EP1075502B1 - Dishwashing detergent with an antibacterial effect - Google Patents

Abstract

The invention relates to a hand dishwashing detergent which can be perfumed in any way, cleans especially well, does not irritate the skin, is temperature and storage stable, and is not harmful to the environment. The detergent has a specific antibacterial effectiveness when used in concentration on wet working surfaces and kitchen appliances by using wet dishcloths, sponges and brushes. The inventive detergent is provided in the form of a mixture which contains anionic surfactants, one or more alkylbenzene sulfonates, benzoic acid, and/or one or more of the salts thereof. Benzoic acid or the salts thereof are suited for use as antibacterial active components in hand dishwashing detergents which contain alkylbenzene sulfonates.

Description

The invention relates to alkylbenzenesulfonate-containing dishwashing detergent, concentrated at Application show an antibacterial effect, i. with undiluted application one Inhibition of bacterial growth and, in addition, a number of Kill bacteria to a considerable extent.

One of the most underestimated health hazards are the hygienic conditions in the kitchen. Pathogenic bacteria can - especially after processing of eggs, raw meat and raw fish - on work surfaces and kitchen appliances, such as e.g. Increase cutting boards and pose a serious danger.

Tried with conventional dishwashing agents to a bacteriostatic effect achieve rapid results when testing antibacterial efficacy, that a number of hand dishwashing detergents even with concentrated use no cause sufficient growth inhibition or even killing germs.

The application of concentrated product on wet work surfaces or kitchen appliances with the help of moist rinse sponges, cloth or brushes also leads inevitably to a dilution of the hand dishwashing detergent and thus to a further reduced antibacterial effect.

A review of the antibacterial effect of hand dishwashing detergent formulations after the quantitative suspension test recognized in the disinfectant test the DGHM (German society for hygiene and microbiology), with which the number Surviving germs after expiration of a defined, practice-relevant exposure time in dependence has been determined by the use concentration, has now been shown that already in use a 50% dishwashing diluent containing a number of preservative-containing Formulations have no sufficient bacteriostatic effect.

The object of the invention was now to formulate a hand dishwashing detergent, that too at 50% dilution still a significant inhibition of bacterial growth and also causes a high degree of germ killing.

In addition, a modern hand dishwashing detergent must also have a special property spectrum have very good cleaning, skin compatibility, temperature and storage stability and ecological compatibility.

Antibacterial rinsing agents are known in the art. As a bacteriostatic component be u.a. Triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether), natural or naturally identical extracts, e.g. Extracts of orange shark, pine oil, geraniol, nerol etc. used.

A use of ecologically and economically acceptable triclosan amounts leads to a sufficient antibacterial effect at 100% use concentration, at Testing of antibacterial properties at a use concentration of 50% but no sufficient inhibitory effect on bacterial growth more.

If one works relatively high amounts of natural or nature-identical extracts, then yield - in addition to problems in the homogeneous incorporation of the active ingredients - also perfuming problems, because the odorous extracts are not or only with difficulty in the vom Developers desired scent direction can be over-perfumed.

At low levels of use, the bacteriostatic effect is not enough to even a sufficient inhibition of bacterial growth when using the hand dishwashing detergent using damp dish cloths, sponges or brushes.

Other agents, e.g. Chloramine-T (toluenesulphonylchloramide-sodium salt), Germall 115 (imidazolidinyl urea), sodium formate, 2-phenoxyethanol, 1-phenoxy-2-propanol, 2-Phenoxy-1-propanol showed in particular at 50% use concentration no adequate antibacterial effect.

Dishwashing liquid containing benzoic acid or its salts are known from US-A-39 6317 and US-A-5 510 052.

None of the compositions proposed in the prior art is therefore suitable as arbitrarily perfumable, very good cleansing, hypoallergenic, temperature and storage-stable and ecologically compatible hand dishwashing detergent with specific antibacterial Efficacy for concentrated use on wet work surfaces, kitchen appliances using damp dishcloths, sponges and brushes.

Easily perfumable, very cleansing, skin-friendly, temperature and storage stable and ecologically compatible products with good antibacterial activity concentrated application is obtained when a surfactant-containing mixture with alkylbenzenesulfonate and optionally other surfactants, especially fatty alcohol ether sulfate, but Also provides alkylpolyglycoside and betaine, together with benzoic acid or salts thereof.

