EP2057257B1 - Laundry detergent additive based on clay minerals and pvp-containing copolymers - Google Patents

Description

The invention relates to a detergent additive for improving the soft feel of textile products, a process for its preparation and its use.

The use of detergent additives that increase the softness of the laundry has long been known and is used in many detergent formulations. In the course of changing guidelines for the use of chemicals both in industrial applications and in the area of household chemicals, many of the substances that have so far been used very successfully to date are put to the test. Also, the ever-increasing number of allergies and intolerances to individual detergent additives requires an increased effort to replace problematic additives. Especially in the field of fabric softeners, ie in formulations that increase the softness of the fabrics, the need for unproblematic substitutes is great. The active substances of the fabric softener are deposited on the textile fibers and thus come into direct contact with the skin over a longer period of time.

The GB 1 400 898 describes a detergent formulation for simultaneous cleaning and softening. For this purpose, anionic, ampholytic and zwitterionic synthetic surfactants, organic or inorganic "builder" and a smectic three-layer clay mineral are used.

The EP 0 313 146 describes a detergent formulation for improving the softening feel. This contains conventional surfactants, a smectic clay mineral and fountain solution, such as polyols, ethers derived therefrom and ester alcohols and mono- and oligosaccharides. Further, the detergent formulation contains polymeric flocculants such as polyethylene oxide, polyacrylamide and polyacrylate.

Detergent additives to improve the soft feel are also used in the US 2005/0170997 described. To improve the properties of the clay mineral, silicone oils and optionally ionic polymers and other auxiliaries, such as builders, bleaches, flocculants and color transfer inhibitors are used.

The EP 0 299 575 describes a softening agent detergent composition consisting of a smectic clay mineral and a polymeric flocculant such as polyethylene oxide having molecular weights between 100,000 g / mol and 10,000,000 g / mol. As further additives quaternary ammonium compounds and anionic, nonionic, amphoteric and zwitterionic surfactants can be used.

In the EP-A-653 480 A1 describes a detergent composition comprising a layered silicate of the formula NaMSi _x O _{2x +} 1yH ₂ O, where M is sodium or hydrogen and x is a number between 1.9 and 4 and y is a number between 0 and 20. Furthermore, the detergent composition contains as flocculant a polymer which consists of polymers and Copolymers selected from monomers such as ethylene oxide, acrylamide, acrylic acid, dimethylaminoethyl methacrylate, vinyl alcohol, vinylpyrrolidone, ethyleneimine and mixtures thereof. The detergent composition contains the layered silicate in a proportion of less than 5% by weight, based on the detergent composition.

In the EP 719 856 A1 describes a fabric softener comprising as plasticizer a clay mineral and crosslinked polymers to prevent a dye transfer. Crosslinked polyvinylpyrrolidone and a cross-linked polyvinylpyrrolidone / vinylimidazole copolymer are described as exemplary polymers.

In the EP 1 188 817 A2 (D3) a soft-washing detergent is described which contains (a) anionic surfactants, nonionic and / or amphoteric surfactants, (b) cationic polymers, (c) zeolites, and (d) optionally phyllosilicates.

In the DE 37 11 299 A1 (D4) describes the use of graft polymers based on polyvinylpyrrolidone as a grayness inhibitor in the washing and aftertreatment of textile fibers containing synthetic fibers. On the polyvinylpyrrolidone, a vinyl ester, for example, vinyl acetate is grafted. The graft polymers can also be adsorbed on the surface of adjusting agents, for example sodium sulfate or builders (zeolites) and other solid excipients of the detergent formulation.

However, the increase in the clay mineral content does not increase to the same extent the soft touch, so that in the prior art must be used to no small extent on other additives. Examples include the quaternary ammonium salts, surfactants, flocculants and Silicone oils, both alone and in combination. However, these additives increase to a not insignificant extent the cost of detergent formulations. In addition, they are less biodegradable compared to formulations with high clay mineral content. In addition, these additives are in many cases of health, especially in terms of skin tolerance and its allergenic potential, questionable. For these reasons, therefore, a further increase of the clay content while improving the soft touch is desirable and useful.

The invention therefore an object of the invention to develop cost-effective detergent additives for especially granular detergent formulations based on clay minerals, which avoid the disadvantages of the prior art, and improved by the use of clay mineral, other health and ecologically harmless additives, and an improved Distinguish soft grip.

According to a first aspect of the present invention, this object is achieved with a detergent additive according to claim 1. Advantageous embodiments of the detergent additive according to the invention are the subject of the dependent claims.

1. a) ein Tonmineral;
2. b) ein PVP-VA Copolymer.

The detergent additive according to the invention for improving the soft feel of textile products has at least the following components:

1. a) a clay mineral;
2. b) a PVP-VA copolymer.

The clay mineral may be both a natural and a synthetically produced clay. The terms clay and clay mineral are used synonymously herein. The construction of particularly advantageous clay minerals will be discussed in detail in the following sections. Of the Influence of clay minerals on the softness of textile fibers, such as cotton, is due to the fact that the clay mineral due to its morphological properties, such as platelet-shaped alumino-silicates with a particle size diameter smaller than 2 microns, and its chemical-physical properties, such as the sliding behavior , deposited between and / or on the cotton fibers. This allows the fibers to slide better with each other, which leads to the improvement of the soft touch. In addition to improving the soft feel, the clay also supports the washing process by absorbing dirt particles and making them easier to remove when washed.

In the case of the detergent additive according to the invention, it has surprisingly been found that when a combination of at least one clay mineral and at least one PVP (polyvinylpyrrolidone) and VA (vinyl acetate) -containing copolymer is used, the softness improves significantly. The copolymers can be present with regular or irregular alternating structural units (for example .ABABA or -AAABBABBB-), as well as block copolymers (eg. A _x -B _y ). Possible non-limiting structures for block copolymers include A _x B _y block copolymers, A _x B _y A _z triblock copolymers, A _x B _y C _z triblock copolymers, A _y (B _x ) _z block copolymers or copolymers having a block A backbone and B side chains (comb polymers) as well as mixtures of the foregoing. The combination of clay mineral and PVP / VA copolymer improves according to one aspect of the invention, the deposition of the clay mineral on the textile fiber and thus increases the softness of the clay mineral.

