DE102009005791A1 - Hand dishwashing detergent with antibacterial effect - Google Patents

Abstract

The invention relates to a cleaning agent for hard surfaces, in particular a hand dishwashing detergent, with a surfactant combination of a nonionic surfactant and an amine oxide and elemental silver and / or a silver compound. The detergents have an antibacterial effect in concentrated and diluted form.

Description

The Invention relates to hard surface cleaners, in particular hand dishwashing detergent, comprising a surfactant combination and silver and / or a silver compound.

In A kitchen can become pathogenic bacteria - especially after processing eggs, raw meat and raw fish - on Work surfaces and kitchen appliances, such as for example, cutting boards, but also in the cleaning utensils used, such as moist rinse sponges, wipes or Brush, multiply and pose a serious danger. Another focus of bacteria is the sink and especially the drain, in which the spent rinse water stands.

conventional Dishwashing detergents can usually already be concentrated Application no sufficient growth inhibition or even killing germs cause.

Antibacterial dishwashing detergents which contain as bacteriostatic component, for example triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether) or essential oils, such as, for example, thymol, menthol or eucalyptol, are already known from the prior art. From the registrations WO 99/57235 A1 and WO 99/29815 A1 Antibacterial dishwashing detergents are known which contain carboxylic acids such as benzoic acid.

In Many products are today silver or silver compounds with used to suppress unpleasant odors and / or kill germs. In particular, silver salts are suitable to achieve these effects.

Indeed silver salts, especially in the presence of reducing ingredients, for reduction, so that on ingredients such as sugar compounds, Aldehydes and other ingredients are omitted in these products must become.

Usually Hand dishwashing detergents contain a surfactant combination from a fatty alcohol ether sulfate, an alkylpolyglucoside and a Betaine or a surfactant combination of an alkylbenzenesulfonate, a Fatty alcohol ether sulfate and a betaine or surfactant combination from an alkylbenzenesulfonate, a fatty alcohol ether sulfate and an alkyl polyglucoside.

Especially the sulfonate and sulfate surfactants tend to react with the Silver ions, with poorly soluble, brown-black silver sulfide fails.

additionally is the foam caused by dishwashing detergent with these Surfactant combinations is produced, very stable and leads to a long-lasting film formation in the sink and in the siphon system. This increases the contact time of the bacteria from the used rinsing liquor with the sink and siphon system, causing the formation of unpleasant odors can lead.

A Object of this invention was therefore to provide an antibacterial Cleaning agent for hard surfaces, in particular a hand dishwashing detergent, which is stable and with no or only a slight residual foam problem is afflicted.

• (a) eine Tensidkombination aus einem nichtionischen Tensid und einem Aminoxid und
• (b) elementares Silber und/oder eine Silberverbindung.

This object is achieved by a cleaning agent for hard surfaces, in particular a hand dishwashing detergent, comprising

• (a) a surfactant combination of a nonionic surfactant and an amine oxide and
• (b) elemental silver and / or a silver compound.

It has surprisingly been found that this particular Surfactant combination together with silver and / or a silver compound to a storage-stable cleaner for hard surfaces leads, which in concentrated, but also diluted Application has an antibacterial effect. Furthermore, the generated Detergents have a lower amount of foam, but consumer expectations equivalent. The same applies to the stability of the generated foam. The foam formed falls apart when the Used rinse liquor quickly and this is the foam residue reduced in sink and siphon.

It is preferable that the silver compound is selected from the group consisting of silver acetate, silver citrate, silver diamine chloride complex, silver cyclodextrin complex, silver dicyanokalium complex, silver phthalimide, Silver phenylcyanamide, silver (ethylene thiourea) complex, silver imidazolate, transition metal NHC-calix [4] arene complexes, silver crown ethers, silver nitrate, and mixtures thereof. The liquid washing, cleaning, after-treatment or washing aid particularly preferably contains silver nitrate.

These Silver compounds have sufficiently high solubility do not fall off the cleaners for hard Surfaces off.

It it is further preferred that the amount of elemental silver and / or the silver compound 0.0001 to 1 wt .-%, based on the total Detergent, amounts to.

Farther it is preferred that the nonionic surfactant is selected is selected from the group consisting of alkoxylated fatty alcohols, alkoxylated Fatty acid alkyl esters, polyhydroxy fatty acid amides, Alkylphenolpolyglycol ethers and mixtures thereof.

