EP2928998A1

EP2928998A1 - Structured cleaning agent having flow limit

Info

Publication number: EP2928998A1
Application number: EP13795529.0A
Authority: EP
Inventors: Detlef Buisker; Ulrich Pegelow
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2012-12-04
Filing date: 2013-11-27
Publication date: 2015-10-14
Also published as: DE102012222186A1; WO2014086634A1

Abstract

The invention relates to a stable liquid cleaning agent having a flow limit and very good dispersing properties. The agent contains at least one anionic surfactant, at least one water-soluble inorganic salt, and at least one water-insoluble abrasive. The invention further relates to the use of said cleaning agent.

Description

"Structured cleaning agent with yield point"

The invention relates to a liquid detergent with yield point, containing abrasive. The cleaning agent is preferably used for manual dishwashing.

Liquid aqueous hand dishwashing detergents are used in countless households.

However, especially in the case of stubborn, encrusted or baked-on soiling, they are reaching the limits of their applicability, since longer soaking times and larger soaking times occur

mechanical force is required to achieve a satisfactory cleaning result. If a quick cleaning is desired, therefore, more detergents are used, such as more alkaline cleaning sprays or abrasives. However, this is desirable neither from an economic nor ecological point of view. Another problem is the limited skin compatibility of many conventional hand dishwashing detergents as well as the additional detergents used.

It is therefore desirable to provide liquid hand dishwashing detergents which also contain abrasives in order to obtain a particularly good cleaning performance even on stubborn stains.

However, it is often problematic to suspend solids in liquids.

In particular, when the solids differ in density from the liquid, they tend to sediment or float.

One method of suspending relatively large particles, such as visible capsules, is based on structured surfactant systems. The term "structured surfactant system" refers to aqueous systems which have surfactant structures that are larger than conventional spherical micelles and whose interaction thixotropes the aqueous medium

Lends properties. These structures may be solid, mesophase, or liquid, and may be in the form of multilayer spherulites, rods, discs, or lamellae that are dispersed or emulsified discontinuously in the system or that form weak network structures.

Three major types of suspending systems have been used in practice, all of which involve an L _a phase in which bilayers of surfactants with the hydrophobic part of the molecule on the inside and the hydrophilic part on the outside of the bilayer (or vice versa) are located. The bilayers lie side by side, for example in a parallel or concentric arrangement, sometimes separated by aqueous layers. L _a - phases can usually be characterized by their characteristic texture under the

Polarizing microscope and / or identified by X-ray diffraction. Most surfactants form an L _a phase at either ambient or slightly higher temperatures when mixed with water in certain specific ratios. However, such L _a phases can not usually be used as structured suspending systems. Useful amounts of solids cause the systems to be no longer flowable and smaller amounts of solids tend to sediment. Also, the concentrations at which L _a phases occur are often significantly higher than the usual and / or desired concentrations in liquid detergents and cleaners.

The main types of structured system used in practice are based on dispersed lamellar, spherulitic and attenuated lamellar phases.

Dispersed lamellar phases are two-phase systems in which the surfactant bilayers are arranged as parallel plates to form areas of L _a phases interspersed with an aqueous phase to form an opaque gel-like system.

Spherolitic phases include spherical bodies, commonly referred to in the art as spherulites, in which surfactant bilayers are arranged as concentric shells. The spherulites usually have a diameter in the range of 0, 1 to 15 μιη and are dispersed in an aqueous phase in the manner of a classic emulsion. The spherulites interact to form a structured system.

Many structured surfactant systems are dispersed between lamellar and spherulitic. The surfactant systems include both types of structures. Usually systems of a more spherulitic character are preferred because they lead to lower viscosities.

A third type of structured surfactant system comprises an extended L _a phase. It differs from the other two structural system types in that it is essentially a single phase and from conventional L _a phases in that it has a wider d-spacing.

Structured surfactant systems having dispersed lamellar or spherulitic phases are typically formed by the interaction of surfactants with dissolved electrolyte salts or bases. Water-soluble salts have been used for some time in hard surface cleaners, for example, for viscosity adjustment or as components of buffer systems. Suspended salt particles also served as abrasives. Thus, WO 2007/085410 A1 introduces a detergent composition in which salt particles can be suspended thanks to an internal structure. However, such structured surfactant systems often have no or no sufficiently high yield strengths and / or very high amounts of electrolyte. Furthermore, there is a risk of phase separation in many systems.

It is therefore an object of the invention to provide a structured liquid detergent having a yield strength which contains stably dispersed particles of an abrasive component and

especially suitable for use as a manual dishwashing detergent.

This problem is solved by a liquid cleaning agent with yield point

containing at least one anionic surfactant selected from the group consisting of sulfonate surfactants, sulfate surfactants and mixtures thereof, at least one water-soluble inorganic salt in an amount of> 25 wt .-% and at least one water-insoluble abrasive in the form of dispersed particles.