In the context of the present invention, it has surprisingly been found that the use of at least one PVP / VA copolymer provides an unexpected improvement of the soft handle.

According to a further preferred embodiment, the detergent additive contains a surfactant. Generally, those skilled in the art common surfactants are used. The surfactants are charged (ionic surfactant) or uncharged (nonionic surfactant), surface-active organic compounds, wherein at least one hydrophilic molecular segment is soluble in polar solvents and poor or insoluble in nonpolar solvents. Furthermore, the surfactant contains at least one further hydrophobic molecular segment which is soluble in non-polar solvents and poorly or not soluble in polar solvents. A general definition of surfactants can also be found, for example, in US Pat Rompp Chemie-Lexikon, 9th edition, Georg Thieme Verlag Stuttgart, 1995, pp 4495-4499 , Accordingly, surfactants are substances which reduce the interfacial tension and have a characteristic structure of at least one hydrophilic and one hydrophobic group.

According to another embodiment, preferred clay minerals are smectite clay minerals. These clays have a structure of layered polysilicate units. Examples of smectic clay minerals are beidellite, hectorite, saponite, stevensite, nontronite and montmorillonite or bentonite.

In a preferred embodiment, the surfactant is a nonionic surfactant. Frequently recurring structural elements in the case of nonionic surfactants are hydrophobic hydrocarbon chains and hydrophilic ethylene oxide chains, propylene oxide chains or polyols. Non-limiting examples of nonionic surfactants are fatty alcohol ethoxylates, polyethylene glycol ethers, alkyl glycosides, alkyl polyglycosides, sorbitan fatty acid esters, alkylphenyl ethoxylates, alkyl phosphine oxides, and silicone surfactants.

In a preferred embodiment, the PVP / VA copolymer is a copolymer containing only polyvinylpyrrolidone and polyvinyl acetate monomer units. After an alternative However, in addition to the vinylpyrrolidone monomer units and the vinyl acetate monomer units, the PVP / VA copolymer contains one or more other monomer units. These other monomer units may be contained in a proportion of 0.1 to 20 mol% in the PVP-VA copolymer. Suitable monomers are, for example, vinylimidazole, vinyl oxazolidone, vinyl propionate, methyl or ethyl (meth) acrylate.

In a preferred embodiment, the PVP / VA copolymer generally has a vinyl pyrrolidone monomer unit content of about 1 to 99%.

It is also preferred that the PVP / VA copolymer has a proportion of vinyl acetate (VA) monomer units of at least about 20%, preferably at least 30%, more preferably at least 40%, more preferably at least 50%. It has thus been found that the improvement of the softness surprisingly increases with increasing content or proportion of the PVP / VA copolymer on VA. Further, it is preferred that the PVP / VA copolymer has a proportion of vinyl acetate monomer units of not more than about 90%, preferably not more than 80%, more preferably not more than 75%.

According to a further preferred embodiment of the detergent additive according to the invention, the PVP / VA copolymer has a ratio of vinylpyrrolidone monomer units to vinyl acetate monomer units of between about 80:20 and 20:80, in particular between about 70:30 and 30:70. From a technical point of view, powdery PVP / VA copolymers are preferably used. Such powdery PVP / VA copolymers preferably have a ratio of vinylpyrrolidone monomer units to vinyl acetate monomer units of between about 70:30 and 60:40. However, it is also possible to use PVP / VA copolymers which are processed in dissolved form, for example as an aqueous alcoholic solution. These have a higher proportion of vinyl acetate monomers on. An exemplary copolymer has a ratio of vinyl pyrrolidone monomer units to vinyl acetate monomer units of about 50:50.

The PVP / VA comonomers preferably have a molecular weight in the range of 100,000 to 1,000,000 g / mol. Preferred ranges for the molecular weight are 300.00 - 900,000 g / mol and 500,000 to 800,000 g / mol.

In another embodiment, the detergent additive contains at least one carrageenan. Surprisingly, it has been found that the carrageenan, both alone and in combination with the clay mineral, the surfactant and / or the PVP / VA copolymer, further improves the soft feel.

Carrageenans are known to the person skilled in the art and it is possible to use all known carrageenans in the context of the present invention. They are the salts of linear galactose polysaccharides (of marine origin).

Commercially significant are λ-carrageenan, K-carrageenan and L-carrageenan. λ-carrageenan is a chain molecule composed of dimeric building blocks, β-D-galactosido (1,4) -α-D-galactose. These dimers are linked 1,3-glycosidically. The primary alcohol group of α-D-galactose is esterified with sulfuric acid, and the hydroxy groups on C2 of both galactoses are also approximately 70% esterified with sulfuric acid. λ-carrageenan thus has a sulphate content between 32 and 39%. K- and L-carrageenans are composed of the dimer carrabiose in which β-D-galactose is 1,4-glycosidically bound to α-D-3,6-anhydrogalactose. These dimers are linked by 1,3-glycosidic bonds to form a chain molecule. The difference between the two carrageenan types lies in the sulfation. In K-carrageenan, the sulfate ester group is located at C-4 of galactose, the sulfate content fluctuates between 25 and 30%. In the case of L-carrageenan, the hydroxyl group on the C-2 of the anhydrogalactose is additionally esterified with sulfuric acid. The sulphate content is between 28 and 35%. The average molecular weight of carrageenan is between 100,000 g / mol and 800,000 g / mol.

Because of their approval in food (carrageenan is approved as E407) carrageenans are health and ecologically harmless additives.

In a preferred embodiment, the detergent additive according to the invention contains at least one carrageenan having a molecular weight of 50,000 g / mol to 1,000,000 g / mol, more preferably 100,000 g / mol to 800,000 g / mol.

