EP1915438B1 - Produit de lavage protegeant les couleurs - Google Patents

Produit de lavage protegeant les couleurs Download PDF

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Publication number
EP1915438B1
EP1915438B1 EP06776638A EP06776638A EP1915438B1 EP 1915438 B1 EP1915438 B1 EP 1915438B1 EP 06776638 A EP06776638 A EP 06776638A EP 06776638 A EP06776638 A EP 06776638A EP 1915438 B1 EP1915438 B1 EP 1915438B1
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EP
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Prior art keywords
hal
triazine
equivalents
general formula
triazinyl
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EP06776638A
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German (de)
English (en)
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EP1915438A1 (fr
Inventor
Josef Penninger
Birgit GLÜSEN
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • 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
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions

Definitions

  • the present invention relates to the use of sulfonated triazine derivatives as dye transfer inhibiting agents in the washing of textiles and detergents containing such compounds.
  • detergents In addition to the ingredients indispensable for the washing process, such as surfactants and builders, detergents generally contain further constituents, which can be summarized by the term washing aids and which comprise such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents, bleach activators and enzymes.
  • auxiliaries also include substances which are intended to prevent dyed textiles from causing a changed color impression after washing. This color impression change washed, i. cleaner, textiles can be based on the one hand on the fact that dye components are removed by the washing process from the textile ("fading"), on the other hand may be deposited by differently colored textiles dyes on the textile ("discoloration").
  • the discoloration aspect may also play a role in undyed laundry items when washed together with colored laundry items.
  • detergents In order to avoid these undesirable side effects of removing dirt from textiles by treatment with usually surfactant-containing aqueous systems, detergents, especially when they are provided as so-called color or colored laundry detergents for colored textiles, contain active ingredients which prevent the detachment of dyes from the textile or At least the deposition of detached, located in the wash liquor to avoid dyes on textiles.
  • Many of the commonly used polymers have such a high affinity for dyes that they draw them more from the dyed fiber, resulting in increased color losses.
  • Triazine derivatives of general formula I are obtainable by reacting 2,4,6-trihalo-1,3,5-triazines with 1 or 2 equivalents of aminoaryl compound, wherein the aryl group of the aminoaryl compound is a 1 to 3-fold sulfonate-substituted benzene or Napthalene unit is.
  • Suitable aminoaryl compounds are, for example, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2-amino-1,3-benzenedisulfonic acid, 4-amino-1,3-benzenedisulfonic acid, 2-amino-1, 3,5-benzenetrisulfonic acid, 2-amino-1-naphthalenesulfonic acid, 3-amino-1-naphthalenesulfonic acid, 4-amino-1-naphthalenesulfonic acid, 2-amino-1,5-naphthalenedisulfonic acid, 7-amino-1,6-naphthalenedisulfonic acid, 2-amino-3,6,8-naphthalenetrisulfonic acid and 7-amino-1,3,6-naphthalenetrisulfonic acid, wherein their sulfonic acid groups are in salt form. It is also possible to use mixtures
  • Omega.-diaminoalkanes are particularly preferred, but if appropriate, oligo- or polyethyleneimines or -propylenimines may also be suitable; preferred oligo- or polyethyleneimines are those of the formula NH 2 -CH 2 CH 2 - (NH-CH 2 CH 2 -) n NH 2 , in which n is a number from 1 to 9, in particular 2 to 5, wherein also Mixtures of oligo- or polyethyleneimines of different degrees of oligo- or polymerization can be used so that n can take as an average value and non-integer values.
  • the diaminostilbene or diaminobiphenyl also additionally has at least 1, in particular 2 or sulfonic acid salt substituents, for example 4,4'-diamino-2,2'-biphenyldisulfonic acid disodium salt or 4,4'-diamino-2,2 ' -stilbendisulfonklare disodium salt.
  • substituents for example 4,4'-diamino-2,2'-biphenyldisulfonic acid disodium salt or 4,4'-diamino-2,2 ' -stilbendisulfonklad salt.
  • these are trans-configured stilbenes, but optionally also the cis-configured stilbenes and mixtures thereof can be used. It is also possible to use mixtures of diaminostilbenes with diamino-biphenylene.
  • An inventive composition preferably contains 0.05 wt .-% to 2 wt .-%, in particular 0.2 wt .-% to 1 wt .-%, dye transfer inhibiting compound of general formula II and / or III and optionally additionally triazine derivative of the general Formula I.
  • the "and / or" formulation is intended to make it clear that the joint use of compounds which correspond in each case to one of the abovementioned formulas is also possible.
  • the compounds of the general formula I, II or III contribute to both the above-mentioned aspects of color constancy, that is to say they reduce both discoloration and fading, although the effect of preventing staining, especially when washing white textiles, is most pronounced is.
  • Another object of the invention is therefore the use of a corresponding compound to avoid the change in the color impression of textiles in their Laundry in particular surfactant-containing aqueous solutions. By changing the color impression is by no means the difference between polluted and clean textile, but the difference between each clean textile before and after the washing process.