It has surprisingly been found that by adding selected amounts of an inorganic salt to a liquid detergent having a specific surfactant system comprising selected anionic surfactants, an internally structured detergent having yield value is obtained. Without the addition of a thickener, this cleaning agent is able to stably disperse particles of an abrasive substance. The possibility of being on polymeric

Thickening agent to be able to do without, has the advantage that the means simpler and

can be produced more cheaply. Accordingly, in a preferred

Embodiment the detergent free of polymeric thickener. Furthermore, the cleaning agent is stable even without the addition of another polymeric stabilizer or dispersant.

This detergent is particularly suitable as a hand dishwashing detergent, with the stubborn, burnt or dried dirt can be removed well. Another object of the present application is accordingly the use of the

Cleaning agent according to the invention for the manual rinsing of dishes.

The cleaning agent according to the invention also has the advantage that it is washed out of a sponge more slowly than a comparable formulation without a flow limit. The long shelf life in the sponge is particularly advantageous if the items to be washed are cleaned under running water, as it leads to lower losses and thus to a higher efficiency.

"Liquid," as used herein in connection with the detergents of the invention, refers to the property of being flowable above the yield stress, and the term therefore also includes gels and pastes various embodiments pseudoplastic or thixotropic, preferably pseudoplastic ("shear thinning").

"Water-soluble" as used herein in connection with inorganic salts refers to the property at room temperature in water to have a solubility of> 1 g / 100g of water.

"Water-insoluble" as used herein in the context of the abrasives refers to the property of having a solubility of <10 mg / 100 g of water at room temperature in water.

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 the teaching of the invention to them

restrict. In particular, the oxo alcohols or their derivatives, which are obtainable, for example, by the RoELEN's oxo synthesis, can also be used correspondingly.

Whenever alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.

Substances which also serve as ingredients of cosmetic products are referred to below, where appropriate, according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds carry an INCI name in English, plant ingredients are listed only after Linne in Latin, so-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The INCI names can be found in the International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997), published by The Cosmetic, Toiletry and Fragrance Association (CTFA), 1 101 17th Street, NW, Suite 300, Washington, DC 20036, USA, and contains more than 9,000 INCI names, as well as references to more than 37,000 trade names and technical names, including its distributors from over 31 countries. The International Cosmetic Ingredient Dictionary and Handbook assigns to the ingredients one or more chemical classes, such as polymer ethers, and one or more functions, such as surfactants-cleansing agents, which are further explained and discussed below possibly also referred to.

The indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service. Unless otherwise stated, amounts given are percentages by weight (% by weight) of the total composition. These percentages refer to active contents.

The composition of the invention contains surfactants in a total amount of usually 7 to 40 wt .-%, preferably 10 to 35 wt .-%, in particular 12 to 25 wt .-%.

The surfactants contain at least one anionic surfactant selected from the group consisting of sulfonate surfactants, sulfate surfactants and mixtures thereof. The content of anionic surfactant is 7 to 20 wt .-% and preferably 8 to 15 wt .-%, each based on the total cleaning agent.

It is preferred that the anionic surfactant is selected from the group comprising

Alkylbenzenesulfonates, olefin sulfonates, alkanesulfonates, ester sulfonates, alk (en) ylsulfates,

Fatty alcohol ether sulfates and mixtures thereof. It has been found that these sulfonate and sulfate surfactants are particularly suitable for the preparation of stable liquid washing detergents with yield point.

Suitable surfactants of the sulfonate type are preferably alkylbenzenesulfonates, in particular linear C ₉ .i ₃ -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and

Hydroxyalkansulfonaten and disulfonates, as obtained for example from Ci ₂ -8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration. Also suitable are alkanesulfonates and the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

The alkyl sulfonates usually have an aliphatic straight-chain or mono- or poly-branched, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably branched, acyclic, saturated, alkyl radical having 6 to 22, preferably 9 to 20, in particular 12 to 18 and especially preferably 14 to 17 carbon atoms.

Accordingly, suitable alkyl sulfonates are the saturated alkanesulfonates, the unsaturated olefin sulfonates and the ether sulfonates which are derived formally from the alkoxylated alcohols on which the alkyl ether sulfates are based, in which terminal ether sulfonates (n-ether sulfonates) having a sulfonate function bonded to the polyether chain are present Ethersulfonate (i-ether sulfonates) with the alkyl-linked sulfonate function distinguishes.

Preference according to the invention is given to the alkanesulfonates, in particular alkanesulfonates having a branched, preferably secondary, alkyl radical, for example the secondary alkanesulfonate sec. Na-Ci3_i7-alkanesulfonate (INCI Sodium C14-17 alkyl lake sulfonates). Alk (en) yl sulfates are the alkali and especially the sodium salts of the Schwefelsäurehalbester C ₂ -C ₈ fatty alcohols, for example coconut fatty alcohol,

Tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Ci ₀ -C ₂ o-oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred.

Fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. The person skilled in the art generally means, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the context of the present invention preferably with longer-chain alcohols, ie. with aliphatic straight-chain or mono- or poly-branched, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably straight-chain, acyclic, saturated, alcohols having 6 to 22, preferably 8 to 18, in particular 10 to 16 and particularly preferably 12 to 14 carbon atoms. As a rule, n moles of ethylene oxide and one mole of alcohol, depending on the

Reaction conditions, a complex mixture of addition products of different degrees of ethoxylation (n = 1 to 30, preferably 1 to 20, especially 1 to 10, particularly preferably 2 to 4). Another embodiment of the alkoxylation is the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. For the purposes of the present invention, very particular preference is given to the sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with from 1 to 6 mol of ethylene oxide. ₂ i -alcohols, such as 2-methyl-branched Cg-n-alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12-18 fatty alcohols having 1 to 4 EO, in particular low-ethoxylated fatty alcohols having 1 to 4 EO, in particular 1 to 2 EO, for example 2 EO, such as Na-Ci ₂ -i4-fatty alcohol + 2EO sulfate.

It is preferred that the liquid detergent contains a mixture of sulfonate and sulfate surfactants.

Liquid detergents containing as anionic surfactant alkylbenzenesulfonates and

Include fatty alcohol ether sulfates, have particularly good dispersing properties.

In a particularly preferred embodiment, the liquid cleaning agent contains a mixture of linear C ₉ . _13- Alkylbenzolsulfonaten and fatty alcohol ether sulfates as anionic surfactant component. The ratio of the sulfate surfactants to sulfonate surfactants is preferably in the range of 3: 1 to 1: 5, and more preferably in the range of 1: 1 to 1: 4. In a particularly preferred embodiment, the liquid detergent or cleaning agent contains

Fatty alcohol ether sulfates and C ₉ .i ₃ -alkylbenzenesulfonates in a mass ratio of 1: 5 to 3: 1, preferably in the range 1: 1 to 1: 4, in particular in the range 1: 4 to 1: 3.

The anionic surfactants are usually as alkali metal, alkaline earth metal and / or mono-, di- or Trialkanolammoniumsalz and / or but also in the form of their with the corresponding Alkali metal hydroxide, alkaline earth metal hydroxide and / or mono-, di- or trialkanolamine used in situ to be neutralized corresponding acid. Preference is given here as alkali metals potassium and sodium in particular, as alkaline earth metals calcium and magnesium in particular, and as alkanolamines mono-, di- or triethanolamine. Particularly preferred are the

Sodium salts.

The agent according to the invention may contain, in addition to the said additional one or more further anionic surfactants, for example (secondary) alkanesulfonates, amphoteric surfactants, in particular betaine surfactants, nonionic surfactants, especially fatty alcohol polyglycol ethers and

Alkylpolyglucoside, and / or cationic surfactants, in particular for improving cleaning effect, flow behavior and / or drying behavior. In preferred

In embodiments, the composition comprises a mixture of sulphate and sulphonate surfactants, as defined above, and additionally a nonionic surfactant.

Nonionic surfactants in the context of the invention are alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, endgroup-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Also suitable are block polymers of ethylene oxide and propylene oxide as well as fatty acid alkanolamides and fatty acid polyglycol ethers. Important classes of nonionic surfactants according to the invention are furthermore the amine oxides and

Sugar surfactants, in particular the alkyl polyglucosides. In various embodiments, the composition comprises a nonionic surfactant selected from alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides,

Polyhydroxyfatty acid amides, Alkylphenolpolyglycolethern, amine oxides, alkyl polyglucosides and mixtures thereof. The content of nonionic surfactant can be in the range from 3 to 15% by weight and preferably from 4 to 10% by weight, based in each case on the total cleaning agent.

According to the invention, alkoxylated fatty alcohols (fatty alcohol polyglycol ethers) are to be understood as meaning ethylene oxide (EO) and / or propylene oxide (PO) alkoxylated, unbranched or branched, saturated or unsaturated C 22 -alcohols having a degree of alkoxylation of up to 30, preferably ethoxylated C 18 -18 alcohols. Fatty alcohols having a degree of ethoxylation of less than 30, preferably having a degree of ethoxylation of 1 to 20, in particular from 1 to 12, particularly preferably from 1 to 8, most preferably from 2 to 5. The alcohol radical may, for example, methyl branched linearly or preferably in the 2-position his or linear and methyl-branched radicals in the mixture, 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, Ci ₂ -i4 alcohols with 3 EO, 4 EO or 7 EO, C ₉ _n-alcohol with 7 EO, C ₁₃ -i ₅ -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-i8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and C ₁₂ -8-alcohol with 7 EO. Set the specified degrees of ethoxylation statistical averages, which can be a whole or a fractional number for a particular product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank 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. Also suitable are also a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as a mixture of a Ci ₆ -8 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO ..

