STRUCTURED WASHING AGENT OR CLEANING AGENT WITH A FLOW LIMIT

Abstract

A structured liquid washing agent or cleaning agent with a flow limit, containing a surfactant system of anionic surfactants, nonionic surfactants and co-surfactants, inorganic salt and an amphiphilic compound, as well as a washing method in which the washing agent or cleaning according to the invention is used, and corresponding uses.

Claims

1. A structured liquid washing agent or cleaning agent with a flow limit between 0.01 and 1000 Pa, comprising, based on the total weight of the agent: (A) 6 to 70 wt %, of a surfactant mixture containing, based on the total weight of the agent: (i) 5 to 50 wt % anionic surfactant, selected from the group consisting of sulfate surfactants, sulfonate surfactants and mixtures thereof; (ii) 0.5 to 35 wt % nonionic surfactant, selected from the group consisting of alkoxylated fatty alcohols with a degree of alkoxylation of 4, alkoxylated fatty acid esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkyl phenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof and (iii) 0.5 to 5 wt % of a co-surfactant selected from the group consisting of alkoxylated C.sub.8-C.sub.18 fatty alcohols with a degree of alkoxylation of <3, aliphatic C.sub.6-C.sub.14 alcohols, aromatic C.sub.6-C.sub.14 alcohols, aliphatic C.sub.6-C.sub.12 dialcohols, monoglycerides of C.sub.12-C.sub.18 fatty acids, monoglycerol ethers of C.sub.8-C.sub.18 fatty alcohols and mixtures thereof; (B) 0.5 to 10 wt % inorganic salt, and (C) 0.1 to 5 wt % of a liquid amphiphilic organic compound selected from mono-, di- or polyhydric alcohols, ethers, esters, dioxolanes and combinations thereof.

2. The structured liquid washing agent or cleaning agent according to claim 1, wherein the inorganic salt is selected from the group consisting of sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, calcium chloride, magnesium chloride and mixtures thereof.

3. The structured liquid washing agent or cleaning agent according to claim 1 also containing 0.1 to 5 wt % of an external structure-imparting polymer.

4. The structured liquid washing agent or cleaning agent according to claim 1 comprising, based on the total weight of the agent, 0.1 to 5 wt % of a hydrotrope selected from the group consisting of C.sub.1-6 alkylbenzene sulfonates and mixtures thereof.

5. The structured liquid washing agent or cleaning agent according to claim 1, wherein the liquid washing agent or cleaning agent contains dispersed particles.

6. The structured liquid washing agent or cleaning agent according to claim 1, wherein the anionic surfactant is selected from the group consisting of C.sub.9-13 alkylbenzene sulfonates, olefin sulfonates, C.sub.12-18 alkane sulfonates, ester sulfonates, alk(en)yl sulfates, fatty alcohol ether sulfates and mixtures thereof.

7. The structured liquid washing agent or cleaning agent according to claim 1, wherein the weight ratio of nonionic surfactant to ionic surfactant is in the range of 1:1 to 1:3.

8. The liquid washing agent or cleaning agent according to claim 1, wherein the agent also contains at least one additional ingredient selected from the group consisting of enzymes, enzyme stabilizers, builders, bleaches, nonaqueous solvents, pH adjusting agents, odor absorbers, deodorizing substances, perfumes, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, antiredeposition agents, soil release agents, shrinkage preventers, anti-wrinkle agents, dye transfer inhibitors, antimicrobial active ingredients, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatics, bitter agents, ironing aids, phobicizing and impregnation aids, swelling and antislip agents, softening components and UV absorbers.

9. A washing method comprising the method steps: a) providing a washing or cleaning solution, comprising a washing agent or cleaning agent according to claim 1, and b) bringing a textile fabric or a hard surface in contact with the washing or cleaning solution according to (a).

10. The structured liquid washing agent or cleaning agent according to claim 3 also containing 0.1 to 0.2 wt % of an external structure-imparting polymer selected from the group consisting of polyacrylates, cellulose, clays, gums and mixtures thereof

11. The structured liquid washing agent or cleaning agent according to claim 4, comprising, based on the total weight of the agent, 1 to 2 wt % of a hydrotrope, selected from the group consisting of cumene sulfonate, toluene sulfonate, xylene sulfonate and mixtures thereof.

12. The structured liquid washing agent or cleaning agent according to claim 5, wherein the liquid washing agent or cleaning agent contains dispersed microparticles.