In a further embodiment, the detergent additive contains more than 0.0001 wt .-%, preferably more than 0.001 wt .-%, particularly preferably more than 0.01 wt .-% carrageenan, based on the mass of the clay mineral. With an addition of more than 0.1 wt .-% usually no further improvement is observed, so that a higher proportion of carrageenan from an economic point of view is no longer or at best limited makes sense. In most cases an addition of up to 0.06 wt .-% is sufficient to obtain the desired properties.

According to a particularly preferred embodiment of the invention, the smectite clay mineral is a bentonite. Such as in R. Fahn, N. Schall, Tenside Detergents, Volume 22, Issue 2, 1985 Bentonite consists for the most part of montmorillonite. The aluminosilicate montmorillonite is a three-layer material, composed of two SiO ₄ tetrahedral layers, between which there is an octahedral layer of predominantly aluminum ions. By isomorphous replacement of the trivalent aluminum ions by divalent ions, such as calcium or magnesium, creates a negative excess charge, which can be compensated for example by Mg ²⁺ , Ca ²⁺ , Na ⁺ . By exchanging these cations, the bentonite also acts as an ion exchanger. In addition to the different charges, cations such as Na ⁺ and Ca ²⁺ also significantly influence the swelling behavior of the bentonite. Thus, stored calcium ions cause a narrower layered structure, while embedded sodium ions allow a more open stratification of the bentonite. In addition, the bentonite is able to store surfactants and thus to change its absorbency of textile fabric.

According to a preferred aspect of the present invention, it has also been found that the particle size of the clay mineral can have an influence on the improvement of the softness. Thus, it has proved to be particularly advantageous if the clay mineral is in particulate form, wherein at least 10 wt .-%, preferably at least 14 wt .-%, more preferably between about 10 and 50 wt .-% of the particles, more preferably between about 10 and 30 wt .-% of the particles have a particle size of less than about 600 nm. The particle sizes can be determined by standard methods such as the laser diffraction method using a Fritsch Particle Sizer Analysette 22 Economy (Fritsch, DE) according to the manufacturer's instructions, also with regard to sample pretreatment. The sample is homogenized in deionized water without addition of auxiliaries and sonicated for 5 minutes. According to an alternative embodiment, the particle size determination is carried out as in Jasmund / Lagaly, "Tonminerale und Tone", Steinkopf-Verlag Darmstadt (1993), page 16 and the one in there Reference Tributh & Lagaly (1986) "Treatment and Identification of Soil and Deposit Entities", GIT Fachz. Lab 30: 524 and 771.

The above preferred particle sizes of the clay mineral are according to an alternative aspect of the present invention also independent of the use of the clay mineral in a detergent or detergent additive in combination with the PVP / VA copolymer, the surfactant and / or the carrageenan.

In a further embodiment of the invention, the clay mineral, especially the bentonite, is in activated form, i. Bi- or trivalent cations stored between the layers are exchanged for monovalent ions, such as sodium ions or protons. Such activated clay minerals are used in a manner known per se, e.g. made with soda. By exchanging the ions, the swelling capacity of the bentonite increases, which in turn influences the absorption properties.

According to a further preferred embodiment, the clay mineral, in particular the bentonite, is characterized in that at least 50%, preferably at least 60% and particularly preferably at least 80% of the cation exchange capacity (CEC) of monovalent cations, such as Na ⁺ , K ⁺ or NH ₄ ⁺ , is formed.

Preferably, the detergent additive contains at least 80 wt .-%, preferably at least 85 wt .-% clay mineral, such as bentonite. The high proportion of clay mineral, such as bentonite, lowers the cost of the detergent additive compared to the surfactant or the other polymeric additives. In addition, at low concentrations of surfactant and polymer or copolymer, no chemical classifications of the product are required. This results in lower costs for storage, transport and later handling of the detergent additive. The percentage data refer to a clay mineral, which still has a residual moisture content of about 10 wt .-%.

The nonionic surfactant of the detergent additive is particularly preferably selected from the group of fatty alcohol ethoxylates and polyethylene glycol ethers. These differ essentially by the manufacturing process. Both groups have the same basic structure of a linear or branched hydrophobic hydrocarbon chain (C _x ) and a hydrophilic ethylene oxide chain (EO _y ) with terminal alcohol group (s). These control both the efficiency, ie the required amount of surfactant, and the temperature sensitivity of the surfactant class. Within the hydrophilic ethylene oxide group, moreover, individual ethylene oxide units can be exchanged for propylene oxide units. The resulting changes in the hydrophobic / hydrophilic character can be used specifically in the selection of surfactants. The fatty alcohol ethoxylates in particular can be obtained from natural raw materials and are generally almost completely biodegradable.

With particular preference the detergent additive contains, based on the mass, clay mineral, more than 0.001% by weight, particularly preferably more than 0.01% by weight. %, particularly preferably more than 0.01% by weight of fatty alcohol ethoxylate and / or polyethylene glycol ether. With an addition of more than 0.1 wt .-%, no further improvement is usually observed, so that a higher proportion of fatty alcohol ethoxylate and / or polyethylene glycol ether from an economic point of view is no longer or at best limited makes sense. In most cases an addition of up to 0.06 wt .-% is sufficient to obtain the desired properties.

Preferably, the detergent additive based on the mass of clay mineral, more than 0.001 wt .-%, more preferably more than 0.01 wt .-%, more preferably more than 0.01 wt .-% polyvinylpyrrolidone-polyvinyl acetate (PVP / VA) copolymer , With an addition of more than 0.1 wt .-% is usually no further improvement observed that a higher proportion of polyvinylpyrrolidone-polyvinyl acetate (PVP / VA) copolymer from an economic point of view is no longer or at best limited makes sense. In most cases an addition of up to 0.06 wt .-% is sufficient to obtain the desired properties.

