EP3107990A1

EP3107990A1 - Concentrated laundry detergents

Info

Publication number: EP3107990A1
Application number: EP15702793.9A
Authority: EP
Inventors: Peter Schmiedel; Kaoru Tachikawa; Yvonne Willemsen; Arnd Kessler; Nicole BODE; Iwona Spill; Reinhard Strey; Anna KLEMMER; Christian Nitsch
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2014-02-19
Filing date: 2015-02-06
Publication date: 2016-12-28
Also published as: WO2015124439A1; DE102014202990A1; US20160348042A1

Abstract

One- or multi-phase non-solid concentrated products, which are capable of producing or maintaining a Winsor type 2 microemulsion system upon dilution in a short liquor technology washing machine, show improved performance for fat and oil-containing stains when used in novel methods in which various Winsor types are passed through starting from Winsor type 2.

Description

WASH CONCENTRATE

The present invention relates to concentrates which are suitable for use as laundry detergents in laundry machines, their use for the formation of microemulsions or a microemulsion system in a washing machine and a textile washing process, which is carried out to form a microemulsion or a microemulsion system.

There is a long felt need to be able to effectively remove fatty soiling. Therefore, usually every washing process aims to remove hydrophobic portions of the stains. In order to then effect the absorption of the hydrophobic components of the soiling in the wash liquor, a thermodynamically attractive environment for these soils must be created.

The state of the art offers different solutions for this purpose. A process for the purification and impregnation of functional textiles is described in the European patent EP 1838915 B1, wherein initially the textiles with a so-called short liquor, i. a liquor, which has a ratio of the weight of the amount of dry textile to the weight of the amount of water greater than 1: 8, are wetted and then washed a predetermined amount of a hydrophobic agent by means of water from the detergent reservoir in the tub and brought into contact with the moistened textiles becomes. According to WO 2010/031675, the finishing composition is sprayed on the pre-moistened items of laundry in the form of fine droplets (spray).

From WO 2005/003268 a washing process is known in which the detergent is dispersed in less water than in conventional processes and the laundry is thus contacted at a greater ratio of the amount of dry textile to the amount of water with a less dilute wash liquor. The detergent formulation itself has no special requirements. The ratio of the weight of the dry laundry amount to the weight of the water amount is 1: 2 to 4: 1.

WO 2013/134168 discloses a washing method in which, in at least two successive sub-washing cycles, the laundry in the first sub-washing cycle is treated with a more concentrated detergent composition than in a second sub-washing cycle. A wash cycle is the period from the creation of a wash liquor to the removal of the wash liquor from the washing machine. A wash cycle may be subdivided into sub-wash cycles whereby at the end of the first sub-wash cycle the wash liquor is not removed but at the beginning of the second cycle new, additional water is fed into the already existing wash liquor. It is preferred that the first sub-washing cycle lasts longer than the second. The detergent formulation itself has no special requirements.

WO 2012/04891 1 discloses a washing method in a washing machine, wherein the cleaning agents and possibly various cleaning agents or components thereof are sprayed into the interior of the washing machine. The process and control of the machine are designed to consume significantly less water for both cleaning and rinsing than traditional processes. Further requirements for the cleaning agents, with the exception of the property that they must be sprayable, are not provided.

It is known that microemulsions are thermodynamically stable emulsions and have extremely low interfacial tensions. A person skilled in the art also knows that in order to remove dirt, the interfacial tension between water and the fat component of the soiling must be lowered.

WO 2013/1 10682 describes detergents, in particular for manual dishwashing, but also for the pretreatment of laundry, the compositions containing 1 to 50% by weight of anionic surfactants and 1 to 36% by weight of salts and which on contact with oils and / or fats spontaneously form a microemulsion. Furthermore, microemulsions are described which contain 1 to 50% by weight of anionic surfactants, 1 to 36% by weight of salts, 10 to 80% by weight of water and 10 to 80% by weight of at least one triglyceride or a mixture of a triglyceride and a or more components from the group consisting of waxes, lipids, terpenes, triterpenes and fatty acids. The formation of the microemulsion takes place in situ with the triglycerides or triglyceride-containing mixtures present on the surface to be cleaned.

US Pat. No. 6,112,120 discloses acidic hard surface cleaners which may be in the form of a microemulsion. An application of such emulsions in a washing machine is not recommended.

The patent applications EP 0160762 and WO 95/27035 propose O / W microemulsions as detergents.

German patent application DE 10129517 proposes the use of microemulsions of water, one or more hydrophobic components and sugar-based nonionic surfactants as stain pretreatment agents for textiles or for cleaning hard surfaces. The suitability of these microemulsions for use in washing machines is not described. Finally, WO 201 1/073062 discloses bicontinuous microemulsion systems which are suitable as stain pretreatment agents and which are capable of dissolving solid and solidified fatty stains in the main wash at neutral pH.

It was the object to provide consumer products that result in improved procedures and machines with lower water consumption to improved removal of particular greasy and oily soils.

The subject of the patent is therefore a mono- or multiphase non-solid concentrate for use as a laundry detergent, which is suitable for giving or maintaining a Winsor Type 2 microemulsion system when diluted in a washing machine with a short liquor washing technique.