13. The structured liquid washing agent or cleaning agent according to claim 14, wherein the liquid washing agent or cleaning agent contains dispersed microparticles, selected from microcapsules, abrasive substances and/or insoluble ingredients of the washing agent or cleaning agent.

14. The structured liquid washing agent or cleaning agent according to claim 6, wherein the anionic surfactant is selected from the group consisting C.sub.9-13 alkylbenzene sulfonates, fatty alcohol ether sulfates and mixtures thereof.

15. The structured liquid washing agent or cleaning agent according to claim 7, wherein the weight ratio of nonionic surfactant to ionic surfactant is in the range of 1:2 to 1:2.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0061] The washing agents or cleaning agents are liquid and contain water as the main solvent. It is preferable for the washing agent or cleaning agent to contain more than 5 wt % water, preferably more than 15 wt % and in particular preferably more than 25 wt %, each based on the total amount of washing agent or cleaning agent.

[0062] In addition, nonaqueous solvents that are different from the aforementioned amphiphilic compounds and hydrotropes can be added to the washing agent or cleaning agent.

[0063] In addition to these ingredients, a washing agent or cleaning agent may also contain dispersed particles preferably having a diameter of 1 to 1000 m along their largest spatial extent.

[0064] Particles in the sense of the present invention may be capsules, abrasive substances as well as powders, granules or compounds of insoluble compounds in the washing agent or cleaning agent, but capsules are preferred.

[0065] The term capsule is understood to refer, on one hand, to aggregates with a core-shell structure and, on the other hand, to aggregates with a matrix. Core-shell capsules contain at least one solid or liquid core enclosed in at least one continuous shell, in particular a shell of polymer(s).

[0066] Sensitive chemically or physically incompatible and volatile components (=active ingredients) of the liquid washing agent or cleaning agent may be enclosed in the interior of the capsules, so that they are stable in storage and shipping, for example, optical brighteners, surfactants, chelating agents, bleaches, bleach activators, dyes and fragrances, antioxidants, builders, enzymes, enzyme stabilizers, antimicrobial active ingredients, soil release agents, antiredeposition agents, pH adjusting agents, electrolytes, detergency enhancers, vitamins, proteins, foam inhibitors and UV absorbers may be contained in the capsules. The capsules fillings may be solids or liquids in the form of solutions or emulsions and/or suspensions.

[0067] The capsules may be in any form within the context determined by production, but they are preferably approximately spherical. Their diameter along their largest spatial extent may be between 1 m and 1000 m, depending on the application and the components present in the interior.

[0068] Alternatively, particles that do not have a core-shell structure but instead have the active ingredient distributed in a matrix of a matrix-forming material may also be used. Such particles are also referred to as speckles.

[0069] In these materials, the matrix is formed by gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions, for example, and is just as well known in the prior art as is the production of particles using these matrix-forming materials. Alginate is one example of a matrix-forming material. To produce alginate-based speckles, an aqueous alginate solution, which also contains the active ingredient(s) to be enclosed is converted to droplets and then hardened in a precipitation bath containing Ca.sup.2+ ions or Al.sup.3+ ions. Alternatively, other matrix-forming materials may also be used instead of alginate.

[0070] The particles can form a stable dispersion in liquid washing agents or cleaning agents. Stable here means that the washing agents or cleaning agents are stable at room temperature for a period of at least 4 weeks, preferably at least 6 weeks, without the particles rising to the top, accumulating or setting out in the agent.

[0071] The active ingredients are usually released from the capsules by destruction of the shell and/or matrix due to mechanical, thermal, chemical or enzymatic action.

[0072] In a preferred embodiment, the liquid washing agents or cleaning agents contain capsules, which themselves contain one or more fragrances.

[0073] Alternatively, the particles may comprise abrasive substances such as beads of plastic or calcium carbonate as well as powders, granules or compounds of compounds insoluble in the washing agent or cleaning agent.

[0074] In a preferred embodiment of the invention, the liquid washing agent or cleaning agent contains the same or different particles in amounts of 0.05 to 10 wt %, in particular 0.1 to 8 wt % and extremely preferably 0.2 to 5 wt %.

[0075] The washing agent or cleaning agent can be used for washing and/or cleaning textile fabrics or hard surfaces. Washing or cleaning methods, i.e., in particular methods for cleaning textiles are characterized in general in that active cleaning substances are applied to the item to be cleaned in one or more method steps and are washed away after the treatment time, or the item to be cleaned is otherwise treated with a washing agent or cleaning agent or a solution of that agent.

