EP2057257B1 - Additif pour détergent à base de minéraux argileux et de copolymères contenant de la pvp - Google Patents

Additif pour détergent à base de minéraux argileux et de copolymères contenant de la pvp Download PDF

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Publication number
EP2057257B1
EP2057257B1 EP07801918A EP07801918A EP2057257B1 EP 2057257 B1 EP2057257 B1 EP 2057257B1 EP 07801918 A EP07801918 A EP 07801918A EP 07801918 A EP07801918 A EP 07801918A EP 2057257 B1 EP2057257 B1 EP 2057257B1
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European Patent Office
Prior art keywords
detergent additive
clay mineral
pvp
copolymer
monomer units
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EP07801918A
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German (de)
English (en)
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EP2057257A1 (fr
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Ulrich Sohling
Jovica Zorjanovic
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Sued Chemie IP GmbH and Co KG
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Sued Chemie IP GmbH and Co KG
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Priority to PL07801918T priority Critical patent/PL2057257T3/pl
Priority to EP07801918A priority patent/EP2057257B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the invention relates to a detergent additive for improving the soft feel of textile products, a process for its preparation and its use.
  • the GB 1 400 898 describes a detergent formulation for simultaneous cleaning and softening.
  • 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.
  • 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.
  • 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.
  • 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.
  • quaternary ammonium compounds and anionic, nonionic, amphoteric and zwitterionic surfactants can be used.
  • the EP-A-653 480 A1 describes a detergent composition
  • 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.
  • 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.
  • 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.
  • a soft-washing detergent which contains (a) anionic surfactants, nonionic and / or amphoteric surfactants, (b) cationic polymers, (c) zeolites, and (d) optionally phyllosilicates.
  • graft polymers based on polyvinylpyrrolidone as a grayness inhibitor in the washing and aftertreatment of textile fibers containing synthetic fibers.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the clay also supports the washing process by absorbing dirt particles and making them easier to remove when washed.
  • 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 ).
  • 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.
  • the detergent additive contains a surfactant.
  • 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.
  • 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.
  • surfactants are substances which reduce the interfacial tension and have a characteristic structure of at least one hydrophilic and one hydrophobic group.
  • 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.
  • the surfactant is a nonionic surfactant.
  • 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.
  • the PVP / VA copolymer is a copolymer containing only polyvinylpyrrolidone and polyvinyl 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.
  • the PVP / VA copolymer generally has a vinyl pyrrolidone monomer unit content of about 1 to 99%.
  • 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%.
  • 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.
  • 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.
  • 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.
  • the detergent additive contains at least one carrageenan.
  • 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).
  • ⁇ -carrageenan is a chain molecule composed of dimeric building blocks, ⁇ -D-galactosido (1,4) - ⁇ -D-galactose. These dimers are linked 1,3-glycosidically.
  • the primary alcohol group of ⁇ -D-galactose is esterified with sulfuric acid, and the hydroxy groups on C2 of both galactoses are also approximately 70% esterified with sulfuric acid.
  • ⁇ -carrageenan thus has a sulphate content between 32 and 39%.
  • K- and L-carrageenans are composed of the dimer carrabiose in which ⁇ -D-galactose is 1,4-glycosidically bound to ⁇ -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.
  • the sulfate ester group is located at C-4 of galactose, the sulfate content fluctuates between 25 and 30%.
  • 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.
  • carrageenans are health and ecologically harmless additives.
  • 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.
  • the smectite clay mineral is a bentonite.
  • 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.
  • divalent ions such as calcium or magnesium, creates a negative excess charge, which can be compensated for example by Mg 2+ , Ca 2+ , Na + .
  • the bentonite 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.
  • the particle size of the clay mineral can have an influence on the improvement of the softness.
  • 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.
  • 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 laborz. 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.
  • the clay mineral is in activated form, i. Bi- or trivalent cations stored between the layers are exchanged for monovalent ions, such as sodium ions or protons.
  • 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.
  • 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.
  • CEC cation exchange capacity
  • the detergent additive contains at least 80 wt .-%, preferably at least 85 wt .-% clay mineral, such as bentonite.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ,
  • PVP / VA polyvinylpyrrolidone-polyvinyl acetate copolymer
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the surfactant and / or PVP-VA copolymer is provided in the form of a common or separate aqueous solution.
  • polar organic solvents such as, for example, methanol, ethanol, formamide, dimethylformamide, pyridine, dimethylsulfoxide-containing solutions are also suitable.
  • 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.
  • a mechanical fluidized bed is preferably produced.
  • the intensive mixers known from the prior art can be used in batchwise or continuous processes.
  • 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).
  • 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.
  • additives are binders, coatings and additives (e.g., carbonates and citric acid) which facilitate dissolution of the molded articles.
  • 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.
  • the process for the preparation of the detergent additive comprises the addition of water glass, in particular in the form of an aqueous solution.
  • a water glass solution solids content preferably about 34-36%
  • module 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.
  • solid water glass 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • test detergent For the following washing tests, a standard test detergent was used.
  • 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).
  • 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%
  • sample material the washed towel or the washed test fabric
  • the samples were 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.
  • 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.
  • 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.
  • 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.
  • 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 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. 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 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
  • 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.
  • the total monovalent cation content Li, K, Na is considered to be 100% of the CEC.
  • the methylene blue value is a measure of the inner surface of the clay materials.
  • 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 Methylenblauans 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.
  • 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.
  • 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.
  • 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 TM 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.
  • EO polyethylene glycol ether
  • 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).
  • 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
  • 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
  • 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).
  • 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 -
  • 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.
  • 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.
  • ashing residue such as a detergent additive containing only the clay mineral.
  • the soft handle index of the inventive sample B17 is substantially improved compared to the detergent additive of pure clay mineral.
  • 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
  • test fabrics standard cotton fabric
  • test detergent composition according to Table 1 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.

