CZ9902467A3 - Antibacterial liquid dishwashing detergent - Google Patents

Abstract

Liquid dishwashing preparations with antibacterial effects, containing a surfactant or hydrotrope and an unsaturated aliphatic terpenic alcohol or its derivatives. The preparations described above are suitable for washing dirty dishes, and the sponge or washcloth does not develop microorganisms after use.

Description

Antibacterial liquid dishwashing detergent

Technical area

The invention relates to liquid dishwashing detergent compositions. These compositions have antibacterial properties.

State of the art

Liquid dishwashing detergents are in high demand among consumers and can be used either neat or diluted. In diluted form, the product is diluted with water to form a washing solution into which the dishes to be cleaned are immersed. In the pure state, the product is applied directly to the dishes, and this method often involves the use of a tool. More precisely, the product is applied to a tool, most often a sponge or washcloth, which is then brought into contact with the dishes to be cleaned.

The problem is that the dishwashing tool remains wet most of the time and therefore provides a good environment for bacteria to grow. A contaminated dishwashing tool that is used to wash dishes will then contaminate the dishes.

We have now discovered that some dishwashing detergents may serve the additional purpose of reducing or eliminating bacterial growth on dishwashing tools.

The essence of the invention

The compositions of the present invention are liquid dishwashing compositions comprising: - a surfactant

-a hydrotrope selected from the group consisting of salts of cumenesulfonate, toluenesulfonate, xylenesulfonate, benzenesulfonate or mixtures thereof and

-unsaturated aliphatic terpenic alcohol or derivative.

The invention further relates to a method of washing dishes with these preparations. Without being bound by theory, it is believed that the antibacterial effectiveness of the said preparations is largely controlled by • 9 ·

9 9 99

99

9 9 9

9 9 9

9

99 synergistic effect between the hydrotrope(s) and the unsaturated aliphatic terpenic alcohol(s) or derivatives.

Detailed description of the invention

The compositions of the present invention are liquid aqueous compositions. Typically they contain from 30% to 90% of the total weight of the composition water, preferably from 40% to 85%.

The compositions of the present invention are liquid and thus typically have a viscosity of from 5 cps to 2000 cps, preferably from 5 cps to 400 cps, most preferably from 5 cps to 350 cps, as measured by a Brookfield Viscometer with a number 18 tip at 20°C.

Surfactants

The compositions of the present invention comprise as a basic ingredient one or more of the following surfactants. Suitable for use in the present invention are amine oxides of the following formula:

r ₃ r ₂ -n—o

R, where R ₂ represents a straight or branched alkyl or alkenyl group having 10 to 16 carbon atoms and R ₃ and R 4 represent a C 1 to C 4 hydrocarbon chain, preferably a methyl or ethyl group. In general, when the number of carbon atoms in R ₂ is less than 10, the detergent effect of the composition is reduced, while when this number is greater than 16, the stability of the composition at lower temperatures is impaired.

Also suitable for use in the present invention are alkyl alkoxylated sulfates of the formula RiO(A) _n SO3M, where Ri is an alkyl or alkenyl group having 9 to 15 carbon atoms, A is an alkoxy group, preferably ethoxy or propoxy, most preferably ethoxy, n represents on average real numbers from 0.5 to 7, and M is an alkali metal, alkaline earth metal, ammonium or alkanolammonium group.

The use of alkyl alkoxylated sulfates with lower n values on a weight basis, typically when n is less than 1.0, improves the grease removal and suds formation performance of the composition due to the molar increase in anionites, but results in an increase in the total amount of non-alkoxylated alkyl sulfate and this makes it acutely unstable at lower temperatures. When different alkyl alkoxylated sulfates with different n values are used, the resulting average number n of alkyl alkoxylated sulfates in the composition will be the weighted molar average of the n values of the individual n values of the different alkyl alkoxylated sulfates used in the composition.

If the average value of n is less than 0.5, the skin action increases and this is not suitable. On the other hand, if the average value of n is higher than 3, the detergent effects are lost.

