WO1999027062A1

WO1999027062A1 - Dish washing detergent with a specific viscosity profile

Info

Publication number: WO1999027062A1
Application number: PCT/EP1998/007346
Authority: WO
Inventors: Brigitte Giesen; Dagmar Zaika; Bernd Richter; Rainer Hofmann; Peter Kittscher; Michel Charuel; Dietmar Pressner
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1997-11-26
Filing date: 1998-11-17
Publication date: 1999-06-03
Also published as: DE59811905D1; JP4365024B2; DE19817833A1; JP2001524589A; EP1036157A1; ATE275188T1; EP1036157B1

Abstract

The invention relates to pourable detergents for washing dishes by hand which remain stable in storage and which have a specific viscosity profile. The detergents contain tenside mixtures of anionic tensides and/or non-ionic tensides and/or betaine tensides and between 0.01 and 5 wt. % polymers, and preferably have (1) a viscosity of between 1,300 and 9,000 mPa.s at 20 °C and with a shear rate of 10 s-1 or a viscosity of between 500 and 8,000 mPa.s at 20 °C and with a shear rate of 30 s-1 and/or (2) 0.2 to 60 wt. % tenside mixture and/or (3) 0.2 to 49.8 wt. % anionic tensides, 0.1 to 14.9 wt. % non-ionic tensides and 0.1 to 14.9 wt. % betaine tensides.

Description

"Dishwashing detergent with a specific viscosity profile"

The invention relates to dishwashing detergents with a specific viscosity profile I containing a thickened surfactant mixture which is not caused by liquid-crystalline structures.

If you try to produce a precisely metered, excellently cleaning, hand-compatible, temperature and storage stable, pourable and ecologically particularly compatible hand dishwashing detergent with conventional agents, you quickly reach the performance limit of the products. The object of the invention was now to formulate a hand dishwashing detergent which, in addition to the surfactant mixtures which are otherwise customary for this product group, contains a component for setting a specific viscosity profile.

Thickened cleaning agents are known in the prior art. Among other things, Polymers, silicas, clays and silicates as well as other ingredients are used.

WO 95/20027 describes liquid or gel-like hand dishwashing detergents which are thickened by adding amine oxide.

WO 95/07971 describes gel-type dishwashing detergents containing protease enzyme, which is intended to ensure hand mildness.

WO 95/06108 describes concentrated or gel-like dishwashing detergents which are thickened by adding calcium salts and xylene sulfonates. The addition of divalent ions to surfactants often leads to dimerization of surfactants and thus to the formation of liquid-crystalline structures in hand dishwashing detergents.

GB 2280682 describes gel-like compositions containing urea which are present in the hexagonal liquid-crystalline phase. The viscosity of such liquid-crystalline compositions in production, storage and use is very difficult to control.

WO 94/09100 proposes to stabilize gel-like hand dishwashing detergents based on polyhydroxy fatty acid amides by adding boric acid. The gel-like machine dishwashing detergents from builder (such as phosphate), alkali (such as soda) and little (generally up to 5% by weight) surfactant mentioned in many publications are not suitable for hand dishwashing detergents, inter alia because of the high proportion of alkali.

If high amounts of typical surfactant mixtures of anionic surfactants, such as fatty alcohol ether sulfate or fatty alcohol sulfate, nonionic surfactants, such as alkyl polyglycoside and zwitterionic surfactants, such as e.g. Betaines, in hand dishwashing detergents, often result in highly viscous, poorly metered and poorly soluble products - presumably because of the formation of liquid crystalline phases. If one tries to ensure the lowering of the viscosity with additional solvents, on the one hand the storage stability of the agents deteriorates in some cases, and on the other hand a low-viscosity product is less precisely dosed. Also, stains can be treated very specifically with burnt-on dirt. Here, a thickened product has clear advantages in use.

However, none of the compositions proposed in the prior art is suitable as a precisely metered, excellent cleaning, hand-compatible, temperature and storage stable, pourable and ecologically particularly compatible hand dishwashing detergent with a specific viscosity profile.

Exactly metered, lightfast, excellent cleaning, hand-compatible, temperature and storage stable, pourable and ecologically particularly compatible products with good casting properties and excellent cleaning performance can be obtained by providing a mixture of fatty alcohol ether sulfate, possibly fatty alcohol sulfate, alkyl polyglycoside and betaine together with a polymer.