The present invention is therefore a hand dishwashing detergent with good antibacterial activity containing anionic surfactants, wherein the agent is an or several alkylbenzenesulfonates and as antibacterial active component benzoic acid and / or one or more of its salts in amounts of 1 to 8 wt .-%.

Likewise provided by the present invention is the use of benzoic acid and / or one or more of their salts as an antibacterial component in alkylbenzenesulfonate-containing Hand dishwashing detergents.

Benzoic acid salts in the context of the present invention are in particular the sodium, potassium, Magnesium or calcium salts and mixtures thereof, alone or together can be used with benzoic acid in the inventive compositions. For the antibacterial effect is irrelevant, whether benzoic acid salts or benzoic acid, optionally together with the corresponding hydroxides, i. Sodium, potassium, magnesium or calcium hydroxide used.

To ensure sufficient inhibition of bacterial growth as well as to The highest possible germ killing rate is a content of benzoic acid and / or its content Salts preferably from 9 to 6% by weight and more preferably from 1 to 4% wt.

It has also been found that, for the purposes of the invention, a benzoic acid and / or benzoic acid salt-containing rinse aid formulation at a pH in the finished product between 4 and 6, preferably between 4.5 and 5.5, in particular between 4.9 and 5.3, the strongest antibacterial activity paired with the most favorable storage stability having. The pH of the compositions according to the invention can be determined by means of customary pH regulators, For example, citric acid or sodium hydroxide can be adjusted.

Alkylbenzenesulfonates in the context of the teaching according to the invention are alkylbenzenesulfonates with straight-chain or branched, saturated or unsaturated C _6-22- alkyl radicals, preferably C _8-18 -alkyl radicals, in particular C _9-14- alkyl radicals, most preferably C _10-13 -alkyl radicals. They are used as alkali metal and / or alkaline earth metal salts, in particular sodium, potassium, magnesium and / or calcium salts, as well as ammonium salts or mono-, di- or triethanolammonium salts but also as alkylbenzenesulfonic acid together with the corresponding alkali metal or alkaline earth metal hydroxide and / or ammonia or mono-, di- or triethanolamine.

Important is u.a. the clarity of the products, discontinuation of phases or ingredients as well as a dull appearance is usually - especially from the user's point of view - not wanted.

Due to the pronounced electrolyte sensitivity of alkylbenzenesulfonate-containing, In particular, alkylbenzenesulfonate sodium salt-containing agents, the incorporation of the for a sufficient antibacterial effect required amount of benzoic acid or Benzoic acid salts cause their expulsion or separation.

However, the incorporation of benzoic acid or benzoic acid salts succeeds problem-free, if the alkylbenzenesulphonates are partially or completely converted in the form of their mono-, di- or trialkanolammonium salts, in particular triethanolammonium salts. In a preferred embodiment of the invention contain the means accordingly Mono-, di- or trialkanolammonium alkylbenzenesulfonate, in particular triethanolammonium alkylbenzenesulfonate, in amounts of, based on the total amount of weight Alkylbenzenesulfonates, from 10 to 100%, preferably from 30 to 100%, in particular from 50 to 100%.

In a likewise preferred embodiment of the invention, the means include Alkylbenzenesulfonates excluding mono-, di- and / or trialkanolammonium alkylbenzenesulfonate, in particular triethanolammonium alkylbenzenesulfonate.

The incorporation of benzoic acid or benzoates also succeeds when the means a Combination of alkylbenzenesulfonates with one or more fatty alcohol ether sulfates contain. In a correspondingly preferred embodiment of the invention the agents alkylbenzenesulfonates and fatty alcohol ether sulfates in a weight ratio from 10: 1 to 1: 5, preferably from 5: 1 to 1: 2, in particular from 2: 1 to 1: 1.5. Here too, in a further preferred embodiment of the invention as alkylbenzenesulfonates exclusively mono-, di- or Trialkanolammoniumalkylbenzolsulfonate included on average.

Other anionic surfactants according to the present invention may be other than the alkylbenzenesulfonates and the aforementioned fatty alcohol ether sulfates aliphatic sulfates such as fatty alcohol sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkanesulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates, and Lingninsulfonate. Also usable in the context of the present invention are fatty acid cyanamides, sulfosuccinic acid esters, fatty acid isethionates, acylaminoalkanesulfonates (Fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates.