According to Winsor microemulsion systems consisting of a water component, an oil component and amphiphile can be subdivided according to their phase equilibria into 4 types.

In a Winsor Type 1 microemulsion system, the surfactant is soluble primarily in water and in an O / W microemulsion form. It consists of a surfactant-rich aqueous phase (07W microemulsion) and an excess but low-surfactant oil phase.

In a Winsor Type 2 microemulsion system, the surfactant is especially soluble in an oil phase and in a W / O microemulsion form. It consists of a surfactant-rich oil phase (W / O microemulsion) and an excess but low-surfactant aqueous phase.

A Winsor Type 3 microemulsion system displays a bicontinuous microemulsion, also called a mid-phase microemulsion, of a surfactant-rich middle phase which coexists with a low surfactant aqueous phase as well as a low surfactant oil phase.

A Winsor Type 4 microemulsion system, on the other hand, is a single phase homogeneous mixture and, unlike Winsor types 1 to 3, which consist of 2 or 3 phases of which only one phase is a microemulsion, is a microemulsion high surfactant concentrations to achieve this single phase, while in Winsor Type 1 and Type 2 microemulsion systems significantly lower surfactant concentrations are required to achieve a stable phase equilibrium. For this reason, while Winsor Type 4 microemulsions are often described in the patent literature, they are seldom or even not used in domestic machine washing processes. The large amount of surfactant required makes such a process uneconomical and is not least environmentally friendly. The consumer product according to the invention is a single- or multiphase concentrate which is not solid, but may be liquid, gelatinous or pasty at room temperature, for example. The teachings of the invention take advantage of the fact that the detergent composition used in the washing machine is intended to be a Winsor Type 2 microemulsion system, but the concentrate which constitutes the consumer product need not already be in the form of a Winsor Type 2 microemulsion system. For the purposes of the invention, it is sufficient if the concentrate can be converted to a Winsor Type 2 microemulsion system on dilution with water and especially in a shortwash washing machine. However, it may be advantageous if the concentrate already exists as a Winsor Type 2 microemulsion system. It may likewise be preferred if the concentrate is present as a Winsor Type 4 microemulsion, if it can be converted into a Winsor Type 2 microemulsion system during the preparation of the wash liquor. Since a Winsor Type 2 microemulsion system is biphasic, it may be desirable in the interests of uniform distribution of the short liquor on the wash that the concentrate from a Winsor Type 2 microemulsion system be non-macroscopically separate during use, but application in a manner An emulsion of the two phases of the Winsor Type 2 system is applied. Such an emulsion can be made, for example, by appropriate mixing, in particular stirring of the microemulsion type before application to the laundry.

According to Bancroft, the type of emulsion depends both on the emulsifier and on the phase in which the emulsifier, for example a surfactant or various surfactants, dissolves. If water-soluble, ie hydrophilic, emulsifiers, for example anionic surfactants, are used, O / W emulsions are formed. However, anionic surfactants can be rendered more hydrophobic by addition of salts by electrostatic shielding the hydrophilic head group of the anionic surfactants so that W / O emulsions are achieved. It is thus possible to carry out a phase inversion by addition of salts and to convert an O / W emulsion with anionic surfactant as emulsifier into a W / O emulsion. This can then interact with the greasy and oily soils, mixing with the dirt on the fiber, thereby lowering the interfacial tension between the existing greasy and oily soils and the water phase. Dilution of the emulsion then lowers the salt concentration, weakens the shielding of the ionic head group of the anionic surfactant and makes the anionic surfactant more hydrophilic. The grease and oil-like dirt can be better separated from the textile together with the microemulsion and dispersed in the aqueous liquor and ultimately transported away with the aqueous liquor.

Likewise, the behavior of the emulsifiers is influenced by the temperature. If hydrophobic emulsifiers, for example nonionic surfactants, are used, W / O emulsions are formed. An addition of salt is not required. Higher application temperatures make the nonionic surfactants more hydrophobic and can interact better with grease and oily dirt. If the temperature is reduced again during dilution of the liquor, the nonionic surfactants become hydrophilic again, the grease and oily soils can be better detached from the textile and dispersed in the aqueous liquor and ultimately transported away with the aqueous liquor.

Thus, by temperature controls and / or addition of salts targeted phase inversions can be achieved.

Short liquor washing technique means the provision of a first sub-wash cycle in which the first contact of the fabric or laundry with water and the example soaked or sprayed detergent, wherein the ratio of the weight of the dry textile or laundry lot to the aqueous liquor is at least 1: 8, but preferably a short liquor is used, in which the ratio of the weight of the dry textile or laundry lot to the aqueous liquor is at least 1: 4, in particular not less than 1: 2, for example 1: 2 to 4: 1, advantageously 1: 2 to 2: 1. According to the invention, the aqueous liquor used in the first sub-wash cycle consists of a Winsor Type 2 microemulsion system. In preferred embodiments of the invention, the upper limit of the weight ratio of the dry fabric or laundry to the Winsor Type 2 aqueous liquor is limited to ensure that the entire batch of laundry may be thoroughly moistened during the first sub-wash cycle. Only then is it ensured that the microemulsion can interact with all contaminants. The lower limit of the weight ratio of the dry textile or laundry lot to the aqueous liquor of Winsor type 2 is limited in preferred embodiments of the invention in that when used in the washing machine as little as possible "free liquor", ie as little as possible excess liquor, which For this reason, a weight ratio of the dry textile or laundry lot to the aqueous liquor of Winsor type 2 is from 1: 2 to 1 : 1, in particular not less than 1: 1, 5.

