..Thickened liquid textile or hard surface treatment agent"

The present invention relates to a thickened liquid textile or hard surface treatment agent comprising a cationic biocidal compound. The present invention also describes a method for cleaning a textile fabric or a hard surface.

The adhesion of microorganisms to surfaces is undesirable, particularly in the case of pathogenic microorganisms. Adhering microorganisms frequently lead to infections or to reinfection in humans, animals and plants.

Delicate textiles, such as e.g. silk or microfibers, are being processed increasingly frequently into clothing which can only be washed at 30 or 40°C. As a result, fungi such as e.g. the human pathogen Candida albicans are not being killed.

In addition to the lower washing temperature, however, it is also common today to use liquid detergents, which are generally free from bleaching agents. In a 60°C wash, as was previously the norm, almost all microbes were reliably destroyed on the one hand by the higher temperature and on the other hand by the bleaching agents contained in the universal detergents that were conventionally used.

Thus, as a result of changing washing behavior, textiles contaminated with viruses, bacteria, molds or yeasts cannot be rendered microbe-free to the required extent and so (re)infection may possibly take place on renewed contact of the consumer with the supposedly clean laundry.

Anti-microbially active compositions and their use in washing or cleaning agents are known in the prior art. These are, for example, textile treatment agents which contain one or more biocidal compounds and are added to the rinse cycle.

WO 2009/065823 A1 discloses a textile treatment agent comprising a biocidal compound, perfume and a nonionic surfactant.

The constant threat of bacterial contamination and the associated repercussions on health is also an important topic in the residential cleaning processes. Accordingly, anti-microbially active compositions are also used in the cleaning processes of kitchen and bath areas. Commonly used biocidal compounds are cationic and compositions containing cationic biocidal compounds have an acidic pH.

Thickened compositions are attributed to be more effective and concentrated by consumers. The problem with liquid textile or hard surface treatment agents comprising cationic biocidal compounds is that due to the acidic pH many commonly used thickeners such as acrylate thickeners cannot be used.

It is an object of the present invention to provide a thickened textile or hard surface treatment agent comprising a cationic biocidal compound.

This object is achieved by a liquid textile or hard surface treatment agent comprising:

A) at least one nonionic, amphiphilic associative thickener and

B) a cationic biocidal compound.

It has surprisingly been found that the use of a nonionic, amphiphilic associative thickener leads to a stable antimicrobial treatment agent comprising a cationic biocidal compound.

It is preferred that the associative thickener is a hydrophobically modified aminoplast/polyether copolymer.

In a preferred embodiment the hydrophobically modified aminoplast/polyether copolymer is selected from among polymers having general formula (I)

(OR), B

^• [Amp— - - ( AO) _x -J (I) wherein Amp denotes an aminoplast monomer or a radical of an aminoplast oligomer or polymer, AO denotes an alkylene oxide group, R denotes hydrogen, C C ₄ -alkyl or C C ₄ -acyl and x and y are numerals greater than 1.

The use of hydrophobically modified aminoplast/polyether copolymers as thickeners in compositions comprising cationic biocidal compounds leads clear and stable liquid textile or hard surface treatment agents having an aesthetically appealing viscosity to consumers. It is especially preferred that the assoziative thickener is selected from the group consisting of PEG-180/octoxynol 40/tetramethoxymethylglycouril (TMMG) copolymers, PEG-180/laureth- 50/tetramethoxymethylglycouril (TMMG) copolymers, PEG-18/dodoxynol-5/PEG-25

tristyrylphenol/tetramethoxymethylglycouril (TMMG) copolymers and mixtures thereof.

In another preferred embodiment the cationic biocidal compound is a quaternary ammonium compound. It is especially preferred that the quaternary ammonium compound is selected from group consisting of dialkyldimethylammonium halides, benzalkonium halides, substituted benzalkonium halides and mixtures thereof.

These cationic biocidal compounds act effectively against viruses, bacteria, moulds or yeasts.

In order to stabilize the treatment agent it may be preferred that the treatment agent additionally comprises a non-ionic surfactant.

The present application also relates to a method for cleaning a textile fabric or a hard surface, the method comprising contacting the fabric or surface with the inventive liquid textile or hard surface treatment agent.