  • triazine derivatives of the general formulas II or III in which, however, in each case X represents a carbon chain interrupted by NH groups, to avoid the transfer of textile dyes of dyed textiles to undyed or differently colored textiles in their joint washing in in particular surfactant-containing aqueous solutions, or to avoid the change in the color impression of dyed textiles in their washing in particular surfactant-containing aqueous solutions, wherein the triazine derivative of general formula II is obtainable by reacting 2 equivalents of such compounds of formula I, the nor 1 or 2 halogens on the triazine radical, with 1 equivalent of oligo- or polyethyleneimine of the formula NH 2 -CH 2 CH 2 - (NH-CH 2 CH 2 -) n NH 2 , in which n is a number from 1 to 9, in particular 2 to 5, and wherein the triazine derivative of general formula III is obtainable by reaction ng of diaminostilbenes or diaminobiphenyl
  • an agent according to the invention may comprise a known dye transfer inhibitor, then preferably in amounts of from 0.1% by weight to 2% by weight, in particular 0.2% by weight 1 wt .-%, which in a preferred embodiment of the invention is a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer thereof.
  • Polyvinylpyrrolidone preferably has an average molecular weight in the range from 10 000 to 60 000, in particular in the range from 25 000 to 50 000, for use in compositions according to the invention.
  • those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 having an average molecular weight in the range of 5,000 to 50,000, especially 10,000 to 20,000 are preferred.
  • the detergents according to the invention which may be in the form of homogeneous solutions or suspensions, in particular in powdered solids, in densified particle form, can in principle contain, in addition to the active ingredient used according to the invention, all known ingredients customary in such agents.
  • the agents according to the invention may in particular be builders, surface-active surfactants, bleaches based on organic and / or inorganic peroxygen compounds, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, grayness inhibitors, foam regulators and colorants Contain fragrances.
  • compositions according to the invention may comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
  • Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Furthermore, corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety, as well as of alkylphenols having 5 to 12 C atoms in the alkyl radical.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alcohols with 7 EO, C 13 -C 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • agents for use in mechanical processes usually extremely low-foam compounds are used. These include preferably C 12 -C 18 -alkylpolyethylenglykol-polypropylene glycol ethers with in each case at to 8 mol ethylene oxide and propylene oxide units in the molecule.
  • low-foam nonionic surfactants such as, for example, C 12 -C 18 -alkylpolyethylene glycol-polybutylene glycol ethers having up to 8 mol of ethylene oxide and butylene oxide units in the molecule and also end-capped alkylpolyalkylene glycol mixed ethers.
  • hydroxyl-containing alkoxylated alcohols as described in the European patent application EP 0 300 305 are described, so-called Hydroxymischether.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x are used, in the R a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is a glycose unit having 5 or 6 carbon atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (IV) in which R 1 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (V), in the R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 5 is a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1 -C 4 alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group.
  • [Z] is also here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, Mannose or xylose received.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, Mannose or xylose received.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be used, for example, according to the teaching of the international patent application WO 95/07331 be transferred by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in the Japanese patent application JP 58/217598 are described or preferably according to the in the international patent application WO 90/13533 be prepared described methods.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called "spacer".
  • This spacer is usually a carbon stalk chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other.
  • Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water.
  • gemini surfactants not only such "dimer”, but also corresponding to "trimeric” surfactants understood.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE 43 21 022 or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates according to the German patent application DE 195 03 061 , End-capped dimeric and trimeric mixed ethers according to the German patent application DE 195 13 391 They are characterized by their bi- and multi-functionality. So own the mentioned End disabilityver fieen surfactants good wetting properties and are low in foam, so that they are particularly suitable for use in machine washing or cleaning processes.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups.
  • surfactants of the sulfonate type are preferably C 9 -C 13 alkylbenzenesulfonates, Olefinsulfonate, that is, mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are, for example, from C 12 -C 18 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12 -C 18 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by ⁇ -sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 C -Atomen in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are prepared, into consideration.
  • ⁇ -sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids although sulfonated products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt. %, can be present.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with not more than 4 C atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester.
