EP1036146A1

EP1036146A1 - Dishwashing detergent with antibacterial action

Info

Publication number: EP1036146A1
Application number: EP98958927A
Authority: EP
Inventors: Brigitte Giesen; Dagmar Zaika; Hans Andree; Michael Heinzel; Norbert Stelter
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1997-12-05
Filing date: 1998-11-28
Publication date: 2000-09-20
Anticipated expiration: 2018-11-28
Also published as: JP2001526301A; DE59812520D1; DE19753982A1; EP1036146B1; ES2236963T3; ATE287940T1; WO1999029815A1

Abstract

The invention relates to an especially compatible hand dishwashing detergent which can be perfumed in any way, cleans excellently, is skin compatible, temperature-stable, stable in storage, and ecological. The detergent has a specific antibacterial activity during concentrated application on wet work surfaces, kitchen appliances while using wet cleaning towels, sponges and brushes. The detergent is provided by adding one or more carboxylic acids and/or the salts thereof having antibacterial action to a tensidic mixture comprised of anionic tensides and/or nonanionic tensides and/or betaine tensides.

Description

"Dishwashing liquid with antibacterial effect"

The invention relates to dishwashing detergents which, when used in concentrated form, show an antibacterial effect, i.e. when used undiluted, inhibit bacterial growth and, in addition, kill a large number of bacteria.

One of the most underestimated health risks is the hygienic conditions in the kitchen. Disease-causing bacteria - especially after processing eggs, raw meat and raw fish - can spread on work surfaces and kitchen appliances, e.g. Increase cutting boards and pose a serious danger.

If one tries to achieve a bacteriostatic effect with conventional dishwashing detergents, it is quickly found when checking the antibacterial effectiveness that a number of hand dishwashing detergents do not sufficiently inhibit growth or even kill germs even with concentrated use.

The use of concentrated product on damp work surfaces or kitchen appliances with the help of damp sponges, cloths or brushes also leads inevitably to a dilution of the hand dishwashing liquid and thus to a further reduced antibacterial effect.

A review of the antibacterial effect of hand dishwashing agent formulations according to the "quantitative suspension test" of the DGHM (German Society for Hygiene and Microbiology) recognized in the disinfectant test, in which the number of surviving germs is determined after a defined, practice-relevant exposure time depending on the concentration in use now shown that even when using a 50% detergent dilution, a number of formulations containing preservatives do not have a sufficient bacteriostatic effect.

The object of the invention was to formulate a hand dishwashing detergent that too with a 50% dilution, there is still a significant inhibition of bacterial growth and, to a large extent, also causes germ killing.

In addition, a modern hand dishwashing detergent must also have a special range of properties, which include excellent cleaning, skin compatibility, temperature and storage stability and ecological compatibility.

Antibacterial detergents are known in the prior art. As a bacteriostatic component, i.a. Triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether), natural or nature-identical extracts, e.g. Extracts from orange peel, pine oil, geraniol, nerol etc. are used.

The use of ecologically and economically justifiable amounts of triclosan leads to a sufficient antibacterial effect at 100% application concentration, but when the antibacterial properties are tested at an application concentration of 50% there is no longer sufficient inhibitory effect on bacterial growth.

If relatively large amounts of natural or nature-identical extracts are worked in, then - in addition to problems with the homogeneous incorporation of the active ingredients - there are also problems with perfuming, since the odor-intensive extracts cannot be perfumed, or only with difficulty, in the fragrance direction desired by the developer.

When used in small quantities, the bacteriostatic effect is not sufficient to guarantee sufficient inhibition of bacterial growth when using the hand dishwashing liquid using moist dishcloths, sponges or brushes.

Other active ingredients, such as chloramine-T (Toluolsulfonsäurechloramid-sodium salt), Germall ^® 115 (imidazolidinyl urea), sodium formate, 2-phenoxyethanol, 1-phenoxy-2-propanol, 2-phenoxy-l-propanol showed particularly at 50% Use concentration not sufficient antibacterial effect.

Accordingly, none of the compositions proposed in the prior art is suitable as an arbitrarily perfumable, excellently cleansing, skin-compatible, temperature- and storage-stable and ecologically particularly compatible hand dishwashing detergent with specific antibacterial activity in concentrated use on moist surfaces. worktops, kitchen appliances using wet dishcloths, sponges and brushes.

Easily perfumed, excellent cleaning, skin-compatible, temperature- and storage-stable and ecologically particularly compatible products with good antibacterial activity with concentrated use are obtained by mixing a mixture of fatty alcohol sulfate, possibly fatty alcohol sulfate, alkyl polyglycoside and betaine together with a carboxylic acid or their Provides salts.