In various embodiments of the invention, the total amount of anionic and nonionic surfactant in the liquid detergent is up to 35% by weight, preferably up to 30% by weight, based on the total liquid detergent.

Suitable betaines which can be used in the detergent of the invention are the alkylbetaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines. These preferably satisfy formula I,

R - [CO-X- (CH ₂ ) _n ] _x -N ⁺ (R ² ) (R ³ ) - (CH ₂ ) _m - [CH (OH) -CH ₂ ] _y -Y- (I) a saturated or unsaturated C ₆ -22-alkyl radical, preferably C ₈ -18 alkyl group, preferably a saturated C ₁₀ -16-alkyl radical, for example a saturated

Ί2-14 ¹ ^■ alkyl radical,

NH, NR ⁴ with the C 1-4 -alkyl radical R ⁴ , O or S,

a number from 1 to 10, preferably 2 to 5, in particular 3,

0 or 1, preferably 1,

independently CI_ ₄ alkyl optionally hydroxysubstituted such as a hydroxyethyl group, especially a methyl radical,

a number from 1 to 4, in particular 1, 2 or 3,

0 or 1 and

COO, S0 ₃ , OPO (OR ⁵ ) 0 or P (0) (OR ⁵ ) 0, wherein R ^{5 is} a hydrogen atom H or a d ^ -alkyl radical.

The alkyl and alkylamido betaines, betaines of the formula I with a carboxylate group (Y = COO), are also referred to as carbobetaines.

Preferred betaines are the alkylbetaines of the formula (Ia), the alkylamidobetaines of the formula (Ib), the sulfobetaines of the formula (Ic) and the amidosulfobetaines of the formula (Id),

R -N ⁺ (CH ₃ ) ₂ -CH ₂ COO ^" (Ia) R-CO-NH- (CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO ^" (Ib) R -N ⁺ (CH ₃₎ 2 CH 2 CH (OH) CH ₂ S03 ^"(Ic) R -CO-NH- (CH ₂₎ 3 N ⁺ (CH ₃₎ ₂ -CH ₂ CH (OH) CH ₂ S0 ₃ (Id) in which R has the same meaning as in formula I.

Particularly preferred betaines are the carbo-betaines, in particular the carbo-betaines of the formula (Ia) and (Ib), most preferably the alkylamido-betaines of the formula (Ib).

A preferred betaine is, for example, cocamidopropyl betaine (cocoamidopropylbetaine).

Sugar surfactants are known surface-active compounds, which include, for example, the sugar surfactant classes of the alkyl glucose esters, aldobionamides, gluconamides (sugar acid amides), glycerolamides, glycerol glycolipids, polyhydroxy fatty acid amide sugar surfactants (sugar amides) and alkyl polyglycosides. Preferred sugar surfactants within the scope of the teaching according to the invention are the alkyl polyglycosides and the sugar amides and their derivatives, in particular their ethers and esters. The ethers are the products of the reaction of one or more, preferably one, sugar hydroxy group with a compound containing one or more hydroxy groups, for example C 1. ₂₂ alcohols or glycols such as ethylene and / or propylene glycol, wherein the Zuckerhydroxygruppe can also carry polyethylene glycol and / or polypropylene propylene glycol. The esters are the reaction products of one or more, preferably one, sugar with a carboxylic acid, in particular a _C6 - ₂₂ - fatty acid.

The alkyl polyglycosides (APG) preferably satisfy the general formula R'O (AO) _a [G] _x , in which R 'is a linear or branched, saturated or unsaturated alkyl radical having 6 to 22, preferably 6 to 18, in particular 8 to 16 , particularly preferably 8 to 14 carbon atoms, [G] is a glycosidically linked sugar residue and x is a number from 1 to 10 and AO is an alkyleneoxy group, for example an ethyleneoxy or propyleneoxy group, and a is the average degree of alkoxylation from 0 to 20. In this case, the group (AO) _{a may} also contain different alkyleneoxy, for example ethyleneoxy or propyleneoxy, where it is at a to the average Gesamtalkoxylierungsgrad, ie the sum of ethoxylation and

Propoxylierungsgrad, acts. Unless otherwise stated below, the alkyl radicals R 'of the APG are linear unsaturated radicals having the stated number of carbon atoms. The index number x indicates the degree of oligomerization (DP degree), i. The distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While x must always be integer in a given compound and can take here especially the values x = 1 to 6, the value x for a particular alkyl glycoside an analytically determined arithmetical variable, which usually represents a fractional number. Preferably

Alkyl glycosides used with a mean degree of oligomerization x of 1, 1 to 3.0. From an application point of view, those alkyl glycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6 are preferred. As glycosidic sugar is preferably xylose, but especially glucose used. APG are nonionic surfactants and are known substances that can be obtained by the relevant methods of preparative organic chemistry.