  • the methyl esters of ⁇ -sulfo fatty acids (MES), but also their saponified disalts are used.
  • Suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof, as in the preparation by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained.
  • alk (en) ylsulfate the alkali and in particular the sodium salts of sulfuric monoesters of C 12 -C 18 fatty alcohols for example, from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 10 -C 20 -oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) ylsulfates of said chain length which contain a synthetic, petrochemical-based straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and C 14 -C 15 -alkyl sulfates are particularly preferred.
  • 2,3-alkyl sulfates which, for example, according to the US patents US 3,234,258 or US 5 075 041 which can be obtained as commercial products of the Shell Oil Company under the name DAN® are suitable anionic surfactants.
  • sulfuric acid monoesters of straight-chain or branched C 7 -C 21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 -alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 - C 18 -fatty alcohols with 1 to 4 EO.
  • EO ethylene oxide
  • the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides).
  • sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate.
  • anionic surfactants are particularly soaps into consideration.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of Laürinklare, myristic acid, Palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Surfactants are present in detergents according to the invention in proportions of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight.
  • An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diene diphosphonic acid, polymeric hydroxy compounds such as dextrin and also polymeric (poly) -carboxylic acids, in particular the polycarboxylates of the European patent specification obtainable by oxidation of polysaccharides or dextrins EP 0 625 992 or the international patent application WO 92/18542 or the European patent specification EP
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, in each case based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of from 30,000 to 100,000.
  • Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50 wt .-%.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) -acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Such polymers can be prepared in particular by methods described in the German patent DE 42 21 381 and the German patent application DE 43 00 772 are generally described, and generally have a molecular weight between 1,000 and 200,000. Further preferred copolymers are those described in the German patent applications DE 43 03 320 and DE 44 17 734 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
  • the organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in paste-form or liquid, in particular water-containing, agents according to the invention.
  • Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • alkali metal silicates alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • Crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials.
  • preferred are the detergent grade crystalline sodium aluminosilicates, particularly zeolite A, P and optionally X, alone or in mixtures, for example in the form of a cocrystal of zeolites A and X (Vegoborid® AX, a commercial product of Condea Augusta SpA) , Amounts near the above upper limit are preferably used in solid, particulate agents.
  • suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
  • Their calcium binding capacity is usually in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O y are used 2x + 1 H 2 O, in which x, the so-called module, a number from 1.9 to 22, in particular 1.9 to 4 and y is a number from 0 to 33 and preferred values for x are 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in the European patent application EP 0 164 514 described.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both .beta.- and ⁇ -sodium (Na 2 Si 2 O 5 y H 2 O) are preferred, with beta-sodium disilicate being obtainable, for example, by the method described in the international patent application WO 91/08171 is described.
  • ⁇ -Sodium silicates with a modulus between 1.9 and 3.2 can according to Japanese Patent Applications JP 04/238 809 or JP 04/260 610 getting produced.
  • Crystalline sodium silicates with a modulus ranging from 1.9 to 3.5, as prepared by the methods of European patents EP 0 164 552 and or EP 0 294 753 are available are used in a further preferred embodiment of the invention means.
  • Crystalline layer-form silicates of formula (I) given above are sold by Clariant GmbH under the trade name Na-SKS, eg Na-SKS-1 (Na 2 Si 22 O 45 .H 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 ⁇ H 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 -xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 ⁇ H 2 O, makatite) , Of these, especially Na-SKS-5 ( ⁇ -Na 2 Si 2 O 5 ), Na-SKS-7 ( ⁇ -Na 2 Si 2 O 5 , Natrosilit), Na-SKS-9 (NaHSi 2 O 5 3H 2 O), Na
  • compositions according to the invention a granular compound of crystalline phyllosilicate and citrate, of crystalline phyllosilicate and of the abovementioned (co) polymeric polycarboxylic acid, as described, for example, in the German patent application DE 198 19 187 or from alkali metal silicate and alkali metal carbonate, as described for example in the international patent application WO 95/22592 or as it is commercially available, for example, under the name Nabion® 15.
  • Builder substances are preferably present in the compositions according to the invention in amounts of up to 75% by weight, in particular 5% by weight to 50.
  • suitable peroxygen compounds are in particular organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide donating inorganic salts, which include perborate, percarbonate, persilicate and / or persulfate Caroat belong into consideration.
