EP2245131B1 - Low-concentration liquid detergents or cleaners containing perfume - Google Patents

Description

The invention relates to a liquid washing or cleaning agent containing a surfactant mixture of anionic and nonionic surfactants and a perfume. The invention also relates to the use of the washing or cleaning agent and a process for its preparation.

In the objective of producing more cost-effective, liquid detergents and cleaners with the same or even improved performance, it is particularly attempted to reduce the amount of surfactant and / or to vary the type of surfactant.

However, it has been shown that with liquid detergents or cleaners with a low surfactant content, that is to say a surfactant content of not more than 25% by weight, the incorporation of higher perfume quantities, ie amounts from 0.4% by weight, is difficult. Thus, problems arise with respect to the storage stability, which in particular during storage at low temperatures, ie temperatures between 0 and 10 ° C show. Presumably, the small amount of surfactant is no longer sufficient to stably disperse in particular the hydrophobic constituents of the perfume oil.

WO01 / 00776 discloses a liquid detergent or cleaning composition containing perfume oil and a nonionic and anionic surfactant surfactant system wherein the ratio of nonionic to anionic surfactants is at least 0.75: 1 and the ratio of nonionic surfactants to perfume oil is between 5: 1 and 30: 1. The examples of D1 include alkanesulfonates and soap as the anionic surfactant.

It is an object of the invention to provide a low-concentration, perfume oil-containing, liquid washing or cleaning agent which is storage-stable under the most diverse climatic conditions and does not undergo phase separation.

This object is achieved by a liquid washing or cleaning agent containing a perfume oil and 5 to 18 wt .-% of a surfactant mixture of nonionic and anionic surfactants, wherein the anionic surfactant contains an alkylarylsulfonate and a soap and wherein the amount of alkylarylsulfonate more than 3 , 2 wt .-%, the amount of perfume oil 0.4 to 1.5 wt .-%, the ratio of nonionic surfactants to anionic surfactants at least 0.75: 1 and the ratio of nonionic surfactants to the perfume oil between 5: 1 and 30: 1.

It is advantageous if the ratio of the nonionic surfactants to the perfume oil is between 5: 1 and 15: 1, and more preferably between 5: 1 and 10: 1.

From an application point of view, liquid detergents and cleaners preferably contain a surfactant mixture of nonionic and anionic surfactants. Thus, nonionic surfactants are particularly effective for fatty soils. Anionic surfactants are used because of their good water solubility and their high washing power at low temperatures. It has now surprisingly been found that high levels of perfume oil can be incorporated into a storage-stable, low-concentration, liquid washing or cleaning agent, if the nonionic surfactants at least 75% of the amount by weight of anionic surfactants, ie at least 0.75 , available. The washing or cleaning agent obtained is storage stable under different climatic conditions and in particular at low storage temperatures.

It is preferred that the amount of the surfactant mixture is from 8 to 15% by weight, based in each case on the total amount of detergent or cleaning agent.

For cost reasons and also from an ecological point of view, it is advantageous to keep the total amount of surfactants as low as possible.

Furthermore, it is preferred that the ratio of nonionic surfactants to anionic surfactants is between 0.75: 1 and 5: 1, preferably between 0.75: 1 and 3: 1.

It has been found that with this ratio of the nonionic surfactants to the anionic surfactants optimum stabilization of the perfume oil takes place with good washing performance.

The anionic surfactants give a liquid detergent or cleaning agent according to the invention, containing a surfactant mixture of nonionic and anionic surfactants, a good cleaning performance on greasy soils.

It is particularly preferred that the anionic surfactant contains an alkylaryl sulfonate and a soap and the amount of alkylaryl sulfonate is more than 3.2% by weight.

Because of their detergency, alkylarylsulfonates are preferably used in the detergents or cleaners according to the invention. However, it has been found that the washing or cleaning agent preferably contains more than 3.2% by weight of these anionic surfactants in order to achieve a sufficiently good cleaning performance, in particular on grease-containing stains of the liquid washing or cleaning agent.

In a particularly preferred embodiment, the washing or cleaning agent contains 2 to 12 wt .-% and preferably 3 to 10 wt .-% of a polyol, each based on the total amount of detergent or cleaning agent, which consists of the group consisting of glycerol, 1 , 2-propanediol, 1,3-propanediol, ethylene glycol, diethylene glycol, dipropylene glycol and mixtures thereof. In a most preferred embodiment, the agent contains glycerin.

