EP2171029B1 - Gentle bleach - Google Patents

Description

The present invention relates to hypochlorite-containing bleaches which have improved textile care during the washing of textiles by optimizing ingredients additionally contained in them.

Efficient cleaning is one of the requirements that influences the acceptance of detergents and cleaners by consumers. This requires providing agents with a wide stain removal potential which can remove, for example, oily and greasy soils from fabrics or hard surfaces such as tiles or tiles. In order to meet this demand, hypochlorite bleach containing agents have been developed, among others, in which hypochlorite, as a strong oxidant, contributes to the chemical degradation, destruction and removal of soils. Another advantage of using hypochlorite is that it acts as an effective disinfectant. However, hypochlorite-containing agents are perceived by some consumers to be too aggressive, be it textiles or even human skin. Prolonged use of hypochlorite-containing detergents may cause the yellowing of some, especially white, textiles; it is also possible to observe a decrease in the softness of the textiles ("stiffness").

As a further disadvantage it is sometimes felt that after contact with human skin, which inevitably results in the use of such agents with bare hands in the so-called hand washing or cleaning hard surfaces and which can not always be avoided, for example by the use of gloves , a smell sticking to the skin develops, which can not always be removed even after repeated washing with water.

In the US patent US Pat. No. 7,214,652 B1 there is proposed a liquid hypochlorite-containing agent which contains a softening emulsion and is free from optical brighteners, the softening emulsion being polyethylene or polypropylene-based and containing an anionic surfactant from the class of di (alkylsulfonylphenyl) oxides.

The international patent application WO 2007/079870 A1 relates to stable chlorine bleaches which reduce the chlorine odor of the skin in contact with the composition and describes agents containing hypochlorite, diphenylmethane and / or diphenyloxide and / or 2-methylnaphthyl ethers and optionally surfactant and chelating agents.

In the European patent application EP 0 606 707 describes agents which contain a polymer component together with a hypochlorite compound and lead to a reduction of malodors of the actual agent as well as the surfaces cleaned therewith. This could be up may be attributed to the high viscosity of these agents, so that compounds responsible for the offensive odor may be trapped in vesicles.

The European patent application EP 0 812 909 A1 describes the use of polycarboxylate polymer in hypochlorite-containing bleaches to avoid unpleasant odors resulting from the contact of such agents with skin surfaces.

Also the European patent application EP 0 622 451 deals with the task of odor formation during and after applying chlorine-containing agents and suggests to use a perfume. However, one encounters the difficulty that on the one hand only a few fragrances are stable in the presence of the strong oxidizing power of chlorine-based bleach, and on the other hand, the smell of chlorine is very strong and difficult to mask by a perfume. EP 0 622 451 proposes to use 0.000002 wt .-% to 2 wt .-% of pale stable fragrances selected from the classes of acetals, aldehydes, esters, alcohols, ketones, ethers, nitriles and terpenes, in such agents.

From the German patent application DE 44 35 386 A1 aqueous, esterquat-based fabric softener dispersions are known which contain polyolefin waxes as thickeners.

A subjective impression of textile care by the use of hypochlorite-containing agents can not be achieved by the consumer by the measures of the prior art. Although the addition of polyolefin wax to hypochlorite bleaches improves the properties of textiles treated with these bleaches, particularly a softer touch on textiles, this does not outweigh the disadvantages of yellowing and odor deterioration and the perceived aggressiveness of hypochlorite from a user's perspective.

An object of the invention which seeks to remedy this is a liquid aqueous hypochlorite-containing bleach, the polyolefin wax, a fragrance selected from the group consisting of diphenylmethane, diphenyloxide, 2-methyl-naphthyl ether and mixtures thereof, chelating agents selected from organophosphonic acid and / or phosphonate, and containing surfactant.