The concentrate preferably contains surfactants which serve as emulsifiers in the Winsor Type 2 microemulsion system. Preferably, the concentrates contain anionic and / or nonionic surfactants, with a combination of anionic and nonionic surfactants being particularly advantageous with regard to the removal of a wide variety of soils. The content of the concentrates of surfactants and in particular of a combination of anionic and nonionic surfactants is preferably from 2 to 35% by weight, in particular from 5 to 30% by weight. The Winsor Type 2 microemulsion systems used in the short liquor washing technique generally have at least 0.2% by weight of surfactants, in particular a combination of anionic and nonionic surfactants. Levels of at least 0.3% by weight, preferably from 0.5 to not more than 15% by weight and in particular from 1 to not more than 10% by weight, of surfactants, in particular of a combination of anionic and nonionic surfactants, are preferred here.

Suitable anionic surfactants include alkylbenzenesulfonic acid salts, olefin sulfonic acid salts, C 12-18 alkanesulfonic acid salts, fatty alcohol sulfate, fatty alcohol ether sulfates, but also fatty acid soaps or a mixture of two or more of these anionic surfactants. Of these anionic surfactants, alkylbenzenesulfonic acid salts, fatty alcohol (ether) sulfates and mixtures thereof are particularly preferred.

Preferred surfactants of the sulfonate type are C9-i3-alkylbenzenesulfonates, olefin-sulfonates, i. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from Ci2-i8 monoolefins with terminal or internal double bond by sulfonation ren with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration. Also suitable are C 12 -is 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.

Alk (en) ylsulfates are the salts of the sulfuric acid half esters of C 12-18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths prefers. From a technical point of view, the Ci2-Ci6-alkyl sulfates and Ci2-Ci5-alkyl sulfates and Ci4-Ci5-alkyl sulfates are preferred. 2,3-alkyl sulfates are also suitable anionic surfactants.

Also fatty alcohol ether sulfates, such as the sulfuric acid monoesters of the straight-chain or branched C7-2i alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C9-n alcohols having on average 3.5 mol of ethylene oxide (EO) or is fatty alcohols having 1 to 4 EO, in particular Ci2-i4 fatty alcohols with 2 EO are suitable.

Further suitable anionic surfactants are fatty acid soaps. Suitable 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. Preferably, the content of the concentrates of fatty acid soaps 0 to 5 wt .-%. The anionic surfactants including the fatty acid soaps may be in the form of their sodium, potassium or magnesium or ammonium salts. Preferably, the anionic surfactants are in the form of their sodium salts and / or ammonium salts. Amines which can be used for the neutralization are preferably choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethylamine or a mixture thereof, with monoethanolamine being preferred.

Suitable nonionic surfactants include alkoxylated fatty alcohols, alkoxylated oxo alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides, and mixtures thereof. The alkoxylated fatty alcohols used are preferably ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and an average of 2 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear. In particular, alcohol ethoxylates having 12 to 18 C atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C 12-14-alcohols with 2 EO, 3 EO, 4 EO or 7 EO, Cg-n-alcohol with 7 EO, C 12 -is alcohols with 3 EO, 5 EO or 7 EO , Ci6-is alcohols with 5 EO or 7 EO and mixtures of these. 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. It is particularly preferred that a Ci2-is-alcohol, in particular a Ci2-Ci4-alcohol or a Ci3-alcohol with an average of 2 EO or 3 EO is used as a nonionic surfactant.

In addition to the pure ethylene oxide adducts, however, corresponding propylene oxide adducts, in particular also EO / PO mixed adducts, are advantageous, with particular preference being given to C 16 -C 18 -alkyl polyglycol ethers having in each case 2 to 8 EO and PO units. In some embodiments, EO / BO mixed adducts and even EO / PO / BO mixed adducts are also preferred. Particularly preferred EO / PO mixed adducts include C 16-18 fatty alcohols having fewer PO than EO units, in particular C 16-18 fatty alcohols having 4 PO and 6 EO or C 16-18 fatty alcohols having 2 PO and 4 EO.

The stated degrees of alkoxylation (EO = ethylene oxide, PO = propylene oxide, BO = butylene oxide) represent statistical averages, which for a particular product may be an integer or a fractional number. Preferred alkoxylates have a narrow homolog distribution.