  • organic peracids or pers acid salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide donating inorganic salts, which include perborate, percarbonate, persilicate and / or persulfate Caroat belong into consideration.
  • solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle.
  • an agent according to the invention contains peroxygen compounds, they are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight.
  • bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and from the German patent applications DE
  • Such bleach activators can, in particular in the presence of the abovementioned hydrogen peroxide-producing bleach, in the usual amount range, preferably in amounts of from 0.5 wt .-% to 10 wt .-%, in particular 1 wt .-% to 8 wt .-%, based on However, total agent, be included, missing when using percarboxylic acid as the sole bleach, preferably completely.
  • Suitable enzymes which can be used in the compositions are those from the class of amylases, proteases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus derived enzymatic agents.
  • the enzymes can be as described, for example, in the European patent EP 0 564 476 or in the international patent application WO 94/23005 be adsorbed to carriers and / or embedded in encapsulating substances to protect against premature inactivation. They are preferably present in the detergents or cleaners according to the invention in amounts of up to 5% by weight, in particular from 0.2% by weight to 4% by weight. If the agent of the invention contains protease, it preferably has a proteolytic activity in the range of about 100 PE / g to about 10 000 PE / g, in particular 300 PE / g to 8000 PE / g.
  • organic solvents which can be used in addition to water include alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C -Atomen, in particular ethylene glycol and propylene glycol, and mixtures thereof and derived from the classes of compounds mentioned ether.
  • Such water-miscible solvents are preferably present in the compositions according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.
  • the compositions according to the invention can contain system- and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid. but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators are present in the compositions according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
  • Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • starch derivatives can be used, for example aldehyde starches.
  • cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, Hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of 0.1 to 5 wt .-%, based on the means used.
  • Detergents according to the invention may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners, although they are preferably free of optical brighteners for use as color detergents.
  • Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl).
  • Mixtures of the aforementioned optical brightener can be used.
  • foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.
  • compositions according to the invention presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, enzymes and possibly other thermally sensitive ingredients such as, for example, bleaching agents optionally being added separately later.
  • Agent with increased bulk density in particular in the range of 650 g / l to 950 g / l, is one from the European patent EP 0 486 592 known method comprising an extrusion step is preferred.
  • Another preferred preparation by means of a granulation process is in the European patent specification EP 0 642 576 described.
  • compositions according to the invention in tablet form, which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers
  • the procedure is preferably such that all constituents - if appropriate one per layer - in one Mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, pressed with compressive forces in the range of about 50 to 100 kN, preferably at 60 to 70 kN.
  • a tablet produced in this way has a weight of 10 g to 50 g, in particular 15 g up to 40 g.
  • the spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm.
  • the size of rectangular or cuboid-shaped tablets, which are introduced predominantly via the metering device, for example the dishwasher, is dependent on the geometry and the volume of this metering device.
  • Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or 24x38 mm.
  • Liquid or pasty compositions according to the invention in the form of customary solvent-containing solutions are generally prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
  • Cyanuric chloride (8.26 g, 0.044 mol) suspended in a mixture of ice and acetone (50 ml) was added at 0 ° C to a stirred aqueous solution of 4-aminonaphthalene-1-sulfonic acid (10.1 g, 0.044 mol ). The mixture was stirred at pH 4.5 to 5 (adjusted with sodium carbonate) and 0 to 5 ° C for 5 hours, then heated to 20 ° C within 1 hour. Seventy-five percent of ethylenediamine (1.78 g, 0.022 mol) was added and the mixture was stirred for 16 hours at 30 ° C and pH 8.5 (adjusted by NaOH). Phosphate buffer mixture (pH 6.5) and then acetone (1.5 L) were added. The precipitated colorless solid was separated (yield 10.9 g, 53.8% purity).
  • Cyanuric chloride (3.24 g, 0.018 mol) suspended in a mixture of ice and acetone (50 ml) was added at 0 ° C to a stirred aqueous solution of 2-aminonaphthalene-3,6,8-trisulfonic acid (66.5 percent, 10 g, 0.017 mol). The mixture was stirred at pH 5 to 5.5 (adjusted with sodium carbonate) and 0 to 5 ° C for 5 hours, then heated to 20 ° C within 1 hour. Seventy-five percent of ethylenediamine (0.70 g, 0.009 mol) was added and the mixture was stirred for 18 hours at 30 ° C and pH 8 to 8.5 (adjusted by NaOH). Phosphate buffer mixture (pH 6.5) and then acetone were added. The precipitated colorless solid was separated (yield 4.14 g, 51% purity).