After the application of such composite funds when washing laundry is not only an objectively measurable cleaning result, but also to the user sensory understandable "feel good" by the interaction of the softness of the laundry with a pleasant fragrance (or at least the absence of often as negative perceived "chlorine smell"), which is not affected by yellowing of the garment. The polyolefin waxes contained in the compositions according to the invention are predominantly linear polyolefins of waxy character, which are in particular products with relatively low molecular weights in the range from 500 to 20,000. The polyolefin waxes are generally prepared by direct low-pressure polymerization or, preferably, high-pressure polymerization of the monomers or by specific depolymerization of products of relatively high molecular weights. The use of modified polyolefin waxes, as can be prepared, for example, by copolymerization of ethylene with suitable other monomers such as vinyl acetate or acrylic acid, is possible. The dispersibility of polyolefins can be improved by oxidative surface treatment. Preference is given to using partially oxidized polyolefin waxes by polymerization of olefins, in particular ethylene, preferably in the absence of a catalyst with premature termination of the polymerization, followed by partial oxidation, for example. Example, by introducing air, or by copolymerization of olefins, in particular ethylene, with suitable other monomers such as acrylic acid, wherein the molar fraction of the acrylic acid units preferably does not exceed 20%, in particular 10%.

The use of high-density polyethylene wax having an average molecular weight in the range of 500 to 10,000 and especially 2,000 to 5,000 is preferred. If desired, it is also possible to use cationic or pseudo cationic polyethylene waxes.

The polyolefin waxes are usually commercially available as aqueous dispersions which have a solids content of from 1% by weight to 25% by weight and in particular from 2% by weight to 15% by weight. These generally contain small amounts of dispersing aids, for example anionic or nonionic surfactants, preference being given to using polyolefin dispersions which are stabilized by nonionic surfactants in the context of the present invention.

Preferably, an agent according to the invention contains from 0.01% by weight to 10% by weight, in particular from 0.1% by weight to 2% by weight, of polyolefin wax.

Surprisingly, it has been found that the combination of the optionally partially oxidized polyolefin waxes with said fragrances, which reduce the chlorine bleach-associated odor on human skin that has come into contact with hypochlorite-containing agents, a further increase in the positive textile properties after the application of the Means.

The fragrance preferably has a combination of diphenylmethane and diphenyl oxide in a weight ratio of 1: 1 to 1:50, in particular from 1:10 to 1: 5. It furthermore preferably has a combination of diphenylmethane and 2-methyl-naphthyl ether in a weight ratio of 50: 1 to 1:10, in particular from 5: 1 to 1: 1. It is also preferred if the fragrance has a combination of diphenyl oxide and 2-methyl-naphthyl ether in a weight ratio of from 250: 1 to 1: 1, in particular from 50: 1 to 5: 1.

Said fragrance, as such or in the form of a preparation containing it, may be applied after the use of the chlorine-containing agent on the skin areas which have come into contact with said agent. However, it is preferred if the fragrance is already part of the composition containing the chlorine bleach, for example part of an agent according to the invention.

Another object of the invention is a method for bleaching stains on textiles, in which one uses an agent according to the invention.

An agent according to the invention is an aqueous liquid which can be used undiluted or optionally after mixing with water on a textile or hard surface and which preferably contains 0.5% by weight to 10% by weight, in particular 1% by weight to 6 Wt .-%, of alkali metal hypochlorite, especially sodium hypochlorite contains.

An agent of the invention preferably contains from 0.0005% to 0.005% by weight of diphenylmethane, from 0.005% to 0.025% by weight of diphenyloxide, and / or from 0.0001% to 0.005% by weight 2 methyl-naphthyl ether.

A composition according to the invention preferably contains 0.1% by weight to 2% by weight of alkali metal hydroxide and up to 5% by weight of palladium-stable surfactant, in particular betaine, amine oxide and / or alkyl ether sulfate.