Particularly preferred in the context of the present invention are the fatty alcohol ether sulfates. Also preferred are fatty alcohol sulfates and combinations of fatty alcohol ether sulfates and fatty alcohol sulfates.

In the context of the present invention are fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms. The former are particularly preferred because of their vegetable base as based on renewable raw materials for environmental reasons, but without limiting the teaching of the invention to them. In particular, the oxo alcohols or their derivatives, which are obtainable, for example, by the ROELEN 's oxo synthesis, can also be used correspondingly.

Fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. The person skilled in the art generally understands the reaction products under alkoxylated alcohols of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the sense of the present invention Invention the longer chain alcohols. Usually arise from n moles Ethylene oxide and one mole of alcohol, depending on the reaction conditions a complex Mixture of addition products of different degrees of ethoxylation. A Another embodiment is preferred in the use of mixtures of the alkylene oxides the mixture of ethylene oxide and propylene oxide. Especially preferred in the sense Lower ethoxylated fatty alcohols (0.5 to 4 moles of EO) are preferred in the present invention 1 to 2.5 moles of EO).

The anionic surfactants are preferably used in amounts of from 0.2 to 40% by weight, in particular from 3 to 35 wt .-%, particularly preferably from 5 to 30 wt .-%.

Suitable surfactant mixtures are especially those of anionic in combination with one or more nonionic surfactants or betaine surfactants, the betaine surfactants in this context is to be equated with the class of amphoteric surfactants. Also the joint additional use of nonionic surfactants and betaine surfactants in Mixture may be advantageous for many applications. Overall, the surfactants are used in amounts of 0.2 to 50 wt .-%, preferably from 1 to 40 wt .-%, in particular of 3 to 35 wt .-% and most preferably from 5 to 30 wt .-%.

Nonionic surfactants in the context of the present invention may be alkoxylates such as Polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped Polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Also useful are ethylene oxide, propylene oxide, block polymers and fatty acid alkanolamides and fatty acid polyglycol ethers. An important class of nonionic surfactants, which can be used in the invention are the polyol surfactants and especially here the glucosurfactants, such as alkylpolyglycoside and fatty acid glucamides. Especially preferred are the alkyl polyglucosides.

Alkylpolyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols according to the relevant processes of preparative organic chemistry, wherein, depending on the nature of the preparation, a mixture of monoalkylated, oligomeric or polymeric sugars is obtained. Preferred alkyl polyglycosides may be alkyl polyglucosides, the alcohol particularly preferably being a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched C ₈ - to C ₁₈ -alkyl chains and the degree of oligomerization (DP) of the sugars between 1 and 10, preferably 1 to 6, in particular 1.1 to 3, more preferably 1.1 to 1.7.

Preferably, the compositions contain nonionic surfactants in amounts of from 0.1 to 14.9 wt .-%, in particular from 0.5 to 8 wt .-% and most preferably from 1 to 6% by weight.

The betaine surfactants which can be used according to the invention include the alkylbetaines, the alkylamidobetaines, the imidazolinium betaines and the aminopropionates as well such as the sulfobetaines and biosurfactants. A preferred ingredient here is alkylamidobetaine.

Preferably, these betaine surfactants in amounts of 0.05 to 10 wt .-%, in particular from 0.1 to 7 wt .-%, most preferably from 0.2 to 5 wt .-%, used.

Advantages in terms of clarity of the products are also obtained - especially in mixtures containing high levels of surfactants - when the formulation contains one or more dicarboxylic acids and / or salts thereof, alone or in admixture, preferably a composition of sodium salts of adipic, succinic and glutaric acid, as it is available, for example, under the trade name Sokalan® DSC Na . The use of from 0.1 to 8% by weight, preferably from 1 to 6% by weight, particularly preferably from 2.5 to 5% by weight, has proven particularly advantageous.

Another favorable component of the agents according to the invention are solvents, for example, alcohols, preferably low molecular weight alkanols having 1 to 4 carbon atoms in the molecule, especially ethanol and isopropanol. They contribute to the incorporation of perfume and dye, prevent the formation of liquid crystalline phases and improve the cold stability of the clear formulations. As a particularly favorable has in this case, a solvent content of up to 8% by weight, preferably from 0.3 to 6% by weight, in particular from 0.5 to 5% by weight.