The present invention accordingly relates to an antibacterial hand dishwashing detergent containing surfactant mixtures of anionic surfactants and / or nonionic surfactants and / or betaine surfactants, which contains one or more carboxylic acids and / or their salts with antibacterial activity.

The present invention also relates to the use of one or more carboxylic acids and / or their salts as antibacterial components in hand dishwashing detergents.

A particular advantage of the hand dishwashing detergent according to the invention is its good antibacterial activity against the kitchen hygiene-relevant herpes viruses, with which cutlery and glasses can be easily contaminated when used by infectious persons.

Carboxylic acids or carboxylic acid salts in the context of the present invention are, in particular, benzoic acid (phenyl formic acid), lactic acid (2-hydroxypropionic acid), salicylic acid (2-hydroxybenzoic acid), sorbic acid (2,4-hexadienoic acid) or mixtures thereof and / or their sodium, Potassium, magnesium or calcium salts and mixtures thereof.

It has surprisingly been found that particularly suitable antibacterial active ingredients are benzoic acid and / or its sodium salt, salicylic acid and / or its sodium salt, lactic acid and / or its sodium salt and mixtures of two or more carboxylic acids and / or their salts. Benzoic acid is particularly suitable.

To ensure sufficient inhibition of bacterial growth and the highest possible rate of germ killing, an application concentration between 0.1 and 8% by weight, preferably between 0.5 and 6% by weight and particularly preferably between 1 and 4% by weight.

Surprisingly, it was also found that 115 enables the combined use of carboxylic acids and / or carboxylic acid salts with imidazolinidyl urea, for example Germall® ^®, - while retaining the good bacteriostatic properties - the use amount of carboxylic acid and / or lower carboxylic acid salt dramatically. The suitable amount of carboxylic acid and / or carboxylic acid salt in the case of a combined use of active ingredient is between 0.05 and 2% by weight, preferably between 0.1 and 1% by weight and particularly preferably between 0.2 and 0.5% by weight. -%. The amount of imidazolidinyl urea used in this case is between 0.05 and 2% by weight, preferably between 0.1 and 1.5% by weight and particularly preferably between 0.2 and 1% by weight.

It has also been found that - for the purposes of the invention - a detergent formulation containing carboxylic acid and / or carboxylic acid salt at a pH in the finished product between 4 and 6, preferably between 4.5 and 5.5, particularly preferably between 4.9 and 5.3, which has the strongest antibacterial activity paired with the most favorable storage stability.

Particularly suitable surfactant mixtures are those made from anionic and nonionic surfactants. However, the additional use of betaine surfactants in a mixture can also be very useful for many applications. In total, the surfactants are used in amounts of 0.4 to 50% by weight, preferably 1 to 45% by weight, particularly preferably 3 to 42% by weight and extremely preferably 5 to 40% by weight.

Anionic surfactants according to the present invention can be aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates, and lingine sulfonates. Fatty acid cyanamides, sulfosuccinic esters, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates can also be used in the context of the present invention. The fatty alcohol ether sulfates are particularly preferred in the context of the present invention. Fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. The person skilled in the art generally understands by alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably the longer-chain alcohols in the sense of the present invention. As a rule, n moles of ethylene oxide and one mole of alcohol form a complex mixture of addition products of different degrees of ethoxylation, depending on the reaction conditions. Another embodiment is the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Low-ethoxylated fatty alcohols (0.5-4 mol EO, preferably 1-2 mol EO) are very particularly preferred for the purposes of the present invention.

The anionic surfactants are preferably used in amounts between 0.2 and 39.8% by weight, preferably 5 to 35% by weight, particularly preferably 10 to 32% by weight. However, amounts up to about 45% by weight can also be used, e.g. B. if the use of fatty alcohol sulfates is intended.

Nonionic surfactants in the context of the present invention can be alkoxyates 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. Ethylene oxide, propylene oxide, block polymers and fatty acid alkanolamides and fatty acid polyglycol ethers can also be used. An important class of nonionic surfactants that can be used according to the invention are the polyol surfactants and here in particular the glucosurfactants, such as alkyl polyglycosides and fatty acid glucamides. The alkyl polyglucosides are particularly preferred.

