EP1685224B1 - Systeme adjuvant soluble - Google Patents

Systeme adjuvant soluble Download PDF

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Publication number
EP1685224B1
EP1685224B1 EP04765743.2A EP04765743A EP1685224B1 EP 1685224 B1 EP1685224 B1 EP 1685224B1 EP 04765743 A EP04765743 A EP 04765743A EP 1685224 B1 EP1685224 B1 EP 1685224B1
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EP
European Patent Office
Prior art keywords
alkyl
acid
composition according
ammonium compound
washing
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EP04765743.2A
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German (de)
English (en)
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EP1685224A1 (fr
Inventor
Rene-Andres Artiga Gonzalez
Heike Schirmer-Ditze
Kathrin Schnepp-Hentrich
Heinz-Jürgen VÖLKEL
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • 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
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions

Definitions

  • This invention relates to a substantially aluminosilicate-free, soluble builder system comprising the ingredients alkali carbonate, (co) polymeric polycarboxylate and cationic surfactant, and the use of such agents, as well as detergents and cleaners containing these agents.
  • Builders or builder systems perform a variety of tasks in detergents and cleaning products, which are subject to increasing change as a result of constant changes in the composition, the supply forms and, ultimately, the production of detergents. Up to about 60% by weight of builder substances can be present in modern detergents so that they undoubtedly rank among the most important classes of substances for the construction of detergents and cleaners.
  • builders Due to the existing variety of detergent systems, the tasks of the builders are varied and not fully definable. The usual main tasks, however, are well described. Worth mentioning here are above all the water softening, the reinforcement of the washing effect, a grayness inhibition and the dirt dispersion.
  • builders should generally contribute to the alkalinity necessary for the washing process, show a high absorption capacity for surfactants, improve the effectiveness of the surfactants, make positive contributions to the properties of the solid products, for example in powder form, and thus have a structuring effect or also reduce the dust problem. These different requirements can usually not or only very inadequately meet with only one builder component alone, so that must be used as a rule to a system of builders and co-builders.
  • a zeolite-free composition which comprises 5 to 40% by weight of surfactant, 30 to 70% by weight of alkali carbonate, 1 to 30% by weight of complexing agents, preferably citrate and 0.05 to 15% by weight of a deposit inhibitor for calcium carbonate contains.
  • This anti-deposition agent is either a phosphate, a phosphonic acid or a polymeric carboxylate.
  • Extruded detergents or cleaning agents having bulk densities above 600 g / l which contain anionic and optionally nonionic surfactants and water-soluble builders such as sodium carbonate and amorphous sodium silicate in the mass that can be partially or completely dispensed with zeolite, without it in the Extrusion to procedural problems in the production of these funds comes.
  • a phosphate- and aluminosilicate-free agent which, in addition to surfactants and polyethylene glycol, contains a builder system based on carbonate, sulfate, silicate and polycarboxylate. Advantages of this agent are the price and environmental performance of the builder system. Preferred embodiments have a ratio of sodium carbonate to sodium sulfate of 1: 1 to 1: 3.
  • a zeolite-free builder system which consists of alkali silicate, alkali carbonate, polymeric polycarboxylate having a molecular weight of less than 10,000 g / mol, phosphonate and an acidic component.
  • This soluble builder system is dosed low, ie less than 40% by weight of the detergent is claimed by this builder system and the alkali product of this agent is in the range of 7.0 to 11.4.
  • this soluble builder system has advantages especially in residue behavior.
  • the present invention therefore relates to detergents or cleaners containing less than 5% by weight of aluminosilicate comprising soluble builder systems which contain the constituents a) alkali carbonate in amounts of 50-90% by weight, b) (co) polymeric polycarboxylate, preferably having a molecular weight of less than 10000 g / mol and / or copolymeric polycarboxylate, preferably having a molecular weight in the range of 20,000 to 70,000 g / mol in amounts of 5 to 20% by weight, and c) cationic surfactant in amounts of 1 to 4% by weight %, wherein the statement wt .-% in a) - c) in each case based on the entire builder system.