The detergent additive preferably contains more than 0.05% by weight, preferably more than 0.5% by weight, particularly preferably more than 1% by weight, of water glass, based on the mass of clay mineral. Under water glass one understands (as in Holleman-Wiberg, Textbook of Inorganic Chemistry, 101 Edition, Walter de Gruyter, 942, 1995 described) sodium and potassium silicates of the general composition M ₂ O • nSiO ₂ with M = Na, K and n ≈ 1,2,3,4, which are soluble in water and are often used in the art as a mineral glue. Since water glass is strongly alkaline and therefore irritating, the proportion of water glass is preferably less than 5 wt .-%, more preferably less than 3 wt .-% selected. The percentages refer to the solids content of the water glass. The modulus (SiO ₂ : Na ₂ O) of the water glass is preferably selected in the range from 2.4 to 3.5, more preferably from 2.6 to 3.4. It has surprisingly been found that with a water glass-based binding system, for example, granules are easier to loosen and thus show improved soft-grip effects. The use of water glass also avoids the formation of compact flakes of charged polymers (partially protonated copolymer PVP / VA) and oppositely charged clay fins, which on the one hand dissolve worse and on the other hand would also deposit on the fiber to a lesser extent. This effect can be circumvented by using an aqueous binder system based on a waterglass. The water glasses are preferably used in a solids content of between 0.5 and 8% by weight, preferably between 3 and 5% by weight. In addition to granules, the detergent additive of the invention may also be in liquid form or in the form of powder or Moldings, such as tablets or balls, are present. The use of water glasses ensures that a sufficiently rapid disintegration of the granules or moldings occurs and thus leads in combination with the specified components of the detergent additive to an increased softness.

1. a) Bereitstellen mindestens eines Tonminerals, insbesondere eines smektischen Tonminerals;
2. b) Bereitstellen mindestens eines PVP-VA Copolymers;
3. c) Mischen des mindestens einen PVP-VA Copolymers und des mindestens einen Tonminerals.

Another aspect of the invention relates to a process for the preparation of a detergent additive comprising at least the following steps:

1. a) providing at least one clay mineral, in particular a smectite clay mineral;
2. b) providing at least one PVP-VA copolymer;
3. c) mixing the at least one PVP-VA copolymer and the at least one clay mineral.

Preferably, the process for the preparation of a detergent additive comprises, before, simultaneously with or after step c), at least one surfactant, in particular a nonionic surfactant, being admixed. This may be provided together with the PVP-VA copolymer and the clay mineral and mixed therewith in the manner known to those skilled in the art.

Particularly preferably, the surfactant and / or PVP-VA copolymer is provided in the form of a common or separate aqueous solution. In addition to water, polar organic solvents, such as, for example, methanol, ethanol, formamide, dimethylformamide, pyridine, dimethylsulfoxide-containing solutions are also suitable.

Preferably, the surfactant and the PVP-VA copolymer are mixed in a first step. This can be done both from the pure substances, and particularly preferably from aqueous solutions of the surfactant and the PVP-VA copolymer. These are then applied to the clay mineral using methods known to those skilled in the art. The application can be done by spraying or by mixing in a mixer with the clay mineral. For intensive mixing, a mechanical fluidized bed is preferably produced. In general, the intensive mixers known from the prior art can be used in batchwise or continuous processes.

Further preferably, the mixture of PVP-VA copolymer, surfactant and clay mineral is then dried and optionally formed into granules, compacts or tablets. The granules are dried and sieved after mixing (wet granulation). Typically, by screening, appropriate particle sizes are set, as are common in the detergent industry, for example in a grain band range between 0.2 and 1.2 mm, 0.4 and 1.4 mm, 1.0 and 2.0 mm. The production of shaped articles, such as e.g. Pressings or tablets can be carried out by the methods and additives known to those skilled in the art. Examples of additives are binders, coatings and additives (e.g., carbonates and citric acid) which facilitate dissolution of the molded articles.

In a preferred embodiment, the method of making the detergent additive comprises adding carrageenan as described herein. This can be added in a separate aqueous solution or mixed in a common solution with surfactant and PVP-VA copolymer with the clay mineral. The addition of carrageenan while the softness is surprisingly further improved.

In a further preferred embodiment, the process for the preparation of the detergent additive comprises the addition of water glass, in particular in the form of an aqueous solution. In this case, for example, a water glass solution (solids content preferably about 34-36%), for example of the module 3.2 used (modulus = SiO ₂ ratio: Na ₂ O). Preferred regions of the module have already been specified above. This solution can be further diluted and mixed, for example, in a ratio of 2-3: 1 with water and then used in the process according to the invention. However, it is also possible to use solid water glass. The use of water glass thereby improves the dissolution of the finished granules and thus prevents flocculation, which impedes a uniform distribution of the clay granules on the textile fiber.

In another aspect of the present invention, the laundry additive described herein is used to improve the softening. The detergent additive is also suitable as a separate softener both in solid, e.g. granular, as well as in liquid form. In addition to improving the soft feel, the components, such as the (nonionic) surfactant or the clay mineral, increase the release of the soil particles and the stabilization of the same in the wash liquor.

In a preferred embodiment, the detergent additive is used as a component of liquid or solid detergents, cleaners and conditioners, with the foregoing advantages. This reduces the consumption of detergent and reduces the costs for the end user and simplifies the washing process. All conventional washing, cleaning and care products can be used, such as, for example, laundry detergents, dishwashing detergents and dishwashing detergents, hand soaps, stain removers, bleaches, shower gels, shampoos, body lotions, creams, cleansing preparations. and care products for eg motor vehicles, ships and aircraft, as well as for surface treatment or impregnation.

Another aspect of the invention relates to the use of the detergent additive of the invention to improve the softness and / or hue preservation of substances and / or textiles (textile materials), in particular selected from the group consisting of cotton, silk, wool, polyester, polyamide, elastane ^®, Nylon ^® , viscose, especially of cotton-containing fabrics.

Yet another aspect of the invention relates to the use of at least one carrageenan in a detergent additive and / or a laundry, cleaning or care composition, in particular for improving the soft feel and / or the color retention of textile materials.