These Nonionic surfactants have one in combination with an amine oxide good cleaning performance on grease-soiled hard surfaces, such as dishes, on.

The The invention also relates to the use of elemental silver and / or a silver compound as an antibacterial component in a detergent for hard surfaces, in particular a hand dishwashing detergent, with a surfactant combination of a nonionic surfactant and an amine oxide.

Further The invention relates to a method for antibacterial purification hard surfaces by diluting a detergent for hard surfaces, in particular a hand dishwashing detergent, comprising (a) a surfactant combination of a nonionic surfactant and an amine oxide, and silver and / or a silver compound having Water to concentrations of 1: 1 to 1: 1000 and bring into contact the hard surface to be cleaned with the obtained Cleaning solution.

in the The invention is intended below, inter alia, by way of examples, be explained in more detail.

The Cleaning agent for hard surfaces contains a surfactant combination of a nonionic surfactant and a Amine oxide.

suitable Nonionic surfactants include alkoxylated fatty alcohols, alkoxylated Fatty acid alkyl esters, polyhydroxy fatty acid amides, Alkylphenol polyglycol ethers and mixtures thereof.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO, 4 EO or 7 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. More preferably, the hard surface cleaner contains a C _12-18 fatty alcohol with 7 EO or a C _13-15 oxo alcohol with 7 EO as the nonionic surfactant.

Of the Content of nonionic surfactants is in the detergent preferably 1 to 30% by weight and preferably 2 to 25% by weight, respectively based on the entire cleaning agent.

Suitable amine oxides include, for example, alkylamine oxides, especially alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides. Preferred amine oxides satisfy formula II, R ⁶ R ⁷ R ⁸ N ⁺ -O ^- (II) R ⁶ - [CO-NH- (CH ₂ ) _w ] _z N ⁺ (R ⁷ ) (R ⁸ ) -O ^- (II) in the R ^{6 is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical, in the Alkylamidoaminoxiden via a Carbonylamidoalkylengruppe -CO-NH- (CH ₂ ) _z - and in the Alkoxyalkylaminoxiden via an oxyalkylene group -O- (CH ₂ ) _z is bonded to the nitrogen atom N, wherein z is in each case a number from 1 to 10, preferably 2 to 5, in particular 3,
R ⁷ , R ^{8 are} independently a C ₁₄ alkyl radical, optionally hydroxy-substituted such. B. is a hydroxyethyl radical, in particular a methyl radical.

Examples suitable amine oxides are the following according to INCI named compounds: Almondamidopropylamine Oxide, Babassuamidopropylamine Oxides, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco-Morpholine Oxide, Decylamine Oxide, Decyltetradecylamines oxides, diaminopyrimidines oxides, dihydroxyethyl C8-10 alkoxypropylamines oxides, dihydroxyethyl C9-11 alkoxypropylamines Oxides, dihydroxyethyl C12-15 alkoxypropylamines oxides, dihydroxyethyl Cocamine oxides, dihydroxyethyl lauramine oxides, dihydroxyethyl stearamines Oxides, Dihydroxyethyl Tallowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallowamine Oxide, Hydroxyethyl Hydroxypropyl C12-15 Alkoxypropylamines oxides, isostearamidopropylamines oxides, isostearamidopropyl Morpholine oxides, Lauramidopropylamine oxides, Lauramine oxides, methyl Morpholine Oxide, Milkamidopropyl Amine Oxide, Minkamidopropylamine Oxides, myristamidopropylamine oxides, myristamine oxides, myristyl / cetyl Amine oxides, Oleamidopropylamine oxides, Oleamine oxides, Olivamidopropylamine Oxides, palmitamidopropylamine oxides, palmitamine oxides, PEG-3 lauramines Oxides, Potassium Dihydroxyethyl Cocamine Oxides Phosphate, Potassium Trisphosphonomethylamine oxides, sesamidopropylamine oxides, soyamidopropylamines Oxides, stearamidopropylamines oxides, stearamines oxides, tallow amidopropyl amines Oxides, tallowamine oxides, undecylenamidopropylamine oxides and wheat Germamidopropylamine oxides.

preferred Amine oxides are, for example, N-cocoalkyl-N, N-dimethylamine oxide, N-tallowalkyl-N, N-di-hydroxyethylamine oxide, myristylcetyldimethylamine oxide or lauryldimethylamine oxide.

Of the Amine oxide content is preferred in the detergent 1 to 15 wt .-% and preferably 2 to 10 wt .-%, each based on the entire cleaning agent.