Surprisingly, it has been found that detergents or cleaners which contain certain amounts of polyol are more stable than detergents or cleaners with other non-polyol-containing solvents. In addition to the storage stability, especially at low storage temperatures, the chemical stability of the ingredients, in particular the enzymes, is increased.

Further, it is preferred that the amount of perfume oil is 0.7 to 1.3% by weight, based on the total amount of detergent or cleaning agent.

Since many consumers buy a washing or cleaning agent due to its fragrance, but especially because of the fragrance which mediates textiles washed with it, it is desirable to incorporate as high amounts of perfume oil as possible into the low-concentration liquid detergent or cleaning agent. However, excessive amounts of perfume oil are also negatively perceived by the user as "over-perfuming", so that the range of 0.4 to 1.5 wt .-% and in particular from 0.7 to 1.3 wt .-%, based on the Total amount of detergent or cleaning agent, has been found to be optimal area.

It is further preferred that the perfume oil contains at least 15% by weight of fragrances having a boiling point above 250 ° C. and a log P value of ≥ 3.0.

Such perfume oils may also be referred to as "hydrophobic perfume oils" and, in particular, have a better scent effect on textiles in terms of appeal, intensity and durability of the scent impression on textiles.

Furthermore, the invention relates to the use of the washing or cleaning agent according to the invention for washing and / or cleaning of textile fabrics.

In a further aspect, the invention relates to a process for the preparation of a liquid detergent or cleaning agent containing a perfume oil and a surfactant mixture of nonionic and anionic surfactants, wherein the agent, the nonionic surfactants at least in the ratio of 0.75: 1 to the anionic surfactants and in Ratio between 5: 1 and 30: 1 added to the perfume oil.

The invention also relates to the use of a surfactant mixture of nonionic and anionic surfactants, wherein the ratio of the nonionic surfactants to the anionic surfactants is at least 0.75: 1, in an amount up to 25% by weight for improving the storage stability of a liquid wash or detergent which comprises a perfume oil, when stored in certain temperature ranges, with the proviso that the ratio of the nonionic surfactants to the perfume oil is between 5: 1 and 30: 1. The stabilization occurs in particular when stored in a temperature range of 0 ° C to 10 ° C, when stored in a temperature range of 10 ° C to 25 ° C when stored in a temperature range of 25 ° C and 40 ° C.

The use of the surfactant mixture according to the invention makes it possible to obtain liquid detergents or cleaners with high perfume contents which are storage-stable under a wide variety of climatic conditions. In particular, the storage stability of the liquid detergents or cleaners in a temperature range of 0 ° C to 10 ° C is improved.

In the following, the invention will be described in more detail, inter alia, by way of examples.

The washing or cleaning agent contains 5 to 18 wt .-% of a surfactant mixture of anionic and nonionic surfactants.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, 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, C _12-14 alcohols with 3 EO, 4 EO or 7 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range 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. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, it is also possible to use mixed alkoxylated nonionic surfactants in which EO and PO units are not distributed in blocks, but randomly. Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

Also suitable is also a mixture of a branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as a mixture of a C _16-18 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO.

In addition, other nonionic surfactants also alkylglucosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol representing a glycoside unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4. Alkyl glucosides are known, mild surfactants.

Another class of nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. Other suitable surfactants are polyhydroxy fatty acid amides.

From a performance point of view and with regard to biodegradability, it is particularly preferable to use a linear, ethoxylated compound having 8 to 18 carbon atoms and, on average, 1 to 12 moles of ethylene oxide (EO) per mole of alcohol.

The content of nonionic surfactants in the washing or cleaning agent is preferably 2 to 12.5 wt .-%, preferably 4 to 10 wt .-% and in particular 5 to 8 wt .-%, each based on the total detergent or cleaning agent ,

In addition to the nonionic surfactant (s), the surfactant mixture of the washing or cleaning agent necessarily contains an anionic surfactant. The anionic surfactant contains an alkylaryl sulfonate and a soap.

Soaps are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.

The anionic surfactants including the soaps may be in the form of their sodium, potassium or magnesium salts. Preferably, the anionic surfactants are in the form of their sodium salts. Another preferred counterion for anionic surfactants is choline.

Alkylarylsulfonates which are preferably used in the invention are preferably alkylbenzenesulfonates and more preferably C _9-13 -alkylbenzenesulfonates.

To ensure a good washing performance on a multiplicity of stains, it is particularly preferred that the washing or cleaning agent according to the invention contains more than 3.2% by weight, based on the total agent, of alkylbenzenesulfonates.

The content of anionic surfactants in a washing or cleaning agent may be up to 14% by weight, based on the total washing or cleaning agent. However, the content of a washing or cleaning agent to anionic surfactants is preferably below 10 wt .-%, based on the total agent.