As already stated above, inorganic salts are not absolutely necessary in order to be able to produce Winsor Type 2 microemulsions. However, concentrates, in particular anionic surfactant-containing concentrates, which contain one or more inorganic salts are preferred. Preferred inorganic salts are alkali metal sulfates and alkali metal halides, especially chlorides, and also alkali metal carbonates. Very particularly preferred inorganic salts are sodium sulfate, sodium hydrogen sulfate, sodium carbonate, Natnumhydogencarbonat and mixtures from these. The content of the concentrates of one or more inorganic salts is preferably 20 to 70% by weight.

In the Winsor Type 2 microemulsion systems to be prepared, the content of one or more inorganic salts is preferably 2 to 20% by weight and more preferably 5 to 15% by weight, with concentrations of 8 to 12% by weight being particularly preferred have exposed.

In preferred embodiments of the invention, the concentrates also contain one or more additional oils. In the context of the present invention, an additional oil which is used additionally and deliberately to the greasy and oily soils present on the textiles to be washed, is in principle any organic non-surfactant liquid which is not miscible with water or forms two phases in combination with water understood, which itself has a grease dissolving ability. In particular, such additional oils are preferred, which not only have a good fat dissolving power, but are also biodegradable and acceptable odor. Particularly preferred concentrates have as additional oil dioctyl ether, oleic acid, limonene, low molecular weight paraffins and / or low molecular weight silicone oils, for example, the well-known from chemical cleaning solvent cyclosiloxane D5 on. Also, aromatic solvents such as toluene are of course effective additive oils for the purposes stated herein; but they are usually omitted for toxicological reasons. The content of the concentrates in one or more additional oils is preferably from 2 to 60% by weight and in particular from 5 to 50% by weight.

The use of one or more additional oils in the concentrate according to the invention has several advantages. At first, additional oils function as solvents for the fats, which are solid at the application temperatures in the washing machine. In addition, the oil and grease-like dirt on the laundry is usually not well defined. It is therefore not known in advance which surfactants must be present in the W / O emulsion in order to actually interact with the soil in such a way that it becomes relaxed and can be flushed out of the textile. In addition, without the presence of additional oils, the grease and oily soils on the fabrics could unbalance the microemulsion system. But if an additional hydrophobic component as defined above (additive oil) is used from the outset in the concentrate, the influence of the grease and oil-like dirt on the laundry on the balance of the microemulsion is negligible and the likelihood of a desired interaction and relaxation of the dirt on the textile fiber is significantly increased. In the Winsor Type 2 microemulsion systems to be produced, the content of one or more additional oils is preferably 0.2 to 20% by weight and in particular 0.5 to 15% by weight, with concentrations of 1 to 12% by weight. -% have been found to be particularly preferred.

In particular, Winsor Type 2 microemulsion systems can be prepared from the concentrates of this invention by dilution with water containing from 0.2% to 5% by weight of surfactants, preferably from 0.3% to 1% by weight of surfactants, with particular preference to less than zero , 1 wt .-% surfactants, and 0.5 to 5 wt .-%, advantageously 1 to 3 wt .-% additional oils. With further preference, the aforementioned Winsor 2 microemulsion systems comprise from 80 to 94.6% by weight of water and from 0.2 to 15% by weight of inorganic salts, preferably from 1 to 12% by weight of inorganic salts, in particular from 5 to 10% by weight .-% inorganic salts.

In further embodiments, it is preferred that the concentrates have inorganic salts and / or additive oils. It has proven to be particularly advantageous, especially when anionic and nonionic surfactants are contained in the concentrates, that the concentrates have both one or more inorganic salts and one or more additional oils. The weight ratio of inorganic salt to additional oil can vary within a wide range, depending on the surfactants used. Weight ratios of inorganic salt / inorganic salts to additional oil (s) of from 15: 1 to 0.3: 1, preferably from 10: 1 to 0.5: 1 and in particular from 5: 1 to 1: 1, are advantageous. Particularly preferred additional oils, which are present in combination with inorganic salts are di-ethers. Di-n-octyl ether is used with particular advantage.

In a preferred embodiment of the invention, the concentrate contains sodium sulfate and di-n-octyl ether in a weight ratio of 10: 1 to 0.5: 1, preferably from 10: 1 to 1: 1 and in particular from 5: 1 to 1: 1.

In addition, the concentrate may further comprise at least one, preferably two or more, selected from the group consisting of builders, bleaches, electrolytes, nonaqueous but water miscible solvents, enzymes, pH modifiers, perfumes, perfume carriers, fluorescers, dyes, hydrotropes , Foam inhibitors, silicone oils, antiredeposition agents, graying inhibitors, shrinkage inhibitors, anti-wrinkling agents, 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, softening components as well as UV absorbers.

Suitable builders which may be present in the concentrate are, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances. Organic builders which may be present in the concentrate 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. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, and mixtures of these. 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.

As builders further polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 600 to 750,000 g / mol. Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of from 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. To improve the water solubility, the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methylallyl sulfonic acid, as monomer.

In the liquid detergents but preferably soluble builders, such as citric acid, or acrylic polymers having a molecular weight of 1,000 to 5,000 g / mol are used.