As for R1, if the average number of carbon atoms in R1 is less than 9, the detergent effect is insufficient, while if it is more than 16, the stability at a lower temperature is lost.

Suitable alkyl alkoxylated materials for use in the present invention may be straight or branched chain. By branched material is meant that Rj is branched, while the branching position and length of the branching group is determined by the position of the CH2OH functional group in the parent alcohol. Increasing the proportion of branched material may improve the physical stability of the formulation at lower temperatures.

In this regard, it is important that the branched alkyl alkoxylated sulfate material should not represent more than 60% by weight of the total alkyl alkoxylated sulfates (branched + linear), otherwise the suds formation of the product will be unacceptably reduced. At the other end of the range, there should be sufficient alkyl alkoxylated sulfate in the product to achieve suitable low temperature stability. This minimum amount depends on the specific needs and can be quantified by plotting the stability of a given matrix at the desired temperature as a function of the presence of branched material. In general, the branched alkyl alkoxylated sulfates should be present in amounts up to 60%, preferably from 10% to 55%, most preferably from 10% to 50%.

Alkyl alkoxylated sulfates are commercially available with various chain lengths, degrees of alkoxylation and degrees of branching under the trade names Empicol® ESA 70 (AE1S) or Empicol® ESB 70 (AE2S) from Albricht & Wilson with a carbon chain length distribution Cl2/14, which is derived from natural alcohols and is 100% linear, Empimin® KSL68/A - AE1S and ·· · • · · • · ♦ · *» · · · · · · · · · · · · · · · · · · · · · · · · *

Empimin® KSN70/LA - AE3S from Albricht & Wilson with a C12/13 chain length distribution and about 60% branching, Dobanol® 23 ethoxylated sulfates from Shell with a Cl2/13 chain length distribution and 18% branching, Lial® 123 ethoxylated sulfates from Condea Augusta with

Cl2/13 chain length distribution and 60% branching and Isalchem® 123 alkoxylated sulfates with Cl2/13 chain length distribution and about 95% branching.

Suitable alkyl alkoxylated sulfates can also be prepared by alkoxylation and sulfation of suitable alcohols as described in Surfactants in Consumer Products (J. Falbe) and Fatty oxoalcohols: Relation between their alkylchain structure and the performance of the derived AE, AS, AES presented at the 4th World Surfactants, Barcelona, 3-7 June 1996, Congress by Condea Augusta. Commercial oxo-alcohols are mixtures of primary alcohols containing several isomers and homologues. Industrial processes allow the separation of these isomers, resulting in alcohols with a linear isomer content ranging from 5 to 10% up to 95%. Examples of alcohols available for alkoxylation and sulfation are Lial® alcohols from Condea Augusta (60% branching), Isalchem® alcohols from Condea Augusta (95% branching), Dobanol® alcohols from Shell (18% linear isomer content).

Other suitable surfactants for use in accordance with the present invention are:

Alkylbenzenesulfonates, in which the alkyl group contains 9 to 15 carbon atoms, preferably 11 to 40 carbon atoms in a straight or branched chain. Particularly preferred linear alkylbenzenesulfonates contain about 12 carbon atoms. U. S. Patent 2,220,099 and 2,477,383 describe these surfactants in detail.

Alkyl sulfates obtained by sulfation of alcohols having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. The alkyl sulfates have the formula ROSO ₃ M ⁺ , where R is a C 8-22 alkyl group and M is a mono- or divalent cation.

Paraffin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms in the alkyl group. These surfactants are commercially available as Hostapur SAS from Hoechst Celanese.

4 4 ·» ·« 44 4 4

444 4444 4444

444 4 444 4 44 4

4444444 44 44 4*4 4*4

444 4444 4 4

4 44 44 44 44

Olefin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. U. S. Patent 3,332,880 contains descriptions of suitable olefin sulfonates.

-Alkyl glyceryl ether sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, in the alkyl group.