The invention is described in greater detail below on the basis of examples, among other things.

In general, the present invention relates to a liquid textile or hard surface treatment agent comprising A) at least one nonionic, amphiphilic associative thickener and B) a cationic biocidal compound.

As biocidal compound in the context of this application, compounds are understood which possess an antimicrobial action and reduce the number of microorganisms on textile fabrics treated therewith as well as in the treating solution.

Depending on the antimicrobial spectrum and mechanism of action, biocidal compounds are differentiated into bacteriostats and bactericides, fungistats and fungicides etc. Suitable cationic biocidal compounds are preferably quaternary ammonium compounds.

The quaternary ammonium compounds (QACs) that are suitable as active biocidal substances have the general formula (R )(R ² )(R ³ )(R ⁴ )N ⁺ X ^~ , in which R to R ⁴ represent the same or different C C ₂ 2 alkyl residues, C ₇ -C ₂ 8 aralkyl residues or heterocyclic residues, wherein two or, in the case of an aromatic bonding as in pyridine, even three residues form the heterocycle, for example a pyridinium or imidazolinium compound, together with the nitrogen atom, and X ^" are halide ions, sulfate ions, hydroxide ions or similar anions.

QACs can be produced by reacting tertiary amines with alkylating agents, such as e.g. methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide. The alkylation of tertiary amines with a long alkyi residue and two methyl groups is achieved particularly readily, and even the quaternization of tertiary amines with two long residues and a methyl group can be carried out under mild conditions with the aid of methyl chloride. Amines having three long alkyi residues or hydroxy-substituted alkyi residues are of low reactivity and are preferably quaternized with dimethyl sulfate.

Suitable QACs are for example benzalkonium chloride (N-alkyl-N,N-dimethylbenzylammonium chloride, CAS No. 8001 -54-5), benzalkon B (m,p-dichlorobenzyldimethyl-Ci ₂ -alkylammonium chloride, CAS No. 58390-78-6), benzoxonium chloride (benzyldodecylbis(2- hydroxyethyl)ammonium chloride), cetrimonium bromide (N-hexadecyl-N,N,N-trimethylammonium bromide, CAS No. 57-09-0), benzethonium chloride (N, N-dimethyl-N-[2-[2-[p-(1 , 1 ,3,3- tetramethylbutyl)phenoxy]ethoxy]ethyl]benzylammonium chloride, CAS No. 121-54-0), dialkyldimethylammonium chlorides such as di-n-decyldimethyl-ammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3),

dioctyldimethylammonium chloride, 1 -cetylpyridinium chloride (CAS No. 123-03-5) and thiazoline iodide (CAS No. 15764-48-1 ) and mixtures thereof. Particularly preferred QACs are

dialkyldimethylammonium chlorides, in particular di-n-decyldimethylammonium chloride, N- octadecyl-N,N,N-trimethylammonium chloride, N-hexadecyl-N,N,N-trimethylammonium chloride and the benzalkonium chlorides with C ₈ -Ci ₈ alkyi residues, in particular Ci ₂ -Ci ₄

alkylbenzyldimethylammonium chloride. Another preferred biocidal compound is methyl-N-(2- hydroxyethyl)-N,N-di(caproyloxyethyl)ammonium methosulfate. Apart from the fact that these biocidal compounds act effectively against numerous microorganisms, the cationic compounds absorb particularly well on to cotton-containing fabrics and mixed fabrics.

The dialkyldimethylammonium halides, the benzalkonium halides and/or substituted

benzalkonium halides are commercially available, for example as Barquat ^® from Lonza, Marquat ^® from Mason, Variquat ^® from Evonik Industries and Hyamine ^® from Lonza.

The cationic biocidal compound is used in a quantity of 0.1 wt.% to 20 wt.%, preferably 0.5 wt.% to 10 wt.% and particularly preferably 1 wt.% to 5 wt.%. It is particularly preferred from a toxicological and ecological viewpoint for the quantity of biocidal compound to be less than 3 wt.%. The nonionic, amphiphilic associative thickener (A) is a polymer containing both hydrophilic and hydrophobic groups. Associative thickeners are water-soluble polymers containing surfactant-like hydrophobic constituents which in a hydrophilic and particularly in an aqueous medium are capable of associating, namely interacting, with themselves as wall as with other hydrophobic substances. The resulting associative network causes the medium to thicken or gel.