The alkyl or alkenyl radical R 'can be derived from primary alcohols having 8 to 18, preferably 8 to 14 carbon atoms. Typical examples are caproic alcohol, caprylic alcohol,

Capric alcohol and undecyl alcohol and their technical mixtures, as obtained for example in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelene's oxo synthesis.

Preferably, however, the alkyl or alkenyl radical R 'is derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol. Also to be mentioned are elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereof.

Particularly preferred APG are not alkoxylated (a = 0) and satisfy the formula RO [G] _x , in which R is as previously described for a linear or branched, saturated or unsaturated alkyl radical having 4 to 22 carbon atoms, [G] for a glycosidically linked sugar radical, preferably glucose residue, and x is a number from 1 to 10, preferably 1, 1 to 3, in particular 1, 2 to 1, 6, stand.

Correspondingly preferred alkylpolyglycosides are, for example, C ₈ -io- and C 12-14 -alkylpolyglucoside with a DP degree of 1, 4 or 1.5, in particular C ₈ -alkyl-1-5-glucoside and C 12-14 -alkyl -1, 4-glucoside.

Suitable further anionic surfactants are in particular aliphatic sulfates such as monoglyceride sulfates and ester sulfonates (sulfo fatty acid esters), lignosulfonates, fatty acid cyanamides, anionic sulfosuccinic acid surfactants, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates.

The amphoteric surfactants (amphoteric surfactants, zwitterionic surfactants) which can be used according to the invention include alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants, of which the alkylamidoalkylamines are used in the context of

inventive teaching are preferred.

Preferred cationic surfactants are the quaternary surface-active compounds, in particular with an ammonium, sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. Through the use of quaternary surface-active compounds with antimicrobial action, the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved. Particularly preferred cationic surfactants are the quaternary ammonium compounds (QAV, INCI Quaternary Ammonium Compounds) according to the general formula (R ^I ) (R ") (R ¹ ") (R ^IV ) N ⁺ X ^" , in which R ¹ to R ^{IV are} identical or different Ci_ ₂ 2-alkyl radicals, C _7, ₂ 8-aralkyl radicals or heterocyclic radicals, where two or in the case of an aromatic inclusion as in pyridine even three radicals together with the nitrogen atom, the heterocycle, for example a pyridinium or

Imidazolinium compound, form, represent and X ^{~ are} halide ions, sulfate ions, hydroxide ions or similar anions. For optimum antimicrobial activity, preferably at least one of the radicals has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.

QACs are prepared by reacting tertiary amines with alkylating agents, e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced. The alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly easy, the quaternization of tertiary amines with two long radicals and one methyl group can be carried out with the aid of methyl chloride under mild conditions. Amines having three long alkyl radicals or hydroxy-substituted alkyl radicals are less reactive and are preferably quaternized with dimethyl sulfate.

Suitable QAVs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (m, p-dichlorobenzyl-dimethyl-C 12 -alkylammonium chloride, CAS No. 58390-78 6), benzoxonium chloride (benzyldodecylbis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethylammonium bromide, CAS No. 57-09-0), benzetonium chloride (N, N-dimethyl-N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzyl ammonium chloride, CAS No. 121-54-0), dialkyldimethylammonium chlorides such as di-n -decyl-dimethyl-ammonium chloride (CAS no.

7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammonium chloride, 1-cetylpyridinium chloride (CAS No. 123-03-5) and thiazoline iodide (CAS No. 15764-48- 1) and their mixtures. Preferred QUATS are the benzalkonium chlorides containing C ₈ -C ₈ - alkyl groups, in particular C ₂ -C ₄ alkyl-benzyl-dimethylammonium chloride. A particularly preferred QAV is the Kokospentaethoxymethylammoniummethosulfat (INCI PEG-5

Cocomonium Methosulfate; Rewoquat ^® CPEM).

In order to avoid possible incompatibilities of the cationic surfactants with the anionic surfactants according to the invention anionic surfactant-compatible and / or cationic surfactant is preferably used or omitted in a particular embodiment of the invention entirely on cationic surfactants.