Estersulfonates of fatty acids of the formula:

R ₁ -CH(SO ₃ 'M ⁺ )CO ₂ R ₂ where Ri is a straight or branched alkyl of C 1 to C 16 , preferably C ₂ to C 16 , and R ₂ is a straight or branched alkyl of C 1 to C 6 , preferably primary C 1 and M + represents a mono- or divalent cation.

Sulfates of secondary alcohols having 6 to 18 carbon atoms, preferably 8 to 16 carbon atoms.

Other suitable cosurfactants for use in the present invention are:

Surfactants based on fatty acid amides:

O

R6—CN(R7) ₂ where ^R6 is an alkyl group containing from 7 to 21 carbon atoms, preferably from 9 to 17 carbon atoms, and each ^R7 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and ( _C2H4O ) _xH , where x ranges from 1 to 3.

Surfactants based on polyhydroxy fatty acid amides of structural formula (I):

About Rl

R2—CNZ ® where R ¹ is H, a C1-C4 hydrocarbon radical, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, with

Preferably C1-C4 alkyl, more preferably C1 or _C2 alkyl, most preferably C1 alkyl (i.e. methyl) and R is a C5-C31 hydrocarbon radical, preferably C7-C19 straight chain alkyl, more preferably C9-C17 straight chain alkyl or alkenyl, most preferably C11-C17 straight chain alkyl or alkenyl • 4 «4 *· 4 • 4 4

4 4 4

44444

4 4

4

4« «4

4 4 4

4 4 4

4 4

44

4 4 *

4 4 4 »44 4 4 4

4

44 or a mixture thereof and Z is a polyhydroxy hydrocarbon having a linear hydrocarbon chain with at least 3 hydroxyls attached directly to the chain or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated). Z will preferably be derived from a reducing sugar by a reductive amination reaction, more preferably Z is glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. Z will be selected from the group consisting of CH ₂ -(CHOH) _n -CH ₂ OH, -CH(CH ₂ OH)-(CHOH) _n .i-CH ₂ OH, -CH ₂ -(CHOH) ₂ (CHOR')(CHOH)CH ₂ OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide and alkoxylated derivatives thereof. Most preferred are glycityls where n is 4, especially -CH ₂ -(CHOH) 4 CH ₂ OH.

In formula (I) R ¹ may be N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.

R ² -CO-N< can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide and the like.

Z can be 1-deoxyglucitol, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygactityl, 1-deoxymannityl, 1-deoxymaltotriotityl and the like.

Betaine detergent surfactants having the general formula:

R—N ⁺ (R1) ₂ -R2COO' where R is a hydrophobic group selected from the group consisting of alkyl groups having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms, alkylaryl and arylalkyl groups having the same number of carbon atoms with a benzene ring taken as equivalent to two carbon atoms and similar structures interrupted by an amide or ether linkage; each R is an alkyl group having from 1 to 3 carbon atoms and R is an alkylene group having from 1 to 6 carbon atoms.

ETHylene oxide condensates, which are broadly defined as compounds formed by the condensation of an ethylene oxide group (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkylaromatic in nature. The length of the hydrophilic or polyoxyalkylene radical that is condensed with any particular hydrophobic *9 4 «ί» ·* ·· · · 9 · · · * · · 9

9 9 9 9 9 9-t 9 9 9 9 · ···· 9 · 9 9 9 9 999 999

9 9 9 9 9 9 9 9 · -»· ·« «· 99 group can be easily adjusted to form a water-soluble compound having the desired balance between hydrophilic and hydrophobic elements.

Examples of such ethylene oxide condensates useful as soap stabilizers are the condensation products of aliphatic alcohols with ethylene oxide. The alkyl chain of the aliphatic alcohol may be either straight or branched and generally contains from 8 to about 18 carbon atoms, preferably from 8 to 14 carbon atoms for best effect as a soap stabilizer, with the ethylene oxide being present in amounts of from 8 moles to 30 moles, preferably from 8 to about 14 moles of ethylene oxide per alcohol molecule.