In addition to the surfactant mixture, the washing or cleaning agent contains a perfume oil. The perfume oil is present in an amount of from 0.4 to 1.5% by weight and preferably from 0.7 to 1.3% by weight.

In addition, the ratio of the perfume oil to the nonionic surfactants is between 1: 5 and 1: 30, preferably 1: 5 and 1:15 and more preferably between 1: 5 and 1:10.

A person skilled in the field of detergents or cleaners is able to recognize the combinations according to the invention or the individual ingredients in the ranges indicated for the ratio of the nonionic surfactants to anionic surfactants, the ratio of the nonionic surfactants to the perfume oil and the total surfactant content (Nonionic surfactant, anionic surfactant and perfume oil) to combine according to the invention to the object of the invention, low-concentrated washing or cleaning agents with a relatively high perfume content, which are stable in a variety of storage conditions to come. The term "relative" in this context does not refer to the absolute amount of perfume that is present throughout the detergent or cleanser, but the amount of perfume that is present (relative) in proportion to the total amount of surfactant.

As perfume oils, individual fragrance compounds, for example, the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures as are available from plant sources.

In a preferred embodiment, the perfume oil contains at least 15% by weight of fragrances having a boiling point above 250 ° C. and a logP value of ≥ 3.0. It has been found that low-concentration detergents or cleaners according to the invention which contain perfume oils with such a minimum amount of perfumes having a boiling point above 250 ° C. and a log P value of ≥ 3.0 have particularly advantageous scent properties. For example, an even longer lasting fragrance impression on the laundry can be achieved. Likewise, the Aufziehverhalten the fragrances in the dryer can be further improved on the laundry, so that the laundry smells even longer and more intense.

The octanol / water partition coefficient of a perfume ingredient is the ratio between its equilibrium concentration in octanol and in water. Since the distribution coefficients of the perfume ingredients are often high, for example 1000 or higher, they are more conveniently expressed in the form of their base 10 logarithm, which is referred to as the log P value. Preferred fragrances of this invention have a logP of ≥ 3.0 or higher, for example, ≥ 3.1, preferably ≥ 3.2, and especially ≥ 3.3.

The logP value of numerous fragrances is documented; For example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc., (Daylight CIS), Irvine, California, contains numerous logP values, along with citations to the original literature. However, the logP values are most conveniently calculated by the "CLOGP" program, which is also available from Daylight CIS. This program also lists the experimental logP values if they are available in the Pomona92 database. The "calculated logP" (ClogP value) is determined by the fragment approximation according to Harsch and Leo (see Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Harsch, PG Sammens, JB Taylor and CA Ransden, Eds., P. 295, Pergamon Press, 1990 incorporated herein by reference). The fragment approximation is based on the chemical structure of each of the perfume ingredients, taking into account the numbers and types of atoms, the atomic bonding ability, and the chemical bond. The ClogP values, which are the most reliable and widely used estimates for this physicochemical property, are preferably used in the present invention instead of the experimental logP values in selecting the perfume ingredients useful in the present invention.

The boiling points of numerous fragrances are given, for example, in "Perfume and Flavor Chemicals" (Aroma Chemicals), S. Arctander, published by the author in 1969.

Other boiling point values can be obtained, for example, from various known chemical manuals and databases. If a boiling point is given only at a different pressure, usually a pressure lower than the normal pressure of 760 mm Hg, the boiling point at normal pressure can be determined approximately with the help of boiling point pressure nomographs such as those in " The Chemist's Companion, AJ Gordon and RA Ford, John Wiley & Sons Publishers, 1972, pp. 30-36 , specified, estimated. Where applicable, the boiling point values can also be calculated by computer programs based on the molecular structure data such as those described in " Computer-assisted Prediction of Normal Boiling Points of Pyrans and Pynoles ", DT Starton et al., J. Chem. Inf. Comput. Sci., 32 (1992), pp. 306-316 , "Computer-assisted Prediction of Normal Boiling Points of Furans, Tetrahydrofurans, and Thiophenes" (computer-assisted prediction of the normal boiling points of furans, tetrahydrofurans and thiophenes), DT Starton et al., J. Chem. Inf. Comput. Sci., 31 (1992), pp. 301-310 , and the references cited therein, and "Predicting Physical Properties from Molecular Structure", R. Murugan et al., Chemtech. June 1994, p. 17-23 ,

