EP2340298B1 - Additif pour détergent, à base de minéraux argileux, ainsi que son utilisation et des procédés pour sa préparation - Google Patents

Additif pour détergent, à base de minéraux argileux, ainsi que son utilisation et des procédés pour sa préparation Download PDF

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EP2340298B1
EP2340298B1 EP09778811.1A EP09778811A EP2340298B1 EP 2340298 B1 EP2340298 B1 EP 2340298B1 EP 09778811 A EP09778811 A EP 09778811A EP 2340298 B1 EP2340298 B1 EP 2340298B1
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EP
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Prior art keywords
monomer units
copolymer
vinylpyrrolidone
detergent additive
clay mineral
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EP09778811.1A
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German (de)
English (en)
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EP2340298A1 (fr
Inventor
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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    • 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
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • 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

Definitions

  • the invention relates to a detergent additive, in particular for improving the softness of textile products, comprising at least one clay mineral and at least one copolymer having cationic monomer units and N-vinylpyrrolidone monomer units. Furthermore, the present invention relates to a process for its preparation, and its use.
  • the GB 1 400 898 describes a detergent formulation for simultaneous cleaning and softening. These are anionic, ampholytic and zwitterionic synthetic Surfactants, organic or inorganic "builder” and a smectic three-layer clay mineral 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, derived ether 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 polymeric flocculant such as polyethylene oxide having molecular weights between 100,000 g / mol and 10,000,000 g / mol.
  • anionic, nonionic, amphoteric and zwitterionic surfactants can be used.
  • WO 2008/025505 a detergent additive for improving the softness of textile products, which contains at least the following components: a) a clay mineral; b) a PVP / VA copolymer.
  • a solid, fabric softening composition comprising a water-soluble carrier, a water-soluble polymer, a fabric softening compound and a perfume.
  • the water-soluble Carrier is preferably present in particulate form and has an enclosure in which the water-soluble polymer, the fabric softening compound and the perfume are included.
  • the preparation of the compositions is described wherein polyethylene glycol having an average molecular weight of 4000 is first melted. The melt is then mixed with sodium chloride as the solid carrier, clay as the fabric softening compound and perfume.
  • WO 2008/058819 A a detergent additive comprising at least one clay mineral and at least one copolymer having cationic monomer units and N-vinylpyrrolidone monomer units.
  • an increase in the clay mineral content does not increase the softness to the same extent, so that often and in no small measure other additives have to be used. Examples include surfactants, flocculants, and silicone oils, both alone and in combination.
  • these additives increase to a not insignificant extent the cost of the 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 that completely or largely dispense with substances with high allergenic potential.
  • such detergent additives should be wholly or largely harmless to health and ecology and provide a very good softness.
  • the detergent additives should enable a cost-effective provision of detergent formulations, in particular granular detergent formulations, to the consumer.
  • the individual components of the detergent additive complement each other favorably and provide favorable interactions with the respective other components.
  • a detergent additive in particular for improving the soft feel of textile products, which contains at least the following components: a) at least one clay mineral; and b) at least one N-vinylpyrrolidone copolymer, wherein the at least one N-vinylpyrrolidone copolymer comprises N-vinylpyrrolidone monomer units and cationic monomer units selected from the group consisting of quaternized N-vinylimidazole monomer units, quaternized N, N-dialkylaminoalkyl (meth) acrylate monomer units and monomer units derived from diallyldimethylammonium salts.
  • the present invention teaches a process for the preparation of such a detergent additive, comprising at least the following steps: a) providing at least one clay mineral, in particular at least one smectite clay mineral; b) providing at least one N-vinylpyrrolidone copolymer, wherein the at least one N-vinylpyrrolidone copolymer comprises N-vinylpyrrolidone monomer units and cationic monomer units selected from the group consisting of quaternized N-vinylimidazole monomer units, quaternized N, N- Dialkyl-aminoalkyl (meth) acrylate monomer units and monomer units derived from diallyldimethylammonium salts; and c) mixing the at least one copolymer comprising N-vinylpyrrolidone monomer units and cationic monomer units and the at least one clay mineral.
  • the present invention teaches uses of the inventive detergent additive as a component of a washing, cleaning, and / or care formulation and / or for the preparation of a washing, cleaning, and / or care formulation.
  • Very good washing results and a very good softness can be obtained, for example, if the cationic monomer units comprise or consist of monomer units which each have at least one quaternized nitrogen atom.
  • detergent additive encompasses both detergent additives that can be added to detergent formulations, as well as their aqueous solutions or can be used for their preparation, as well as detergent additives before or after use a detergent formulation on the laundry or in the washing liquid or can be introduced.
  • Detergent additive also includes formulations such as detergent powders, liquid detergents, fabric softeners which may be in the form as provided to consumers or in any preparation precursors thereof.
  • the at least one clay mineral can be both a natural and a synthetically produced clay.