Cationic quaternary ammonium surfactants of the general formula:

[R^OR ² ^] [R ³ (OR ² ) _y ] ₂ R ⁴ N ⁺ X' or amine surfactants of the general formula:

[R ¹ (OR ² )y][R ³ (OR ² ) _y ] R ⁴ N where R ¹ is an alkyl or alkylbenzyl group having from 6 to 16 carbon atoms in the alkyl chain; each R ² is selected from the group consisting of -CH2-CH2-, -C^CHyCHj)-, CH2CH(CH2OH)-, -CH2CH2CH2- and mixtures thereof, each R ₃ is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl and hydrogen, when y is not 0, R ⁴ is the same as R ³ or is an alkyl chain, wherein the total number of carbon atoms of R ¹ plus R ⁴ is from 8 to about 16, each y is from 0 to 10 and the sum of y is from 0 to 15 and X is any compatible anion.

The compositions of the present invention typically comprise from 10% to 60% by weight of the total composition of surfactant or mixture thereof, preferably from 10% to 55%, most preferably from 10% to 50%.

Hydrotropes

The compositions of the present invention comprise as a second major component a hydrotrope selected from the group consisting of salts of cumenesulfonate, toluenesulfonate, xylenesulfonate, benzenesulfonate and mixtures thereof. Preferred salts are ammonium and sodium salts.

The compositions of the present invention typically contain 1% to 15% of the total weight of the composition of said hydrotropes, preferably 1% to 10%, most preferably 2% to 6%.

9 9 · · · · · • ·

Unsaturated aliphatic terpenic alcohols or derivatives

The compositions of the present invention comprise as a third essential component an unsaturated aliphatic terpenic alcohol or its derivatives (i.e. unsaturated aliphatic terpenic alcohols where the alcohol group is functionalized, e.g. to acetate, formate, propionate, etc.) or mixtures thereof. Suitable alcohols or their derivatives for use in the present invention include geraniol, nerol, citronellol, linalool, citronellyl acetate, geranyl acetate, linalyl acetate, citronellyl formate, geranyl formate, linalyl formate, citronellyl propionate, geranyl propionate and linalyl propionate.

Most preferred for use in the present invention is geraniol.

The compositions of the present invention typically contain 0.1% to 3% by total weight of the composition of said unsaturated aliphatic terpenic alcohol, preferably 0.2% to 2.5%, most preferably 0.4% to 2%.

Other folders

The compositions of the present invention may include a number of additional optional ingredients, which are listed below:

The first possible, but preferred, component is a phenolic compound of the general formula

where R, R ¹ , R ² , R ³ and R ⁴ are independently H, a linear or branched, saturated or unsaturated hydrocarbon chain having 1 to 20 carbon atoms, preferably 1 to 10, more preferably from 1 to 4, an alkoxylated hydrocarbon chain of the general formula Ra(A) _n , where R is a linear or branched, saturated or unsaturated hydrocarbon chain having 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 4, where A is butoxy, propoxy and/or ethoxy and n is an integer from 1 to 4, preferably from 1 to 3 or an aryl chain having 1 to 20 carbon atoms, preferably from 1 to • ·

I · · 4 ► · · · • 44 444 and more preferably from 1 to 4 or mixtures thereof. Highly preferred of this class of compounds are eugenol and thymol.

The compositions of the present invention may contain from 0.1% to 4%, preferably from 0.2% to 1.5% of the total weight of the composition of these phenolic compounds or mixtures thereof.

Magnesium ions:

The compositions of the present invention preferably contain 0% to 2.0%, preferably 0.1% to 1.5%, most preferably from 0.2% to 1% by weight of the composition of magnesium ions, which may be added to the liquid detergent compositions of the present invention to improve stability, as well as to improve lather formation and to increase the gentleness of the composition to the skin.