In the following, some odoriferous substances which fulfill the criteria boiling point> 250 ° C and ClogP ≥ 3 are listed by way of example in Table 1. Table 1: Examples of fragrances Perfume ingredients with a boiling point> 250 ° C and a ClogP ≥ 3.0 Approximate boiling point (° C) ClogP Allylcylclohexanpropionat 267 3,935 ambrettolide 300 6.261 amyl benzoate 262 3,417 Amylcinnamat 310 3,771 amyl cinnamic aldehyde 285 4,324 Amylzimtaldehyddimethylacetal 300 4,033 iso-amyl salicylate 277 4,601 aurantiol 450 4,216 benzophenone 306 3,120 benzyl 300 4,383 para-tert-butylcyclohexyl acetate > 250 4,019 iso-butylquinoline 252 4,193 beta-caryophyllene 256 6,333 cardinene 275 7,346 cedrol 291 4,530 cedryl acetate 303 5,436 Cedrylformiat > 250 5,070 cinnamyl cinnamate 370 5,480 cyclohexyl 304 5,265 Cyclamenaldehyd 270 3,680 Dihydroisojasmonat > 300 3,009 diphenylmethane 262 4,059 diphenyl 252 4,240 Dodecanlacton 258 4,359 iso E awesome > 250 3,455 Ethylbrassylat 3321 4,554 ethyl methyl phenyl glycidate 260 3,165 ethyl undecylenate 264 4,888 exaltolide 280 5.346 galaxolid > 250 5,482 Geranylanthranilat 312 4,216 geranyl phenylacetate > 250 5,233 hexadecanolide 294 6,805 hexenyl 271 4,716 hexyl cinnamic aldehyde 305 5,473 hexyl salicylate 290 5,260 alpha-Iron 250 3,820 Lilial (pt-bucinal) 258 3,858 Linalyl benzoate 263 5,233 2-methoxynaphthalene 274 3,235 Methyldihydrojasmon > 300 4.843 gamma-n-methyl ions 252 4,309 Musk indanone > 250 5,458 Musk ketone FP = 137 ° C 3,014 Musk Tibetin FP = 136 ° C 3,831 myristicin 276 3,200 Oxahexadecanolide-10 > 300 4,336 Oxahexadecanolide-11 FP = 35 ° C 4,336 patchouli 285 4,530 Phantolide 288 5,977 phenylethyl benzoate 300 4,058 phenylethyl phenylacetate 325 3,767 Phenylheptanol 261 3,478 phenylhexanol 258 3,299 alpha-Santalol 301 3,800 Thibetolid 280 6,246 delta-undecalactone 290 3,830 gamma-undecalactone 297 4,140 Vetiverlyacetat 285 4,882 Yara-yara 274 3,235 FP stands for the melting point; these ingredients have a boiling point higher than 250 ° C.

This table gives a sufficient number of nonlimiting examples of fragrances which are preferred for use in this invention. The perfume oils of the washing or cleaning agents according to the invention preferably contain at least 3 different fragrances, more preferably at least 4 different fragrances, and even more preferably at least 5 different fragrances.

In addition to the surfactants and the perfume oil, the washing or cleaning agent may contain further ingredients which further improve the performance and / or aesthetic properties of the washing or cleaning agent. In the context of the present invention, the washing or cleaning agent preferably additionally contains one or more substances from the group of builders, bleaching agents, bleach catalysts, bleach activators, enzymes, electrolytes, nonaqueous solvents, pH adjusters, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, Silicone oils, anti redeposition agents, graying inhibitors, anti-shrinkage agents, wrinkle inhibitors, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, plasticizing components and UV absorbers.

Suitable builders which may be present in the washing or cleaning agent are, for example, silicates, aluminum silicates (in particular zeolites), phosphates or carbonates.

For reasons of aesthetics, however, preference is given to using soluble, organic builders in the liquid detergents or cleaners.

Organic builders which may be present in the washing or cleaning agent are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA) and derivatives thereof and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder effect, the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

As builders further polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those containing as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Citric acid, or its salts, are preferably used as soluble, organic builders in liquid detergents or cleaners.

The liquid detergent or cleaning agent may also contain an enzyme or a mixture of enzymes. Particularly suitable are those from the classes of hydrolases such as proteases, (poly) esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases, hemicellulases, cutinases, β-glucanases, oxidases, peroxidases, mannanases, perhydrolases, Oxireductases and / or laccases. Proteases, amylases, lipases, cellulases, mannanases, laccases, tannanases and esterases / polyesterases and mixtures of two or more of these enzymes are preferably used in the context of the present invention.