The cleaning agent according to the invention also contains one or more water-soluble inorganic salts. Inorganic salts which can be used according to the invention are preferably selected from the group consisting of colorless water-soluble halides, sulfates, sulfites, carbonates, bicarbonates, nitrates, nitrites, phosphates and / or oxides of the alkali metals Alkaline earth metals, aluminum and / or transition metals; Furthermore, ammonium salts can be used. Preferably usable inorganic salts include sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, calcium chloride, magnesium chloride and mixtures thereof, since these salts are very soluble in water. Particularly preferred are halides, carbonates and sulfates of the alkali metals; Preferably, therefore, the inorganic salt is selected from the group comprising sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium carbonate, potassium carbonate and mixtures thereof. In a preferred embodiment

Sodium sulfate, sodium chloride, sodium carbonate or mixtures thereof.

The cleaning agent according to the invention contains> 25 wt .-% of at least one water-soluble inorganic salt. It should be noted that the salt concentration in the cleaning agent according to the invention must be so high that the salt is not completely dissolved, the

Saturation point is exceeded. Furthermore, a salt is to be preferred, whose

Water solubility changes only slightly over a wide temperature range. The amount of salt is preferably in the range of> 25 to <50 wt .-%, particularly preferably 27 to 48 wt .-%.

According to the invention, the amount of inorganic salt can be chosen such that the ratio of total amount of surfactants to inorganic salt in the range of 1: 1, 2 or less, preferably 1: (> 1, 2), for example 1: 1, 5, 1: 1, 8, 1: 2 or smaller, ie 1: (> 2).

The addition of the inorganic salt results in the formation of lamellar structures to an internally structured liquid cleaning agent with very good dispersing properties.

The liquid detergent is extremely stable and does not show any phase separation and / or precipitation of the anionic surfactants and, if present, the nonionic, amphoteric or cationic surfactants. The washing or cleaning agent is macroscopically single-phase and has a yield point. The yield value is preferably above 5 Pa (at room temperature, i.e., 20 ° C), more preferably 10 Pa or more, and may be, for example, 50 Pa or more, or 90 Pa or more.

In addition, the inorganic salt has an influence on the viscosity of the cleaning agent and with the aid of the inorganic salt, the viscosity can be adjusted so that the cleaning agent is easy to dose and a container with the cleaning agent a good

Remaining emptying has. In general, the agent according to the invention is structurally viscous and flowable and readily meterable when the force is above the yield point.

In a preferred embodiment, the cleaning agent is free of polymeric

Thickener. The cleaning agent additionally contains dispersed particles of at least one abrasive. The dispersed particles can along their largest spatial extent one

Diameter of 1 to 2000 μιη possess. The size is chosen so that the particles on the one hand have the desired abrasive properties on the other hand but can be stably dispersed in the liquid cleaning agents. The preferred size is in a range of about 5 to 100 μιη particle diameter. Stable means that the detergents are stable at room temperature for a period of at least 4 weeks, and preferably for at least 6 weeks, without the particles creaming or sedimenting in the medium. The particles can have any shape.

The abrasive particles may be beads containing or consisting of plastic or calcium carbonate, or powders, granules or compounds of other compounds insoluble in the detergent. Also possible are mixtures of different abrasives. Preferably, the abrasive is about

Calcium carbonate.

In a preferred embodiment of the invention, the liquid cleaning agents contain identical or different particles in amounts of 0.05 to 10 wt .-%, in particular 0.1 to 8 wt .-% and most preferably 0.2 to 5 wt .-%.

The detergents are liquid and contain water as the main solvent, i. they are aqueous cleaning agents. The water content of the aqueous agent of the present invention is usually 15 to 70% by weight, preferably 20 to 60% by weight. In different

Embodiments, the water content is more than 5 wt .-%, preferably more than 15 wt .-% and particularly preferably more than 25 wt .-%, each based on the total amount of detergent.

In addition, non-aqueous solvents may be added to the detergent. Suitable non-aqueous solvents include mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the specified concentration range.

The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexyleneglycol, ethylene glycol methyl ether, ethylene glycol ethyl ether,

Ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether,

Diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether,

Propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures thereof

Solvent. The one or more nonaqueous solvents are usually in an amount of 0.1 to 10 wt .-%, preferably 1 to 8 wt .-% based on the

Total composition included.

In addition to the components mentioned so far, the compositions according to the invention may contain further ingredients which further improve the performance and / or aesthetic properties of the cleaning agent. These include, for example, additives for improving the drainage and drying behavior, for adjusting the viscosity, for stabilization and other customary in manual dishwashing detergents and additives, such as UV stabilizers, perfume, pearlescing agents, dyes, corrosion inhibitors, preservatives, bittering agents, organic salts, disinfectants , Enzymes, structuring polymers, defoamers, encapsulated ingredients (eg encapsulated perfume, enzymes), pH adjusters and skin feel enhancing or nourishing additives.

To further improve the drainage and / or drying behavior, the

Composition according to the invention one or more additives from the group of surfactants, polymers and builders (builder), usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4 wt .-%, in particular 0, 1 to 3 wt .-%, particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1, 5 wt .-%, for example 1 wt .-%.