  • the alkali carbonates used in the builder system are preferably sodium and / or potassium carbonate, with the use of sodium carbonate in particular being preferred.
  • the alkali metal carbonate in amounts of from 50 to 90 wt .-%, preferably from 50 to 75 wt .-%, based on the total builder system, in the builder system. The advantage of these amounts is to be seen in view of the necessary alkalinity of the washing and / or cleaning agent or the wash liquor, in which the agent is advantageously used.
  • the (co) polymeric polycarboxylates are preferably homopolymers or copolymers which contain acrylic acid and / or maleic acid units.
  • particularly preferably homopolymers are used in combination used with copolymers, in which case polyacrylates are again preferred.
  • the polyacrylates are used in the form of sodium salts.
  • polyacrylates which preferably have a molecular weight of from 3,000 to 8,000 and more preferably from 4,000 to 5,000 g / mol have proven to be particularly suitable according to the invention.
  • the molecular weights indicated in this specification for polymeric polycarboxylates are weight average molecular weights M w, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector has been. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally higher than the molecular weights specified in this document.
  • the copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid, which have a molecular weight between 20 000 and 70 000 g / mol.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid, have proved to be particularly suitable.
  • the polymers may also allylsulfonic acids, such as in the EP-B-727 448 Allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
  • biodegradable polymers of more than two different monomer units for example, those according to the DE-A-43 00 772 as monomers, salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to the DE-C-42 21 381 as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • Further preferred copolymers are those described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • both these copolymers and the polyacrylates essential to the invention are used in the process, wherein the ratio of the polyacrylate to the acrylic acid-maleic acid copolymer in the range 2: 1 to 1: 20, preferably 1: 1 to 1:15 , lies.
  • the polymeric and / or copolymeric polycarboxylates are contained in the composition in amounts of from 5 to 20% by weight, preferably in amounts of from 5 to 15% by weight, based on the total builder system.
  • the advantage of these amounts is that in the application of the funds in the washing process the potential precipitation of poorly soluble alkaline earth metal salts on the laundry or on the heating elements of the washing machine is optimally counteracted, and that the color brilliance of the laundry is promoted because the polycarboxylates in these quantities in terms of Graying inhibition work optimally.
  • the agents contain, in addition to the polymeric polycarboxylate having a molecular weight of less than 10,000 g / mol, no further polymer of acrylic acid, in particular no copolymer of acrylic acid with maleic acid.
  • the agent may contain additional complexing agents.
  • the agent contains at least one additional complexing agent, preferably phosphonate and / or a citrate.
  • the phosphonates are in particular hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the HEDP (1- (hydroxyethylidene) bisphosphonate) is preferably used.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned. Such phosphonates are advantageously present in the compositions in amounts of from 0.05 to 2.0% by weight, preferably in amounts of from 0.1 to 1% by weight.
  • Citrates are the salts of citric acid. Particularly preferred according to the invention are the alkali metal citrates.
  • the citrates are advantageously present in the compositions in amounts of from 2.5 to 10% by weight, in particular in amounts of from 3.5 to 6.0% by weight.
  • citrates and / or phosphonates can be used as a substitute (or if necessary also in addition).
  • Tertiary amines in particular tertiary alkanolamines (amino alcohols), can also be used as complexing agents.
  • the alkanolamines have both amino and hydroxy and / or ether groups as functional groups.
  • Particularly preferred tertiary alkanolamines are triethanolamine and tetra-2-hydroxypropylethylenediamine (N, N, N ', N'-tetrakis- (2-hydroxypropyl) ethylenediamine).
  • alkali metal silicates are those having a module M 2 O: SiO 2 from the range of 1: 1.9 to 1: 3.3, where M is an alkali metal ion, in particular amorphous sodium silicates with a Modulus Na 2 O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are advantageously delay-delayed and have secondary washing properties.
  • the dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • amorphous is also understood to mean “X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections in X-ray diffraction experiments, as they are typical for crystalline substances, but at most one or a plurality of maxima of the scattered X-rays having a width of several degrees of the diffraction angle.
  • the silicate particles may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray-amorphous silicates which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in the German patent application DE-A-44 00 024 described.