  • 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 influence of clay minerals on the softness of textile fibers, such as cotton, can be explained by the fact that the clay mineral shows its morphological properties (such as platelet-shaped alumosilicates with a particle size diameter smaller than 2 ⁇ m) and its physicochemical properties (Such as the sliding behavior), deposited between and / or on fibers, especially 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 cationic monomer unit comprises less than 4 quaternized nitrogen atoms, according to a further embodiment less than 3 nitrogen atoms. In one embodiment, the cationic monomer unit contains a quaternized nitrogen atom.
  • the quaternized nitrogen atom of the cationic monomer unit according to one embodiment carries at least one
  • the quaternized nitrogen atom of the cationic monomer unit carries at least one alkyl group selected from methyl group, ethyl group and propyl group.
  • a cationic monomer unit may comprise one or more groups having a negative charge, for example carboxylic acid groups, but is preferably free of these groups.
  • the proportion of N-vinylpyrrolidone monomer units in the copolymer is preferably at least 10 mol%, according to a further embodiment at least 20 mol%.
  • the proportion of N-vinylpyrrolidone monomer units can be greater than 30 mol%, according to one embodiment, and greater than 40 mol% according to another embodiment.
  • the proportion of N-vinylpyrrolidone monomer units in the copolymer is less than 90 mol%, in another embodiment less than 80 mol%.
  • the proportion of N-vinylpyrrolidone monomer units in the copolymer can be less than 60 mol%, according to one embodiment less be as 50 mol%.
  • the proportion of the cationic monomer units in the copolymer is, according to one embodiment, at least 5 mol%, according to a further embodiment at least 10 mol%. In one embodiment, the proportion of cationic monomer units in the copolymer is less than 60 mol%, according to another embodiment less than 50 mol% and, according to another embodiment, less than 45 mol%.
  • quaternized nitrogen describes a nitrogen atom having bonds to four carbon atoms, wherein two of these bonds can also be made to the same carbon atom.
  • An advantageous soft hand can be obtained in particular if the at least one cationic monomer unit has an advantageous size in a specific size range and comprises, for example, between 6 and 40 atoms, preferably between 7 and 35, preferably between 7 and 28 atoms.
  • a cationic monomer unit may comprise between, for example, 5 and 36, preferably between 6 and 18, preferably between 6 and 12 carbon atoms.
  • a cationic monomer unit may comprise, for example, 0 to 6, preferably 2 to 4, oxygen atoms.
  • cationic monomer units used are monomer units derived from N-vinyl or N-allyl compounds, which in one embodiment comprise at least one further nitrogen atom which, according to one embodiment, is a quaternary nitrogen atom is present.
  • the cationic monomer units are derived from (meth) acrylates which comprise at least one quaternary nitrogen atom.
  • the term "monomer unit” describes a component of the copolymer as it is present in a polymer, in particular copolymer, after polymerization of the respective monomers in polymerized form in the polymer, in particular copolymer.
  • a copolymer comprising 100 monomer units, of which 30 monomer units are N-vinylpyrrolidone monomer units, has a content of N-vinylpyrrolidone monomer units of 30 mol%.
  • Detergents or detergent additives with very advantageous washing results, in particular a very advantageous softening can be obtained, in particular, if the cationic monomer units consist of monomer units or comprise one or more monomer units selected from the group consisting of quaternized N-vinylimidazole monomer units, quaternized N, N-dialkylaminoalkyl (meth) acrylate monomer units and monomer units derived from diallyldimethylammonium salts.
  • Quaternized N-vinylimidazole monomer units may have the following Formula I and quaternized N, N-dialkylaminoalkyl (meth) acrylate monomer units may have the following Formula II:
  • the element -Z- can be a straight-chain or branched alkyl or alkenyl chain.
  • the element -Z- may, for example, have from 1 to 30 carbon atoms, preferably from 1 to 8 carbon atoms, preferably from 2 to 6 carbon atoms.
  • the straight-chain or branched alkyl or alkenyl chain may comprise, for example, from 0 to 4, in one embodiment from 1 to 3 double bonds, although it may also be application-specifically free of double bonds.
  • the alkyl or alkenyl chain may have one or more substituents selected from the group consisting of -OH, -NH 2 , -NHR 1 , -NR 1 R 2 , -NR 1 R 2 R 3 +, and -SH as Substituents, wherein R 1 , R 2 , R 3 are defined below.
  • the alkyl or alkenyl chain preferably has 0 to 3 of these abovementioned substituents, these being identical or different substituents.
  • the radicals -R 1 , -R 2 , -R 3 may in particular be straight-chain or branched, saturated alkyl radicals having a chain length of 1 to 24 carbon atoms, preferably of 1 to 6 carbon atoms, more preferably methyl, ethyl and Propyl radicals act.
  • -R 4 may be -CH 3 or -H;
  • the quaternized N, N-dialkylaminoalkyl (meth) acrylate monomer units are N, N-dialkylaminoalkyl methacrylate monomer units.