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Claims (10)

  1. Procédé pour le lavage de textiles colorés dans des solutions aqueuses contenant un ou plusieurs agents tensioactifs, caractérisé en ce qu'on met en oeuvre une solution aqueuse contenant un ou plusieurs agents tensioactifs, qui contient un dérivé de triazine répondant aux formules générales

            T(NH-Ar(SO3Na)a)bHalc     (I)

            X(NH-T(NH-Ar(SO3Na)a)eHalf)2     (II)

            X(NH-T(NH-Ar(SO3Na)d-NH-T(NH-Ar(SO3Na)a)Hal)Hal)2     (III)

    dans lesquelles
    T représente un résidu de 1,3,5-triazinyle ;
    Ar représente un groupement naphtalène ou benzène ;
    X représente une chaîne carbonée contenant de 1 à 20, en particulier de de 2 à 12 atomes de carbone, linéaire ou ramifiée, facultativement interrompue par des groupes NH ou un groupement stilbène ou biphényle facultativement substitué une ou plusieurs fois avec un groupe -SO3Na ;
    Hal représente un atome de chlore, un atome de brome ou un atome d'iode ;
    a et d sont égaux, indépendamment l'un de l'autre, à 1, 2 ou 3 ;
    b est égal à 1 et c est égal à 2 ou bien b est égal à 2 et c est égal à 1 ;
    e est égal à 1 et f est égal à 1 ou bien e est égal à 2 et f est égal à 0 ;
    et les substituants -NH- de même que -Hal- se trouvent aux positions 2, 4 et 6 du noyau triazinyle.
  2. Agent de lavage contenant un inhibiteur du transfert des couleurs sous la forme d'un dérivé de triazine répondant à la formule générale II

            X(NH-T(NH-Ar(SO3Na)a)eHalf)2     (II)

    dans laquelle
    T représente un résidu de 1,3,5-triazinyle ;
    Ar représente un groupement naphtalène ou benzène ;
    X représente une chaîne carbonée interrompue par des groupes NH ;
    Hal représente un atome de chlore, un atome de brome ou un atome d'iode ;
    a est égal à 1, 2 ou 3 ;
    e est égal à 1 et f est égal à 1 ou bien e est égal à 2 et f est égal à 0 ;
    et les substituants -NH- de même que -Hal- se trouvent aux positions 2, 4 et 6 du noyau triazinyle, à côté de composants habituels compatibles avec ce constituant, caractérisé en ce que le dérivé de triazine répondant à la formule générale II peut être obtenu par mise en réaction de 2 équivalents des composés répondant à la formule I, qui portent encore 1 ou 2 atomes d'halogène sur le résidu de triazine, avec 1 équivalent d'oligoéthylèneimine respectivement de polyéthylèneimine répondant à la formule NH2-CH2CH2-(NH-CH2CH2)nNH2, dans laquelle n représente un nombre de 1 à 9, en particulier de 2 à 5.
  3. Agent selon la revendication 2, caractérisé en ce que le diaminostilbène ou le diaminobiphényle présente également en outre au moins 1, en particulier 2 substituants de sel d'acide sulfonique.
  4. Agent de lavage contenant un inhibiteur du transfert des couleurs sous la forme d'un dérivé de triazine répondant à la formule générale III