  • densified / compacted amorphous silicates compounded amorphous silicates and overdried X-ray amorphous silicates.
  • Granular amorphous alkali metal silicates with bulk densities of at least 700 g / l can be, for example, according to one in the patent application WO 97/34977 described method, which starts from the spray drying and includes the compression of the spray-dried bead.
  • the spray-dried bead is ground and granulated simultaneously or subsequently with the addition of a liquid granulation aid, bulk densities of at least 700 g / l, up to above 1000 g / l - be set.
  • crystalline, layered sodium silicates of the general formula Na 2 Si x O 2 ⁇ + 1 .yH 2 O are used, where x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in the European patent application EP-A-0 164 514 described.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • both beta and delta sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • the total content of alkali silicate in the compositions is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.
  • these preferred amounts result in a substantially optimal contribution to the alkalinity of the detergent or the wash liquor, in which the agent according to the invention will preferably be received, and so enhance the overall cleaning power and contribute to the corrosion inhibition of certain washing machine components.
  • the agent contains an acidic component.
  • acidic component all suitable for use in detergents and cleaners acidic components are suitable.
  • carboxylic acids are advantageously polycarboxylic acids, such as in particular citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such an application is not objectionable for environmental reasons, and mixtures thereof, preferably.
  • these acids can be used anhydrous or in the form of their hydrates.
  • the usable mineral acids are in particular sulfuric acid, phosphoric acid, carbonic acid and hydrochloric acid, and their acid salts, to call.
  • Citric acid and / or sodium hydrogen sulfate are preferably used in the compositions according to the invention as acidic components, the sole use of citric acid being a particularly advantageous embodiment.
  • the content of the agent on the acidic component is preferably not more than 10.0% by weight; in particularly preferred embodiments it is in the range 0.1 and 5 wt .-%.
  • the acidic component can in principle be added at any stage of preparation of the agent.
  • the acid-acting component is admixed to the washing or cleaning agent subsequently, wherein the acidic component is present either alone or in the form of compounds with other, preferably neutral, detergent or cleaning agent ingredients.
  • the salts of the carboxylic acids preferably the salts of citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids and / or nitrilotriacetic acid and / or mixtures thereof may advantageously also be contained in the composition.
  • Cationic surfactant is contained in the composition in amounts of from 1 to 4% by weight, in particular in amounts of from 1 to 3% by weight, based on the total builder system.
  • cationic surfactant is effective at least within the builder system according to the invention as a builder component and synergistically with the other components of the builder system according to the invention, preferably with alkali carbonate and (co) polymeric polycarboxylate , cooperates.
  • the cationic surfactant present in the middle is a quaternary ammonium compound, preferably an alkylated quaternary ammonium compound.
  • this is a quaternary ammonium compound of the formula (I) (I) R 1 (R 2 ) (R 3 ) (R 4 ) N + X - , wherein R 1 , R 2 and R 3 are independently selected from C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl and - (C 2 H 4 O) x H, where x is 2 to 5, and wherein R4 is a C 8 -C 22 alkyl, and wherein X- is an anion, preferably a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof.
  • R 6 is a -CH 2 CH 2 OH group
  • R 7 is independently a C 1 -C 4 -alkyl, with m being 1 or 2
  • R 5 is a linear C 6 -C 14 -alkyl group is.
  • the builder systems according to the invention which contain quaternary ammonium compound of the formula (I) and / or (II) are advantageous because, when applied appropriately, they not only make textiles very soft and supple, they have a reduced drying time and are easier to iron and possibly even antistatic, but that also adjust some significant improvements in incrustation tendency, whiteness, graying or Sekundänrvaschrial.
  • incrustations on substrate surfaces.
  • textiles a significant reduction in incrustation, and significant improvement in the whiteness can be observed.
  • significant improvements in the graying and secondary washing effect are achieved.
  • the cationic surfactant is a C 8 -C 16 alkyl di (hydroxyethyl) methyl ammonium compound, preferably a C 12 -C 14 alkyl di (hydroxyethyl) methyl ammonium - Compound, and / or a C 8 -C 16 alkyl (hydroxyethyl) -dimethyl ammonium compound, preferably C 12 -C 14 alkyl (hydroxyethyl) dimethyl ammonium compound, is, in particular to the respective halides, methosulfates , Methophosphate or phosphates and mixtures of these.