  • Monomer units derived from diallyldimethylammonium salts have a structure of the following formula:
  • quaternized N, N-dialkylamino-alkyl methacrylate monomer units may be one or more quaternized monomer units selected from the group consisting of ethyl-quaternized N, N-dimethylaminomethylmethacrylate, ethyl-quaternized N, N-diethyl-aminomethylmethacrylate ethyl group quaternized N, N-dimethylaminoethyl methacrylate, ethyl group quaternized N, N-diethylaminoethyl methacrylate, ethyl group quaternized N-ethyl-N-methylaminomethyl methacrylate, methyl group quaternized N, N-dimethylaminomethyl methacrylate, methyl group quaternized N, N-diethylaminomethyl methacrylate methyl group quaternized N, N-dimethylaminoethyl methacrylate, N-
  • quaternized N-vinylimidazole monomer units may be used as cationic monomer units be used. It has surprisingly been found experimentally, for achieving a good softness, the proportion of quaternized N-vinylimidazole monomer units in the copolymer, for example, from 0 to less than 45 mol%, preferably from 0 to less than 30 mol%, more preferably from 0 to less than 20 mol%, more preferably from 0.5 to less than 20 mol%, preferably from 0 to less than 12 mol%, especially from 0 to less than 5 mol% may be. In one embodiment, the at least one N-vinylpyrrolidone copolymer may be free of quaternized N-vinylimidazole monomer units.
  • copolymers lead to particularly satisfactory washing results, in particular a good softness, which at least partially comprise cationic monomer units which have a structural mobility of the cationic, in particular a cationic, at least one quaternized nitrogen atom having monomer unit.
  • structurally determined mobility can be brought about, for example, by the presence of at least one straight-chain or branched alkyl chain which is in particular connected to the quaternized nitrogen atom and can comprise at least one, preferably at least two, preferably at least three carbon atoms.
  • Preparation processes for cationic compounds which have, for example, a quaternized nitrogen atom are known to a person skilled in the art and are described, for example, in US Pat J. March, "Advanced Organic Chemistry", 3rd ed., 1985, ISBN 0-471-85472-7, J. Wiley & Sons, Inc., pp. 364-5 and the references cited therein.
  • a quaternization can be carried out, for example, and in a non-limiting manner, inter alia by reaction with methyl chloride or with dimethyl sulfate.
  • Generation or introduction of a positively charged group, for example a quaternization of a nitrogen atom can be carried out both before and after the copolymerization.
  • the quaternization can be carried out by addition of a methyl or ethyl radical to the nitrogen atom.
  • the N-vinylpyrrolidone copolymer comprising cationic monomer units may also comprise, in addition to the vinylpyrrolidone monomer units and the cationic monomer units according to one embodiment, at least one further comonomer unit which does not carry a cationic charge.
  • the at least one further comonomer unit preferably does not comprise a quaternized nitrogen atom. According to one embodiment, the at least one further comonomer unit is uncharged.
  • the at least one further comonomer unit is derived from an N-vinyl compound according to one embodiment.
  • the at least one further comonomer unit is derived from a monomer selected from the group of N-vinylimidazole and N-vinylcaprolactam.
  • the proportion of the at least one further comonomer unit in the copolymer is less than 75 in one embodiment mol%, according to another embodiment less than 55 mol% and according to yet another embodiment less than 45 mol%. According to one embodiment, the proportion of the at least one further comonomer unit is at least 2 mol%, according to a further embodiment at least 5 mol%.
  • the N-vinylpyrrolidone copolymer comprising cationic monomer units may comprise N-vinylcaprolactam monomer units, wherein the proportion of N-vinylcaprolactam monomer units in the copolymer is preferably between 0.1 and 75 mol%, preferably between 2 and 55 mol%. %, is. Particularly advantageous washing results can be obtained, for example, if the ratio of N-vinylcaprolactam monomer units to N-vinylpyrrolidone monomer units is preferably from 1: 8 to 8: 1, preferably from 1: 2 to 2: 1, based on the number of monomer units.
  • the ratio of N-vinylcaprolactam monomer units to cationic monomer units having, for example, at least one quaternized nitrogen atom may preferably be from 10: 1 to 1: 1, preferably from 9: 1 to 2: 1, based on the number of monomer units.
  • the detergent additive according to the invention it has surprisingly been found that a high quality softness is achieved when using a combination of at least one clay mineral and at least one N-vinylpyrrolidone monomer units and cationic, for example at least one quaternized nitrogen atom-containing monomer units.
  • the detergent additives of the present invention have resulted in many applications to wash results, particularly softening, washing results using clay mineral based detergent additives and copolymers comprising these monomer units -Combination do not include, are superior.
  • the N-vinylpyrrolidone copolymers can be present either with regular or irregularly alternating structural units (for example -ABABA or -AAABBABBB-), as well as block copolymers (for example 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.