• Figur 1 zeigt die Ergebnisse aus Waschversuchen zum Weichgriffindex bei Verwendung eines erfindungsgemäßen Waschmitteladditivs;
• Figur 2 zeigt den Einfluss verschiedener Waschmitteladditive auf den Weichgriffindex.
• Figur 3 zeigt den Einfluss eines erfindungsgemäßen Waschmitteladditivs (mit PVP/VA Copolymer) und eines Vergleichs-Waschmitteladditivs (mit PVP/VI Copolymer) auf den Weichgriffindex.
• Figur 4 zeigt die Abhängigkeit der Weichgriffverbesserung verschiedener erfindungsgemäßer Waschmitteladditive vom Anteil der VA-Monomereinheiten im PVP/VA Copolymer.

The invention will be explained in more detail below with reference to the test and investigation methods used, examples and figures. These are for illustration only and do not limit the invention in any way.

• FIG. 1 shows the results of washing tests for Weichgriffindex when using a detergent additive according to the invention;
• FIG. 2 shows the influence of various detergent additives on the Weichgriffindex.
• FIG. 3 shows the influence of a detergent additive according to the invention (with PVP / VA copolymer) and a comparison detergent additive (with PVP / VI copolymer) on the soft handle index.
• FIG. 4 shows the dependence of the soft handle improvement of various inventive detergent additives on the proportion of VA monomer units in the PVP / VA copolymer.

1. Used materials and methods 1.1 Test detergent

For the following washing tests, a standard test detergent was used. For this purpose, the test detergent IEC 60456, which was commissioned by the Wfk Research Institute for Cleaning Technology e. V., used. The composition of this test detergent is shown in Table 1. The components sodium perborate tetrahydrate and tetraacetylethylenediamine were not part of the test detergent and were mixed with the test detergent before dosing. These components were also produced by the Wfk Research Institute for Cleaning Technology e. V. related. The data on the mass concentration of these components in the test detergent are also given in Table 1. Table 1: Composition of IEC 60456 (reference basic detergent type A). In addition to the base detergent, the bleaching components sodium perborate tetrahydrate and tetraacetylethylenediamine were added. component Wt .-% Linear Na-alkyl-benzenesulfonate 8.8% Ethoxylated fatty alcohol C _12-18 (7 EO) 4.7% Na-soap 3.2% Defoamer DC2-4248S 3.9% Zeolite 4A 28.3% Na-carbonate 11.6% Na salt of a copolymer of acrylic and maleic acid (Sokalan CP5) 2.4% Na-silicate 3.0% carboxymethylcellulose 1.2% Dequest 2066 2.8% Optical brightener 0.2% Na sulfate 6.5% protease 0.4% Total basic detergent: 77% Sodium tetrahydrate 15.3% Tetraacetylethylenediamine (TAED) 7.7%

1.2 washing tests

Commercially available towels of the company Frottana-Textil GmbH & Co. KG were used for the washing tests, quality: 4264 g / m ² , size: 50x100 cm used. There were always ever 8 towels in a washing machine washed. As a reference towels were used, which had been washed only with test detergent. In each wash series, cotton test fabric was also washed for analysis. Per wash, 90 g of test detergent including sodium perborate tetrahydrate and tetraacetylethylenediamine and 10 g of the detergent additive were used (the composition of the additive granules is shown in the corresponding examples of the washing experiments). All washing tests were carried out with washing machines from BOSCH, type WFG 2460, washing program "Cotton, 60 ° C". The water hardness was 21 ° DH. This corresponds to a Ca ²⁺ content of 3.7 mmol / l. The towels were air dried in a sealed room at room temperature.

1.3 Soft grip test

In the soft-grip test, 15 people each judge by gripping and feeling with their hands which towels are softer or harder in comparison with each other. Care was taken to ensure that only a certain area or part of the cloth is grasped by a person only once. If you z. For example, eight towels each, which were compared with the test detergent and detergent additive with the same number of towels washed only with test detergent, each towel is evaluated twice at different locations (duplicate). On a rating scale, each towel can be max. Reach 30 points. The score is then expressed as a percentage or as a soft grip index (0 points equals 0% and 30 points equals 100%). The percentage or Weichgriffindex means that in z. For example, 50% of the cases (when the score was 15) found the corresponding sample softer than the reference sample.

1.4 Determination of the ashing residue

For the determination of the ashing residue, approximately 5 g of sample material (the washed towel or the washed test fabric) was weighed into the porcelain crucible, ashed and then calcined in the oven at 850 ° C. for 60 minutes. After cooling in the desiccator, the samples were weighed and the tissue washes were calculated in weight percent of the tissue weighed. For comparison, samples were also ashed, which were not washed at all and only with test detergent. From the difference of the ashing residues of the samples, with corresponding additives or granules and the samples, which were washed only with test detergent, the "net ashing residue" was determined.

1.5 Determination of cation exchange capacity (CEC) and cation content

Principle: The clay (eg bentonite) is treated with a large excess of aqueous NH ₄ -Cl solution, washed out and the amount of NH ₄ ⁺ remaining on the clay determined according to Kjeldahl.

Me ⁺ (clay) ^- + NH ₄ ⁺ - NH ₄ ⁺ (clay) ^- + Me ⁺

(Me ⁺ = H ⁺ , K ⁺ , Na ⁺ , 1/2 Ca ²⁺ , 1/2 Mg ²⁺ ....)

