkyleneimine comprising a polyalkyleneimine backbone having a weight average molecular weight of 200 g/mol or more and less than 1000 g/mol and a hydrophobic moiety covalently attached to the backbone of the polyalkyleneimine, and optionally A method of protecting a fabric care composition against microbial contamination or growth comprising the biocide 4,4'-dichloro-2-hydroxydiphenyl ether, wherein said fabric care composition contains 2-phenoxyethanol, glutaraldehyde , 2-bromo-2-nitropropane-1,3-diol, preferably in an amount ranging from 10 ppm to 2% by weight of the composition, more preferably each by weight. 2-phenoxyethanol from 0.1% to 2%, 2-bromo-2-nitropropane-1,3-diol from 20 ppm to 1000 ppm and/or glutaraldehyde from 10 ppm to 2000 ppm of the composition in an amount of Method. 14. A method of washing fabrics or cleaning hard surfaces, comprising the step of treating the fabric or hard surface with a composition according to any one of claims 1-13. 14. A fabric care composition according to any one of claims 1 to 13, for enhancing the color care effect during washing and/or treatment of colored fabrics and/or for achieving an antimicrobial effect on fabrics during washing. Use of. 14. Use of a fabric care composition according to any one of claims 1 to 13 for preparing laundry detergents, fabric conditioners, pre-treatments, tumble dryer sheets and post-wash spray products.