It is preferred to introduce magnesium ions by neutralizing the acid form of the alkylethoxy surfactants with magnesium oxide or a solution of magnesium hydroxide in water. Normally, this method is limited by the amount of anionic surfactant in the formulation. An alternative method is to use MgCl ₂ , MgSO ₄ or other inorganic magnesium salts. These materials are less desirable because they can cause corrosion problems (chloride salts), reduce the solubility of the formulation or cause problems with stability or formulatability of the formulations. For these reasons, it is desirable to limit the addition of inorganic salts to less than 2%, preferably less than 1% by weight of the anionic inorganic counterion.

Polymers with antigelatinizing effects

Another optional ingredient in the compositions of the present invention may be polymers with anti-gelatinizing properties which improve the resistance of the composition to gelation. Suitable polymers for use in the present invention have a molecular weight of at least 500, preferably from 500 to 20,000, more preferably from 1,000 to 5,000, and most preferably from 1,000 to 3,000.

The required amount of antigelatinizing polymer can be readily determined by trial and error, but generally the compositions of the present invention contain from 0.5% to 6% by weight of the total composition of antigelatinizing polymer or mixtures thereof, preferably from 0.5% to 4%, most preferably from 1.5% to 3%.

• · • · · · · · • · ·« ··

Suitable polymers for use in the present invention include:

- polyalkylene glycols, preferably polyethylene glycol and polypropylene glycol,

-polyamines, particularly suitable polyamine polymers for use in the present invention are alkoxylated or polyalkoxylated polyamines. These materials can be easily represented as molecules of empirical structure with repeating units:

Py Kl ⁿ Amine form (alkoxy)ya

R ¹

-,Jt+-R]—n nX' Quaternary form

I (alkoxy)y where R is a hydrocarbon group, usually 2 to 6 carbon atoms, R ¹ can be a C 1 to C 20 hydrocarbon, alkoxy groups are ethoxy, propoxy and the like, y is 2 to 30, most preferably 10 to 20, n is an integer, at least 2, preferably from 2 to 20, most preferably from 3 to 5 and X' is an anion such as halide or methyl sulfate, formed by the quaternization reaction.

The most preferred polyamines for use according to the present invention are the so-called ethoxylated polyethyleneamines, i.e. the products of the polymerization reaction of ethylene oxide with ethyleneimine, having the general formula:

(EtO)—[N—CH ₂ —CH ₂ ]—η—N—(EtO)y (EtO)y (EtO)y where y = 2 to 30. Particularly preferred for use in the present invention is ethoxylated polyethyleneamine, especially ethoxylated tetraethylenepentaamine and quaternized ethoxylated hexamethylenediamine.

- Terephthalate-based polymers; Suitable terephthalate polymers for use in the present invention include polymers of the general formula:

• · • ·

0 0 0

X—(OCH ₂ CH ₂ ) _n -[(-O(Í—R1-C0-R2-)u(-OC—R1-C0-R3-)v-]

OO —oíJ-R-ϋθ—(CH ₂ CH ₂ O)ņ- ^x where each R is a 1,4-phenylene group, R is necessarily a 1,2-propylene unit, R is necessarily a polyoxyethylene unit -(CH2CH ₂ O) _q -CH2-CH2-, each X is ethyl or preferably methyl, each n is from 12 to 45, q is from 12 to about 90, the average value of u is from 5 to about 20, the average value of v is from 1 to about 10, the average value of u+v is from 6 to about 30, the ratio of u to v is from 1 to about 6.

Highly preferred polymers for use in the present invention are polymers of the following formula:

O O from H , if

X—(OCH ₂ CH ₂ )n-(OC-Rl-CO-R2-)u

OO (—OC-R1-(Io)—(CH ₂ CH ₂ O) η- ^x where X can be any capping group, each X being selected from the group consisting of 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, most preferably alkyl. Furthermore, the alkyl group may contain anionic, cationic or nonionic substituents such as sulfonate, sulfate, ammonium, hydroxy and the like. n is selected for water solubility and is in a range that generally ranges from 10 to 50, preferably from 10 to 25. There should be very little material, preferably less than 10 mol%, more preferably less than 5 mol%, most preferably less than 1 mol%, in which u is greater than 5. Furthermore, there should be at least 20 mol% of material, preferably at least 40 mol% of material in which u is in the range from 3 to 5.