The present invention accordingly relates to a pourable storage-stable hand dishwashing detergent containing a surfactant mixture of anionic surfactants and / or nonionic surfactants and / or betaine surfactants, which contains between 0.01 and 5% by weight of polymers.

In the context of the present invention, unless otherwise stated, fatty acids or fatty alcohols or their derivatives are representative of branched or unbranched carboxylic acids or alcohols or their derivatives, preferably having 6 to 22 carbon atoms. The former are preferred for ecological reasons, in particular because of their vegetable basis than based on renewable raw materials, but without restricting the teaching according to the invention to them. In particular, the wise available according to RoELEΛ /'s oxo synthesis oxo alcohol or their derivatives can be used accordingly.

Particularly suitable surfactant mixtures are those made from anionic and nonionic surfactants. However, the use of betaine surfactants in a mixture, in particular in combination with anionic and nonionic surfactants, can also be very useful for many applications; in total, the surfactants are used in amounts of 0.2 to 60% by weight, preferably 1 to 55% by weight .-%, particularly preferably 3 to 50 wt .-% and extremely preferably 5 to 45 wt .-%.

Polymers for the purposes of the present invention are polycarboxylates or carboxyvinyl polymers, preferably homo- and copolymer polymers of acrylic acid, in particular acrylic acid polymers and acrylic acid-methacrylic acid copolymers, heteropolysaccharides (xanthan, guar, propoxylated guar) and somewhat less preferably others known in the market polymeric thickeners.

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 linginine sulfonates. Fatty acid cyanamides, sulfosuccinic acid esters, fatty acid isethionates, acylaminoalkane sulfonates (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 alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the sense of the present invention preferably with longer-chain alcohols. As a rule, a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. Another embodiment of the alkoxyation consists in using mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. For the purposes of the present invention, very particularly preferred are low-ethoxylated fatty alcohols with 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1, 3 EO. The anionic surfactants are preferably used in amounts between 0.2 and 49.8% by weight, preferably 5 to 45% by weight, particularly preferably 10 to 40% by weight.

In a preferred embodiment of the invention, the agents contain 0.5 to 15% by weight of fatty alcohol sulfates.

Nonionic surfactants in the context of the present invention can be alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Ethylene oxide, propylene oxide, block copolymers 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, which, depending on the type of production, results in a mixture of monoalkylated, oligomeric or polymeric sugars. Preferred alkyl polyglycosides can be alkyl polyglucosides, the alcohol being particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched C ₈ to C ₁₈ alkyl chains and the degree of oligomerization (DP) of the sugars between 1 and 10, preferably 1 to 6, in particular 1.1 to 3, most preferably 1.1 to 1.7.

The alkyl polyglycosides are preferably used in amounts between 0.1 to 14.9% by weight, in particular 1 to 8% by weight and very preferably 1 to 5% 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 amino oxides, sulfobetaines and biosurfactants. A preferred ingredient is alkyl amido betaine.

These zwitterionic surfactants are preferably used in amounts between 0.1 to 14.9% by weight, in particular between 0.5 to 10% by weight, most preferably between 1 to 8% by weight.

In a preferred embodiment of the hand dishwashing detergent according to the invention, the surfactant mixture contains (a) 0.2 to 49.8% by weight, preferably 5 to 45% by weight, particularly preferably 10 to 40% by weight, of anionic surfactants, in particular fatty alcohol ether sulfates,

(b) 0.1 to 14.9% by weight, preferably 1 to 8% by weight, of nonionic surfactants, in particular alkyl polyglucosides, and

(c) 0.1 to 14.9% by weight, preferably 0.5 to 10% by weight, betaine surfactants, in particular alkylamido betaines.

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

The Brookfield viscosity favorable for the agents according to the invention (measured with the spindle recommended for the respective viscosity range) is 20 ° C. and a shear rate of 10 s ¹ between 1,000 and 10,000 mPa s, preferably between 1,300 and 9,000 mPa s and particularly preferred between 1,500 and 7,000 mPa-s or at 20 ° C. and a shear rate of 30 s ^"1 between 500 and 8,000 mPa-s, preferably between 900 and 7,000 mPa-s and particularly preferably between 1,100 and 6,000 mPa-s.

Preferred zero shear viscosity values η ₀ for favorable storage properties are between 1,000 and 10,000 Pa s, preferably between 1,000 and 5,000 Pa s.