  • an N-vinylpyrrolidone copolymer may comprise at least 20, preferably at least 30 monomer units.
  • an N-vinylpyrrolidone copolymer for example, at least 5, preferably at least 15 cationic, in particular in each case at least one quaternized nitrogen atom having monomer units.
  • the detergent additive based on the total weight of the at least one clay mineral, more than 0.001 wt .-%, more preferably more than 0.01 wt .-%, particularly preferably more than 0.1 wt .-% N-vinylpyrrolidone copolymer has.
  • the detergent additive based on the total weight of the at least one clay mineral, more than 0.001 wt .-%, more preferably more than 0.01 wt .-%, particularly preferably more than 0.1 wt .-% N-vinylpyrrolidone copolymer has.
  • With an addition of more than 0.3 wt .-% usually no further improvement is observed, so that a higher proportion of N-vinylpyrrolidone copolymer from an economic point of view is no longer or at most limited useful.
  • an addition of up to 0.06 wt .-% is usually sufficient to obtain the desired washing properties.
  • Detergent additives which give a very good soft feel may, for example, have a total weight of cationic monomer units of the N-vinylpyrollidone copolymer (s), for example up to 0.15% by weight, preferably up to 0.1% by weight, preferably up to 0.09% by weight, more preferably up to 0.05% by weight, even more preferably up to 0.03% by weight, in particular 0.001 to 0.09 wt .-%, based on the total weight of the at least one clay mineral.
  • a total weight of cationic monomer units of the N-vinylpyrollidone copolymer (s) for example up to 0.15% by weight, preferably up to 0.1% by weight, preferably up to 0.09% by weight, more preferably up to 0.05% by weight, even more preferably up to 0.03% by weight, in particular 0.001 to 0.09 wt .-%, based on the total weight of the at least one clay mineral.
  • the detergent additive based on the total weight of the at least one clay mineral, more than 0.001 wt .-%, preferably more than 0.01 wt .-% of copolymer comprising N-vinylpyrrolidone monomer units and quaternized N-vinylimidazole monomer units containing and / or more than 0.001% by weight, preferably more than 0.01% by weight of copolymer comprising N-vinylpyrrolidone monomer units and quaternized N, N-dialkylaminoalkylmethacrylates.
  • the detergent additive may further comprise at least one surfactant, which surfactant may be selected based on the general knowledge and teaching of the present invention.
  • 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 poorly soluble or non-soluble 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.
  • Clay minerals used may be clay minerals known to the person skilled in the art. Particularly advantageous washing results, in particular a particularly good softness could be obtained when the 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 at least one surfactant comprises at least one 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 at least one N-vinylpyrrolidone copolymer comprises only N-vinylpyrrolidone monomer units and cationic monomer units, and optionally N-vinylcaprolactam monomer units.
  • the at least one copolymer contains, in addition to the N-vinylpyrrolidone monomer units and cationic monomer units, one or more other monomer units. These one or more other monomer units may be contained in a proportion of 0.1 to 20 mol% in the N-vinylpyrrolidone copolymer.
  • Suitable monomers which are present as monomer units after polymerization are, for example, vinylimidazole, vinyl oxazolidone, vinyl propionate, vinyl acetate, N, N-dialkylaminoalkyl (meth) acrylates, methyl and / or ethyl (meth) acrylate and in particular monomers which, after polymerization Monomer units give the cationic, for example, at least one quaternized nitrogen atom having monomer unit in uncharged form, for example in not correspond to quaternized form, that is, for example, N-vinylimidazole or one of the respective cationic, at least one quaternized nitrogen atom having monomer unit by elimination of a positive alkyl group and the corresponding counter anion derived N, N-dialkylaminoalkyl (meth) acrylate.
  • a copolymer may be composed of at least two different monomer units, but optionally it may be composed of any number of different monomer units, for example, two to four monomer units.
  • the N-vinylpyrrolidone copolymer generally has a content of N-vinylpyrrolidone monomer units of about 1 to 99 mol%, preferably 5 to 90 mol%, preferably 35 to 85 mol%.
  • the at least one N-vinylpyrrolidone copolymer may contain at least about 5 mol%, preferably at least 10 mol%, more preferably at least 20 mol% of cationic, monomeric units having at least one quaternized nitrogen atom, more preferably at least 30 mol%, in particular 5 to 40 mol%.
  • the improvement of the softening surprisingly increases with increasing content or proportion of cationic monomer units in the at least one N-vinylpyrrolidone copolymer.
  • the N-vinylpyrrolidone copolymer has a content of cationic monomer units of not more than about 96 mol%, preferably not more than 80 mol%, more preferably not more than 45 mol%.
  • Detergent additives in which an extremely good softening has been achieved may comprise, for example, at least one N-vinylpyrrolidone copolymer in which the total weight cationic monomer units from 9 to 45% by weight, preferably from 28 to 38% by weight, preferably from 32 to 34% by weight, based on the total weight of monomer units of the at least one N-vinylpyrrolidone copolymer, wherein the weight the counterions of the cationic monomer units are not taken into account.