[0076] In the aforementioned washing or cleaning method, in particular washing method, temperatures of up to 95 C. or less, 90 C. or less, 60 C. or less, 50 C. or less, 40 C. or less, 30 C. or less or 20 C. or less are used in various embodiments of the invention. These temperature specifications are based on the temperatures used in the washing or cleaning steps.

[0077] The washing agent or cleaning agent is produced by conventional and known methods and processes. For example, the ingredients of the washing agents or cleaning agents are combined in stirred vessels, with water being added first. Then the nonaqueous solvents and surfactants including the co-surfactant as well as the amphiphilic compounds and optionally the hydrotrope and/or the polymeric structuring agent are added. Next, the fatty acid, if any, is added and the fatty acid component is saponified and the anionic surfactants used in acid form are neutralized. Then the additional ingredients are added, preferably in portions. The inorganic salt may be added as a solid or in the form of a concentrated solution at various times during the production process.

[0078] The flow limits of the washing agents or cleaning agents can be measured at 23 C. by using a rotational rheometer from TA Instruments, model AR G2. This is a so-called controlled shear stress rheometer.

[0079] To measure the flow limit using a controlled shear stress rheometer, various methods with which those skilled in the art are familiar are described in the literature.

[0080] To determine the flow limits in the context of the present invention, the following procedure is used at 23 C.

[0081] The samples are subjected to a shear stress s(t) which increases over time in the rheometer. For example, the shear stress may be increased from the lowest possible value (e.g., 2 mPa) to 10 Pa, for example, over a period of 10 minutes. The deformation of the sample is measured as a function of this shear stress. The deformation is plotted as a function of shear stress in a double logarithmic plot. If the sample tested has a flow limit, one will be able to differentiate two regions distinctly in this plot. Below a certain shear stress, one finds a purely elastic deformation. The slope of the curve () (log log plot) is one in this range. The flow range begins above this shear stress and the slope of the curve is suddenly higher. The shear stress at which the curve has a discontinuity, i.e., the transition from elastic deformation to plastic deformation marks the flow limit. A convenient method of determining the discontinuity in the curve is by applying tangents to the two curve parts. Samples without a flow limit do not have the characteristic discontinuity in the function ().

[0082] In various embodiments, the flow limit is between 0.01 and 1000 Pa, preferably in the range of 0.01 to 100 Pa or 0.2 to 100 Pa, even more preferably 1 to 50 Pa or 0.01 to 10 Pa.

[0083] The agents may be packaged in film bags, for example. Packaging bags of water-soluble films make it unnecessary for the package to be opened by the consumer. This permits a convenient dosing of a single portion measured for one wash cycle by placing the bag directly in the washing machine or by adding the bag to a certain amount of water, for example, in a bucket, a pan or a hand-washing basin. The film bag surrounding the washing portion then dissolves without leaving a residue on reaching a certain temperature.

[0084] There are numerous state-of-the-art methods for producing water-soluble washing agent portions that are fundamentally also usable within the scope of the present invention. The best-known methods are the tube film methods using horizontal and vertical sealing seams. In addition, the thermoforming method (deep drawing method) is also suitable for producing film bags or washing agent portions in a stable form. However, the water-soluble sheathings need not necessarily be made of a film material but instead may also be containers of a stable form that can be obtained, for example, by an injection molding method.

[0085] In addition, methods for producing water-soluble capsules from polyvinyl alcohol or gelatin are also known, making it possible in principle to provide capsules having a high degree of filling. These methods are based on the fact that the water-soluble polymer is introduced into a molding cavity. The capsules are filled and sealed either in synchronization or in successive steps. In the latter case, the capsules are filled through a small opening. Filling of the capsules here preferably takes place through a filling wedge, which is situated above two drums which have hemispherical shells on their surface and rotate in opposition to one another. The drums carry polymer strips that cover the hemispherical shell cavities. Sealing takes place in the positions in which the polymer strip on one drum comes in contact with the polymer strip on the opposite drum. In parallel with that the filling material is injected into the resulting capsule, with the injection pressure of the filling liquid pressing the polymer strips into the hemispherical shell cavities. A method for producing water-soluble capsules in which the filling takes place first and the sealing is performed next is based on the so-called Bottle Pack method, in which a tubular parison is guided into a two-part cavity. The cavity is closed whereupon the lower portion of tube is sealed. Then the tube is inflated to form the capsule shape in the cavity, filled and next sealed.