The viscosity of the agents according to the invention can be determined by polymer amounts between 0.01 and 5% by weight, preferably between 0.02 and 4% by weight, particularly preferably between 0.05 and 3% by weight, in particular between 0.1 and 1.5% by weight and most preferably between 0.2 and 0.9% by weight. The amounts can vary from polymer to polymer. The surfactant composition used also plays a role in the choice of quantity. Methacrylic acid-acrylic acid copolymers and acrylic acid polymers have proven to be particularly suitable.

It has been found by aschend that particularly suitable polymers insondere an acrylic acid polymer of the Fa. Goodrich (Carbopol ^® EX 473), an acrylic acid copolymer of the company. 3VSigma (PolygeP W30) and a methacrylic acid-acrylic acid copolymer of the company. Polymer latex (Rohagif SD 15) are. Natural polymers, such as guar or xanthan, do not meet the high requirements for solubility and storage stability that consumers place on modern hand dishwashing detergents in every respect and are therefore less preferred. The clarity of the products is particularly important here - especially from the point of view of the user. Deposition of phases or ingredients as well as a cloudy appearance is usually not desirable.

In this regard, particular advantages are obtained if one or more dicarboxylic acids and / or their salts are added to the thickened mixtures, alone or in a mixture, in particular a composition of sodium salts of adipic, succinic and glutaric acid, as described, for example, under the trade name Sokalan ^® DSC Na is available. The use of 0.1 to 8 wt.%, Preferably 0.5 to 7 wt.%, Particularly preferably 0.8 to 6 wt.% And extremely preferably 1 to 4 wt. %, shown.

A change in the dicarboxylic acid (salt) content - especially in amounts above 2% by weight - can contribute to a clear solution of the ingredients. It is also possible to influence the viscosity of the mixture by this agent within certain limits. This component also affects the solubility of the mixture.

Instead of or in addition to the dicarboxylic acids and / or their salts, other salts can also be used advantageously individually or in mixtures, such as sodium formate, sodium acetate, sodium tartrate, sodium chloride and magnesium chloride or salts of the aforementioned anions with other alkali or alkaline earth metals.

The dicarboxylic acid or salt component serves to achieve clear, homogeneous formulations and influences the viscosity as well as the cold and dissolving behavior. Without this auxiliary component, the agents can have an opaque to slightly cloudy appearance. The combination of polymer with this auxiliary component enables the production of clear gel-like agents with good cold and dissolving behavior.

Another cheap component of the agents according to the invention are solvents (e.g. alcohols, especially low molecular weight alcohols such as 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. However, too much solvent causes the viscosity to drop too much. Therefore, according to the invention, between 3 and 12% by weight of one or more solvents are contained, preferably between 4 and 10% by weight, particularly preferably between 5 and 10% by weight.

The amount of solvent also has an influence on the homogeneity and the viscosity of the agents according to the invention. With low amounts of solvent, especially below 3% by weight, inhomogeneities can occur depending on the composition of the agent. The viscosity can be reduced by increasing the amount of solvent.

A key factor is solubility. Agents according to the invention naturally have a different dissolving behavior than conventional hand dishwashing agents. Care must therefore be taken to ensure a sufficiently fast dissolution time.

Agents according to the invention dissolve in the usual dilution in the hand-rinse basin between 10 and 240 seconds, preferably between 15 and 120 seconds, particularly preferably between 20 and 100 seconds. The dissolution time depends on the thickening and the selected surfactant combinations.

The lightfastness of the products is a particularly important factor. The consumer prefers colored - i.e. dye-containing products in translucent bottles. This places high demands on the lightfastness of the agents. The use of acrylic acid polymers as well as acrylic acid-methacrylic acid copolymers is particularly suitable.

In this context, UV stabilizers can also be used according to the invention. From the point of view of production costs, however, dispensing with such agents is particularly advantageous since they often do not contribute to cleaning performance.

Many of the mixtures investigated according to the invention have a viscosity profile that changes over time. This is particularly desirable since a more fluid composition is preferred in the production process, but in terms of storage stability and ease of use, emphasis is placed on higher-viscosity products.

A further improved cleaning performance, especially in the case of burnt-on dirt, is obtained when using abrasives, preferably water-soluble abrasives, in particular alkali metal bicarbonate, alkali metal sulfate and others.

In addition, other ingredients common in hand dishwashing detergents, such as Defoamers, structuring agents, perfumes, dyes, corrosion inhibitors and preservatives can be contained in amounts of up to 5% by weight.