Also advantageous in this respect in the compositions according to the invention the optional Presence of solubilizers, for example, alkanolamines, polyols such as Ethylene glycol, 1, 2-propylene glycol, glycerol and other monohydric and polyhydric alcohols and alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical, in particular Cumene, toluene and xylene sulfonate, in amounts of up to 5 wt .-%, preferably 0.05 to 3 wt .-%, in particular 0.1 to 2 wt .-%, from.

In addition to the ingredients mentioned so far, more, in hand dishwashing detergents usual ingredients, e.g. UV stabilizers, defoamers (such as silicone oils, Paraffin oils or mineral oils), structuring agents, perfumes, dyes, corrosion inhibitors, Preservatives or the like, preferably in amounts of up to 5 wt .-%, included be.

The hand dishwashing detergents according to the invention can be obtained by stirring together individual components in any order and leaving the mixture to stand until Create freedom from blisters. The order of attachment is not for the preparation of the agent crucial.

Examples

The compositions E1 to E5 according to the invention were prepared as described above and their pH, their viscosity, their clouding or clearing point and partly also their antibacterial activity and their rinsing power were determined.

The compositions of the compositions E1 to E5 according to the invention in% by weight and the specific properties are reproduced in Table 1. In addition, agents E1 to E5 according to the invention contained traces of dye. The pH of the agents E1 to E5 according to the invention was adjusted with citric acid.

The viscosity was determined at 20 ° C. using a Brookfield LV DV II + viscometer (spindle 25, shear rate 30 min ^-1 ).

The cold cloud point was determined by cooling a sample in the cryostat with a cooling rate of 0.2 ° C · min ^-1 , wherein as the cold cloud point is the temperature at which a slight turbidity was first detected. After the sample was completely clouded, heating was effected at a heating rate of 0.2 ° C.min ^-1 . The clear point is the temperature at which the sample was for the first time completely clear.

The rinsing power of the agents E1 to E3 and E5 according to the invention was determined in a semi-automatic plate test apparatus using two different soils (beef tallow or olive oil / porcine grease stain). It was at a constant temperature of 40 or 45 ° C in 5 liters of water with 16 ° German hardness under constant conditions compared to a high-quality classical hand dishwashing detergent as a laboratory standard soiled with the test soil dish rinsed until the - formed before the start of foam - destroyed was and the plates were not clean anymore. The concentration of the agent was 4 ml per 5 liters of water. The number of rinsed plates is set in relation to the laboratory standard with a rinsing capacity of 100% (the average over both soils is indicated). E1 E2 E3 E4 E5 C _10-13 ABA Na salt 9.4 9.1 8.5 - 8.5 C _10-13 ABA TEA salt - - - 9 9.5 C _12/14 Alcohol Ether Sulfate (2EO) Na salt 9.5 9 10.5 9 3.5 C _12/16 alkyl polyglucoside, DP = 1.4 - 4 - 4 - cocoamidopropyl 0.3 - 0.3 - - Benzoic acid, techn. 3 3 - - 3 Sodium benzoate - - 3.5 3.5 - ethanol 0.9 - - - - Cumenesulfonate Na salt - 1.5 0.2 0.9 - Perfume 0.2 0.4 0.2 0.4 0.2 Water ad 100 100 100 100 100 PH value 5.1 5.1 5.0 5.0 5.1 Viscosity at 20 ° C [MPa.s] 935 955 1175 1100 525 Cold cloud / clear point [° C] -3 / + 3 -2 / + 5 -3 / + 2 + 2 / + 5 -3 / + 4 Appearance clear Clear clear Clear Clear cleaning power [%] 97 102 93 - 102 DGHM suspension test > 5,08 > 5,08 - - - EN 1040 (best. = passed) - - spec. spec. -

Claims (18)