[0086] The shell material used to produce the water-soluble portion is preferably a water-soluble thermoplastic polymer, especially preferably selected from the group of (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymer, polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, blends and composites, inorganic salts and mixtures of the aforementioned materials, preferably hydroxypropylmethyl cellulose and/or polyvinyl alcohol blends. The polyvinyl alcohols are commercially available, for example, under the trademark Mowiol (Clariant). Polyvinyl alcohols that are especially suitable within the scope of the present invention include, for example, Mowiol 3-83. Mowiol 4-88, Mowiol 5-88, Mowiol 8-88 as well as Clariant L648. The water-soluble thermoplastic used to produce the portion may additionally comprise polymers selected from the group consisting of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and/or mixtures of the aforementioned polymers. It is preferable if the water-soluble thermoplastic to be used comprises a polyvinyl alcohol having a degree of hydrolysis of 70 to 100 mol %, preferably 80 to 90 mol %, especially preferably 81 to 89 mol % and in particular 82 to 88 mol %. It is further preferable for the water-soluble thermoplastic used to comprise a polyvinyl alcohol with a molecular weight in the range of 10,000 to 100,000 gmol.sup.1, preferably 11,00 to 90,000 gmol.sup.1, especially preferably 12,000 to 80,000 gmol.sup.1 and in particular 13,000 to 70,000 gmol.sup.1. It is also preferable if the thermoplastics are present in amounts of at least 50 wt %, preferably of at least 70 wt %, especially preferably of at least 80 wt % and in particular of at least 90 wt %, each based on the weight of the water-soluble thermoplastic polymer.

[0087] All the facts, objects and embodiments described for the agents according to the invention can also be applied to the subject matter of the invention, the methods and/or use. Reference is therefore made explicitly at this point to the disclosure in the corresponding location, with the notation that this disclosure is also applicable to the methods and uses described herein.

EXAMPLES

[0088] The following formulations were prepared according to the method described above:

TABLE-US-00001 TABLE 1 Liquid washing agent with a flow limit F1 F2 F4 F5 F6 (wt %) (wt %) (wt %) (wt %) (wt %) C.sub.11-13 alkylbenzene sulfonic acid 23.0 26.0 9.0 3.0 6.0 (C.sub.12-14) fatty alcohol ether sulfate with two 9.0 4.6 6.0 units of ethylene oxide C.sub.13-15 alkyl alcohol branched in position 2 and 24.0 27.0 6.0 3.0 ethoxylated with 8 mol ethylene oxide Fatty alcohol ether ethoxylated with 7 mol 3.7 ethylene oxide C.sub.12-C.sub.18 fatty alcohol alkoxylated with 2 mol 4.0 2.0 2.5 1.0 ethylene oxide i-C.sub.13H.sub.27O(CH.sub.2CH.sub.2O).sub.3H 2.0 1.5 1.0 Propylene carbonate 5.0 1.0 1.0 0.5 1.5 1,2-Propyleneglycol 3.5 2.0 1.0 3-Methoxy-3-methyl-1-butanol 2.0 2,2-Dimethyl-4-hydroxymethyl-1,2-dioxolane 1.0 Ethanol 0.5 0.2 0.4 2-Aminoethanol 6.8 6.8 Cumene sulfonate 1.5 1.0 1.5 Sodium hydroxide 4.0 0.6 2.0 Ethoxylated polyethyleneimine 5.0 5.0 C.sub.12-18 fatty acid 7.5 7.5 1.0 1.3 3.0 Diethylenetriamine-N,N,N,N,N-penta- 0.6 0.6 3.0 0.2 1.0 (methylenephosphonic acid), heptasodium salt (sodium DTPMP) Citric acid to to 2.0 pH 8.5 pH 8.5 Boric acid 1.0 0.5 1.0 Sodium bisulfite 0.1 0.1 Sodium chloride 2.5 1.5 4.0 2.0 4.5 Sodium sulfate 1.5 2.5 Denatonium benzoate 0.001 0.001 0.001 0.001 0.001 Soil-release polymer of ethylene terephthalate 1.0 1.0 0.5 0.5 and polyethylene oxide terephthalate Sokalan HP 56 0.2 Perfume, dye, protease, amylase, lipase, 1.7 1.7 2.6 1.0 2.6 cellulase, optical brightener Water to 100 to 100 to 100 to 100 to 100