The pH of the agents according to the invention can be adjusted by means of conventional pH regulators, for example citric acid or NaOH, whereby - essentially because of required hand tolerance - a range from 5.5 to 8, preferably 6 to 7.5, in particular 6.5 to 7.1, is preferred.

The hand dishwashing detergents according to the invention can be produced by stirring the individual components together in any order and leaving the mixture to stand until there are no bubbles. The order of preparation is not decisive for the preparation of the agent.

Water, surfactants and, if appropriate, further ingredients mentioned above are preferably stirred together. If perfume and / or dye are used, they are then added to the solution obtained. Finally, the polymer is added, optionally in the form of an aqueous solution, to facilitate its homogeneous dissolution. Finally, the pH is adjusted as previously described.

Examples

example 1

The agents E1 to E30 according to the invention were prepared as described above and their pH, their viscosity, their clouding or clearing point as well as their dissolution time were determined.

The compositions of the agents E1 to E30 according to the invention in% by weight and the specific properties are shown in Tables 1 to 4. In addition, agents E1 to E30 according to the invention contained traces of dye. The pH of the agents E1 to E30 according to the invention was adjusted to between 6.5 and 7.1 with citric acid.

The viscosity was determined at 20 ° C according to Brookfield (Brooltfield LV DV // + viscometer; spindle 25; shear rate 30 min ^"1 ).

The cold cloud point was determined by cooling a sample in the cryostat at a cooling rate of 0.2 ° C. min ^-1 , the cold cloud point being the temperature at which a slight cloudiness was first detected. After the sample was completely cloudy, the mixture was heated at a heating rate of 0.2 ° C min ^'1 . The temperature at which the sample is completely clear for the first time is given as the clear point.

To determine the dissolution time, 1 ml of the medium was added with stirring at 325 revolutions min ^"1 in 900 ml of tap water at 40 ° C. and the time until the detergent was completely dissolved.

The rinsing performance of the recipes according to the invention was also largely determined. The determination was determined in a semi-automatic plate test apparatus using two different pure grease stains (the average is indicated) and a greasy mixed stain. Plates were soiled with the test dirt at a constant temperature of 40 or 45 ° C in 5 l of water with a hardness of 16 ° under constant conditions compared to a high-quality classic hand dishwashing liquid as a laboratory standard until the foam - which had formed before the start of the test - was destroyed was and the plates were no longer clean. The concentration of the agent was 2 ml per 5 l of water or, in the case of agents E25 to E28, 4 ml per 5 l of water. The number of dishes washed is in relation to the laboratory standard with a washing performance of 100%. Table 1

E1 E2 E3 E4 E5 E6 E7

C-i2 alcohol ether sulfate (2EO) Na salt 31.5

C-i2 / 14 alcohol ether sulfate (2EO) Na salt 20.0 20.0 - -

Ci2 / l4 alcohol ether sulfate (1, 3EO) Na salt - - - 31, £ 31, 5 31, 5 31, 5

Cl2 / 14- ^{A |} alcohol sulfate Na salt 11, 5 11, 5 - -

C-12 alkyl polyglucoside, DP = 1, 2 - - 5.0 -

C "| 2/16 ^{A, k} ylporyglucoside, DP = 1.4 5.0 5.0 - 5.0 3.0 3.0 3.0

Cocoamidopropyl betaine 3.0 3.0 3.0 3.0 5.0 5.0 5.0

Dicarboxylic acid mixture 2.5 2.5 2.5 2.5 2.5 2.5 2.5

(Sokalan® DCS Na)

Na formate

Na chloride

Ethanol 5.0 5.0 5.0 5.0 5.0 5.0 5.0

Perfume 0.7 0.7 0.7 0.7 0.7 0.7 0.7

Polymer (Carboposs EX 473) 0.2 0.3 0.2 0.4 0.6

Polymer (Polygeß W30)

Polymer (Rohagil® SD 15) 0.2 0.05

Water ad 100 100 100 100 100 100 100 pH 6.7 6.8 6.9 6.8 7.0 6.7 6.7

Viscosity at 20 ° C [mPa-s] 2650 3100 3050 2300 2200 3750 2350

Cold turbidity / clear point [° C] + 4 / + 8 + 4 / + 6 + 3 / + 5 + 3 / + 5 + 3 / + 4 + 4 / + 6 + 4 / + 6