  • detergent additives in which an extremely good softening has been achieved comprise at least one N-vinylpyrrolidone copolymer, wherein the total weight of N-vinylpyrrolidone monomer units from 39 to 80 wt .-%, preferably from 62 to 72 wt .-% , preferably from 66 to 68 wt .-%, based on the total weight of monomer units of the at least one N-vinylpyrrolidone copolymer, wherein the weight of the counterions of the cationic monomer units is not taken into account.
  • detergent additives may comprise at least one N-vinylpyrrolidone copolymer wherein the total weight of N-vinylpyrrolidone monomer units is preferably from 39 to 80% by weight and the total weight of cationic monomer units is preferably from 9 to 45% by weight, respectively on the total weight of monomer units of the at least one N-vinylpyrrolidone copolymer, wherein the weight of the counterions of the cationic monomer units is not taken into account.
  • the N-vinylpyrrolidone copolymer has a weight ratio of the total weight of N-vinylpyrrolidone monomer units contained in the N-vinylpyrrolidone copolymer to the total weight of cationic, for example at least one quaternized, nitrogen contained in the N-vinylpyrrolidone copolymer having monomer units between about 90:10 and 10:90, in particular between about 70:30 and 30:70, wherein the weight of counterions of the cationic monomer units is not taken into account.
  • aqueous fluids in particular aqueous solutions (for example 10 to 30% by weight, preferably 18 to 22% by weight, preferably about 20% by weight, based on the total weight of the aqueous Fluids) of N-vinylpyrrolidone copolymers.
  • Nonlimiting N-vinylpyrrolidone copolymers may have a weight ratio of the total weight of N-vinylpyrrolidone monomer units contained in the N-vinylpyrrolidone copolymer to the total weight of cationic monomer units, especially dimethylaminomethylmethacrylate quaternized with an alkyl group such as an ethyl group.
  • cationic monomer units especially dimethylaminomethylmethacrylate quaternized with an alkyl group such as an ethyl group.
  • N-vinylpyrrolidone copolymers may have a weight ratio of the total weight of other comonomer units contained in the N-vinylpyrrolidone copolymer, especially N-vinylcaprolactam monomer units, to the total weight of N-vinylpyrrolidone monomer units contained in the N-vinylpyrrolidone copolymer Total weight of cationic monomer units contained in the N-vinylpyrrolidone copolymer, especially N-vinylimidazole monomer units quaternized with a methyl group (excluding the weight of the counterions) in the range of (45 to 55) :( 35 to 45) :( 5 to 15 ) exhibit.
  • the N-vinylpyrrolidone copolymers preferably have a molecular weight in the range of 100,000 to 1,000,000 g / mol. Preferred areas for the molecular weight are 300,000 - 1,000,000 g / mol and 500,000 to 1,000,000 g / mol.
  • the detergent additive contains at least one carrageenan.
  • the carrageenan both taken alone and in combination with the clay mineral, the surfactant and / or the N-vinylpyrrolidone copolymer, further improves the softness.
  • 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 -Carrageenan are composed of the dimer carrabiose in which ⁇ -D-galactose is 1,4-glycosidically linked 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 varies between 25 and 30%.
  • the -Carrageenan is additionally the hydroxy group at the C-2 of Anhydrogalactose 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 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.
  • more than 0.1 wt .-% usually no further improvement is observed, so that a higher proportion of carrageenan from an economic point of view no longer or at best makes limited sense. In most cases an addition of up to 0.06 wt .-% is sufficient to obtain the desired properties.
  • 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
  • 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. How to effect stored calcium ions 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 reference cited therein Tributh & Lagaly (1986) "Processing and Identification of Soil and Deposit Sounds", GIT horrz. Lab 30: 524 and 771 , stated.
  • the above preferred particle sizes of the clay mineral according to an alternative aspect of the present invention are also independent of the use of the clay mineral in a detergent additive in combination with the N-vinylpyrrolidone 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 + , in particular of Na + , is formed.
  • CEC cation exchange capacity
  • the detergent additive in particular a detergent additive which is used as additive to detergent formulations or for the preparation of detergent formulations, preferably contains at least 80% by weight, preferably at least 85% by weight of clay mineral, such as bentonite, based on the total weight of detergent additive.
  • clay mineral such as Bentonite
  • the high proportion of clay mineral, such as Bentonite reduces the cost of the detergent additive compared to the surfactant or other polymeric additives.
  • no chemical classifications of the product are required at low concentrations of surfactant and polymer or copolymer. This results in lower costs for storage, transport and later handling of the detergent additive.
  • the at least one 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 preferably contains more than 0.001% by weight, more preferably more than 0.01% by weight, particularly preferably more than 0.01% by weight, of fatty alcohol ethoxylate and / or based on the total weight of the at least one clay mineral polyethylene glycol ethers.