            X(NH-T(NH-Ar(SO3Na)d-NH-T(NH-Ar(SO3Na)a)Hal)Hal)2     (III)

    dans laquelle
    T représente un résidu de 1,3,5-triazinyle ;
    Ar représente un groupement naphtalène ou benzène ;
    X représente une chaîne carbonée contenant de 1 à 20, en particulier de de 2 à 12 atomes de carbone, linéaire ou ramifiée, facultativement interrompue par des groupes NH ou un groupement stilbène ou biphényle facultativement substitué une ou plusieurs fois avec un groupe -SO3Na ;
    Hal représente un atome de chlore, un atome de brome ou un atome d'iode ;
    a et d sont égaux, indépendamment l'un de l'autre, à 1, 2 ou 3 ;
    et les substituants -NH- de même que -Hal- se trouvent aux positions 2, 4 et 6 du noyau triazinyle, à côté de composants habituels compatibles avec ce constituant, caractérisé en ce que le dérivé de triazine répondant à la formule générale III peut être obtenu par mise en réaction de diaminostilbènes ou de diaminobiphényles avec 2 équivalents de la 2,4,6-trihalogéno-1,3,5-triazine, par mise en réaction ultérieure avec 2 équivalents d'un composé de diaminoaryle, à nouveau par mise en réaction ultérieure avec 2 équivalents de la 2,4,6-trihalogéno-1,3,5-triazine et mise en réaction ultérieure avec 2 équivalents d'un composé d'aminoaryle.
  5. Agent selon l'une quelconque des revendications 2 à 4, caractérisé en ce qu'il contient de 0,1 % en poids à 2 % en poids, en particulier de 0,2 % en poids à 1 % en poids d'un dérivé de triazine inhibant le transfert des couleurs, répondant à la formule générale II et/ou III, et de manière facultative en outre un dérivé de triazine répondant à la formule générale I.
  6. Agent selon l'une quelconque des revendications 2 à 5, caractérisé en ce qu'il contient en outre un polymère de vinylpyrrolidone, de vinylimidazole, du N-oxyde de vinylpyridine ou un copolymère desdits polymères.
  7. Utilisation de dérivés de triazine répondant à la formule générale II

            X(NH-T(NH-Ar(SO3Na)a)eHalf)2     (II)

    dans laquelle
    T représente un résidu de 1,3,5-triazinyle ;
    Ar représente un groupement naphtalène ou benzène ;
    X représente une chaîne carbonée interrompue par des groupes NH ; Hal représente un atome de chlore, un atome de brome ou un atome d'iode ;
    a est égal à 1, 2 ou 3 ;
    e est égal à 1 et f est égal à 1 ou bien e est égal à 2 et f est égal à 0 ;
    et les substituants -NH- de même que -Hal- se trouvent aux positions 2, 4 et 6 du noyau triazinyle, pour éviter le transfert de colorants textiles de textiles colorés sur des textiles non colorés ou d'une autre couleur lors de leur lessive commune dans des solutions aqueuses en particulier contenant un ou plusieurs agents tensioactifs, caractérisée en ce que le dérivé de triazine répondant à la formule générale II peut être obtenu par mise en réaction de 2 équivalents des composés répondant à la formule I, qui portent encore 1 ou 2 atomes d'halogène sur le résidu de triazine, avec 1 équivalent d'oligoéthylèneimine respectivement de polyéthylèneimine répondant à la formule NH2-CH2CH2-(NH-CH2CH2)nNH2, dans laquelle n représente un nombre de 1 à 9, en particulier de 2 à 5.
  8. Utilisation de dérivés de triazine répondant à la formule générale III

            X(NH-T(NH-Ar(SO3Na)d-NH-T(NH-Ar(SO3Na)a)Hal)Hal)2     (III)

    dans laquelle
    T représente un résidu de 1,3,5-triazinyle ;
    Ar représente un groupement naphtalène ou benzène ;
    X représente une chaîne carbonée contenant de 1 à 20, en particulier de de 2 à 12 atomes de carbone, linéaire ou ramifiée, facultativement interrompue par des groupes NH ou un groupement stilbène ou biphényle facultativement substitué une ou plusieurs fois avec un groupe -SO3Na ;
    Hal représente un atome de chlore, un atome de brome ou un atome d'iode ;
    a et d sont égaux, indépendamment l'un de l'autre, à 1, 2 ou 3 ;
    et les substituants -NH- de même que -Hal- se trouvent aux positions 2, 4 et 6 du noyau triazinyle, pour éviter le transfert de colorants textiles de textiles colorés sur des textiles non colorés ou d'une autre couleur lors de leur lessive commune dans des solutions aqueuses en particulier contenant un ou plusieurs agents tensioactifs, caractérisée en ce que le dérivé de triazine répondant à la formule générale III peut être obtenu par mise en réaction de diaminostilbènes ou de diaminobiphényles avec 2 équivalents de la 2,4,6-trihalogéno-1,3,5-triazine, par mise en réaction ultérieure avec 2 équivalents d'un composé de diaminoaryle, à nouveau par mise en réaction ultérieure avec 2 équivalents de la 2,4,6-trihalogéno-1,3,5-triazine et mise en réaction ultérieure avec 2 équivalents d'un composé d'aminoaryle.
  9. Utilisation de dérivés de triazine répondant à la formule générale II