The amount of enzyme or of the enzymes is based on the total agent 0.01 to 10 wt .-%, preferably 0.12 to about 3 wt .-%. The enzymes are preferably used as enzyme liquid formulation (s).

To stabilize the enzymes detergents or cleaning agents according to the invention may contain stabilizing agents such as boric acid or borates, boric acid derivatives or amino alcohols.

As electrolytes from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. The proportion of electrolytes in the washing or cleaning agent is usually 0.1 to 5 wt .-%.

Non-aqueous solvents that can be used in the washing or cleaning agent, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range. It can be solvents from ethanol, n- or i-propanol, butanols, glycol, propane- or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, 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, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ethers and mixtures of these solvents are selected. Non-aqueous solvents may be used in the detergent or cleaning agent in amounts between 0.5 and 25 wt .-%, but preferably below 20 wt .-% and in particular below 15 wt .-%.

However, it is preferred that the washing or cleaning agent contain certain amounts of a polyol as a nonaqueous solvent. It is preferred that the washing or cleaning agent contains from 2 to 10% by weight of a polyol. The polyol may include glycerol, 1,2-propanediol, 1,3-propanediol, ethylene glycol, diethylene glycol and / or dipropylene glycol. Particularly preferably, the washing or cleaning agent contains glycerol.

In order to bring the pH of the washing or cleaning agent in the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited.
The pH of the detergent or cleaner is preferably between 4 and 10, preferably between 6.5 and 9, and most preferably between 7 and 8.8.

The liquid detergents or cleaners preferably have viscosities in the range from 200 to 5000 mPas, with values between 300 and 2000 mPas and in particular 400 and 1000 mPas being particularly preferred. The viscosity was determined using a Brookfield LVT-II viscometer at 20 rpm and 20 ° C., spindle 3.

In order to improve the aesthetic impression of the washing or cleaning agent, they can be dyed with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of detergents or cleaning agents and to light and no pronounced substantivity to textile fibers so as not to stain them.

Suitable foam inhibitors which can be used in the detergents or cleaners are, for example, soaps, paraffins or silicone compounds, in particular silicone oils, which are optionally present as emulsions.

Suitable soil-release polymers, which are also referred to as "anti redeposition agents", are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose and the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene and / or polypropylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. Suitable derivatives include the sulfonated derivatives of the phthalic and terephthalic acid polymers.

Optical brighteners (so-called "whiteners") can be added to the detergents or cleaners to eliminate graying and yellowing of the treated fabrics. Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives. The optical brighteners are usually used in amounts of between 0% and 0.3% by weight, based on the finished washing or cleaning agent.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof are preferably used in amounts of from 0.1 to 5% by weight, based on the total amount of detergent or cleaning agent ,

In order to effectively suppress dye release and / or dye transfer to other fabrics during washing and / or cleaning of dyed fabrics, the washing or cleaning agent may contain a dye transfer inhibitor. It is preferred that the dye transfer inhibitor is a polymer or copolymer of cyclic amines such as vinylpyrrolidone and / or vinylimidazole. Suitable color transfer inhibiting polymers include polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride, and mixtures thereof. Particular preference is given to using polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) as color transfer inhibitor. Polyvinylpyrrolidones (PVP) are for example commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90 or from BASF as Sokalan® HP 50 or Sokalan® HP 53. PVP / PVI copolymers are commercially available, for example, from BASF under the name Sokalan® HP 56.

The amount of dye transfer inhibitor based on the total amount of the detergent or cleaning agent is preferably from 0.01 to 2% by weight, preferably from 0.05 to 1% by weight, and more preferably from 0.1 to 0.5% by weight. -%.

Alternatively, however, it is also possible to use enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which produces hydrogen peroxide in water as a color transfer inhibitor. The addition of a mediator compound for the peroxidase, for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, wherein additionally the above-mentioned polymeric dye transfer inhibitors can be used.

The detergents or cleaners according to the invention may contain preservatives, it being preferred to use only those which have no or only a low skin-sensitizing potential. Examples are sorbic acid and its salts, benzoic acid and its salts, salicylic acid and its salts, phenoxyethanol, formic acid and its salts, 3-iodo-2-propynyl butylcarbamate, sodium N- (hydroxymethyl) glycinate, biphenyl-2-ol and mixtures thereof. Further suitable preservatives are isothiazolones, mixtures of isothiazolones and mixtures of isothiazolones with other compounds, for example tetramethylolglycoluril.

In order to avoid the catalyzed by heavy metals decomposition of certain detergent ingredients, substances that complex heavy metals can be used. Suitable heavy metal complexing agents are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA), methylglycinediacetic acid trisodium salt (MGDA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.