  • a significant advantage of this latter embodiment is that such builder systems containing these particular cationic surfactants show excellent wash results, particularly with regard to incrustations.
  • the tendency to incrustation, in particular in the context of a machine laundry process, is when using such builder systems z. T. drastically reduced.
  • incrustations when using a detergent, which contains the soluble builder system according to the invention greatly reduced.
  • the whiteness is preferably improved significantly on these textiles.
  • cationic compound are extremely well predestined in the context of this invention, but other cationic surfactants can be used, but advantageously alkylated quaternary ammonium compounds, preferably with two hydrophobic groups, in particular via ester or Amidoitatien with a quaternized di- or Triethanolamine or an analogous compound are linked.
  • R9 is an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds
  • R 10 is H, OH or in particular O (CO) R 12
  • R 11 is, independently of R 10, H, OH or O (CO) R 13
  • R 12 and R 13 are each independently an aliphatic alkyl radical with 12 to 22 carbon atoms having 0, 1, 2 or 3 double bonds
  • a, b and c can each independently of one another have the value 1, 2 or 3
  • X- is a suitable anion, preferably a halide, methosulfate, Methophosphat- or phosphate ion and mixtures thereof
  • / or the formula (IV) is:
  • R 14 , R 15 and R 16 independently represent a C 1-4 alkyl, alkenyl or hydroxyalkyl group, R 17 and R 18 each independently selected a C 8-28 alkyl group having 0, 1, 2 or 3 double bonds and u is
  • Preferred representatives of this type are N-methyl-N (2-hydroxyethyl) -N, N- (ditallowcacyloxy-ethyl) ammonium methosulfate or N-methyl-N (2-hydroxyethyl) -N, N- (dipalmitoyl-ethyl) methosulfate.
  • Another object of the invention are detergents and / or cleaning agents which contain an agent according to the invention which has at least one of the aforementioned properties.
  • a washing and / or cleaning agent according to the invention is characterized in that it contains the soluble builder system according to the invention in amounts of from 25 to 45% by weight, based on the total washing or cleaning agent.
  • Aluminosilicates or zeolites are not included in the compositions or only in small amounts. If they are included, it is not because of their water softening effect or their carrier function. They can only be present if they are used as granulating aids or for powdering.
  • the washing and / or cleaning agents contain less than 3 wt .-%, more preferably less than 2 wt .-%, in a very advantageous
  • zeolites A P, X and Y are used as aluminosilicates.
  • mixtures of A, X, Y and / or P are also suitable.
  • zeolite P for example, zeolite MAP TM (commercial product from Crossfield) is particularly preferred.
  • zeolite MAP TM commercial product from Crossfield
  • co-crystallized sodium / potassium aluminum silicate of zeolite A and zeolite X which is commercially available as VEGOBOND AX TM (commercial product from Condea Augusta S.p.A.).
  • anionic, zwitterionic, amphoteric and / or nonionic surfactants in particular anionic surfactants, which are preferably present in the washing and / or cleaning agents according to the invention at least in amounts of 0.5% by weight.
  • anionic surfactants include in particular sulfonates and sulfates, but also soaps.
  • Cationic surfactants are included as part of the builder system according to the invention in detergents and cleaning agents, but not beyond.
  • surfactants of the sulfonate type are preferably C 9 -C 13 alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and Hydroxyalkansulfonaten and disulfonates, such as those from C 12 -C 18 monoolefins having 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 alpha sulfo fatty acids (ester sulfonates), z.
  • esters of alpha sulfo fatty acids esters of alpha sulfo fatty acids (ester sulfonates), z.
  • esters of alpha sulfo fatty acids esters of alpha sulfo fatty acids (ester sulfonates), z.
  • esters of alpha sulfo fatty acids esters of alpha sulfo fatty acids (ester sulfonates), z.