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Claims (15)

  1. Additif pour lessives, destiné à améliorer la souplesse au toucher de produits textiles, contenant au moins les composants suivants :
    a) un minéral argileux ;
    b) un copolymère PVP/VA.
  2. Additif pour lessives selon la revendication 1, caractérisé en ce que ledit additif pour lessives contient un agent tensioactif, notamment un agent tensioactif non-ionique, choisi préférentiellement dans le groupe constitué par les éthoxylates d'alcools gras et l'éther de polyéthylène glycol.
  3. Additif pour lessives selon l'une des revendications précédentes, caractérisé en ce que ledit minéral argileux est un minéral argileux smectique, notamment une bentonite.
  4. Additif pour lessives selon l'une des revendications précédentes, caractérisé en ce que ledit copolymère PVP/VA présente une teneur en unités monomères de vinylpyrrolidone allant d'environ 1 à 99 %.
  5. Additif pour lessives selon l'une des revendications précédentes, caractérisé en ce que ledit copolymère PVP/VA présente proportion d'unités monomères d'acétate de vinyle d'au moins environ 20 %, de préférence d'au moins 30 %, et de préférence ne dépassant pas environ 90 %, notamment ne dépassant pas 80 %, de façon encore préférée ne dépassant pas 75 %.
  6. Additif pour lessives selon l'une des revendications précédentes, caractérisé en ce que ledit copolymère PVP/VA présente un rapport entre les unités monomères de vinylpyrrolidone et les unités monomères d'acétate de vinyle entre environ 80 : 20 et 20 : 80, notamment entre environ 70 : 30 et 30 : 70, par rapport à la quantité totale d'unités monomères de vinylpyrrolidone et d'unités monomères d'acétate de vinyle.
  7. Additif pour lessives selon l'une des revendications précédentes, caractérisé en ce que ledit copolymère PVP/VA contient outre les unités monomères de vinylpyrrolidone et les unités monomères d'acétate de vinyle encore une ou plusieurs autres unités monomères.
  8. Additif pour lessives selon l'une des revendications précédentes, caractérisé en ce que ledit additif pour lessives contient au moins un carraghénane, notamment un carraghénane ayant une masse moléculaire comprise entre 50 000 g/mol et 1 000 000 g/mol, de préférence entre 100 000 g/mol et 800 000 g/mol.
  9. Additif pour lessives selon la revendication 8, caractérisé ce que ledit additif pour lessives contient plus de 0,0001 % en poids, de préférence plus de 0,001 % en poids, de carraghénane, par rapport à la masse dudit minéral argileux.
  10. Additif pour lessives selon l'une des revendications précédentes, caractérisé en ce que
    - ledit minéral argileux se présente sous forme de particules, au moins 10 % en poids, de préférence au moins 14 % en poids, de façon encore préférée entre environ 10 et 50 % en poids des particules, de façon encore préférée entre environ 10 et 30 % en poids des particules présentant une taille de particule inférieure à environ 600 nm ; et/ou
    - ledit minéral argileux, plus particulièrement la bentonite, est activé, l'activation étant réalisée avec une préférence particulière au moyen de carbonate de sodium ; et/ou
    - les cations monovalents représentent au moins 50 % de la capacité d'échange de cations (CEC), de préférence au moins 60 % et, avec une préférence particulière, au moins 80 % chez ledit minéral argileux, s'agissant plus particulièrement de bentonite ; et/ou
    - ledit additif pour lessives contient au moins 80 % en poids, de préférence au moins 85 % en poids, de minéral argileux, s'agissant plus particulièrement de bentonite.
  11. Additif pour lessives selon l'une des revendications précédentes, caractérisé en ce que
    - ledit additif pour lessives contient, par rapport à la masse dudit minéral argileux, plus de 0,001 % en poids, de préférence plus de 0,01 % en poids, d'éthoxylate d'alcools gras et/ou d'éther de polyéthylène glycol ; et/ou
    - ledit additif pour lessives contient, par rapport à la masse dudit minéral argileux, plus de 0,001 % en poids, de préférence plus de 0,01 % en poids, de copolymère PVP/VA ; et/ou
    - ledit additif pour lessives contient, par rapport à la masse dudit minéral argileux, plus de 0,05 % en poids, de préférence plus de 0,5 % en poids, de métasilicate de sodium.
  12. Procédé de préparation dudit additif pour lessives, comprenant au moins les étapes suivantes :
    a) mise à disposition d'au moins un minéral argileux, notamment d'un minéral argileux smectique ;
    b) mise à disposition d'au moins un copolymère PVP/VA ;
    c) mélange de l'au moins un copolymère PVP/VA et de l'au mois un minéral argileux,
    au moins un agent tensioactif, notamment un agent tensioactif non-ionique, y étant préférentiellement incorporé avant, pendant ou après l'étape c).
  13. Procédé selon la revendication 12, caractérisé en ce que ledit agent tensioactif et/ou ledit copolymère PVP/VA sont mis à disposition sous forme d'une solution aqueuse.
  14. Procédé selon les revendications 12 ou 13, caractérisé en ce que
    - l'on mélange d'bord le copolymère PVP/VA et l'agent tensioactif pour ensuite les appliquer sur le minéral argileux ; et/ou
    - le mélange de copolymère PVP/VA, d'agent tensioactif et de minéral argileux est séché et, le cas échéant, soumisà un formage de façon à obtenir des granulés, des corps pressés ou des comprimés ; et/ou
    - l'on ajoute du carraghénane ; et/ou
    - l'on ajoute du métasilicate de sodium.
  15. Utilisation dudit additif pour lessives selon l'une des revendications 1 à 11, ou préparé selon l'une des revendications 12 à 14, en tant que composant d'une formulation de lavage, de nettoyage et/ou d'entretien, notamment pour améliorer la souplesse au toucher.
EP07801918A 2006-08-28 2007-08-27 Additif pour détergent à base de minéraux argileux et de copolymères contenant de la pvp Not-in-force EP2057257B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL07801918T PL2057257T3 (pl) 2006-08-28 2007-08-27 Dodatek do detergentu na bazie minerałów ilastych i kopolimerów zawierających pvp
EP07801918A EP2057257B1 (fr) 2006-08-28 2007-08-27 Additif pour détergent à base de minéraux argileux et de copolymères contenant de la pvp