In addition to the additional oils, nonaqueous solvents which are miscible with water can be added to the concentrate. Suitable non-aqueous solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers. For example, the solvents are selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methyl propanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n- butyl ether, diethyl englykolmethylether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxy triglycol, ethoxy triglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol and mixtures of these solvents. However, it should be noted that the type and amount of non-aqueous, but water-miscible solvents must be selected so that when creating the short liquor a microemulsion system of Winsor type 2 can arise. Preferred concentrates therefore contain only such organic solvents as the stated ethers and di-ethers, in particular di-n-octyl ethers, which may already be used as additional oils. Organic solvents used in conventional liquid detergents are used and which are miscible with water without forming 2 phases, for example, ethanol, propylene glycol or glycerol, are used, if at all, only in minor amounts, wherein omitted in particularly preferred embodiments, such with water without formation of 2 phases miscible organic solvent becomes.

In a further embodiment of the invention, anhydrous or at least nearly anhydrous concentrates are used. In the context of the present invention, anhydrous is understood to mean that the content of water in the concentrates is not more than 2% by weight, preferably not more than 1% by weight. In a preferred embodiment of the invention, the concentrates are in the form of an anhydrous paste which contains surfactants, in particular a mixture of anionic and nonionic surfactants. Advantageously, the surfactant content, in particular the mixture of anionic and nonionic surfactants, in the anhydrous pastes in the same areas as in the aqueous concentrates. The same applies to the other constituents of the concentrates. In place of the water, the pastes in preferred embodiments may contain additional finely divided solids, for example aluminosilicates, such as zeolites or smectites or bentonites, or else silicic acids, for example of the Aerosile® type. These finely divided additives do not affect the phase boundaries and stability of Winsor Type 2 microemulsion systems to be prepared from the pastes.

The concentrates of the invention may be prepared by any method known in the art.

It is also preferred to offer the concentrates according to the invention in the form of disposable portions. These include in particular containers of water-soluble materials which are filled with the concentrates according to the invention. Particular preference is given to single-chamber or multi-chamber containers, in particular of polyvinyl alcohol or polyvinyl alcohol derivatives or copolymers with vinyl alcohol or vinyl alcohol derivatives as monomer. These disposable portions ensure that the correct amount of the concentrate according to the invention is used in the first sub-washing cycle for the preparation of the Winsor Type 2 microemulsion system and for the corresponding power associated therewith. Optionally, depending on the amount of textile or laundry to be washed, multiple disposable portions may also be used.

A further embodiment of the invention provides that the concentrates are in granulated form on a carrier. Suitable carrier materials are the carrier materials known from the prior art for detergents. Particular preference is given to ingredients of detergents such as builders and alkali metal, for example alkali metal carbonates or zeolites, or bleaching agents such as percarbonates or enzyme granules, but also sodium sulfates or silicates and in particular those substances which have a high absorption capacity for liquids, for example silicic acids. Such granulated products may also be powdered with fancy materials known in the art for this purpose. Particular preference is given to silicic acids, zeolites or other aluminosilicates, but also mixtures of silicic acids and zeolites.

Another object of the invention is the use of a concentrate as described above for forming a short liquor of a Winsor Type 2 microemulsion system. All facts and embodiments described for the concentrates are also valid for use.

Another object of the invention is a textile washing method in a washing machine, in particular in a household washing machine, with a washing cycle with at least two successive Unterwaschzyklen, wherein

the laundry item to be cleaned is placed in the laundry room of the washing machine,

a concentrate as described above or a granulated concentrate as described above are placed in a detergent storage room of the washing machine and

transported, preferably sprayed or pumped, in the first sub-washing cycle with the simultaneous formation of a short liquor in the laundry treatment room of the washing machine, whereby a Winsor Type 2 microemulsion system is formed or maintained as a short liquor,

an interaction of the short liquor of the Winsor type 2 with the dirt present in the laundry lot takes place in the first sub-wash cycle, whereby the interfacial tension between the existing greasy and oily soils and the water phase is lowered

- subsequently diluting the liquor with water in at least one further sub-washing cycle and further diluting with water until a long liquor is formed,

- while the dirt from the laundry item is released and

- At the end of the last sub-washing cycle, the dirt is removed together with the long liquor from the laundry treatment room.

The method provides that a wash cycle is performed with at least 2 consecutive sub-wash cycles. A washing cycle is the period of time from the creation of a first wash liquor containing detergent to the removal of the wash liquor from the washing machine. The washing cycle is subdivided into at least two sub-washing cycles, whereby the washing liquor is not removed at the end of the first to penultimate sub-washing cycle. In the preferred embodiment, which provides a wash cycle with 2 consecutive sub-wash cycles, at the beginning of the first sub-wash cycle, the short liquor is in the form of a microemulsion. Winsor Type 2 system or maintained in the case that the concentrate used was already as Winsor Type 2 microemulsion system, while at the beginning of the second sub-washing cycle, new, additional water is fed into the existing wash liquor to form a long liquor.

Such a method is preferably carried out in a washing machine, in particular in a household washing machine which allows a short liquor washing technique. The statements already made above regarding the short liquor washing technology and the short liquor apply accordingly. The machines in question allow the use of concentrates or granulated concentrates to create a short liquor in the machine.