When essential ingredient contains the cleaning agent for hard surfaces elemental silver and / or a silver compound.

According to the invention Silver either in elemental form or in the form of its compounds used. If the silver is used in elementary form, then points it preferably has particle sizes of 0.1 to 100 microns on. Leave even finer particle sizes of silver reach by using elemental silver in colloidal form, where the silver particle sizes from 0.001 to 0.1 μm.

It however, it is preferred that the agent is a silver compound contains and selected this silver compound is selected from the group consisting of silver acetate, silver citrate, silver diamine chloride complex, Silver cyclodextrin complex, silver dicyanokalium complex, silver phthalimide, Silver phenylcyanamide, silver (ethylene thiourea) complex, silver imidazolate, transition metal NHC-calix [4] arene complexes, Silver Crown Ether, Silver Nitrate and mixtures thereof. The silver compounds are preferably in the form of solutions, suspensions or dispersions used. Particularly preferably contains the cleaning agent silver nitrate, which in the form of an aqueous Solution is used.

The Amount of elemental silver and / or silver compound is preferably 0.0001 to 1% by weight and more preferably between 0.001 and 0.25 wt .-%, based on the total detergent for hard surfaces. Very particularly preferred cleaning agents contain 0.01 to 0.1 wt .-% of elemental silver and / or a Silver compound, based on the entire cleaning agent.

additionally can the agent, in particular for improving the cleaning effect, Run-off behavior and / or drying behavior, in addition contain one or more amphoteric surfactants and / or cationic surfactants.

To the amphoteric surfactants (amphoteric surfactants, zwitterionic surfactants), which may continue to be included in the funds Alkylamidoalkylamines, alkyl substituted amino acids, acylated Amino acids or biosurfactants.

The Agent may additionally contain one or more cationic surfactants (Cationic surfactants, INCI quaternary ammonium compounds), usually in an amount of 0.001 to 5 wt .-%.

preferred cationic surfactants are the quaternary surfactants Compounds, in particular with an ammonium, sulfonium, phosphonium, Iodonium or arsonium group. Through the use of quaternary Surface-active compounds with antimicrobial activity can already do that by the elemental silver and / or the silver compound existing antimicrobial effect can be improved. Suitable QAC For example, benzalkonium chloride, benzoxonium chloride, benzetonium chloride or dialkyldimethylammonium chlorides such as di-n-decyl-dimethyl-ammonium chloride.

The Cleaning agent is preferably aqueous, in particular an aqueous hand dishwashing detergent. In addition to water it may advantageously additionally one or more contain water-soluble organic solvents, usually in an amount of 0 to 15% by weight, preferably 0.1 to 10% by weight, in particular 3 to 8 wt .-%.

The Solvent becomes especially necessary as a hydrotrope and viscosity regulator used.

It acts solubilizing especially for surfactants and electrolyte as well as perfume and dye, if any, and thus contributes to their incorporation prevents the Formation of liquid crystalline phases and has a share the formation of clear products. The viscosity of the invention Agent decreases with increasing amount of solvent.

Preferably the solvent is selected from the group comprising methanol, ethanol, propanol, isopropanol, ethylene glycol, Butyl glycol, propylene glycol, polypropylene glycols and mixtures the same. The cleaning agent particularly preferably contains for hard surfaces use ethanol as solvent.

The Agent may further contain hydrotropes. This is it to solubilizer. Suitable hydrotropes are, for example Urea, butyl glycol, or aliphatic short-chain anionic or amphoteric solubilizers.

The viscosity which is favorable for the medium is 20 ° C. and a shear rate of 30 min ^-1 - measured with a Brookfield LV DV II viscometer and spindle 31 - in the range of 5 to 1500 mPa · s, preferably 10 to 1200 mPa · s, in particular 20 to 1000 mPa · s.

to Adjusting the viscosity may continue to be the means or more water-soluble salts as electrolytes. These may be inorganic and / or organic salts.

to further improvement of the drainage and / or drying behavior The agent may contain one or more additives from the group of polymers and the builders, usually in an amount of 0.001 to 5 wt .-%.

Besides can still one or more more - in particular in hand dishwashing detergents and cleaning agents for hard surfaces - usual auxiliary and Additives, in particular UV stabilizers, perfume, pearlescing agents, Dyes, corrosion inhibitors, preservatives, disinfectants, Enzymes, pH adjusters and skin feel-improving or nourishing additives in quantities of usually no more be contained as 5 wt .-%.