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06017916A EP1894993A1 (fr) 2006-08-28 2006-08-28 Additif détergent au base de minéraux d'argile et des copolymers contenant du PVP
PCT/EP2007/007494 WO2008025505A1 (fr) 2006-08-28 2007-08-27 Additif pour détergent à base de minéraux argileux et de copolymères contenant de la pvp
EP07801918A EP2057257B1 (fr) 2006-08-28 2007-08-27 Additif pour détergent à base de minéraux argileux et de copolymères contenant de la pvp

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EP2057257A1 EP2057257A1 (fr) 2009-05-13
EP2057257B1 true EP2057257B1 (fr) 2012-11-21

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EP06017916A Withdrawn EP1894993A1 (fr) 2006-08-28 2006-08-28 Additif détergent au base de minéraux d'argile et des copolymers contenant du PVP
EP07801918A Not-in-force EP2057257B1 (fr) 2006-08-28 2007-08-27 Additif pour détergent à base de minéraux argileux et de copolymères contenant de la pvp

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JP (1) JP5260522B2 (fr)
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DE102008050360A1 (de) * 2008-10-02 2010-04-08 Süd-Chemie AG Waschmitteladditiv auf der Basis von Tonmineralien, sowie dessen Verwendung und Verfahren zu dessen Herstellung
ITUA20164581A1 (it) * 2016-06-22 2017-12-22 Manteco S P A Metodo di rimozione di sostanze contaminanti dai tessuti
DE102016213568A1 (de) * 2016-07-25 2018-01-25 Henkel Ag & Co. Kgaa Polymere aus Vinylpyrrolidon und/oder Vinylacetat als textilpflegende Inhaltsstoffe
CH713397A1 (de) * 2017-01-31 2018-07-31 Bonyf Ag Verfahren zur Entfernung von Milchrückständen sowie Zusammensetzung einer Reinigungstablette oder eines Reinigungspulvers.

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ES2399832T3 (es) 2013-04-03
EP2057257A1 (fr) 2009-05-13
MX2009001921A (es) 2009-03-09
EP1894993A1 (fr) 2008-03-05
PT2057257E (pt) 2013-02-19
PL2057257T3 (pl) 2013-09-30
BRPI0716412A2 (pt) 2013-09-24
JP2010501686A (ja) 2010-01-21
JP5260522B2 (ja) 2013-08-14
WO2008025505A1 (fr) 2008-03-06

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