Particularly preferred associative thickeners are hydrophobically modified aminoplast/polyether copolymers. Particularly preferred aminoplasts are glycoluril and derivatives thereof. Suitable alkylene polyethers are the polyalkylene oxide diols, prfereably polyethylene oxide diols. These can have a degree of ethoxylation from 20 to 500, preferably from 60 to 350 and particularly from 100 to 250.

According to the invention, a suitable hydrophobically modified aminoplast/polyether copolymer is selected from among polymers having general formula (I)

wherein Amp denotes an aminoplast monomer or a radical of an aminoplast oligomer or polymer, AO denotes an alkylene oxide group, R denotes hydrogen, C C ₄ -alkyl or C C ₄ -acyl and x and y are numerals greater than 1.

Particularly preferred are the reaction products formed by acid-catalyzed polycondensation of (a) 1 ,3,4,6-tetramethoxymethylglycoluril and (b) a polyethylene oxide diol with a degree of ethoxylation from 20 to 500, preferably from 50 to 350 and particularly from 100 to 250, and (c) an optionally ethoxylated hydrophobic alcohol, alkylphenol, thiol, carboxamide, carbamate or hydrophobic carboxylic acid.

Preferred associative thickeners encompass PEG-180/octoxynol 40/tetramethoxymethylglycouril (TMMG) copolymer, PEG-180/laureth-50/tetramethoxymethylglycouril (TMMG) copolymer, PEG- 18/dodoxynol-5/PEG-25 tristyrylphenol/tetramethoxymethylglycouril (TMMG) copolymer and mixtures thereof. These associative thickeners are sold by Rockwood Additives under the trade name Pure® Thix. The associative thickener is used in a quantity of 0.1 wt.% to 10 wt.%, preferably 0.5 wt.% to 5 wt.% and particularly preferably 1 wt.% to 4 wt.%. It is particularly preferred that the associative thickener is used in the liquid textile or hard surface treatment agent in a quantity of 1 .5 wt.% to 3 wt.%.

Preferably, the textile or hard surface treatment agent is an aqueous textile or hard surface treatment agent and contains water as main solvent.

In addition to the associative thickener and the cationic biocidal compound, a liquid textile or hard surface treatment agent may contain further ingredients that further improve the applications- engineering or aesthetic properties of the textile or hard surface treatment agent. In the context of the present invention, the liquid textile or hard surface treatment agent by preference additionally contains one or more substances from the group of nonionic surfactants, builder, enzymes, nonaqueous solvents, pH adjusting agents, fluorescing agents, dyes, hydrotopes, silicone oils, anti- redeposition agents, anti-gray agents, shrinkage preventers, wrinkle protection agents, dye transfer inhibitors, corrosion inhibitors, antistatic agents, bittering agents, ironing adjuvants, proofing and impregnation agents, swelling and anti-slip agents, softening compounds and UV absorbers.

From the above mentioned further ingredients nonionic surfactants, enzymes, non-aqueous solvents, pH adjusting agents, fluorescing agents, dyes, silicone oils, soil-release polymers, anti- gray agents, dye transfer inhibitors are most preferred included into a textile or hard surface treatment agent.

Preferably, the textile or hard surface treatment agent additionally contains a perfume composition in order to impart a pleasant scent to the laundry treated therewith and to the textile or hard surface treatment agent itself.

In a preferred embodiment, the textile or hard surface treatment agent contains a perfume composition in a quantity of usually up to 3 wt.%, preferably 0.1 to 2 wt.%, particularly 0.2 to 1 .5 wt.% and particularly preferably 0.5 to 1 wt.%.

The perfume composition can contain individual fragrance compounds, for example the synthetic products of the type of the esters, ethers, aldehydes, ketones, alcohols and hydrocarbons.