            X(NH-T(NH-Ar(SO3Na)a)eHalf)2     (II)

    dans laquelle
    T représente un résidu de 1,3,5-triazinyle ;
    Ar représente un groupement naphtalène ou benzène ;
    X représente une chaîne carbonée interrompue par des groupes NH ; Hal représente un atome de chlore, un atome de brome ou un atome d'iode ;
    a est égal à 1, 2 ou 3;
    e est égal à 1 et f est égal à 1 ou bien e est égal à 2 et f est égal à 0 ; et les substituants -NH- de même que -Hal- se trouvent aux positions 2, 4 et 6 du noyau triazinyle, pour éviter la modification de l'impression de couleur laissée par des textiles colorés lors de leur lessive dans des solutions aqueuses en particulier contenant un ou plusieurs agents tensioactifs, caractérisée en ce que le dérivé de triazine répondant à la formule générale II peut être obtenu par mise en réaction de 2 équivalents des composés répondant à la formule I, qui portent encore 1 ou 2 atomes d'halogène sur le résidu de triazine, avec 1 équivalent d'oligoéthylèneimine respectivement de polyéthylèneimine répondant à la formule NH2-CH2CH2-(NH-CH2CH2)nNH2, dans laquelle n représente un nombre de 1 à 9, en particulier de 2 à 5.
  10. Utilisation de dérivés de triazine répondant à la formule générale III

            X(NH-T(NH-Ar(SO3Na)d-NH-T(NH-Ar(SO3Na)a)Hal)Hal)2     (III)

    dans laquelle
    T représente un résidu de 1,3,5-triazinyle ;
    Ar représente un groupement naphtalène ou benzène ;
    X représente une chaîne carbonée contenant de 1 à 20, en particulier de de 2 à 12 atomes de carbone, linéaire ou ramifiée, facultativement interrompue par des groupes NH ou un groupement stilbène ou biphényle facultativement substitué une ou plusieurs fois avec un groupe -SO3Na ;
    Hal représente un atome de chlore, un atome de brome ou un atome d'iode ;
    a et d sont égaux, indépendamment l'un de l'autre, à 1, 2 ou 3 ;
    et les substituants -NH- de même que -Hal- se trouvent aux positions 2, 4 et 6 du noyau triazinyle, pour éviter la modification de l'impression de couleur laissée par des textiles colorés lors de leur lessive dans des solutions aqueuses en particulier contenant un ou plusieurs agents tensioactifs, caractérisée en ce que le dérivé de triazine répondant à la formule générale III peut être obtenu par mise en réaction de diaminostilbènes ou de diaminobiphényles avec 2 équivalents de la 2,4,6-trihalogéno-1,3,5-triazine, par mise en réaction ultérieure avec 2 équivalents d'un composé de diaminoaryle, à nouveau par mise en réaction ultérieure avec 2 équivalents de la 2,4,6-trihalogéno-1,3,5-triazine et mise en réaction ultérieure avec 2 équivalents d'un composé d'aminoaryle.
EP06776638A 2005-08-19 2006-08-05 Produit de lavage protegeant les couleurs Not-in-force EP1915438B1 (fr)

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DE102022200093A1 (de) 2022-01-06 2023-07-06 Henkel Ag & Co. Kgaa Farbschützende Waschmittel
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US8785362B2 (en) 2014-07-22
PL1915438T3 (pl) 2012-05-31
ES2377452T3 (es) 2012-03-27
US20080234167A1 (en) 2008-09-25
WO2007019981A1 (fr) 2007-02-22
US8263541B2 (en) 2012-09-11
EP1915438A1 (fr) 2008-04-30
US20120196785A1 (en) 2012-08-02
ATE538196T1 (de) 2012-01-15
JP2009504854A (ja) 2009-02-05
DE102005039580A1 (de) 2007-02-22

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