Of the pH of the agent can be determined by means of customary pH regulators, for example, acids such as mineral acids or citric acid, Benzoic acid and / or alkalis such as sodium or potassium hydroxide, be set, wherein - especially when desired Hand tolerance - a range from 4 to 9, preferably 5 to 8, in particular 5.5 to 7.5, is preferred.

to Adjustment and / or stabilization of the pH may be the means contain one or more buffer substances.

At the Use of benzoic acid, salicylic acid or lactic acid as pH regulators and / or buffer substances they can Compounds the antibacterial effect of silver and / or the Support or reinforce silver compound.

to Cleaning a hard surface is the invention Detergent either directly, that is undiluted, for example, by means of a sponge, on the surface to be cleaned applied and then removed again with water.

alternative can the inventive cleaning agent first diluted with water to concentrations of 1: 1 to 1: 1000 and then the resulting cleaning solution brought into contact with the surface to be cleaned.

In In both cases an antibacterial cleansing occurs hard surface in which the number of existing ones Germs and bacteria during the actual cleaning process clearly is reduced more than with a cleaning agent without added antibacterial agent.

EXAMPLES

In Table 1, the compositions of two comparative formulations V1 and V2 and the compositions of a hard surface cleaner according to the invention E1 (all amounts are in wt.% Of active agent, relative to the agent) are shown: TABLE 1 V1 V2 E1 C _13-15 oxo alcohol with 7 EO - - 12 N-coco-N, N-dimethylamine - - 8th AgNO ₃ - - 0,017 Sec. C _14-17 alkanesulfonate, Na salt 5 5 - Sodium lauryl ether sulfate 2EO 20 20 - cocoamidopropyl 5 5 1.61 salicylic acid - 0.3 - water Ad 100 Ad 100 Ad 100 PH value 6.0 4 7.1

From All three agents were determined to have the olfactory odor factor (OFG).

In A first test was done with a sponge 10 times each each 2 minutes in a 35 ° C warm rinse (4 ml detergent V1, V2 or E1 to 5 liters of water). The water of the rinse liquor had a degree of hardness from 16 dH up. In addition, the rinse water contained 10 g of artificial dirt (IKW test dirt no. 2, high-fat).

In In a second test, 6 ml of the cleaning agents V1, V2 and E1 each on a sponge.

The such pretreated sponges were each for 48 hours in a thin layer chromatography chamber Stored glass with a neutral atmosphere and then of 10 test persons with regard to the odor (grade 1 = neutral smell, grade 10 = strong natural bad smell).

The results are shown in Table 2. Table 2 V1 V2 E1 OFG TEST 1 7 7 5 OFG TEST 2 6 4 2.5

The Determination of the olfactory odor factor (OFG) clearly shows that with the cleaning agent according to the invention E1 not only with concentrated use of the cleaning agent (TEST 2) caused the formation of unpleasant odors by bacteria, can be reduced, but also in dilute Use (TEST 1).

Table 3 sets forth the compositions of seven hard surface cleaners of the invention, E2 to E8 (all amounts are in weight percent of active, based on agent): TABLE 3 E2 E3 E4 E5 C _13-15 oxo alcohol with 7 EO 10 8th 4 2 N-coco-N, N-dimethylamine 2 4 8th 10 AgNO ₃ 0,017 0,017 0,017 0,017 water Ad 100 Ad 100 Ad 100 Ad 100 PH value 6.8 6.9 7 7 Foam volume [ml] 210 210 276 306 Table 3 (continued) E6 E7 E8 C _13-15 oxo alcohol with 7 EO 24 16 16 N-coco-N, N-dimethylamine 8th 4 2 AgNO ₃ 0,017 0,017 0,017 water Ad 100 Ad 100 Ad 100 PH value 7.1 7.1 7 Foam volume [ml] 289 205 210

All inventive cleaning agents E2 to E8 were clear and stable even after 10 weeks of storage. In the detergents E2 to E8 could also contain other ingredients, in particular Dyes and / or perfume and / or ethanol, easily be incorporated. The cleaning agents obtained showed also after 10 weeks storage no change in appearance.

to Determination of the foam volume was a SITA Foam Tester R-2000 used. This uses a rotor defined to generate foam Geometry, the mechanical air bubbles in the liquid brings. The foam volume is measured by a needle sensor, which scans the foam surface and a precise determination the foam volume allowed even with uneven foam surface. The measurement conditions were as follows: Quantity of product solution: 250 ml, dosage: 1.2 g / l, water hardness 16 ° d, number of revolutions: 2000 rpm, temperature of the product solution 40 ° C.