The R ¹ residues are necessarily 1,4-phenylene units. In this text, the term R ¹ are necessarily 1,4-phenylene units means that the compound contains as R ¹ exclusively 1,4-phenylene units or is partially substituted with other alkarylene units, alkylene units, alkenylene units or mixtures thereof. Arylene and alkarylene units that can partially replace 1,4-phenylene units include 1,311

phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2-biphenylene, 4,4'-biphenylene and mixtures thereof. Alkylene and alkenylene units which may partially replace 1,4-phenylene units include 1,2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene, 1,4-cyclohexylene and mixtures thereof.

R ¹ preferably contains exclusively (i.e. 100%) 1,4-phenylene units, i.e. each R ¹ unit is 1,4-phenylene.

With respect to ^R2 units, suitable ethylene or substituted ethylene units include ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene, 3-methoxy-1,2-propylene and mixtures thereof. Preferably, ^R2 is exclusively an ethylene unit or preferably a 1,2-propylene unit or

And a mixture thereof. Preferably, about 75% to 100%, more preferably about 90% to 100% of the R units are formed by 1,2-propylene units.

The average value of n is at least 10, but there is a distribution of n values. The value of each n typically ranges from 10 to about 50. Preferably, the value of each n ranges on average from 10 to about 25.

The most preferred polymers for use in this invention are polymers of the following general formula:

About About

II, II

X—(OCH ₂ CH ₂ ) _n -(OC-Rl-CO—r2-) _u

OO (—OC—Rl-CO)—(CH ₂ CH ₂ O)g—X where X is methyl, n is 16, R ¹ is a 1,4-phenylene unit, R ² is a 1,2-propylene unit and a is necessarily between 3 and 5.

Solvent:

As an additional optional ingredient, the compositions of the present invention may contain a solvent in an effective amount to achieve the desired viscosity.

Suitable solvents for use in the present invention include low molecular weight alcohols such as C1 to C10, preferably C1 to C4 mono- or difunctional alcohols, preferably ethyl alcohol, isopropyl alcohol, propylene glycol and hexylene glycol.

The compositions of the present invention comprise from 3% to 20% by weight of the total composition of alcohol or a mixture thereof, preferably 3% to 15%, most preferably 5% to 10%.

The compositions of the present invention are preferably formulated as clear liquid compositions. By clear is meant isotropic, stable and transparent. The use of solvents and hydrotropes to achieve an isotropic composition is well known to those skilled in the art of dishwashing formulation. These clear compositions are preferably packaged in transparent containers, which are typically made of plastic or glass.

In addition to the other optional ingredients described above, the compositions of the present invention may contain other ingredients suitable for use in liquid dishwashing compositions such as perfumes, colors, opacifiers, enzymes, binders and chelants, and pH buffers, such that the compositions generally have a pH in the range of 5 to 11, preferably from 6.0 to 10.0, most preferably from 7 to 9, measured at a 10% solution in water.

Ways:

In this method aspect of the invention, the soiled dishes are contacted with an effective amount, typically about 0.5 ml to 20 ml (per 25 plates), preferably about 3 ml to about 10 ml, of a detergent composition of the invention. The actual amount of liquid detergent composition used will be at the discretion of the user and will typically depend on factors such as the particular product formulation, including the concentration of active ingredients in the composition, the number of dishes to be washed, the degree of soiling of the dishes, and the like.

The specific formulation of the product will, in turn, depend on many factors, such as the market (i.e. USA, Europe, Japan, etc.) intended for the product.

According to this method, the dirty dishes are preferably immersed in a water bath with or without the above-described liquid detergent composition. A dishwashing aid, i.e. an aid suitable for absorbing the liquid dishwashing agent such as a sponge or washcloth, is placed directly in the means or is allowed to contact a separate amount of the above-described undiluted liquid dishwashing agent for a period of time typically in the range of 3 to 10 seconds. The absorbent aid and thereby the undiluted liquid dishwashing agent are then contacted with the surface of each piece of dirty dishes to remove said soil. The absorbent aid is typically allowed to contact the surface of the dishes for a period of 5 to 30 seconds, although the specific application time will depend on factors such as the degree of soiling of the dishes. The contact of the absorbent aid with the surface of the dirty dishes is preferably accompanied by simultaneous scrubbing.