Equipment: sieve, 63 μm; Erlenmeyer grinding flasks, 300 ml; Analytical balance; Membrane filter chute, 400 ml; Cellulose nitrate filter, 0.15 μm (Sartorius); Drying oven; Reflux condenser; hot plate; Distillation unit, VAPODEST-5 (Gerhardt, No. 6550); Volumetric flask, 250 ml; Flame AAS (FAAS) Chemicals: 2N NH ₄ Cl solution Nessler's reagent (Merck, item No. 9028); Boric acid solution, 2%; Caustic soda, 32%; 0.1 N hydrochloric acid; NaCl solution, 0,% -ig; KCl solution, 0.1%

Procedure: 5 g of clay are sieved through a 63 μm sieve and dried at 110 ° C. Then weigh exactly 2 g on the analytical balance in differential weighing into the Erlenmeyer grinding flask and add 100 ml of 2N NH ₄ Cl solution. The suspension is boiled under reflux for one hour. In the case of strongly CaCO ₃ -containing clays, ammonia development can occur. In this case, as long as NH ₄ Cl solution must be added until no ammonia smell is perceived. Additional control can be done with a wet indicator paper. After a standing time of about 16 h, the NH ₄ ⁺ clay is filtered through a membrane filter and washed until the substantial freedom from ion with deionized water (about 800 ml). The proof of the ionic freedom of the wash water is carried out on NH ₄ ⁺ ions with the sensitive Nessler's reagent. The washing rate may vary between 30 minutes and 3 days depending on the type of clay. The washed out NH ₄ ⁺ clay is removed from the filter, dried at 110 ° C for ₂ hours, ground, sieved (63 micron sieve) and dried again at 110 ° C for 2 hours. Thereafter, the NH ₄ ⁺ content of the clay is determined according to Kjeldahl.

Calculation of the CEC: The CEC of the clay is the Kjeldahl NH ₄ ⁺ content of the NH ₄ ⁺ clay (CEC of some clay minerals, see Appendix). The data are given in meq / 100 g clay.

Example: nitrogen content = 0.93%;

CEC = 66,4 meq/100 g NH₄ ⁺-TonMolecular weight: N = 14.0067 g / mol $$\mathrm{CEC}\mathrm{=}\frac{\mathrm{0}\mathrm{.}\mathrm{93}\mathrm{x}\mathrm{1000}}{\mathrm{14}\mathrm{.}\mathrm{0067}}\mathrm{=}\mathrm{66}\mathrm{.}\mathrm{4}\mathrm{meq}\mathrm{/}\mathrm{100}\mathrm{G}$$

CEC = 66.4 meq / 100 g NH ₄ ⁺ clay

Exchanged cations and their proportions:

The cations released by the exchange are in the wash water (filtrate). The proportion and the type of monovalent cations ("exchangeable cations") was determined spectroscopically in the filtrate according to DIN 38406, part 22. For example, the wash water (filtrate) is concentrated for AAS determination, transferred to a 250 ml volumetric flask and filled with deionized water to the measuring mark. Suitable measuring conditions for FAAS can be found in the following tables. Table 2: Parameters for FAAS determination Part 1 element calcium potassium lithium magnesium sodium Wavelength (nm) 422.7 766.5 670.8 285.2 (202.6) 589.0 Gap width (nm): 0.2 0.5 0.5 0.5 0.2 Integral time (sec): 3 3 3 3 3 Flame gases: N ₂ O / C ₂ H ₂ Air / C ₂ H ₂ Air / C ₂ H ₂ N ₂ O / C ₂ H ₂ Air / C ₂ H ₂ Underground Comp .: No No No Yes No Measurement type: conc. conc. conc. conc. conc. Ionization buffer: 0.1% KCl 0.1% NaCl 0.1% NaCl 0.1% KCl 0.1% KCl Burner position 15-20 ° - - - - Calibration level (mg / l): 1-5 mg / l 1-5 mg / l 2-10 mg / l 0.5-3 mg / l (5-40 mg / l) 1-5 mg / l element aluminum iron Wavelength (nm): 309.3 248.3 Gap width (nm): 0.5 0.2 Integral time (sec): 3 3 Flame gases: N ₂ O / C ₂ H ₂ Air / C ₂ H ₂ Untergrundkomp .: Yes No Measurement type: conc. conc. Ionisationspuffer: 0.1% KCl - Burner position - - Calibration mode. (Mg / l): 10-50 mg / l 1-5 mg / l

Calculation of cations:

Molmassen (g/mol): Ca=20,040; K=39,096; Li=6,94; Mg=12,156; Na=22,990; Al=8,994; Fe=18,616 $$\mathrm{me}\mathrm{=}\frac{\mathrm{me}\mathrm{-}\mathrm{value}\left(\mathrm{mg}\mathrm{/}\mathrm{l}\right)\mathrm{x}\mathrm{100}\mathrm{x\; dilution}}{\mathrm{4}\mathrm{x\; weight}\left(\mathrm{in\; g}\right)\mathrm{x\; molecular\; weight}\left(\mathrm{G}\mathrm{/}\mathrm{mol}\right)}\mathrm{=}\mathrm{meq}\mathrm{/}\mathrm{100}\mathrm{G}$$

Molar masses (g / mol): Ca = 20.040; K = 39.096; Li = 6.94; Mg = 12.156; Na = 22.990; Al = 8.994; Fe = 18.616

In the case of so-called overactivated clays, ie those which have been activated with a greater than stoichiometric amount of, for example, soda, the sum of the determined amounts of monovalent cations can exceed the CEC determined as indicated above. In such cases, the total monovalent cation content (Li, K, Na) is considered to be 100% of the CEC.

Determination of montmorillonite content via methylene blue adsorption

The methylene blue value is a measure of the inner surface of the clay materials.

a) Preparation of a tetrasodium diphosphate solution

5.41 g tetrasodium diphosphate are weighed to 0.001 g exactly in a 1000 ml volumetric flask and shaking to the mark with dist. Water filled up.

b) Preparation of a 0.5% methylene blue solution

In a 2000 ml beaker, 125 g of methylene blue in about 1500 ml dest. Water dissolved. The solution is decanted off and distilled to 25 l with dist. Water filled up.