Alkyl polyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols according to the relevant methods of preparative organic chemistry. Depending on the type of preparation, a mixture of monoalky cheerful, oligomeric or polymeric sugars results. Preferred alkyl polyglycosides can be alkyl polyglucosides, the alcohol being a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched alkyl chain lengths between Cg and C ₁₈ and the degree of oligomerization of the sugars being between 1 and 10 being particularly preferred. The alkyl polyglycosides are particularly preferably used in amounts between 0.1 to 14.9% by weight, preferably 0.5 to 8% by weight and particularly preferably 1 to 6% by weight.

The zwitterionic surfactants or amphoteric surfactants which can be used according to the invention include the alkyl betaines, the alkyl amido betaines, the imidazolinium betaines and the aminopropionates, as well as the sulfobetaines and biosurfactants. A preferred ingredient is alkyl amido betaine.

These amphoteric surfactants are preferably used in amounts between 0.1 to 14.9% by weight, preferably 0.5 to 8% by weight and particularly preferably 1 to 6% by weight.

In a preferred embodiment of the invention, the hand dishwashing detergent contains as surfactant mixture (a) 0.2 to 39.8% by weight, preferably 5 to 35% by weight, particularly preferably 10 to 32% by weight, anionic surfactants, preferably fatty alcohol ether sulfates and / or fatty alcohol sulfates, (b) 0.1 to 14.9% by weight, preferably 0.5 to 8% by weight and particularly preferably 1 to 6% by weight, nonionic surfactants, preferably alkyl polyglucosides, and (c) 0.1 to 14.9% by weight, preferably 0.5 to 8% by weight and particularly preferably 1 to 6% by weight, betaine surfactants, preferably alkylamido betaines.

As solubilizers, for example for dyes and perfume oils, for example alkanolamines, polyols such as ethylene glycol, propylene glycol, 1,2 glycerol and other mono- and polyhydric alcohols, and also alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical can be used.

It is important, among other things, that the clarity of the products, the discontinuation of phases or ingredients, and a cloudy appearance is generally not desirable.

Particular advantages are obtained - especially in the case of mixtures containing high surfactants - if the formulation is admixed with a composition of sodium salts of adipic succinic and glutaric acid, as described, for. B. is available under the trade name Sokalan ^® DSC. The use of 0.1 to 8% by weight, preferably 1 to 6% by weight, particularly preferably 2.5 to 5% by weight, has proven to be particularly advantageous.

Another cheap component of the agents according to the invention are solvents, solvents, for example one or more low molecular weight alcohols, for example ethanol. They contribute to the incorporation of perfume and dye, prevent the formation of liquid-crystalline phases and play a part in the formation of clear products. According to the invention, between 0 and 12% by weight, preferably between 3 and 10% by weight, particularly preferably between 5 and 8% by weight, of solvents can be present.

In addition to the previously mentioned ingredients, other ingredients that are customary in hand dishwashing detergents, such as defoamers (such as silicone oils, paraffin oils or mineral oils), structuring agents, perfume substances, dyes, corrosion inhibitors, preservatives or the like, common ingredients in hand dishwashing detergents in amounts of up to 5% by weight. be included.

Examples

example 1

The antibacterial effect of the hand dishwashing detergent according to the invention is exemplified by the following recipes (in the tables of Examples 1 and 2, the unit% stands for% by weight). The specified pH values were adjusted with citric acid.

Basic formulation: 31.5% by weight of C ₁₂ .ι ₄ fatty alcohol ether sulfate (1.3 EO) 3.0% by weight of C ₈ .i6-alkyl polyglucoside d _p l, 4 5.0% by weight of cocoamidopropylbetaine 3, 5 wt .-% of dicarboxylic acid (Sokalan ^® DSC-Na) x wt .-% ethanol y wt .-% of active ingredient 100.0 wt .-% water

Recipe 1 2 3 4 5 6 7

Active ingredient 2.0% 3.0% 0.3% 0.1% 0.2% 3.0% 0.5% BenzoeMilchGerTriclosan Chloramine Benzyl-Imidazolic acid acid mall ^® 115 (Irgasan T (Halal alcohol nidyl - + DP300) mid) urea

0.2% (GerSalicyl-mall ^® 115) acid

Ethanol 7.0% 7.2% 7.5% 7.5% 7.5% 6.5% 7.5% pH 5.15 5.1 5.2 6.8 7.0 6.8 6.7 log. Reduction rate *

Salmonella> 5.6 4.1 2.7 0.2 - 0.2 0.7 0.07 enteritidis

* Test method: quantitative suspension test based on the DGHM test methodology Test germ: Salmonelle Enteritidis (practice isolate)

Test concentration: 50% in DGHM water (17 ° dH) Test temperature: room temperature Exposure time: 15 minutes Example 2

The antibacterial effect of the hand dishwashing detergent according to the invention is further exemplified by formulations 8 and 9, which are completely effective against herpes viruses, on the basis of the following basic formulation. In addition, both formulations contained small amounts of color and fragrance. A pH of 5.2 was set in each case with citric acid.