In a particular embodiment of the invention, the additives mentioned are dispensed with.

Although it is preferable to dispense with polymer thickeners and to adjust the viscosity and structure of the cleaning agent according to the invention by means of the inorganic salt, in specific embodiments the composition according to the invention may additionally contain one or more polymeric thickeners.

For the purposes of the present invention, polymeric thickeners are the polycarboxylates which have a thickening effect as polyelectrolytes, preferably homopolymers and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, and other customary thickening polymers.

Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, for example propoxylated guar, and also their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, may alternatively or preferably be used in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropylmethyl or hydroxyethyl methyl cellulose or cellulose acetate. Acrylic acid polymers suitable as polymeric thickeners are, for example

high molecular weight with a polyalkenyl, in particular an allyl ether of sucrose, pentaerythritol or propylene, crosslinked homopolymers of acrylic acid (INCI Carbomer), which are also referred to as carboxyvinyl polymers.

However, particularly suitable polymeric thickeners are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably C-. _4- alkanols formed esters (INCI Acrylates Copolymer), which include about the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) include; (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of Ci ₀ -3o-alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with Ci-4 Alkanols formed, esters (INCI acrylates / C 10-30 alkyl acrylate crosspolymer) include.

The content of polymeric thickener is usually not more than 8 wt .-%, preferably between 0.1 and 7 wt .-%, particularly preferably between 0.5 and 6 wt .-%, in particular between 1 and 5 wt .-% and most preferably between 1, 5 and 4% by weight, for example between 2 and 2.5% by weight.

However, as described above, in a preferred embodiment of the invention, the agent is free of polymeric thickeners.

To stabilize the composition of the invention, particularly at high surfactant content, one or more dicarboxylic acids and / or salts thereof may be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, for example as available under the trade name Sokalan ^® DSC is. The use is advantageously carried out in amounts of 0.1 to 8 wt .-%, preferably 0.5 to 7 wt .-%, in particular 1, 3 to 6 wt .-% and particularly preferably 2 to 4 wt .-%.

This component is particularly preferably used at high surfactant contents, in particular at surfactant contents above 30 wt .-%.

However, if it is possible to dispense with their use, this is the agent according to the invention

preferably free from dicarboxylic acid (salts) n.

In addition, one or more further auxiliary agents and additives customary in hand dishwashing detergents and hard surface cleaners, in particular UV stabilizers, perfume, pearlescing agents (INCI Opacifying Agents, for example glycol distearate, eg Cutina AGS of the company Cognis, or mixtures containing it, eg the Euperlane of the company Cognis), dyes, corrosion inhibitors, preservatives (for example the technical 2-bromo-2-nitropropane-1,3-diol (also referred to as bronopol) CAS 52-51-7) which is commercially available is), organic salts, disinfectants, enzymes, pH-adjusting agents and skin feel-improving or skin-care additives (eg dermatologically effective substances, for example, as Myacide ^® BT or as Boots Bronopol BT from Boots such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol, sericerin, collagen partial hydrolyzate, various vegetable protein partial hydrolysates, protein hydrolyzate-fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as lecithin, soybean oil, etc.,

Plant extracts such as e.g. Aloe vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, A.H.A. complexes, glycerol, urea, quaternized hydroxyethyl cellulose) in amounts of usually not more than 5% by weight.

The pH of the composition according to the invention can be determined by means of customary pH regulators, for example acids such as mineral acids or citric acid and / or alkalis such as sodium or potassium

Potassium hydroxide, are set, wherein - in particular with the desired hand compatibility - a range of 4 to 9, preferably 5 to 8, especially 5.5 to 7.5, is preferred.

For adjusting and / or stabilizing the pH, the agent according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5 wt .-%, preferably 0.005 to 3 wt .-%, in particular 0 , 01 to 2 wt .-%, particularly preferably 0.05 to 1 wt .-%, most preferably 0, 1 to 0.5 wt .-%, for example, 0.2 wt .-%. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents

(Chelators, INCI Chelating Agents). Particularly preferred buffer substances are the citric acid or the citrates, in particular the sodium and potassium conduction rates, for example trisodium citrate-2 H ₂ O and tripotassium citrate H ₂ O.

The composition according to the invention can be used for cleaning hard surfaces, in particular for manual cleaning of dishes. Due to the contained surfactant combination, it is characterized by a good drainage and drying behavior, thanks to the abrasive effect of the abrasives it contains, it also has a very good cleaning performance even on stubborn and burnt soiling, and finally it also has a high skin friendliness.