Dissolution time [see] 40 46 43 38 44 75 37

Rinsing performance on greasy dirt [%] 100 100 - 100 107 107 107

Rinsing performance on mixed dirt [%] 102 102 - 102 110 110 110

Table 2

E8 E9 E10 E11 E12 E13 E14

Ci2 alcohol ether sulfate (2EO) Na salt - - - - - - -

Ci2 / l4 alcohol ether sulfate (2EO) Na salt 20.0 - 20.0 -

Ci2 / i4 alcohol ether sulfate (1.3EO) Na salt - 31.5 - 31, 5 31, 5 31, 5 31, 5

C-] 2/14 alcohol sulfate Na salt 11.5 - 11.5 - - - -

Ci2-alkyl polyglucoside, DP = 1, 2 - - - - - - - ci2 / i6- ^{A | k} yip ^{o |} y9 ' ^ucos 'd> ^D - ° ⁼ 1, 4 3.0 3.0 3.0 3.0 3.0 3.0 1, 5

Cocoamidopropyl betaine 5.0 5.0 5.0 7.0 7.0 7.0 7.0

Dicarboxylic acid mixture 2.5 2.5 2.5 1.0 2.5 2.5 2.0

(Sokalan® DCS Na)

Na formate - - - - - - -

Na chloride - - - - - - -

Ethanol 5.0 5.0 5.0 6.0 7.0 7.0 5.5

Perfume 0.7 0J 0.7 0.7 0.7 0.7 0.7

Polymer (Carboposs EX 473) - - - 0.4 1, 5 1, 5 0.4

Polymer (Polygeß W30) - 0.3 0.7 - - - -

Polymer (Rohagiß SD 15) 0.35 - - - - - -

Water ad 100 100 100 100 100 100 100

PH 6.5 6J 7.1 6.9 6.7 6.6 6.7

Viscosity at 20 ° C [mPa-s] 3350 2500 3800 1950 2150 2950 2000

Cold turbidity / clear point [° C] + 4 / + 6 + 3 / + 4 + 3 / + 4 + 4 / + 5 + 1 / + 3 -2 / + 1 + 4 / + 6

Dissolution time [see] 54 44 58 48 33 33 46

Rinsing performance on grease dirt. [%] 107 107 107 - - - 113

Rinsing performance on mixed dirt [%] 110 110 110 - - - 118 Table 3

E15 E16 E17 E18 E19 E20 E21

Ci2 aikohol ether sulfate (2EO) Na salt - - - - - - -

C-] 2/14 alcohol ether sulfate (2EO) - Na salt - - - 18.0 - - 18.0

Ci2 / l4 alcohol ether sulfate (1,3EO) Na salt 31,5 30,0 33,0 - 27,0 27,0 -

C 12/14 alcohol sulfate Na salt - - - 9.0 - - 9.0

Ci2-Alkylpolyglucosιd, DP = 1.2 - - - - - - -

Ci2 / l6- ^{A |} kylpolyglucosιd, DP = '1, 4 1, 5 3.0 1, 5 2.5 2.5 2.5 2.5

Cocoamidopropyl betaine 7.0 7.0 7.0 2.5 2.5 2.5 2.5

Dicarboxylic acid mixture 2.0 1.5 2.0 2.5 2.5 2.5 -

(Sokalan® DCS Na)

Na formate - - - - - - 3.0

Na chloride - - - - - - -

Ethanol 5.5 5.5 5.5 6.0 7.0 5.0 5.0

Perfume 0.7 0.7 0.7 0.6 0.6 0.6 0.4

Polymer (Carboposs EX 473) - 0.5 0.45 0.2 1, 2 0.2 0.4

Polymer (Polygeß W30) 0.3 - - - - - -

Polymer (Rohagiß SD 15) - - - - - - -

Water ad 100 100 100 100 100 100 100 pH 6.7 6.8 6.8 6.5 6.7 6.7 6.5

Viscosity at 20 ° C [mPa s] 2050 1950 2000 1950 2150 4000 3900

Cold haze / clear point [° C] + 3 / + 5 + 4 / + 5 + 4 / + 4 + 2 / + 5 + 2 / + 5 + 4 / + 5 + 3 / + 6