Preferably, however, mixtures of various fragrances are used which together produce an attractive scent. The perfume composition can also contain natural fragrance compounds as may be obtained from plant sources. The perfume composition of the textile or hard surface treatment agent can also contain at least one aromatherapy component such as an essential oil. In another preferred embodiment, the fabric washing liquid composition comprises an encapsulated perfume and a free perfume.

The liquid textile or hard surface treatment agent may also contain a non-ionic surfactant as additional ingredient at a level up to 5 % by weight of the liquid textile or hard surface treatment agent. It is preferred that the liquid textile or hard surface treatment agent additionally comprises a non-ionic surfactant.

The nonionic surfactant that can be used are by preference alkoxylated, advantageously ethoxylated, in particular primary alcohols having by preference 8 to 18 carbon atoms and an average of 1 to 12 mol ethylene oxide (EO) per mol of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position, or can contain mixed linear and methyl- branched residues, such as those that are usually present in oxo alcohol residues. Particularly preferred, however, are alcohol ethoxylates having linear residues made up of alcohols of natural origin having 12 to 18 carbon atoms, e.g. from coconut, palm, tallow, or oleyl alcohol, and an average of 2 to 8 EO per mol of alcohol. The preferred ethoxylated alcohols include, for example, C -12-14 alcohols with 3 EO, 4 EO, 5 EO, or 7 EO, C ₉ _n alcohols with 7 EO, C _3-15 alcohols with 3 EO, 5 EO, 7 EO, or 8 EO, Ci _2- 18 alcohols with 3 EO, 5 EO, or 7 EO, and mixtures thereof, such as mixtures of Ci _2- 14 alcohol with 3 EO and Ci _2- 18 alcohol with 7 EO. The degrees of ethoxylation indicated represent statistical averages, which can correspond to an integral or a fractional number for a specific product. Preferred alcohol ethoxylates exhibit a restricted distribution of homologs (narrow range ethoxylates, NRE). In addition to these non-ionic active detergent species, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO, or 40 EO. Nonionic active detergent species that contain EO and PO groups together in the molecule are also usable according to the present invention. Block copolymers having EO-PO block units or PO-EO block units, but also EO-PO-EO copolymers or PO-EO-PO copolymers, can be used in this context. Also usable, of course, are mixed alkoxylated nonionic active detergent species in which EO and PO units are distributed statistically rather than in block fashion. Such products are obtainable by the simultaneous action of ethylene oxide and propylene oxide on fatty alcohols. These non-ionic surfactants are obtainable, for example, under the commercial name Dehydol ^® (from Cognis).

The treatment agent according to the present invention can be used to clean hard surfaces or textile fabrics. For the purposes of the present invention, hard surfaces for example comprise surfaces of stone or ceramic materials, rigid plastics materials, glass, porcelain or metal. Hard surfaces may be, for example, tableware, walls, tiles, work surfaces, painted surfaces, flooring or sanitary articles.

The textile or hard surface treatment agent is manufactured using usual and known methods and processes. For example, the constituents of the textile or hard surface treatment agent can be simply mixed in agitator vessels, the water, non-aqueous solvent, and surfactants usefully being prepared first. After cooling under stirring, if necessary at all, the further constituents are then added in portions.

Table 1 below shows the composition of a liquid textile treatment agent E1 and a liquid hard surface treatment agent E2 according to the present invention. Quantities are indicated in wt% of active matter.

Table 1 :

E1 E2

C12-C14 alkylbenzyldimethylammonium chloride 2.5 di-n-decyldimethylammonium chloride 2.5

Cecils fatty alcohol with 7 EO 1 2

2-propanol 1 1

PEG-180/laureth-50/TMMG copolymer* 2.5 2.5

Perfume 0,2 0,9

Dyes + +

Water to make 100 wt.%

*Pure Thix® 1450 purchased from Rockwood Additives

The treatment agents E1 and E2 according to the invention were clear and stable at storage temperatures of 0°C, 25°C and 40°C for 4 weeks.

The viscosity of the treatment agents was measured using a Brookfield viscometer LVT-II at 10 rpm and 20°C, spindle 31. Without adding the nonionic, amphiphilic associative thickener the viscosity of the treatment agents was 0 mPas, whereas treatment agents E1 and E2 exhibited viscosities of 60 mPas each.