After the dirty dishes are cleaned, the dishwashing aid is preferably contacted, e.g. soaked, with the product itself and allowed to dry. There is no or little bacterial growth in the dishwashing aid during prolonged use. Contaminated dishwashing aids (i.e. aids contaminated by previous use with another agent) are decontaminated after one or more uses of the method of the present invention.

Examples of embodiments of the invention

The following examples, illustrating the invention, are made by mixing all of the listed ingredients together in the listed proportions.

· • · • · 9 9 9 9

99 99 99

Example 1 Example 2 Alcohol ethoxylate (2.2) sulfate 22 Alcohol ethoxylate (2.2) sulfate 22 Amine oxide 3 Amine oxide 3 Non-ionic 7 Non-ionic 7 Glucosamide 5 Glucosamide 5 Betaine 2 Betaine 2 Mg2+ 0.5 Mg2+ 0.5 Ethanol 7 Ethanol 7 Sodium cumene sulfonate 5 Sodium cumene sulfonate 5 Polypropylene glycol (2000) 2.00 Polypropylene glycol 2000 2.00 Propylene glycol 1.00 Propylene glycol 1.00 Geraniol 0.60 Geraniol 0.25 Water recalculated Thymol 0.25 Eugenol 0.25 Water recalculated pH (10% in water) 7.8 pH (10% in water) 7.8

Example 3 Example 4 Alcohol ethoxylate (3.0) sulfate 19 Alcohol ethoxylate (3.0) sulfate 11 Alkyl polyglycoside 2 Non-ionic 6 Non-ionic 13 Amide 2DEA Amide 2DEA Amine oxide 7 Amine oxide 6 Mg2+ 0.04 Mg2+ 0.02 Sodium toluene sulfonate 8.00 Ethanol 3 Geraniol 0.30 Sodium toluene sulfonate 5 Thymol 0.30 Next time 3 Eugenol 0.30 Geraniol 0.60 Water recalculated Water recalculated

« *

pH (10% in water) 6.4 pH (10% in water) 6.8 Curse ad 5 Curse ad 6 Alcohol ethoxylate (0.6) sulfate 26 Alcohol ethoxylate (0.6) sulfate 26 Amine oxide 2 Amine oxide 2 Betaine 2 Betaine 2 Glucosamide 1.5 Glucosamide 1.5 Non-ionic 5 Non-ionic 5 Mg2+ 0.50 Mg2+ 0.50 Ethanol 7 Ethanol 7 Sodium toluene sulfonate 3 Sodium toluene sulfonate 5 Geraniol 0.60 Geraniol 0.20 Water recalculated Thymol 0.20 Eugenol 0.20 Water recalculated pH (10% in water) 7.8 pH (10% in water) 7.8

Example 7 Example 8 Alcohol ethoxylate (2.2) sulfate 27 Sodium paraffin sulfate 7 Amine oxide 6 Alcohol ethoxylate (2.2) sulfate 22 Non-ionic 4 Non-ionic 0.50 GS-base 6 Amide 0.3 DEA Ethanol 6 Betaine 0.50 Calcium xylene sulfonate 4 Ethanol 0.60 Geraniol 0.60 Sodium toluenesulfonate 5 Triclosan 0.25 Water recalculated Water recalculated pH (10% in water) 7.80 pH (10% in water) 6.30