Dissolution time [see] 44 43 51 28 32 35 35

Rinsing performance of grease soiling [%] 113 95 95 95 95

Rinsing performance of mixed dirt [% 1 118 83 83 83 83

Table 4

E22 E23 E24 E25 E26 E27 E28

C 2 alcohol ether sulfate (2EO) Na salt - - 18.0 - - - -

C 12/14 alcohol alcohol sulfate (2EO) - Na salt 18.0 18.0 - - - 9.0 9.0

C2 / 14 alcohol ether sulfate (1,3EO) Na salt - - - 13.5 13.5 - -

C 2/14 alcohol sulfate Na salt 9.0 9.0 9.0 - - 4.5 4.5

C 2-Alkylpolyglucosιd, DP = 1, 2 - - 2.5 - - - 2.0

Ci2 / i6- ^A lkylpolyglucosιd, DP = 1, 4 2.5 2.5 - 2.0 2.0 2.0 -

Cocoamidopropyl betaine 2.5 2.5 2.5 1, 3 1, 3 1, 3 1, 3

Dicarboxylic acid mixture - - 2.5 - - - -

(Sokalan® DCS Na)

Na formate 3.0 3.0 - - - - -

Na chloride - - - 1, 0 1, 2 0.75 0.8

Ethanol 5.0 5.0 5.0 - - - -

Perfume 0.4 0.4 0.4 0.3 0.3 0.3 0.3

Polymer (Carboposs EX 473) - - 0.15 - - - 1, 0

Polymer (Polygeß W30) 0.25 - - 0.4 0.4 0.5 -

Polymer (Rohagiß SD 15) - 0.2 - - - - -

Water ad 100 100 100 100 100 100 100 pH 7.0 7.1 6.9 6.8 6.8 6.9 6.5

Viscosity at 20 ° C [mPa s] 3690 3800 2700 5950 6700 4450 2550

Cold haze / clear point [° C] + 3 / + 6 + 3 / + 6 + 3 / + 5 + 1 / + 5 + 2 / + 5 + 1 / + 4 + 1 / + 3

Dissolution time [see] 35 31 32 25 27 22 23

Rinsing performance of grease soiling [%] 95 95 - 92 92 92 92

Rinsing performance of mixed dirt [%] 83 83 - 89 89 89 89 Table 5

E29 E30

^A lkoholethersulfat CI2 (2EO) -Na-salt Ci2 / L4 ^A lkoholethersulfat (2EO) -Na-salt Ci2 / I4 ^A lkoholethersulfat (1,3EO) -Na-salt 31 5 33 ^c 12/14 ^{_A |} koholsulfat Na salt CI2 ^A lkylpolyglucosid, DP = 1, 2

Ci2 / i6- 'poly-polyglucoside, DP = 1, 4 5 6

Cocoamidopropyl betaine 3 3

Dicarboxylic acid mixture - -

(Sokalan® DCS Na)

Na citrate 4 -

Na acetate - 4th

Ethanol 5 5

Perfume 0.7 0.7

Polymer (Carboposs EX 473) 0.1 0.1

Polymer (Polygeß W30) - -

Polymer (Rohagiß SD 15) - -

Water ad 100 100 pH 6.8 7.0

Viscosity at 20 ° C [mPa-s] 2800 2500

Cold turbidity / clear point [° C] + 4 / + 6 + 4 / + 6

Dissolution time [see] 41 83

Rinsing performance on greasy dirt [%] - -

Rinsing performance on mixed dirt [%] - -

Example 2

The thickening effect of the polymers and the further positive influence of the thickeners on the other properties of the hand dishwashing detergents according to the invention are also illustrated by way of example using the following recipes (preparation and methods, unless stated otherwise, as in Example 1).

Recipe: 31.5% by weight of C ₁₂ alcohol ether sulfate (2EO) Na salt 5% by weight of C ₁₂ alkyl polyglucoside d _p 1, 2 3% by weight of cocoamidobetaine

2.5% by weight of dicarboxylic acid mixture (Sokalan®-DSC-Na) 5% by weight of ethanol 0.7% by weight of perfume 1.0% by weight of polymer Traces of dye water ad 100

Acrylic acid polymer, acrylic acid-methacrylic acid copolymer and carboxy vinyl polymer were used as polymers.

The following parameters were observed in the case of the acrylic acid polymer:

Viscosity (20 ° C) 5700 m-Pas; Cold cloud point +2 ° C / + 6 ° C; Dissolution time 81 seconds

A change in the Sokalan DSC ^® content in amounts above 2% by weight resulted in a clear solution of the ingredients. The viscosity of the mixture can also be influenced by this agent within certain limits. Another influence of the Sokalan DSC was found on the solubility of the mixture.