in der R¹ eine Alkyl- oder Alkenylgruppe mit 6 bis 22 Kohlenstoffatomen oder eine Gruppe R⁴CO-NH-(CH₂)_n- ist, R² Wasserstoff oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen ist, R³ Wasserstoff oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen ist, R⁴ eine Alkyl- oder Alkenylgruppe mit 6 bis 22 Kohlenstoffatomen ist, m eine Zahl von 1 bis 6 und n eine Zahl von 1 bis 3 ist. Beispiele für besonders geeignete Vertreter dieser Klasse von Tensiden umfassen C_12-18-Alkyl-dimethylbetain, kommerziell erhältlich als Kokosnußbetain, und C_10-16-Alkyl-dimethylbetain, kommerziell erhältlich als Laurylbetain. Eine weitere Klasse besonders bevorzugter Tenside sind die Alkylethersulfate, die durch Umsetzung von Alkoholen (vorzugsweise mit 6 bis 22 Kohlenstoffatomen) mit Alkylenoxiden, insbesondere Ethylenoxid, und anschließende Sulfatierung und Neutralisation erhältlich sind, insbesondere ein mit 2 Equivalenten Ethylenoxid alkoxyliertes C_12-14-Fettalkoholethersulfat. In den Ethersulfaten ist das korrespondierende Kation vorzugsweise Natrium. Eine weitere Klasse besonders bevorzugter Tenside sind die Aminoxide, die mindestens einen Alkylrest mit 6 bis 22 C-Atomen und bis zu zwei kürzere Alkylreste mit 1 bis 4 C-Atomen, die gegebenenfalls auch hydroxysubstituiert sein können, am Stickstoffatom der NO-Gruppierung tragen. Gewünschtenfalls können die erfindungsgemäßen Mittel zusätzlich auch noch andere Tenside, vorzugsweise in Mengen nicht über 1 Gew.-%, enthalten. Darunter sind insbesondere Seifen (Alkalisalze, insbesondere Natrium- und/oder Kaliumsalze von Fettsäuren mit vorzugsweise 12 bis 18 C-Atomen) zu nennen. Tenside sind insgesamt vorzugsweise in Mengen bis zu 5 Gew.-%, insbesondere von 0,01 Gew.-% bis 3 Gew.-% in erfindungsgemäßen Mitteln enthalten.Among the betaines, particular preference is given to those of the general formula I

wherein R ^{1 is} an alkyl or alkenyl group having 6 to 22 carbon atoms or a group R ^{4 is} CO-NH- (CH ₂ ) _n -, R ^{2 is} hydrogen or an alkyl group having 1 to 4 carbon atoms, R ^{3 is} hydrogen or an alkyl group with 1 to 4 carbon atoms, R ^{4 is} an alkyl or alkenyl group having 6 to 22 carbon atoms, m is a number from 1 to 6 and n is a number from 1 to 3. Examples of particularly suitable members of this class of surfactants include C _12-18 alkyl dimethyl betaine, commercially available as coconut betaine, and C _10-16 alkyl dimethyl betaine, commercially available as lauryl betaine. Another class of particularly preferred surfactants are the alkyl ether sulfates obtainable by reacting alcohols (preferably having 6 to 22 carbon atoms) with alkylene oxides, especially ethylene oxide, followed by sulfation and neutralization, especially a C _12-14 fatty alcohol ether sulfate alkoxylated with 2 equivalents of ethylene oxide , In the ether sulfates, the corresponding cation is preferably sodium. Another class of particularly preferred surfactants are the amine oxides which carry at least one alkyl radical having 6 to 22 carbon atoms and up to two shorter alkyl radicals having 1 to 4 carbon atoms, which may also be hydroxy-substituted, on the nitrogen atom of the NO group. If desired, the compositions according to the invention may additionally contain other surfactants, preferably in amounts of not more than 1% by weight. These include in particular soaps (alkali metal salts, in particular sodium and / or potassium salts of fatty acids having preferably 12 to 18 carbon atoms). Surfactants are contained in total preferably in amounts of up to 5 wt .-%, in particular from 0.01 wt .-% to 3 wt .-% in inventive compositions.

in der R⁵ Wasserstoff, eine Gruppe -(CH₂)_x(CHCH₃)_y-NH₂->O oder ein Alkalimetall ist, x eine Zahl von 1 bis 4 und y 0 oder 1 ist. Unter den besonders bevorzugten Aminoxidphosphonsäuren ist das Aminoxid auf der Basis der Aminotrimethylenphosphonsäure. Vorzugsweise sind in den erfindungsgemäßen Mitteln 0,01 Gew.-% bis 2 Gew.-% Chelatisierungsmittel enthalten.The preparations according to the invention additionally comprise chelating agents selected from organophosphonic acid and / or phosphonate, preferably alkylphosphonic acids, and among these in particular those having at least one amine oxide substituent on the alkyl group, referred to herein as amine oxide phosphonic acids, and / or phosphonomic polyacrylic acids, also in the form of their alkali metal salts may be present. The incorporation of such complexing agents surprisingly leads to particularly good preservation of the color impression of white textiles which are treated with the compositions containing them. Amine oxide phosphonic acids are normally prepared by oxidation of aminoalkyl phosphonic acids. They preferably belong to the group of compounds according to general formula (II),

wherein R ^{5 is} hydrogen, a group - (CH ₂ ) _x (CHCH ₃ ) _y -NH ₂ -> O or an alkali metal, x is a number from 1 to 4 and y is 0 or 1. Among the more preferred amine oxide phosphonic acids is the amine oxide based on aminotrimethylene phosphonic acid. The agents according to the invention preferably contain from 0.01% by weight to 2% by weight of chelating agent.