Since a Winsor Type 2 microemulsion system is biphasic, it is preferred that, in the interests of uniform distribution of the short liquor on the laundry, that the Winsor Type 2 microemulsion system not be macroscopically separate during application, but as an emulsion of the two phases placed in the laundry treatment room and applied to the laundry items. This temporary emulsion can be formed, for example, by vigorous mixing, in particular by stirring.

The machine measures the weight of the dry fabric or laundry and supplies the amount of water required to form the short liquor. This is mixed with the concentrates according to the invention in the above-mentioned mixing device to form a Winsor Type 2 microemulsion system. In order to make a temporary emulsion of the Winsor Type 2 intrinsically biphasic microemulsion system, it may be preferred that the machine provide a space in which a temporary emulsion of the concentrate and the water supplied thereto can be formed. This can be supported by the provision of a mixing device, preferably a stirring device in this mixing chamber. In this case, the mixing space for producing a temporary emulsion may be the dispensing rinsing chamber of a washing machine, in particular a domestic washing machine, but also an additional space in the machine, in particular the household washing machine.

It is further preferred that the machine after reading the weight of the laundry item displays its weight readable for the consumer, so that the consumer can dose the appropriate amount of the concentrate. The corresponding metered quantities of the concentrates, depending on the weight of the laundry lot, which are required to form the Winsor Type 2 microemulsion system, can be read by the consumer on the overwrap of the concentrates and / or indicated by the machine itself in a suitably programmable machine. Since a free wash liquor, so fleet, which can not be absorbed by the laundry items and remains in Laugensumpf the machine, which would result in an unnecessary dilution of the system and possibly even a deterioration of the washing result, the inventive method provides that as little as possible free fleet arises. It has proved to be advantageous if, in the first sub-washing cycle, a ratio of the weight of the dry textile or linen lot to the short liquor is at least 1: 8, preferably at least 1: 4, in particular not less than 1: 2, for example 1: 2 to 4: 1 is formed. In particular, it is preferable if, in the first sub-washing cycle, a ratio of the weight of the dry textile or the laundry lot to the short liquor is not less than 1: 1.5. In particular, this ratio may be 1: 1, 2 to 1, 2: 1, ideally 1: 1.

The uniform distribution of the short liquor on the laundry items takes place in the washing machine, in particular a household washing machine, preferably by an injection, spraying or pumping system, for example a circulating pump.

In a preferred embodiment of the invention, a method is proposed, which provides a ratio of the weight of the dry textile or laundry lot to short liquor of 1: 2 to 1: 1, 5, whereby the distribution of the short liquor takes place by means of a circulating pump.

At the end of the first sub-wash cycle, the wash liquor is not removed. At the beginning of the second sub-wash cycle, additional feed of water occurs, ultimately leading to the formation of a liquor known from conventional washing processes. In the context of the present invention, this most dilute liquor is called a long liquor for better distinction from the short liquor. The liquor, which includes the dilution stages of the short liquor up to the long liquor, is called diluent liquor in the context of the present invention. During the dilution of the short liquor to the formation of the long liquor, the concentration of the detergent in the liquor is reduced. In addition, in a preferred embodiment, the dilution of the concentration of the salt preferably contained increases the hydrophilicity and water solubility of a preferably contained nonionic surfactant. As a result, a phase inversion is caused, wherein first a microemulsion system of the Winsor type 3 and finally with further dilution a microemulsion system of the Winsor type 1 is formed. Without wishing to be limited by this theory, the Applicant believes that the formation of the Winsor Type 3 microemulsion system is responsible for the improved release of the soil relaxed by the Winsor Type 2 microemulsion system. The skilled person knows that the interfacial tension in the three-phase region of the Winsor Type 3 microemulsion system is very low. It is also known that low interfacial tensions promote the detachment of fat. Another advantage of the low interfacial tensions of the Winsor Type 3 microemulsion systems is that The better fat dissolving power of less surfactant can be used than with conventional Winsor Type 4 microemulsions, making the process more economical and environmentally friendly.

Only the interplay of the Winsor Type 2 microemulsion system in the short liquor in the first sub-wash cycle and the Winsor Type 3 and Winsor Type 1 microemulsion systems in the second sub-wash cycle or sub-wash cycles will result in particularly good wash results.

As already stated, the second sub-washing cycle is started by the supply of water, whereby the short liquor is diluted. If the remaining addition of the water until final dilution and thus formation of the long liquor without further time interruption, the phase inversion takes place via the Winsor Type 3 microemulsion system to the Winsor Type 1 microemulsion system in the second subwash cycle.