The amount of ethanol also has an influence on the homogeneity and the viscosity. A variation in the amount of solvent in the above formulation reveals an inhomogeneity below 4% by weight. However, this can differ from recipe to recipe. The viscosity can be influenced (reduced) by increasing the amount of solvent.

In a usual smell test by experts, the different recipes performed differently, but overall did well. In a test for light resistance (Xenotest 150), in which the stability of a UV-sensitive component (dye) was tested, the different formulations performed differentially well.

In a test of a mixture according to the invention flushing a composition analogous recipe but with 0.7 wt .-% Carbopof EX ^® 473 (acrylic polymer) is performed.

The viscosity was 3500 to 4000 m-Pas, the dissolution time between 45 to 70 seconds.

The cleaning performance of dirt was very good, the cleaning performance of grease was above average, the foaming power with and without oil addition was good, as was the emulsifying power.

The thickened product therefore has a stronger effect than comparable hand dishwashing detergents.

Claims

claims

1. Pourable storage-stable hand dishwashing detergent, containing a surfactant mixture of anionic surfactants and / or nonionic surfactants and / or betaine surfactants, characterized in that it contains between 0.01 and 5% by weight of polymers.

2. Composition according to claim 1, characterized in that at 20 ° C and a shear rate of 10 s ^"1 a viscosity between 1,000 and 10,000 mPa-s, preferably between 1,300 and 9,000 mPa-s, particularly preferably between 1,500 and 7,000 mPa -s or at 20 ° C and a shear rate of 30 s " ^{1 has} a viscosity between 500 and 8,000 mPa-s, preferably between 900 and 7,000 mPa-s, particularly preferably between 1,100 and 6,000 mPa-s.

3. Composition according to claim 1 or 2, characterized in that the surfactant mixture contains anionic and nonionic surfactants.

4. Composition according to one of claims 1 to 3, characterized in that the surfactant mixture contains betaine surfactants.

5. Composition according to one of claims 1 to 4, characterized in that it contains alkyl polyglycosides, preferably alkyl polyglucosides, as a nonionic surfactant.

6. Composition according to one of claims 1 to 5, characterized in that it is between 0.05 and 3 wt .-%, preferably 0.1 to 1, 5 wt .-% and particularly preferably between 0.2 and 0.9 % By weight, contains polymers.

7. Composition according to one of claims 1 to 6, characterized in that the polymers are selected from the group of acrylic acid polymers, acrylic acid-methacrylic acid copolymers and carboxyvinyl polymers.

8. Composition according to one of claims 1 to 7, characterized in that it is 0.2 to 60 wt .-%, preferably 1 to 55 wt .-%, particularly preferably 3 to 50 wt .-%, extremely preferably 5 to 45 Wt .-%, surfactant mixture contains.

9. Agent according to one of claims 1 to 8, characterized in that it

(a) 0.2 to 49.8% by weight, preferably 5 to 45% by weight, particularly preferably 10 to 40% by weight, of anionic surfactants, in particular fatty alcohol ether sulfates, (b) 0.1 to 14.9% by weight, preferably 1 to 8% by weight, of nonionic surfactants, in particular alkyl polyglucosides, and

(c) 0.1 to 14.9% by weight, preferably 0.5 to 10% by weight, of betaine surfactants, in particular alkylamido betaines.

10. Composition according to one of claims 1 to 9, characterized in that additionally between 0.5 and 15 wt .-% fatty alcohol sulfates are included.

11. Agent according to one of claims 1 to 10, characterized in that one or more dicarboxylic acids and / or their salts or sodium formate, sodium acetate, sodium tartrate, sodium chloride or magnesium chloride or salts of the further ingredient the aforementioned anions with other alkali or alkaline earth metals, alone or in a mixture, preferably in amounts of 0.1 to 8% by weight, particularly preferably between 0.5 and 7% by weight, are present.

12. Composition according to one of claims 1 to 11, characterized in that a solvent, for example one or more low molecular weight alcohols, e.g. Ethanol, in amounts preferably between 3 and 12 wt .-%, in particular between 4 and 10 wt .-%, is contained.

13. Composition according to one of claims 1 to 12, characterized in that it contains further ingredients customary in hand dishwashing detergents, such as UV stabilizers, defoamers, solvents, structuring agents, perfumes, dyes, corrosion inhibitors, preservatives or the like.