  • the alpha-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids prepared by alpha-sulfonation of methyl esters of fatty acids of plant and / or animal origin with 8 to 20 carbon atoms in the fatty acid molecule and subsequent neutralization to water-soluble monosalts be considered.
  • alpha-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow wherein also sulfonation of unsaturated fatty acids, such as oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt .-%, are present could be.
  • alpha-sulfofatty acid alkyl esters 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 the alpha - 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) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the 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, produced on a petrochemical basis 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 U.S. Patents 3,234,258 or 5,075,041 which are obtainable as commercial products of the Shell Oil Company under the name DAN TM are suitable anionic surfactants.
  • sulfuric acid monoesters of the 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 containing 1 to 4 EO are suitable. They are used in detergents due to their high foaming behavior only in relatively small amounts, for example in amounts of 1 to 5 wt .-%.
  • Preferred anionic surfactants are also 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 in themselves constitute nonionic surfactants (see description below).
  • 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). Particularly preferred are the sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate.
  • anionic surfactants are in particular soaps, preferably in amounts of from 0.2 to 5 wt .-% based on the total washing and / or cleaning agent into consideration.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, for.
  • coconut, palm kernel or tallow fatty acids, derived soap mixtures may be used.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts, as well 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.
  • the anionic surfactants are in the washing and / or cleaning agents according to the invention or in the process according to the invention preferably in amounts of 1 to 30 wt .-% and in particular in amounts of 5 to 25 wt .-% or used.
  • anionic surfactants In addition to the anionic surfactants and zwitterionic and amphoteric surfactants, especially nonionic surfactants are preferred.
  • 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 linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • 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 containing 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.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x, in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is a Glykoseiki with 5 or 6 C-atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number - the size to be determined analytically can also take broken values - between 1 and 10; preferably x is 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (V) in which R 19 is CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 20 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 (VI) in the R 21 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 22 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 23 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 radical is available.
  • Z is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • 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 converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettklaamide.
  • nonionic surfactants used either alone 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 having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as 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.
  • Preferred nonionic surfactants are C 12 -C 18 fatty acid methyl esters having an average of from 3 to 15 EO, in particular having an average of from 5 to 12 EO, while as binders - as described above - especially higher ethoxylated fatty acid methyl esters are advantageous.
  • C 12 -C 18 fatty acid methyl esters with 10 to 12 EO can be used both as surfactants and as binders.
  • 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.
  • gemini surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called “spacer”. This spacer is typically a carbon 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 is understood to mean not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or dimer alcohol bis- and trimeralcohol trissulfates and ether sulfates according to the German patent application DE-A-195 03 061 , End-capped dimeric and trimeric mixed ethers according to the German patent application DE-A-195 13 391 They are characterized by their bi- and multi-functionality. Thus, the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides as described in international patent applications WO 95/19953 .
  • WO-A-95119954 and WO95-A- / 19955 to be discribed.
  • the sodium perborate tetrahydrate, the sodium perborate monohydrate and the sodium percarbonate have particular significance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • sodium percarbonate is used as a bleaching agent.
  • the other detergent ingredients include graying inhibitors (soil carriers), foam inhibitors, bleach activators, optical brighteners, enzymes, fabric softening substances, dyes and fragrances and neutral salts such as sulfates and chlorides in the form of their sodium or potassium salts.
  • 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 acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from the German patent
  • Such bleach activators are in the usual amount range, preferably in amounts of 1 wt .-% to 10 wt .-%, in particular 2 wt .-% to 8 wt .-%, based on the total washing and / or cleaning agent.
  • 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 silica or bistearylethylenediamide.
  • mixtures of different foam inhibitors are used, for.
  • 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.
  • mixtures of paraffins and bistearylethylenediamides are preferred.
  • Suitable enzymes are, in particular, those from the class of the hydrolases, such as the proteases, lipases or lipolytic enzymes, amylases, cellulases or mixtures thereof. Oxireductases are also suitable.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and beta-glucosidases, which are also called cellobiases, or mixtures thereof used. Since the different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the cellulases can be used to set the desired activities.
  • the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.