0.5 g of wet test bentonite with a known internal surface are weighed to the nearest 0.001 g in an Erlenmeyer flask. Add 50 ml of tetrasodium diphosphate solution and heat the mixture to boiling for 5 minutes. After cooling to room temperature, 10 ml of 0.5 molar H ₂ SO _{4 are} added and 80 to 95% of the expected final consumption of methylene blue solution is added. With the glass rod, a drop of the suspension is taken and placed on a filter paper. It forms a blue-black spot with a colorless yard. It is then added in portions of 1 ml more Methylenblaulösung and repeated the dot sample. The addition takes place until the yard turns slightly light blue, so that the added Methylenblaumenge is no longer absorbed by the test bentonite.

c) Testing of clay materials

The test of the clay material is carried out in the same way as for the test bentonite. From the used amount of methylene blue solution, the inner surface of the clay material can be calculated.

381 mg methylene blue / g clay correspond to a content of 100% montmorillonite according to this method.

2. Examples Preparation of a granulate of the detergent additive

The clay mineral provided (the clay minerals used are described in Table 4) is mixed with an aqueous solution of the surfactant and the PVP / VA copolymer. First, the following solutions 1 and 2 were prepared:

Solution 1: In 250 ml of a mixture of water glass (Silicate de Soude 38/40, Type 16 N 34, Brenntag SA, Chassieu, FR) and water in a ratio of 2: 1, 0.1 g of carrageenan was dissolved (Satiagel ™ ME4 , Molecular weight 100,000-800,000, Degussa Testurant Systems GmbH & Co. KG, Hamburg, DE). To this solution was added 1.5 ml of a 5% C ₁₂ -C ₁₄ alcohol polyethylene glycol ether (EO) ₇ (Marlipal 24/70, Sasol & Surfactants, Marl, DE) solution.

Solution 2: In 1 L of distilled water was dissolved 2.5 g of PVP / VA copolymer (PVP / VA S-630, ISP Global Technologies, Texas City, US).

500 g of clay 1 (Table 4) were subsequently introduced into a mixer (DiTO-SAMA, F 23200 AUBUSSON, Made in France) and granulated with 72 g of solution 1 and 36 g of solution 2. The granules were then dried to a residual water content of 10-15%, sieved through a sieve of 0.4-1.4 mm and so used in the washing tests. Table 4: Overview of the clays used (bentonites) Sound 1 Sound 2 Sound 3 Sound 4 Main interlayer cation Na ⁺ Ca ²⁺ / Mg ²⁺ Na ⁺ Ca ²⁺ Share Ca ²⁺ at the CEC 0% 80% 0% 78% Proportion of Na ⁺ at the CEC 100% 20% 100% 22% CEC [meq / 100g] * 72 76 90 95 Montmorillonite content [%] ** 75 80 90 94 * Total cation exchange capacity of the sample
** Determination with methylene blue method

Results from the soft grip test, comparison of the test detergent without and with the addition of the detergent additive according to the invention

FIG. 1 shows the results of the soft grip index experiments. The composition of the samples W3 and W10 corresponds to the composition given above and differs only in the type of clay mineral used and the surfactant. The clay minerals and surfactants used in samples W3 and W10 are shown in Table 5. Table 5: Variable composition of samples W0, W3 and W10 sample volume surfactant W3 Sound 1 C ₁₀ EO ₄ W10 Sound 3 C _12-14 EO ₇ W0 * - - * Test detergent

Compared to the sample W0 with the pure test detergent, the softening with both the sample W3 and the sample W10 is increased by a factor of 2-3. Both samples contain an activated clay mineral. However, an improvement of the soft touch can also be achieved with a non-activated clay mineral. The soft touch can be increased by about 50% compared to the test detergent (not shown).

Influence of the individual additives on the softness of the examined samples

FIG. 2 shows the influence of the individual additives according to the invention on the softness. The composition of the samples is shown in Table 6. The driveways correspond to those in Example 1 except for the respectively omitted components FIG. 2 can be seen, one achieves the best softness in the use of all additives of the invention in sample B17. It turned out that the best increase in softness results from the combination of the individual components. (B18) and carrageenan (B19) omitted - In comparison, in the samples corresponding to non-ionic surfactant was ₍₁₄ EO ₇ C ₁₂ -C ₁₄ alcohol polyethylene glycol ether (7 EO) C _12). The Weichgriffindex thereby reduced in comparison to the sample B17, which contains all components of the invention. FIG. 2 also shows that surprisingly, by the addition of surfactant in sample B19, as well as by the further addition of carrageenan in sample B17, the soft hand can be further improved.

In addition, it has been found in this series of tests that, surprisingly, Sample B17 (with all the components according to the invention) has approximately the same ashing residue (not shown), such as a detergent additive containing only the clay mineral. However, the soft handle index of the inventive sample B17 is substantially improved compared to the detergent additive of pure clay mineral.

This effect can also be confirmed on the basis of optical micrographs (not shown), whereby test fabrics, which on the one hand were treated with a detergent additive containing only bentonite and on the other hand with a detergent additive according to the invention according to sample B17, were first dyed with methylene blue. This makes it possible to visualize the colored bentonite particles on the test fabrics when viewed under the light microscope (100 × magnification). It can be seen that the amount of clay particles present on the test fabrics is approximately the same when comparing the test fabrics treated with samples B17 and the pure clay mineral, respectively. In that regard, the according to FIG. 2 proved significantly improved softness of the composition according to the invention very surprising and not due to a different amount of absorbed on the fibers clay particles. Table 6: Composition of samples B17-B19 additives B17 B18 B19 Sound 1 X X X C ₁₂ -C ₁₄ -alcohol-polyethylene glycol-colether (7 EO) X X K-carrageenan X X PVP-VA copolymer X X X Water glass solution (2: 1) X X X

In a further experiment, the effect of using the PVP / VA copolymer according to the invention (composition corresponding to sample B17, see above) having the effect of using a PVP / VI (vinylimidazole) copolymer (composition according to sample B17, PVP / VA copolymer only by PVP / VI copolymer replaced). The results of the soft-grip tests (performed as described above) are in Fig. 3 shown. It shows clearly the surprisingly better effect of the sample according to the invention with PVP / VA copolymer over the comparison sample with PVP / VI copolymer.