A preferred class of complexing agents are the phosphonates present in the detergent or cleaning agent in amounts of 0.01 to 2.5% by weight, preferably 0.02 to 2% by weight and in particular 0.03 to 1, 5 wt .-% are included. These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2 , 4-tricarboxylic acid (PBS-AM), which are used mostly in the form of their ammonium or alkali metal salts. Alternative complexing agents which can be used in the detergent or cleaning agent are iminodisuccinate (IDS) or ethylenediamine-N, N'-disuccinate (EDDS).

The washing or cleaning agents according to the invention can be used for washing and / or cleaning textile fabrics.

The preparation of the washing or cleaning agent by means of conventional and known methods and methods. For example, the components of detergents or cleaners can be simply in stirred kettles are mixed, wherein water, the acidic components, if any, such as the alkylarylsulfonates, citric acid, boric acid, phosphonic acid, the fatty alcohol ether sulfates, etc., and the nonionic surfactants are conveniently presented. The nonaqueous solvents, if present, are preferably also added at this time, but the addition may be made at a later time. Subsequently, if present, the fatty acid is added and the saponification of the fatty acid moiety is carried out at 50 to 60 ° C. Then the further ingredients are preferably added in portions. It is crucial, however, that the amount of active ingredient added to nonionic surfactants is at least equal to the amount of active ingredient added to the anionic surfactants and that the amount of perfume oil added is between 0.5 and 1.5 wt .-%, based on the total amount of wash - or detergent, lies.

Table 2 below shows the compositions of three comparative formulations V1 and V2 and the compositions of three detergents or cleaners E1-E4 according to the invention (all amounts are given in% by weight of active ingredient based on the composition): Table 2: Composition of washing or cleaning agents V1 and V2 and E1 to E4 (in% by weight) V1 V2 E1 E2 E3 E4 C _12-18 fatty alcohol with 7 EO 5.2 5.5 6.4 6.4 6.8 7.2 Linear C ₁₀ -C ₁₃ -alkylbenzenesulfonate (Na salt) 6.85 6.42 6.42 5.35 4.82 4.28 C _12-18 fatty acid (Na salt) 1.98 1.98 1.98 1.98 1.98 1.98 Citric acid (Na salt) 1 1 1 1 1 1 phosphonic 0.5 0.5 0.5 0.5 0.5 0.5 Boric acid (Na salt) 1 1 1 1 1 1 Polyacrylate thickener 0.3 0.3 0.3 0.3 0.3 0.3 Optical brightener 0.08 0.08 0.08 0.08 0.08 0.08 glycerin 3 3 3 3 3 3 ethanol 1 1 1 1 1 1 Silicone antifoam 0.01 0.01 0.01 0.01 0.01 0.01 Enzymes (protease & amylase) 0.6 0.6 0.6 0.6 0.6 0.6 Perfume A 1.0 1.0 1.0 1.0 1.0 1.0 Dye, preservative + + + + + + water Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ratio of nonionic surfactant to anionic surfactant 0.58: 1 0.65: 1 0.76: 1 0.87: 1 1: 1 1.15: 1

The resulting washing or cleaning agents V1 - V2 and E1 - E4 were subjected to storage tests simulating different climatic conditions. Table 3: Visual assessment of washing or cleaning agents V1 - V3 and E1 - E4 after storage under different climatic conditions. week V1 V2 E1 E2 E3 E4 24 ° C to 40 ° C 2 OK OK OK OK OK OK 4 OK OK OK OK OK OK 8th OK OK OK OK OK OK 24 ° C to 40 ° C Assessment: RT 2 OK OK OK OK OK OK 4 OK OK OK OK OK OK 8th OK OK OK OK OK OK 10 ° C to 30 ° C 2 OK OK OK OK OK OK 4 OK OK OK OK OK OK 8th OK OK OK OK OK OK 10 ° C to 30 ° C Assessment: RT 2 OK OK OK OK OK OK 4 OK OK OK OK OK OK 8th OK OK OK OK OK OK 0 ° C to 10 ° C 2 UNSTABLE UNSTABLE OK OK OK OK 4 UNSTABLE UNSTABLE OK OK OK OK 8th UNSTABLE UNSTABLE OK OK OK OK 0 ° C to 10 ° C Assessment: RT 2 UNSTABLE UNSTABLE OK OK OK OK 4 UNSTABLE UNSTABLE OK OK OK OK 8th UNSTABLE UNSTABLE OK OK OK OK OK: No findings
ACCEPTABLE: Medium shows slight inhomogeneities, but is acceptable
INSTABILITY: mean is unacceptable (severe cloudiness, creaming or phase separation)
RT: room temperature; corresponds to 20 ° C.