  • more than 0.1 wt .-% usually no further improvement is observed, so that a higher proportion of fatty alcohol ethoxylate and / or polyethylene glycol ether from 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 total weight of the at least one clay mineral, more than 0.05 wt .-%, preferably more than 0.5 wt .-%, more preferably more than 1 wt .-% water glass.
  • the weight ratio of N-vinylpyrrolidone copolymer comprising N-vinylpyrrolidone monomer units and cationic monomer units to water glass can be from 1:10 to 1:40, preferably from 1:15 to 1:25.
  • 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 flocs of charged polymers and oppositely charged clay fins, which on the one hand dissolve worse and on the other hand would therefore 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 according to the invention may also be present in liquid form or in the form of powder or shaped articles, such as, for example, tablets or spheres, or in combinations thereof.
  • 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 detergent additive can also i.a. oxidizing substances, complexing substances, for example gallic soap, dyes, in particular UV-active dyes, fragrances, antibacterial substances, antiviral substances, fungicides, bleaching components, in particular sodium perborate tetrahydrate and tetraacetylethylenediamine, sodium alkylbenzenesulphonates, in particular having a straight-chain alkyl group, ethoxylated fatty alcohols, soaps, Zeolites, sodium carbonate, sodium silicate, carboxymethyl cellulose, optical brighteners, sodium sulfate, enzymes, e.g. protease, etc.
  • complexing substances for example gallic soap, dyes, in particular UV-active dyes, fragrances, antibacterial substances, antiviral substances, fungicides, bleaching components, in particular sodium perborate tetrahydrate and tetraacetylethylenediamine, sodium alkylbenzenesulphonates, in particular having a straight-chain
  • the proportion of quaternized N-vinylimidazole monomer units in the copolymer may be between 0 and 45 mol%.
  • the cationic monomer units may preferably comprise cationic monomer units each having at least one quaternized nitrogen atom. Preferred proportions of the N-vinylpyrrolidone monomer units, of the cationic monomer units and of any other comonomer units present as well as further preferred embodiments of the N-vinylpyrrolidone copolymer have already been described above.
  • 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.
  • a surfactant in particular a nonionic surfactant
  • This may be provided together with the N-vinylpyrollidone copolymer and the clay mineral and mixed therewith in the manner known to those skilled in the art.
  • the surfactant and / or N-vinylpyrollidone 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 N-vinylpyrollidone 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 N-vinylpyrollidone 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 N-vinylpyrollidone 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 Kornband Scheme between 0.2 and 1.2 mm, 0.4 and 1.4 mm, 1.0 and 2.0 mm.
  • the production of moldings, such as compacts 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 (eg carbonates and citric acid), which facilitate the dissolution of the moldings.
  • the method of making the detergent additive comprises adding carrageenan as described herein. This may be added in a separate aqueous solution or mixed in a common solution with surfactant and N-vinylpyrollidone 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, eg 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. It is possible to use all conventional washing, cleaning and care agents, such as, for example, laundry detergents, dishwashing and dishwashing detergents, stain removers, bleaching agents, cleaning and care products for e.g. Motor vehicles, ships and aircraft, as well as for surface treatment or impregnation.
  • washing, cleaning and care agents such as, for example, laundry detergents, dishwashing and dishwashing detergents, stain removers, bleaching agents, cleaning and care products for e.g. Motor vehicles, ships and aircraft, as well as for surface treatment or impregnation.
  • Another aspect of the invention relates to the use of the inventive detergent additive for improving the soft feel and / or the color retention of textile products, in particular of fabrics and / or textiles (textile materials), wherein the textile products preferably made of a material selected from the group of Cotton, silk, wool, in particular sheep wool, polyester, polyacrylonitrile, Polyamide, Elastan ® , nylon ® , viscose, especially cotton-containing fabrics, consist of or include this.
  • 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.
  • the percentages of clay relating to clay mineral refer to clay mineral which still has a residual moisture content of 10% by weight, the indication of the residual moisture being based on the weight of the clay mineral dried at 110 ° C. to constant weight.
  • 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 from 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%
  • Nessler's reagent (Merck, item No. 9028); Boric acid solution, 2%; Caustic soda, 32%; 0.1 N hydrochloric acid; NaCl solution, 0.1%; KCl solution, 0.1%
  • 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 Untergrundkomp .: No No No Yes No Measurement type: conc. conc. conc. conc. conc. conc.
  • Ionisationspuffer 0.1% KCl 0.1% NaCl 0.1% NaCl 0.1% KCl 0.1% KCl torch 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 - torch 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.
  • Luviquat ® Sensation (Polyquaternium-87) is a copolymer of N-vinylpyrrolidone monomer, N-vinyl imidazole monomer units and monomer units derived from diallyldimethylammonium chloride.
  • FIG. 1 shows the results reproduced in Table 5 from experiments on Weichgriffindex.