  • the detergents and / or cleaning agents may contain further enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1 wt .-% sodium formate can be used.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • calcium salts magnesium salts also serve as stabilizers.
  • boron compounds for example, is particularly advantageous of boric acid, boric oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), of metaboric acid (HBO 2) and of pyroboric acid (tetraboric acid H 2 B 4 O 7 ).
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, 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.
  • soluble starch preparations and other than the above-mentioned starch products can be used, for. Degraded starch, aldehyde levels, etc. Also, polyvinylpyrrolidone is useful.
  • cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and polyvinylpyrrolidone, for example, in amounts of from 0.1 to 5% by weight, based on the washing composition. and / or cleaning agents used.
  • the detergents and / or cleaning agents may contain as optical brighteners derivatives of diaminostilbene disulfonic acid or its alkali metal salts.
  • brighteners of the type of substituted Diphenylstyryle be present, for.
  • the washing and / or cleaning agents according to the invention may have any bulk densities.
  • the bulk density is even above 800 g / l, with bulk densities above 850 g / l being particularly advantageous.
  • the advantages of the soluble builder system are particularly evident, since such compact detergents and / or cleaners make special demands on the ingredients in order to be readily dispersible.
  • the detergents and / or cleaners are preferably prepared by mixing together various particulate components which contain detergent and / or detergent ingredients and together form at least 60% by weight of the total detergent and / or cleaning agent.
  • the acid-acting component is added to the washing or cleaning agent subsequently, wherein the acidic component is admixed either alone or in the form of compounds with other, preferably neutral-reacting, washing or cleaning agent ingredients.
  • the particulate components can be prepared by spray drying, simple mixing or complex granulation processes, for example fluidized bed granulation. It is preferred in particular that at least one surfactant-containing component is produced by fluidized bed granulation.
  • aqueous preparations of the alkali silicate and of the alkali carbonate are sprayed together with other detergent and / or cleaning agent ingredients in a drying device, wherein granulation can take place simultaneously with the drying.
  • the drying device in which the aqueous preparation is sprayed, it may be any dry equipment.
  • the drying is carried out as spray drying in a drying tower.
  • the aqueous preparations in a known manner exposed to a drying gas stream in finely divided form.
  • the spray drying can also be carried out with superheated steam.
  • the mixtures are then subjected to a compaction step, with further ingredients are added to the detergents and / or cleaning agents only after the compaction step.
  • the compaction of the ingredients takes place in a preferred embodiment of the invention in a press agglomeration process.
  • the press agglomeration process to which the solid premix (dried base detergent) is subjected, can be realized in various apparatuses. Depending on the type of agglomerator used, different press agglomeration processes are distinguished. The four most common and in the present invention preferred press agglomeration processes are the extrusion, the roll pressing or compaction, the hole pressing (pelletizing) and tableting, so that in the present invention preferred press agglomeration processes extrusion, Walzenkompaktmaschines-, pelletizing or Tabletting operations are.
  • a further subject of the invention is the use of a substantially aluminosilicate-free soluble builder system according to the invention or the use of a washing and / or cleaning agent according to the invention for incrustation inhibition.
  • this use for incrustation inhibition relates to at least partially hydrophobic or hydrophobized substrate surfaces, preferably textiles, in particular in the context of a machine textile washing process.
  • hydrophobic substrate surfaces are meant all those surfaces which are substantially hydrophobic, for example, many plastic surfaces, thus many synthetic fiber fabric or tissues containing at least partially synthetic fibers.
  • Hydrophobicity is the constitutional property of a molecule or group of molecules to behave exophilically towards water, i. they show a tendency not to penetrate into water or a tendency to leave the aqueous phase.
  • the hydrophobicity is linked, for example, to aromatic groups or to hydrocarbon chains.
  • Hydrophobic substrate surfaces are thus substantially water-repellent.
  • These hydrophobic substrate surfaces are, in particular, hydrophobicized textiles or plastic surfaces, e.g. B. consisting of rubber, polycarbonate or polypropylene or similar materials.
  • Water-repellent textiles can be obtained, for example, by a water-repellent impregnation of textile substrates.