The washing or cleaning agents according to the invention were stored at the indicated temperatures, the temperatures in each case fluctuating within a defined cycle within the specified temperature range. The evaluation was done either at room temperature or at the lowest temperature of a temperature range.

From the stability tests it is clear that when the ratio according to the invention of nonionic surfactants to anionic surfactants of at least 0.75: 1 is adjusted to low (the total surfactant content is between 13.87% by weight in Example E1 and 13.46% by weight in Example E4) washing or cleaning agents are obtained, which are stable in a variety of climatic conditions. In addition, it is clear that the washing or cleaning agents according to the invention are able to disperse the perfume oil at a lower total surfactant storage stability and homogeneous.

Table 4 below shows the compositions of two comparative formulations V3 and V4 as well as two formulations E5 and E6 according to the invention (all amounts are given in% by weight of active ingredient based on the composition): Table 4: Composition of washing or cleaning agents V3 and V4 and E5 and E6 (in% by weight) V3 V4 E5 E6 C _12-18 fatty alcohol with 7 EO 5.2 5.2 6.4 6.4 Lin. C ₁₀ -C ₁₃ -alkylbenzenesulfonate (Na salt) 6.85 6.85 5.35 5.35 C _12-18 fatty acid (Na salt) 1.98 1.98 1.98 1.98 Citric acid (Na salt) 1.2 1.2 1.2 1.2 phosphonic 0.5 0.5 0.5 0.5 Boric acid (Na salt) 1.06 1.06 1.06 1.06 Polyacrylate thickener 0.3 0.3 0.3 0.3 Optical brightener 0.08 0.08 0.08 0.08 glycerin 3 3 3 3 ethanol 1 1 1 1 Silicone antifoam 0.01 0.01 0.01 0.01 Enzymes (protease & amylase) 0.1 0.1 0.1 0.1 Perfume B 0.8 1.0 0.8 1.0 Dye, preservative + + + + water Ad 100 Ad 100 Ad 100 Ad 100 Ratio of nonionic surfactant to anionic surfactant 0.59: 1 0.59: 1 0.87: 1 0.87: 1 week V3 V4 E5 E6 24 ° C to 40 ° C 2 OK OK OK OK 4 OK OK OK OK 8th OK OK OK OK 24 ° C to 40 ° C Assessment: RT 2 OK OK OK OK 4 OK OK OK OK 8th OK OK OK OK 10 ° C to 30 ° C 2 OK OK OK OK 4 OK OK OK OK 8th OK OK OK OK 10 ° C to 30 ° C Assessment: RT 2 OK OK OK OK 4 OK OK OK OK 8th OK OK OK OK 0 ° C to 10 ° C 2 UNSTABLE UNSTABLE OK OK 4 UNSTABLE UNSTABLE OK OK 8th UNSTABLE UNSTABLE OK OK 0 ° C to 10 ° C Assessment: RT 2 UNSTABLE UNSTABLE OK OK 4 UNSTABLE UNSTABLE OK OK 8th UNSTABLE UNSTABLE OK OK

From the stability tests it is clear that when the ratio of nonionic surfactants according to the invention to anionic surfactants of at least 0.75: 1 low concentrated (the total surfactant content is 13.73 wt .-% in Examples E5 and E6) washing or cleaning agents with high Perfume oil can be obtained, which are storage stable under various climatic conditions.

Table 6 below shows the compositions of three formulations E7 to E9 according to the invention (all amounts are given in% by weight of active ingredient based on the composition): Table 6: Composition of washing or cleaning agents E7 to E9 (in% by weight) E7 E8 E9 C _12-18 fatty alcohol with 7 EO 6.4 6.4 6.4 Lin. C ₁₀ -C ₁₃ -alkylbenzenesulfonate (Na salt) 5.35 5.35 5.35 C _12-18 fatty acid (Na salt) 1.98 1.98 1.98 Citric acid (Na salt) 1.2 1.2 1.2 phosphonic 0.5 0.5 0.5 Boric acid (Na salt) 1.06 1.06 1.06 Polyacrylate thickener 0.3 0.3 0.3 Optical brightener 0.08 0.08 0.08 glycerin 3 3 3 ethanol 1 1 1 Silicone antifoam 0.01 0.01 0.01 Enzymes (protease & amylase) 0.1 0.1 0.1 Perfume C 0.78 1.0 1.2 Dye, preservative + + + water Ad 100 Ad 100 Ad 100 Ratio of nonionic surfactant to anionic surfactant 0.87: 1 0.87: 1 0.87: 1

All three compositions were undetectable for 8 weeks at the six different storage and assay conditions given above ("OK").