  • the granules 31 and 32 were each prepared as described above and washing experiments were carried out as described in the methods section with the respective granules as detergent additives.
  • a was Reference experiment carried out that is, a washing test in which only 90 g of test detergent was used per wash.
  • a comparative experiment was carried out "with 10% pure bentonite" in which Laundrosil ® DGA 212, that is, a standard compound for a 2in1 detergent formulation was used as a detergent additive in a washing test which was carried out as described above.
  • Laundrosil DGA 212 ® is available from Süd-Chemie AG, consisting of 100% of the bentonite, as described in Table 4, clay. 1
  • the two granules GR 31 and GR 32 show a very significant increase of the Weichgriffindexes compared to the reference experiment.
  • FIG. 2 shows a further comparison of washing tests.
  • a washing experiment was compared to granules GR31 as a detergent additive, which was carried out as described in the Methods section above, with a washing experiment using 90 g of the test detergent described above per wash (reference), as well as washing tests using "Laundrosil ® DGA 212" or EXM 1943 as a detergent additive, these washing tests were carried out as described in the method section above.
  • the results of the soft-grip test are summarized in Table 6.
  • Table 6 Results of soft-grip tests sample Soft grip index (%) Reference, without bentonite 19 DGA 212 43 EXM 1943 60 Granules GR 31 78
  • a use of the granules GR31 as a detergent additive in a washing test as described in the method section above also leads to a significantly higher softening effect than a use of the granules EXM 1943 as a detergent additive in such a washing test.
  • the granules EXM 1943 comprises both a clay mineral and a PVP / VA copolymer and was prepared according to the method described in US Pat WO 2008/025505 prepared in the section "Preparation of a granulate of the detergent additive" example.
  • Table 7 summarizes the results of soft-grip tests performed on granules 31 and granules 38.
  • the granules 38 were prepared as described above.
  • a test with pure bentonite and with the granules EX was described analogously to the granules 31 and 32 1943 performed.
  • the results are in FIG. 3 graphically reproduced.

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Claims (14)

  1. Additif pour détergent, en particulier pour améliorer la douceur au toucher de produits textiles, contenant au moins les composants suivants :
    a) au moins un minéral d'argile ; et
    b) au moins un copolymère de N-vinylpyrrolidone, ledit au moins un copolymère de N-vinylpyrrolidone comprenant des unités monomères de N-vinylpyrrolidone et des unités monomères cationiques, qui sont choisies dans le groupe constitué par les unités monomères de N-vinylimidazole quaternisé, les unités monomères de (méth)acrylate de N,N-dialkylaminoalkyle quaternisé et les unités monomères dérivées de sels de diallyldiméthylammonium.
  2. Additif pour détergent selon la revendication 1, le copolymère comprenant au moins une autre unité comonomère, qui ne porte pas de charge cationique.
  3. Additif pour détergent selon la revendication 2, ladite au moins une autre unité comonomère étant choisie parmi les unités monomères de N-vinylcaprolactame et les unités monomères de N-vinylimidazole, la proportion de ladite au moins une autre unité comonomère par rapport au copolymère étant de préférence située entre 0,1 et 75% en mole, de préférence entre 2 et 55% en mole.
  4. Additif pour détergent selon l'une quelconque des revendications précédentes, caractérisé en ce que le minéral d'argile est un minéral d'argile smectique.
  5. Additif pour détergent selon l'une quelconque des revendications précédentes, caractérisé en ce que la proportion d'unités monomères de N-vinylpyrrolidone dans le copolymère est d'environ 1 à 99% en mole.
  6. Additif pour détergent selon l'une quelconque des revendications précédentes, caractérisé en ce que le minéral d'argile se trouve sous forme de particules, au moins 10% en poids, de préférence au moins 14% en poids, plus préférablement entre environ 10 et 50% en poids des particules, encore plus préférablement entre environ 10 et 30% en poids des particules présentant une grosseur de particule inférieure à environ 600 nm.
  7. Additif pour détergent selon l'une quelconque des revendications précédentes, caractérisé en ce qu'au moins 50% de la capacité d'échange cationique (CEC), de préférence au moins 60% et de manière particulièrement préférée au moins 80%, du minéral d'argile, en particulier la bentonite, sont formés par des cations monovalents.
  8. Additif pour détergent selon l'une quelconque des revendications précédentes, caractérisé en ce que l'additif pour détergent contient au moins 80% en poids, de préférence au moins 85% en poids de minéral d'argile, en particulier la bentonite, par rapport au poids total de l'additif pour détergent.