• * · »· 00 09 00

099 0 0 9 0 0009

9909 9099 0909

9090090 90 00 000 00« • ·0 »000 0 0 · 9· 00 99 09

Example 9 Example 10 Alcohol ethoxylate (0.6) sulfate 13 Alcohol ethoxylate (0.6) sulfate 13 Amine oxide 0.8 Amine oxide 0.8 Betaine 0.8 Betaine 0.8 Glucosamide 0.6 Glucosamide 0.6 Non-ionic 2 Non-ionic 2 Mg2+ 0.20 Mg2+ 0.20 SCS-Sodium cumene sulfonate 2.5 SCS-Sodium cumene sulfonate 2.0 PEG 4000 - PEG 4000 - Geraniol 0.60 Geraniol 2.0 BHT 0.02 BHT 0.02 Ethanol - Ethanol - Viscosity (cps) 280 Viscosity (cps) 380 pH (10% in water) 7.0 pH (10% in water) 7.8

Example 11 Alcohol ethoxylate (0.6) sulfate 13 Amine oxide 0.8 Betaine 0.8 Glucosamide 0.6 Non-ionic 2 Mg2+ 0.20 SCS-Sodium cumene sulfonate 6.0 PEG 4000 - Geraniol 0.6 BHT 0.02 Ethanol - Viscosity (cps) 5 pH (10% in water) 7-7.8

• 9 · • · * * * · ♦ ♦ · · · · ♦

9 9

99 *·

9 9 9 9 9 9 9 • 9 99 9 9 9 9

99 99 999 99 9

9 9 9 9 9 • · 9 9 9 9 99

Industrial applicability

Liquid dishwashing preparations with antibacterial effects, containing a surfactant or hydrotrope and an unsaturated aliphatic terpenic alcohol or its derivatives. The preparations are suitable for washing dirty dishes, while the sponge or washcloth does not develop microorganisms after use.

Claims (9)

An aqueous liquid dishwashing composition comprising - surfactant - a hydrotrope selected from the group consisting of cumene sulphonate, toluene sulphonate, xylene sulphonate, benzene sulphonate or mixtures thereof, and - unsaturated aliphatic terpenic alcohol or its derivatives An aqueous liquid dishwashing composition according to claim 1 comprising from 10% to 60% of the total weight of the composition of said surfactant, from 1% to 15% of the total weight of the composition of said hydrotrope, and from 0.1% to 3% the total weight of the preparation of said unsaturated aliphatic terpenic alcohol or derivative thereof. 3. A dishwashing liquid composition according to claim 2 comprising from 10% to 55% of the total weight of said surfactant composition, from 1% to 10% of the total weight of said hydrotrope composition, and from 0.2% to 2.5% of the total weight of the composition of said unsaturated aliphatic terpenic alcohol. An aqueous liquid dishwashing composition according to claims 1 to 3, wherein said salts of cumene sulfonate, toluene sulfonate, xylene sulfonate, benzene sulfonate are sodium salts. 5. The aqueous dishwashing detergent composition of claims 1-4, wherein said unsaturated aliphatic terpene alcohol is geraniol. An aqueous liquid dishwashing composition according to claims 1 to 5 further comprising a phenolic compound of formula I R Rl 9 9 9 9 99 99 9 Wherein R, R ¹ , R ² , R ³ and R ⁴ are independently H, a linear or branched, saturated or unsaturated hydrocarbon chain having 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 4 carbon atoms, an alkoxylated hydrocarbon chain of formula Ra (A) _n , wherein Ra is a linear or branched, saturated or unsaturated hydrocarbon chain having 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 4, wherein A is butoxy, propoxy and / or ethoxy and n is an integer from 1 to 4, preferably from 1 to 3, or an aryl chain having from 1 to 20 carbon atoms, preferably from 1 to 10, and more preferably from 1 to 4, or mixtures thereof. The aqueous dishwashing liquid composition of claim 6, wherein said phenolic compound is eugenol or thymol or mixtures thereof. An aqueous liquid dishwashing composition according to claims 6 to 7 comprising 0.1% to 4% by weight of the total composition of said phenolic compound or mixtures thereof. 9. A method of dishwashing, wherein an effective amount of the composition of claims 1 to 8 is applied to a detergent and said detergent is then contacted with the cleaned containers.