The perfume oils A to C used in the context of this invention each contain at least 15% by weight of fragrances having a boiling point above 250 ° C. and a logP value or ClogP value of ≥ 3.0. The content of these fragrances in the respective perfume oils A to C increases in the following order: perfume oil A <perfume oil B <perfume oil C.

In washing tests with detergents or cleaning agents containing a surfactant mixture of nonionic and anionic surfactants, wherein the ratio of nonionic surfactants to anionic surfactants is at least 0.75: 1, it has been found that it is advantageous if the detergents or cleaning agents contains more than 3.2 wt .-% of an alkylaryl sulfonate. Table 7: Composition of detergents or cleaners E10 to E12 (in% by weight) E10 E11 E12 C _12-18 fatty alcohol with 7 EO 6.4 7.2 8.0 Lin. C ₁₀ -C ₁₃ -alkylbenzenesulfonate (Na salt) 5.35 4.28 3.20 C _12-18 fatty acid (Na salt) 1.98 1.98 1.98 Citric acid (Na salt) 1.2 1.2 1.2 phosphonic 0.5 0.5 0.5 Boric acid (Na salt) 1.06 1.06 1.06 Polyacrylate thickener 0.3 0.3 0.3 Optical brightener 0.08 0.08 0.08 glycerin 3 3 3 ethanol 1 1 1 Silicone antifoam 0.01 0.01 0.01 Enzymes (protease & amylase) 0.1 0.1 0.1 Perfume C 0.78 1.0 1.2 Dye, preservative + + + water Ad 100 Ad 100 Ad 100 Ratio of nonionic surfactant to anionic surfactant 0.87: 1 1.15: 1 1.54: 1

All three compositions were undetectable for 8 weeks at the six different storage and assay conditions given above ("OK").

However, the washing or cleaning agent E12 showed a poorer cleaning performance of greasy stains: Table 8: Comparison of the cleaning performance of the detergent or cleaning agent E12 with the detergents or cleaners E10 and E11. staining Compared to E10 Compared to E11 lipstick - 4.1% - 5.4% Make up -12.7% - 8.1% motor oil - 2.1% - 0.9%

Claims (8)

1. A liquid washing or cleaning agent containing a perfume oil and from 5 to 18 wt.% of a surfactant mixture consisting of non-ionic and anionic surfactants, wherein the anionic surfactant contains an alkyl aryl sulfonate and a soap, and wherein the quantity of alkyl aryl sulfonate is more than 3.2 wt.%, the quantity of perfume oil is from 0.4 to 1.5 wt.%, the ratio of the non-ionic surfactants to the anionic surfactants is at least 0.75:1 and the ratio of the non-ionic surfactants to the perfume oil is between 5:1 and 30:1.
2. The washing or cleaning agent according to claim 1, characterized in that the ratio of the non-ionic surfactants to the perfume oil is between 5:1 and 15:1, and more preferably between 5:1 and 10:1.
3. The washing or cleaning agent according to either claim 1 or claim 2, characterized in that the quantity of surfactant mixture is from 8 to 15 wt.%.
4. The washing or cleaning agent according to one of claims 1 to 3, characterized in that the ratio of the non-ionic surfactants to the anionic surfactants is between 0.75:1 and 5:1, preferably between 0.75:1 and 3:1.
5. The washing or cleaning agent according to one of claims 1 to 4, characterized in that the quantity of perfume oil is from 0.7 to 1.3 wt.%.
6. The washing or cleaning agent according to one of claims 1 to 5, characterized in that the perfume oil contains at least 15 wt.% fragrance substances having a boiling point above 250 °C and a logP value of ≥ 3.0.
7. The use of the washing or cleaning agent according to one of claims 1 to 6 for washing and/or cleaning textile fabrics.
8. A method for producing a liquid washing or cleaning agent containing a perfume oil and from 5 to 18 wt.% of a surfactant mixture consisting of non-ionic and anionic surfactants, wherein the anionic surfactant contains an alkyl aryl sulfonate and a soap, the quantity of alkyl aryl sulfonate is more than 3.2 wt.% and the quantity of perfume oil is from 0.4 to 1.5 wt.%, and wherein the non-ionic surfactants are added to the agent at least in a ratio of 0.75:1 to the anionic surfactants and in a ratio of between 5:1 and 30:1 to the perfume oil.