In a further experiment, the effect when using different PVP / VA copolymers according to the invention with different proportions of VA monomer units or ratio of VP monomer units to VA monomer units (composition otherwise according to sample B17, see above) was compared. The following PVP / VA copolymers were used: product Ratio of VP Monomer Units to VA Monomer Units (VP: VA) source MIHAPOL® PNW64 / S-630 70:30 Miwon Commercial Co. Ltd., KR Luvitec® VA 64 / Lu-viskol® VA 64 60: 40 BTC Specialty Chemical Distribution GmbH, DE Luviskol® VA 55 I 50:50 BASF AG, DE

The results of the soft-grip tests (performed as described above) are in Fig. 4 shown. It clearly shows the surprisingly better effect of the sample according to the invention with the PVP / VA copolymer, which has the highest proportion of VA monomer units (50%).

Influence of the additives according to the invention on the color retention of the examined samples

There were 14 colored test fabrics (standard cotton fabric) with a) the test detergent composition according to Table 1 and b) with the test detergent composition according to Table 1 with the addition of 3% of the inventive additive prepared before Table 4 with Clay 1, but with 3-fold Content of PVP / VA copolymer washed at 60 ° C 5 times. The colored test textiles would then be checked for color retention after the 5th wash according to ISO 105-A05.

It was found that when using the detergent additive according to the invention significantly better color retention is provided. Thus, the color change was on a scale of 1 (very strong color change) to 5 (not worth mentioning Color change in experiment a), ie without the inventive detergent additive at 4.3, while with the detergent additive according to the invention a value of 4.4 could be achieved. The values given concern average values from 14 sections of the test textiles and are statistically significant.

Claims (15)

1. Detergent additive for improving the softness of textile products, containing at least the following components:

   a) a clay mineral;

   b) a PVP/VA copolymer.
2. Detergent additive according to claim 1, characterized in that the detergent additive contains a surfactant, in particular a non-ionic surfactant, preferably selected from the group which is formed by fatty alcohol ethoxylates and polyethylene glycol ether.
3. Detergent additive according to one of the previous claims, characterized in that the clay mineral is a smectic clay mineral, in particular a bentonite.
4. Detergent additive according to one of the previous claims, characterized in that the PVP/VA copolymer has a level of vinyl pyrrolidone monomer units of approximately 1 to 99%.
5. Detergent additive according to one of the previous claims, characterized in that the PVP/VA copolymer has a proportion of vinyl acetate monomer units of at least approximately 20%, preferably at least 30%, and preferably of not more than approximately 90%, in particular not more than 80%, further preferably not more than 75%.
6. Detergent additive according to one of the previous claims, characterized in that the PVP/VA copolymer has a ratio of vinyl pyrrolidone monomer units to vinyl acetate monomer units of between approximately 80:20 and 20:80, in particular between approximately 70:30 and 30:70, relative to the total quantity of vinyl pyrrolidone monomer units and vinyl acetate monomer units.
7. Detergent additive according to one of the previous claims, characterized in that, in addition to the vinyl pyrrolidone monomer units and the vinyl acetate monomer units, the PVP/VA copolymer also contains one or more other monomer units.
8. Detergent additive according to one of the previous claims, characterized in that the detergent additive contains at least one carrageenan, in particular a carrageenan with a molecular weight of from 50,000 g/mol to 1,000,000 g/mol, preferably 100,000 g/mol to 800,000 g/mol.
9. Detergent additive according to claim 8, characterized in that the detergent additive, relative to the mass of clay mineral, contains more than 0.0001 wt.-%, preferably more than 0.001 wt.- %, carrageenan.
10. Detergent additive according to one of the previous claims, characterized in that

    - the clay mineral is present in particle form, wherein at least 10 wt.-%, preferably at least 14 wt.-%, further preferably between approximately 10 and 50 wt.-% of the particles, further preferably between approximately 10 and 30 wt.-% of the particles have a particle size of less than approximately 600 nm; and/or

    - the clay mineral, in particular the bentonite, is activated, in particular preferably activated with soda; and/or

    - at least 50% of the cation exchange capacity (CEC), preferably at least 60% and particularly preferably at least 80% of the clay mineral, in particular bentonite, is formed by monovalent cations; and/or

    - the detergent additive contains at least 80 wt.-%, preferably at least 85 wt.-% clay mineral, in particular bentonite.
11. Detergent additive according to one of the previous claims, characterized in that

    - the detergent additive contains, relative to the mass of clay mineral, more than 0.001 wt.-%, preferably more than 0.01 wt.-%, fatty alcohol ethoxylate and/or polyethylene glycol ether; and/or

    - the detergent additive contains, relative to the mass of clay mineral, more than 0.001 wt.-%, preferably more than 0.01 wt.-%, PVP/VA copolymer; and/or

    - the detergent additive contains, relative to the mass of clay mineral, more than 0.05 wt.-%, preferably more than 0.5 wt.-%, water glass.
12. Method for producing the detergent additive, comprising at least the following steps:

    a) providing at least one clay mineral, in particular a smectic clay mineral;

    b) providing at least one PVP/VA copolymer;

    c) mixing the at least one PVP/VA copolymer and the at least one clay mineral,
    wherein at least one surfactant, in particular a non-ionic surfactant, is preferably added either before, at the same time as or after step c).
13. Method according to claim 12, characterized in that the surfactant and/or PVP/VA copolymer is provided in the form of aqueous solution.
14. Method according to claim 12 or 13, characterized in that

    - PVP/VA copolymer and surfactant are mixed first and then applied to the clay mineral; and/or

    - the mixture of PVP/VA copolymer, surfactant and clay mineral is dried and optionally shaped into granules, compacts or tablets; and/or

    - carrageenan is added; and/or

    - water glass is added.
15. Use of the detergent additive according to one of claims 1 to 11 or produced according to one of claims 12 to 14 as component of a washing, cleaning and/or care formulation, in particular for improving softness.

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