The preparation of the cleaning agent by means of conventional and known methods and methods. Thus, for example, the ingredients of the detergent can be mixed in stirred tanks, initially water is introduced. Then the nonaqueous solvents and surfactants are added. Subsequently, if present, the fatty acid is added and the saponification of the fatty acid portion and the neutralization of the anionic surfactants, which are used in the acid form. Then the others Ingredients, preferably in portions added. The inorganic salt may be added as a solid or in the form of a concentrated solution at various times in the manufacturing process.

The flow limits of the detergents or cleaning agents were measured using a rotary rheometer from TA-Instruments, type AR G2. This is a so-called Schubspannungskontrolliert.es rheometer.

To measure a yield point with a shear stress controlled rheometer various methods are described in the literature, which are known in the art.

The flow limits in the context of the present invention were determined as follows at 23 ° C.

The samples were loaded in the rheometer with a time-increasing shear stress s (t). For example, the shear stress in the course of 10 minutes from

smallest possible value (e.g., 2 mPa) at e.g. 10 Pa can be increased. As a function of this shear stress, the deformation γ of the sample is measured. The deformation is plotted against the shear stress in a double-logarithmic plot. If the examined sample has a yield point, clearly two areas can be distinguished in this plot.

Below a certain shear stress, one finds a purely elastic deformation. The slope of the curve γ (σ) (log-log plot) in this area is one. Above this shear stress, the flow range begins and the slope of the curve is suddenly higher. the one

Shear stress at which the bending of the curve takes place, ie the transition from the elastic to a plastic deformation, marks the yield point. A convenient provision of the

Break point is possible by applying tangents to the two curve parts. Samples without yield point do not show a characteristic kink in the function γ (σ).

embodiments

Two formulations according to the invention were prepared, the compositions of which are shown in the table below. The quantities are in wt .-%. The hand dishwashing detergents obtained were stable, pourable and readily dosed and had good cleaning, drainage and drying behavior.

E1 E2

Alkylbenzenesulfonic acid 10.49 10.49

Fatty alcohol ether sulfate 2.8 2.8

Fettalkoholethoxylat

Sodium carbonate 15

Sodium chloride 2 3

Sodium sulfate 30.57 24.88

Calcium carbonate 3 3

Sodium hydroxide (50%) 1, 3 1, 4

Preservative 0.02 0.02

Dye / fragrance 0.26 0.26

pearlizing

Binder 0.62 0.62

Water 33.94 53.53

Yield point (Pa) 90 1 1, 5

Claims

claims

A liquid hard surface fluid detergent having at least one anionic surfactant selected from the group consisting of sulfonate surfactants, sulfate surfactants and mixtures thereof, at least one water-soluble inorganic salt in an amount> 25% by weight and at least one water-insoluble Abrasive material in the form of dispersed particles.

2. Liquid detergent according to claim 1, characterized in that the at least one anionic surfactant is selected from the group comprising C ₉ . _13- Alkylbenzolsulfonate, Olefinsulfonate, Ci ₂ -i 8-alkanesulfonates, ester sulfonates, alk (en) ylsulfate, fatty alcohol ether sulfates and mixtures thereof, in particular C ₉ .i ₃ -alkylbenzenesulfonates and fatty alcohol ether sulfates.

3. Liquid detergent according to claim 2, characterized in that the

Detergent C ₉ .i ₃ -alkylbenzenesulfonates and fatty alcohol ether sulfates and the ratio of alkylbenzenesulfonate and fatty alcohol ether sulfate in the range of 5: 1 to 1: 3, preferably in the range 4: 1 to 1: 1, in particular in the range 4: 1 to 3: 1 lies.

4. Liquid detergent according to one of claims 1 to 3, characterized in that the cleaning agent contains 7 to 20 wt.% Of the at least one anionic surfactant.

5. Liquid detergent according to one of claims 1 to 4, characterized in that the at least one water-soluble inorganic salt is selected from the group comprising sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, calcium chloride, magnesium chloride and mixtures thereof, in particular of sodium sulphate, sodium chloride and sodium carbonate.

6. Liquid detergent according to one of claims 1 to 5, characterized in that the at least one water-insoluble abrasive is a water-insoluble inorganic salt, in particular calcium carbonate.

7. Liquid detergent according to one of claims 1 to 6, characterized in that the cleaning agent further comprises a nonionic surfactant, in particular selected from the group consisting of alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, Polyhydroxyfettsäureamiden,

Alkylphenolpolyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof.

8. Liquid detergent according to one of claims 1 to 7, characterized in that the ratio total amount of surfactants to inorganic salt 1: 1, 2 or less.

9. Liquid detergent according to one of claims 1 to 8, characterized in that the washing or cleaning agent more than 5 wt .-%, preferably more than 15 wt .-% and particularly preferably more than 25 wt .-%, each based to the total amount of detergent or cleaning agent containing water.

10. Use of the cleaning agent according to one of claims 1 to 9 for cleaning hard surfaces, in particular as a manual dishwashing detergent.