The Measurement was carried out after the product solution 6 times for Foamed for 10 seconds.

conventional Hand dishwashing detergents comprising a surfactant combination a fatty alcohol ether sulfate, an alkylpolyglucoside and a Betaine or a surfactant combination of an alkylbenzenesulfonate, a fatty alcohol ether sulfate and a betaine or a surfactant combination from an alkylbenzenesulfonate, a fatty alcohol ether sulfate and an alkyl polyglucoside, produce foam volumes in the range from 400 to 700 ml. The amounts of foam produced according to the invention Detergents E2 to E8 are lower than conventional ones Dishwashing agents, so that thereby the residual foam problem is reduced. The amounts of foam produced are sufficient Consumer expectations for a hand dishwashing detergent.

The rinsing power of the cleaning agents according to the invention was determined in a semi-automatic plate test apparatus using a fatty Mischanschmutzung. It was at a konstan th temperature was washed from 40 to 45 ° C in 5 l of water hardness of 16 ° under constant conditions compared to the hand dishwashing detergent V1 soiled with test soil plate until the foam formed before the start of the experiment was destroyed. The concentration was 3 ml per 5 liters of water.

The Detergents E2 to E8 according to the invention Although a lower, but compared to the cleaning agent V1 still sufficiently high flushing power.

As well is it possible rinse aid for the machine Cleaning dishes with an antibacterial effect.

• *Genapol^® EP 2564 (ex Clariant)

Table 4 shows the composition of a rinse aid E9 according to the invention and a rinse aid V3 not according to the invention for use in a dishwashing machine. Table 4 E9 V3 C _12-15 oxo alcohol with EO / PO * 14 14 N-coco-N, N-dimethylamine 2 2 Citric acid × 1 H ₂ O 3 3 AgNO ₃ 0.02 - Perfume, dye + + water Ad 100 Ad 100 OFG 1.5 4.5

• * Genapol ^® EP 2564 (ex Clariant)

To determine the olfactory odor factor, commercially available dishwashers were used to rinse dishes and cutlery that were soiled with an average of 45 ° C. with the addition of a detergent (Somat ^® ex Henkel) and rinse aid E9 or V3. After completing the wash program, the machines remained loaded. After 2 days, the smell in the interior was evaluated by a panel of 12 trained participants (grade 1 = neutral odor, grade 10 = strong natural bad smell). The results clearly show that the silver-containing rinse aid composition was evaluated better and reduces the formation of bad odor more.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• WO 99/57235 A1 [0004]
• WO 99/29815 A1 [0004]

Claims (6)

Cleaners for hard surfaces, in particular hand dishwashing detergent, comprising (A) a surfactant combination of a nonionic surfactant and a Amine oxide, and (b) elemental silver and / or a silver compound. Cleaning agent for hard surfaces according to claim 1, characterized in that the silver compound is selected from the group consisting silver acetate, silver nitrate, silver diamine chloride complex, silver cyclodextrin complex, Silver dicyanokalium complex, silver phthalimide, silver phenylcyanamide, Silver (ethylene thiourea) complex, silver imidazolate, transition metal NHC-calix [4] arene complexes, Silver Crown Ether, Silver Nitrate and mixtures thereof. Cleaning agent for hard surfaces according to claim 1 or claim 2, that the amount of elemental silver and / or silver compound 0.0001 to 1 % By weight, based on hard surface cleaners is. Cleaning agent for hard surfaces according to one of claims 1 to 3, characterized characterized in that the nonionic surfactant is selected is selected from the group consisting of alkoxylated fatty alcohols, alkoxylated Fatty acid alkyl esters, polyhydroxy fatty acid amides, Alkylphenolpolyglycol ethers and mixtures thereof. Use of silver and / or a silver compound as an antibacterial component in a cleanser for hard surfaces, in particular a hand dishwashing detergent, with a surfactant combination of a nonionic surfactant and an amine oxide. Method for antibacterial cleaning of hard Surfaces by dilution of a cleaning agent for hard surfaces, in particular hand dishwashing detergents, full (a) a surfactant combination of a nonionic Surfactant and an amine oxide, and (b) silver and / or a silver compound With Water to concentrations of 1: 1 to 1: 1000 and contacting the hard surface to be cleaned with the obtained Cleaning solution.