1. Antibacterial hand dishwashing detergent containing anionic surfactants, characterized in that it contains one or more alkyl benzenesulfonates and, as antibacterial active component, benzoic acid and/or one or more of its salts in quantities of 1 to 8% by weight.
2. Detergent as claimed in claim 1, characterized in that it contains mono-, di- or trialkanolammonium alkyl benzenesulfonate, more particularly triethanolammonium alkyl benzenesulfonate, preferably in quantities - based on the total quantity by weight of alkyl benzenesulfonates - of 10 to 100%, preferably 30 to 100% and more particularly 50 to 100%.
3. Detergent as claimed in claim 2, characterized in that it contains only mono-, di- or trialkanolammonium alkyl benzenesulfonate, more particularly triethanolammonium alkyl benzenesulfonate, as alkyl benzenesulfonates.
4. Detergent as claimed in any of the preceding claims, characterized in that it contains one or more fatty alcohol ether sulfates.
5. Detergent as claimed in claim 4, characterized in that it contains alkyl benzenesulfonates and fatty alcohol ether sulfates in a quantity ratio by weight of 10:1 to 1:5, preferably 5:1 to 1:2 and more particularly 2:1 to 1:1.5.
6. Detergent as claimed in any of the preceding claims, characterized in that it has a pH value of 4.0 to 6.0, preferably between 4.5 and 5.5 and more particularly between 4.9 and 5.3.
7. Detergent as claimed in any of the preceding claims, characterized in that it contains anionic surfactants in combination with one or more nonionic surfactants or betaine surfactants.
8. Detergent as claimed in claim 7, characterized in that it contains nonionic surfactants and betaine surfactants.
9. Detergent as claimed in claim 7 or 8, characterized in that it contains one or more alkyl polyglycosides, preferably alkyl polyglucosides, as a nonionic surfactant component.
10. Detergent as claimed in any of the preceding claims, characterized in that it contains benzoic acid and/or one of its salts in quantities of 3 to 8% by weight.
11. Detergent as claimed in any of the preceding claims, characterized in that it contains sodium, potassium, magnesium or calcium benzoate or mixtures thereof on their own or together with benzoic acid.
12. Detergent as claimed in any of the preceding claims, characterized in that it contains 0.2 to 50% by weight, preferably 1 to 40% by weight, more preferably 3 to 35% by weight and most preferably 5 to 30% by weight of surfactant mixture.
13. Detergent as claimed in any of the preceding claims, characterized in that it contains

    (a) 0.2 to 40% by weight, preferably 1 to 40% by weight and more particularly 3 to 35% by weight of anionic surfactants, more particularly - besides the alkyl benzenesulfonates - fatty alcohol ether sulfates,

    (b) 0.1 to 14.9% by weight, preferably 0.5 to 8% by weight and more particularly 1 to 6% by weight nonionic surfactants, more particularly alkyl polyglucosides, and

    (c) 0.5 to 10% by weight, preferably 0.1 to 7% by weight and more particularly 0.2 to 5% by weight betaine surfactants, more especially alkyl amidobetaines.
14. Detergent as claimed in any of the preceding claims, characterized in that it contains a solvent, preferably one or more low molecular weight alcohols, more particularly ethanol, in quantities of up to 8% by weight, preferably in quantities of 0.3 to 6% by weight and more particularly in quantities of 0.5 to 5% by weight.
15. Detergent as claimed in any of the preceding claims, characterized in that it contains one or more solubilizers from the group of alkanolamines, polyols, more particularly ethylene glycol, 1,2-propylene glycol, glycerol and alkyl benzenesulfonates with 1 to 3 carbon atoms in the alkyl chain, more particularly cumene, toluene and xylene sulfonates in quantities of up to 5% by weight, preferably in quantities of 0.05 to 3% by weight and more particularly in quantities of 0.1 to 2% by weight.
16. Detergent as claimed in any of the preceding claims, characterized in that it contains one or more dicarboxylic acids and/or salts thereof individually or in admixture in quantities of 0.1 to 8% by weight, preferably in quantities of 1 to 6% by weight and more particularly in quantities of 2.5 to 5% by weight as an additional ingredient.
17. Detergent as claimed in any of the preceding claims, characterized in that it contains other ingredients typical of hand dishwashing detergents, such as UV stabilizers, defoamers, solubilizers, structurants, perfumes, dyes, corrosion inhibitors or preservatives.
18. Use of benzoic acid and/or one or more of its salts in quantities of 1 to 8% by weight as an antibacterial component in hand dishwashing detergents containing alkyl benzenesulfonate.