However, it may be advantageous if the dilution of the short liquor to the long liquor takes place in individual stages, that is, with interruptions of the addition of water. In a particularly preferred embodiment of the invention, therefore, a textile washing process is carried out as described above, in which the phase inversion takes place during the second sub-washing cycle or during the further sub-washing cycles, wherein first a microemulsion system of Winsor type 3 and last of Winsor type 1 is formed. Particularly preferred is a process characterized by passing through at least 3 sub-washing cycles, the second sub-washing cycle comprising the preparation of a Winsor Type 3 microemulsion system as dilution liquor and the third sub-washing cycle the long liquor washing process, ie the final amount of water introduced, optionally until the long fleet has been removed. The second sub-wash cycle may comprise multiple stages representing different levels of dilution, but at all stages there is a Winsor Type 3 microemulsion system. Once the dilution has progressed to phase inversion to Winsor Type 1, the third sub-wash cycle begins. Further addition of water in this third sub-wash cycle is of course possible, but not required for performance reasons, nor desirable for environmental or economic reasons and therefore not preferred.

In a further preferred embodiment of the method, in the first sub-washing cycle and only in the first sub-washing cycle, the heating of the machine is switched on while the heating in the second sub-washing cycle and, if present, further sub-washing cycles and in optionally subsequent rinsing cycles is switched off. This is particularly advantageous when the Winsor Type 2 microemulsion system in the short liquor contains nonionic surfactants. Niotenoids become more hydrophobic with increasing temperature, and more hydrophilic with decreasing temperature. The heated nonionic surfactants cause higher hydrophobicity of the short liquor, thereby improving the interaction with fat and oily soils and their relaxation on the fabrics, while the nonionic surfactants in the cooling dilution liquor and the colder long liquor become more hydrophilic and coexist with the water Rinse the dirt better and have it removed.

In a preferred embodiment of the method it is therefore provided that the first sub-washing cycle is carried out at temperatures of 10 to 60 ° C, preferably of at least 20 to 40 ° C.

In addition, the method has the advantage that, in contrast to conventional methods, heating energy is consumed only in the first sub-wash cycle. Since the first sub-washing cycle involves only a short liquor, this saves energy, in contrast to conventional processes in which a long liquor, that is to say a larger quantity of aqueous liquor, has to be heated up.

Finally, the dirt, together with the long liquor, if appropriate, is transported away after passing through further sub-washing cycles and removed from the laundry treatment space of the washing machine.

In further washing, cleaning or care cycles, a non-aqueous liquor can be provided, wherein less than 10 wt .-%, based on the liquor, of water is supplied to the preparation of the non-aqueous liquor in the present invention. In these further washing, cleaning or care cycles, further cleaning steps or care steps, for example impregnation of textiles with respect to water and / or dirt, can be carried out. This further washing, cleaning or care step or the further steps may take place before and / or after the rinsing cycles, depending on their intention.

Examples

Example 1: washing performance

The following soils were examined:

stained olive oil

dyed lard

Pigment / lanolin

Pigment / sebum.

WFK 10A cotton lumps were stained with 0.3 ml of olive oil or lard for the preparation of the native stain stains olive oil and lard. For the two other soils, commercially available soiled polyester / cotton test fabrics were selected 50:50.

The washing experiments were carried out in a Launder-Ometer ^® (ATLAS Textile Test Products) with a 60-minute wash cycle at 40 ° C. For this purpose, 2 cotton lobes (olive oil and lard) and in another test 2 soiled test cloths made of polyester / cotton 50/50 were placed together with 10 filling laps WFK 10A (2.2 g each) and 10 steel balls each. The amount of dry textile (sum of soiled lobules and Füllläppchen) was thus 26.6 g.

Concentrates K1 to K5 (Table 1) were prepared and converted to Winsor Type 2 (M1 to M5) microemulsions by mixing with water. The cotton lobules / test cloths as well as the stuffing lobules were sprayed by a trigger pump to 100% moisture penetration of the fabrics (the weight ratio of the dry test fabrics to the microemulsion system of the Winsor Type 2 was 1: 1).

Then the washing program was started with the formation of a long fleet. After the wash, 3 rinses followed for 10 minutes at 20 ° C. After the wash and after each rinse, the liquors were poured off and the lobes briefly expressed. For each rinse, 200 ml of water was added. After hanging drying and lack of Stoffläppchen / test fabric whose whiteness was determined spectrophotometrically.

1st comparison experiment

The experiment according to the invention was repeated with a commercial premium solid detergent (liquid detergent). For this purpose, a concentrate of 30, 15 g of premium solid detergent was dissolved / emulsified in one liter of water (V1). V1 was sprayed onto the test fabrics for 100% moisture so that the weight ratio of the dry test fabrics to V1 was 1: 1 as in the experiment according to the invention. Thus, 0.8 g of the premium washing detergent were used in this experiment. 2nd comparison experiment (standard)

A liquor of 4.07 g / l of the same premium full detergent was prepared as in the first comparative experiment and a liquor of 200 ml was provided in the wash cycle. Thus, the amount of premium solid detergent used was 0.8 g, as in the first comparative test.

The experiments were repeated twice. The results listed in Table 2 are mean values of 3 lobes / test fabrics each with 6 measurements.

TABLE 1 Concentrates K1 / M1 to K5 / M5 (amounts in% by weight)

Table 2: Whitenesses (differences dY)

The concentrates according to the invention and the Winsor Type 2 microemulsion systems prepared therefrom show significantly better performance both compared to a conventional washing process with a commercially available premium liquid detergent and also with respect to the new process with the commercially available premium liquid laundry detergent. It can also be seen that conventional liquid premium heavy-duty detergents in the new process (V1) sometimes perform significantly worse than in standard washing processes (V2).