The compositions preferably contain 0.5% by weight to 2% by weight of silicate, in particular alkali metal silicate. Optionally, in addition or instead, carbonate, in particular alkali metal carbonate, in amounts of preferably 0.1 wt .-% to 2% wt .-%, to be contained in them.

If desired, the agents according to the invention may contain dyes or pigments.

The compositions according to the invention can be prepared in a simple manner by mixing water with the abovementioned ingredients in the stated amounts. As such or after dilution with water, in particular in amounts of from 1 part by volume to 200 parts by volume, in particular from 2 parts by volume to 150 parts by volume, per 1 part by volume of the composition, in machine or manual textile washing processes or in textile pretreatment before or optionally also instead of a washing process ( that is, as a so-called stain remover) are used; also their corresponding use for cleaning hard surfaces is possible.

Examples

Compositions of the compositions given below (in% by weight) M1 M2 NaOCl 2 3.24 NaOH 1.25 1.25 fatty alkyl ether sulfate 1 2.1 Lauryldimethylamine N-oxide 0.5 - fatty acid 0.25 - Aminotrimethylene-N- 0.6 0.1 oxide sodium silicate 2 - polyethylene wax 0.2 0.2 Perfume * 0,025 0.01 water ad 100 * Mixture of diphenylmethane, diphenyloxide and 2-methyl-naphthyl-ether were used in concentrations of 0.75 wt .-% in aqueous washing liquors for washing cotton towels (liquor ratio 1:20). After 20 minutes, the wash liquor was diluted to twice its volume with water and the towels were spun and air dried. The softness of the towels was compared to towels which otherwise had been washed equally but with agents lacking the polyethylene wax, the fragrance, the chelating agent or all three of the said active ingredients, by an experienced panel of testers. The towels washed with the agents according to the invention were rated better on average over the entire test panel with at least 2 units.

Claims (11)

1. A liquid aqueous hypochlorite-containing bleaching agent containing polyolefin wax, a fragrance selected from the group encompassing diphenyl methane, diphenyl oxide, 2-methyl naphthyl ether and mixtures thereof, chelating agent selected from organophosphonic acid and/or phosphonate and surfactant.
2. The agent according to claim 1 containing 0.5 wt.% to 10 wt.%, in particular 1 wt.% to 6 wt.%, of alkali metal hypochlorite, in particular sodium hypochlorite.
3. The agent according to claim 1 or 2 containing 0.01 wt.% to 10 wt.%, in particular 0.1 wt.% to 2 wt.%, of polyolefin wax.
4. The agent according to one of claims 1 to 3 containing 0.1 wt.% to 2 wt.% of alkali metal hydroxide and up to 5 wt.% of bleach-resistant surfactant, in particular betaine, amine oxide and/or alkyl ether sulfate.
5. The agent according to one of claims 1 to 4 containing 0.01 wt.% to 2 wt.% of organophosphonic acid and/or phosphonate.
6. The agent according to one of claims 1 to 5 containing 0.0005 wt.% to 0.005 wt.% of diphenyl methane, 0.005 wt.% to 0.025 wt.% of diphenyl oxide and/or 0.0001 wt.% to 0.005 wt.% of 2-methyl naphthyl ether.
7. The agent according to one of claims 1 to 6 containing diphenyl methane and diphenyl oxide in a weight ratio of 1:1 to 1:50, in particular 1:10 to 1:5.
8. The agent according to one of claims 1 to 7 containing diphenyl methane and 2-methyl naphthyl ether in a weight ratio of 50:1 to 1:10, in particular 5:1 to 1:1.
9. The agent according to one of claims 1 to 8 containing diphenyl oxide and 2-methyl naphthyl ether in a weight ratio of 250:1 to 1:1, in particular 50:1 to 5:1.
10. The agent according to one of claims 1 to 9 containing 0.5 wt.% to 2 wt.% of silicate, in particular alkali metal silicate, and/or carbonate, in particular in amounts of 0.1 wt.% to 2 wt.%.
11. A method for bleaching soiling on textiles, wherein an agent according to one of claims 1 to 10 is used.