  9. Procédé pour la préparation de l'additif pour détergent, comprenant les étapes suivantes :
    a) mise à disposition d'au moins un minéral d'argile, en particulier d'au moins un minéral d'argile smectique ;
    b) mise à disposition d'au moins un copolymère de N-vinylpyrrolidone, ledit au moins un copolymère de N-vinylpyrrolidone comprenant des unités monomères de N-vinylpyrrolidone et des unités monomères cationiques, qui sont choisies dans le groupe constitué par les unités monomères de N-vinylimidazole quaternisé, les unités monomères de (méth)acrylate de N,N-dialkylaminoalkyle quaternisé et les unités monomères dérivées de sels de diallyldiméthylammonium et
    c) mélange dudit au moins un copolymère de N-vinylpyrrolidone, qui comprend des unités monomères de N-vinylpyrrolidone et des unités monomères cationiques, et dudit au moins un minéral d'argile.
  10. Procédé selon la revendication 9, caractérisé en ce qu'au moins un agent tensioactif, en particulier un agent tensioactif non ionique, est incorporé avant, en même temps que ou après l'étape c).
  11. Procédé selon l'une quelconque des revendications 9 ou 10, caractérisé en ce qu'on mélange d'abord ledit au moins un copolymère, qui comprend des unités monomères de N-vinylpyrrolidone et des unités monomères cationiques, et l'agent tensioactif, qui sont ensuite appliqués sur le minéral d'argile.
  12. Utilisation de l'additif pour détergent selon l'une quelconque des revendications 1 à 8 ou pouvant être obtenu selon l'une quelconque des revendications 9 à 11 comme composant d'une formulation de lavage, de nettoyage et/ou d'entretien et/ou pour la préparation d'une formulation de lavage, de nettoyage et/ou d'entretien.
  13. Utilisation d'un additif pour détergent pour améliorer la douceur au toucher de produits textiles, l'additif pour détergent comprenant
    a) au moins un minéral d'argile ; et
    b) au moins un copolymère de N-vinylpyrrolidone, ledit au moins un copolymère de N-vinylpyrrolidone comprenant des unités monomères de N-vinylpyrrolidone et des unités monomères cationiques, qui sont choisies dans le groupe constitué par les unités monomères de N-vinylimidazole quaternisé, les unités monomères de (méth)acrylate de N,N-dialkylaminoalkyle quaternisé et les unités monomères dérivées de sels de diallyldiméthylammonium.
  14. Utilisation selon la revendication 13 pour améliorer la douceur au toucher et/ou la conservation des couleurs de produits textiles, en particulier de tissus et/ou de textiles, les produits textiles étant de préférence constitués par, ou comprenant, un matériau choisi dans le groupe constitué par le coton, la soie, la laine, en particulier la laine de mouton, le polyester, le polyamide, l'élasthanne, le polyacrylonitrile, le nylon, la viscose.
EP09778811.1A 2008-10-02 2009-10-02 Additif pour détergent, à base de minéraux argileux, ainsi que son utilisation et des procédés pour sa préparation Not-in-force EP2340298B1 (fr)

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DE200810050360 DE102008050360A1 (de) 2008-10-02 2008-10-02 Waschmitteladditiv auf der Basis von Tonmineralien, sowie dessen Verwendung und Verfahren zu dessen Herstellung
PCT/EP2009/007088 WO2010037560A1 (fr) 2008-10-02 2009-10-02 Additif pour détergent, à base de minéraux argileux, ainsi que son utilisation et des procédés pour sa préparation

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EP2340298B1 true EP2340298B1 (fr) 2015-12-23

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EP (1) EP2340298B1 (fr)
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Publication number Priority date Publication date Assignee Title
ZA734721B (en) 1972-07-14 1974-03-27 Procter & Gamble Detergent compositions
EP0299575B1 (fr) 1987-07-14 1994-01-12 The Procter & Gamble Company Compositions détergentes
EP0313146B2 (fr) 1987-10-19 2001-09-05 The Procter & Gamble Company Compositions détergentes
JP4055544B2 (ja) * 2002-10-11 2008-03-05 ライオン株式会社 液体柔軟剤組成物
JP4589622B2 (ja) * 2003-12-25 2010-12-01 ライオン株式会社 液体柔軟剤組成物
EP1561802B1 (fr) 2004-02-03 2008-08-20 The Procter & Gamble Company Une composition destinée au lavage ou au traitement du linge
JP4566828B2 (ja) * 2005-06-09 2010-10-20 花王株式会社 柔軟剤組成物
DE102006016578A1 (de) * 2006-04-06 2007-10-11 Henkel Kgaa Feste, Textil-weichmachende Zusammensetzung mit einem wasserlöslichen Polymer
DE102006016575A1 (de) * 2006-04-06 2007-10-11 Henkel Kgaa Feste, textil- und/oder hautpflegende Zusammensetzung
EP1894993A1 (fr) 2006-08-28 2008-03-05 Süd-Chemie Ag Additif détergent au base de minéraux d'argile et des copolymers contenant du PVP
DE102006054436A1 (de) * 2006-11-16 2008-05-21 Henkel Kgaa Feste, textil- und/oder hautpflegende Zusammensetzung

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MX2011003408A (es) 2011-10-06
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EP2340298A1 (fr) 2011-07-06

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