Basic formulation: 31.5% by weight of C ₁₂ . ₁₄ -fatty alcohol ether sulfate (1.3 EO) 5.0% by weight Cs-i _ö alkyl polyglucoside d _p l, 4 3.0% by weight cocoamidopropylbetaine 3.5% by weight dicarboxylic acid mixture (Sokalan ^® -DSC-Na ) 6.5 wt .-% ethanol y wt .-% active ingredient ad 100.0 wt .-% water

Recipe 8 9

Active ingredient 2.35% sodium benzoate 1.75% sodium benzoate + 1.50% lactic acid logarithmic reduction factor herpes virus

Test conc. 0.04% at 30 ° C> 5.5> 5.5

Test conc. 0.20% at 40 ° C not determined> 5.5

The test methodology was based on the guidelines of the Federal Health Office (BGA) and the German Association for Combating Virus Diseases (DVV) for testing chemical disinfectants for their effectiveness against viruses in the version dated September 1, 1982 {Bundesgesundheitsblatt 1982, 25, No. 12, 397- 398) with the following deviations that 1.) instead of the test viruses prescribed there herpes simplex-Viτus, strain HV342 (cultivation on the Nero cells specified in the guideline) was used, 2.) instead of the room temperature specified there the test temperatures given above of 30 and 40 ° C and

3.) deviating from the guideline, an additional load on the test approach by fetal calf serum was dispensed with. The exposure time was 15 minutes at the test concentrations shown in the table.

Claims

claims

1. Antibacterial hand dishwashing detergent, containing surfactant mixtures of anionic surfactants and / or nonionic surfactants and / or betaine surfactants, characterized in that it contains one or more carboxylic acids and / or their salts with antibacterial activity.

2. Composition according to claim 1, characterized in that it has a pH between 4 and 6 means.

3. Composition according to one of the preceding claims, characterized in that the surfactant mixtures contain anionic and nonionic surfactants.

4. Composition according to claim 3, characterized in that it additionally contains betaine surfactants.

5. Composition according to claim 3 or 4, characterized in that it contains as a nonionic surfactant alkyl polyglycosides, preferably alkyl polyglucosides.

6. Agent according to one of the preceding claims, characterized in that it contains between 0.1 and 8 wt .-% carboxylic acid and / or carboxylic acid salts.

7. Composition according to one of the preceding claims, characterized in that it contains benzoic acid, lactic acid, salicylic acid, sorbic acid or mixtures thereof and / or their sodium, potassium, magnesium or calcium salts as the carboxylic acid.

8. Agent according to one of the preceding claims, characterized in that it contains an active ingredient combination consisting of carboxylic acids and / or carboxylic acid salts and imidazolinidyl urea as antibacterial ingredient.

9. Composition according to claim 8, characterized in that the active ingredient combination contains between 0.05 and 2 wt .-% carboxylic acids and / or carboxylic acid salts and between 0.05 and 2 wt .-% imidazolidinyl urea.

10. Agent according to one of the preceding claims, characterized in that it contains 0.4 to 50 wt .-% surfactant mixture.

11. Agent according to one of the preceding claims, characterized in that it (a) 0.2 to 39.8 wt .-% anionic surfactants, preferably fatty alcohol ether sulfates and / or fatty alcohol sulfates, (b) 0.1 to 14.9 wt. % nonionic surfactants, preferably alkyl polyglucosides, and (c) 0.1 to 14.9% by weight betaine surfactants, preferably alkyl amido betaines.

12. Composition according to one of the preceding claims, characterized in that it contains, as a further ingredient, one or more dicarboxylic acids and / or their salts, alone or in a mixture, in amounts of 0.1 to 8% by weight.

13. Agent according to one of the preceding claims, characterized in that it contains solvents, for example one or more low molecular weight alcohols, e.g. Ethanol, in amounts of up to 12 wt .-%, preferably between 3 and 10 wt .-%, contains.

14. Composition according to one of the preceding claims, characterized in that it contains further ingredients customary in hand dishwashing detergents, such as UN stabilizers, defoamers, solvents, structuring agents, perfumes, dyes, corrosion inhibitors, preservatives or the like.

15. Use of one or more carboxylic acids and / or their salts as an antibacterial component in hand dishwashing detergents.