Example 2:

Table 3 shows anhydrous concentrates (pastes) and Winsor Type 2 microemulsion systems obtainable therefrom. Table 3: (amounts in% by weight)

As a substitute for Aerosil also finely divided aluminosilicates, especially zeolites can be used. Both do not affect the phase boundaries.

Example 3:

Table 4 shows another example of the composition of a short liquor in the form of a Winsor Type 2 microemulsion system (M1 1) having a surfactant content of less than 1% by weight.

Table 4: (amounts in% by weight)

Composition M1 1

C10-C13 alkylbenzene 0.43

Zolsulfonat, Na salt

Marlox® RT 42 (C16- 0.41

C18 polyalkylene glycol ether; Manufacturer:

Sasol)

Di-n-octyl ether 1, 98

Sodium sulfate 9.72

Water on 100

Claims

claims

1. A single- or multi-phase non-solid concentrate for use as a laundry detergent, characterized in that the concentrate is suitable when diluting in a washing machine with Kurzflottenwaschtechnik a microemulsion system of Winsor type 2 to give or maintain.

2. Concentrate according to claim 1, characterized in that it contains surfactants, in particular a combination of anionic and nonionic surfactants, preferably in amounts of 2 to 35 wt .-%

3. Concentrate according to claim 1 or 2, characterized in that it contains one or more inorganic salts, preferably in amounts of 20 to 70 wt .-%.

4. Concentrate according to one of claims 1 to 3, characterized in that it contains one or more additional oils, preferably in amounts of 2 to 60 wt .-%.

5. Concentrate according to one of claims 1 to 4, characterized in that it contains one or more inorganic salts, preferably sodium sulfate, and one or more additional oils, preferably di-ethers, in particular di-n-octyl ether.

6. Concentrate according to one of claims 1 to 5, characterized in that it is present as an anhydrous paste and surfactants, in particular a mixture of anionic and nonionic surfactants.

7. Concentrate according to one of claims 1 to 6, characterized in that it can be converted by dilution with water in a microemulsion system of Winsor type 2, which 0.2 to 5 wt .-% of surfactants and 0.5 to 5 wt. -% additional oils and preferably 80 to 94.6 wt .-% water and 0.2 to 15 wt .-% inorganic salts.

8. agent, characterized in that a concentrate according to any one of claims 1 to 7 is present in granulated form on a carrier.

9. Use of a concentrate according to any one of claims 1 to 7 or an agent according to claim 8 for the formation of a short liquor from the microemulsion system Winsor type 2.

10. textile washing process in a washing machine with a washing cycle with at least two consecutive sub-washing cycles, characterized in that the laundry item to be cleaned is placed in the laundry treatment room of the washing machine, a concentrate according to any one of claims 1 to 7 or an agent according to claim 8 in a Waschmittelbeforatungsraum the washing machine given and transported in the first sub-washing cycle with simultaneous formation of a short liquor in the laundry room of the washing machine, preferably sprayed or pumped, being formed as a short liquor, a microemulsion system of Winsor type 2 or maintained, an interaction of the short liquor Winsor type 2 with the existing in the laundry items dirt in the first sub-washing cycle, causing a relaxation of the grease and oil-like dirt on the fiber is then diluted in at least one other sub-washing cycle fleet with water and continue to form a long liquor with water is diluted, the dirt is released from the laundry items, and at the end of the last sub-washing cycle, the dirt is transported together with the long liquor from the laundry treatment room.

1 1. A textile washing process according to claim 10, characterized in that the microemulsion system of Winsor type 2 is not present macroscopically separated during application, but introduced as an emulsion of the two phases of the microemulsion system of Winsor type 2 in the laundry treatment room of the machine and applied to the laundry items

12. A textile washing method according to claim 10 or 1 1, characterized in that in the first sub-washing cycle, a ratio of the weight of the dry textile or linen lot to the short liquor of not smaller than 1: 2, with particular preference of not less than 1: 1, 5 is formed becomes.

13. The textile washing method according to claim 10, characterized in that phase inversion takes place during the sub-washing cycle following the first sub-washing cycle or the further sub-washing cycle following the first sub-washing cycle, first a Winsor type 3 microemulsion system and finally a Winsor type 1 microemulsion system is trained.

14. A textile washing process according to any one of claims 10 to 13, characterized in that at least 3 sub-washing cycles are traversed, wherein the second sub-washing cycle, the production of a microemulsion system of Winsor type 3 as dilution liquor and the third sub-washing cycle, the washing process with the long liquor, so the final amount the water introduced, if necessary, until the removal of the long fleet.

15. textile washing method according to one of claims 10 to 14, characterized in that in the first sub-washing cycle, the heating of the washing machine is turned on while the heating is switched off in the second sub-washing cycle and, if present, further sub-washing cycles and, if appropriate, subsequent rinsing cycles.