  • the water repellents used for this purpose coat the textile substrate, for example, with a thin layer, the z. B. has relatively many water-repellent, hydrophobic groups.
  • groups are for. B., inter alia, longer alkyl chains or siloxane groups.
  • Suitable hydrophobizing agents are, for example, silicones, alkylalkoxysilanes.
  • water repellents for substrate surfaces are, for example, paraffins, waxes and / or metal soaps, for example with additions of aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, silicones , Tin-organic. Compounds and glutaric dialdehyde.
  • Hard or soft substrates or substrate surfaces, for example textile fabric can be rendered hydrophobic with such or other hydrophobizing agents.
  • the hydrophobing can also be carried out with tetrachloroethane-soluble additives, as used in "chemical cleaning" use. It is also possible to use perfluorinated compounds for hydrophobing.
  • textiles can also be rendered hydrophobic by coating with plastics or rubbers.
  • textiles per se may be hydrophobic, depending on which fiber genera were predominantly used in their manufacture.
  • a further preferred embodiment is the use of a substantially aluminosilicate-free soluble builder system according to the invention or the use of a washing and / or cleaning agent according to the invention to increase the whiteness and / or color brilliance of the laundry, in particular of at least partially hydrophobic or hydrophobicized textiles the textile laundry.
  • the incrustation was determined after the 25th wash by incineration.
  • Table 1 the amount of ash in% by weight is given for each type of fabric.
  • Formulation B the textile washing of all four types of fabric consistently yielded incrustation advantages compared to the results obtained with the comparative detergent A, Formulation A, as manifested in the respective lower ash content.
  • the ashes reduction was particularly significant for hydrophobically-treated cotton (Noblesse) and viscose. For both types of fabric, an asher reduction of more than 40% was achieved.
  • the whiteness was preferably improved in the textiles when a detergent according to the invention (formulation B) and thus builder system was used.
  • This is documented in Table 2 by the consistently higher numerical values for the tristimulus value Y, which was determined in each case after the 25th wash.
  • Table 2 Graying ⁇ / u> Numerical values: Tristimulus value Y (International Electrotechnical Commission) WFK H-FT-B noblesse viscose Detergent formulation A 80.5 77.5 84 85.7 Detergent formulation b 82.2 83.3 85.7 87.5

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Claims (12)

  1. Agent de lavage ou de nettoyage, contenant moins de 5% en poids d'aluminosilicate par rapport à la totalité de l'agent de lavage ou de nettoyage, comprenant un système de builder, soluble, en des quantités de 25-50% en poids, par rapport à la totalité de l'agent de lavage ou de nettoyage, contenant les constituants
    a) carbonate alcalin en des quantités de 50-90 % en poids,
    b) polycarboxylate (co)polymère en des quantités de 5-20 % en poids,
    c) agent tensioactif cationique en des quantités de 1-4 % en poids,
    l'indication % en poids pour a)-c) se rapportant à chaque fois à la totalité du système de builder.
  2. Agent selon la revendication 1, caractérisé en ce que le système de builder contenu contient au moins un complexant supplémentaire, de préférence un phosphonate et/ou un citrate.
  3. Agent selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que le système de builder contenu contient un silicate alcalin, présentant de préférence un module M2O:SiO2 situé dans la plage de 1:1,9 à 1:3,3, M représentant un ion de métal alcalin.
  4. Agent selon la revendication 3, caractérisé en ce qu'il s'agit, pour le silicate alcalin, d'un silicate de sodium amorphe, présentant de préférence un module Na2O:SiO2 situé dans la plage de 1:2 à 1:2,8.
  5. Agent selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le système de builder contenu contient un composant à effet acide, de préférence un acide carboxylique, avantageusement des acides polycarboxyliques, en particulier l'acide citrique.
  6. Agent selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'il s'agit, pour l'agent tensioactif cationique, d'un composé d'ammonium quaternaire, de préférence un composé d'ammonium quaternaire alkylé.
  7. Agent selon la revendication 6, caractérisé en ce qu'il s'agit d'un composé d'ammonium quaternaire selon la formule (I),

            (I)     R1(R2)(R3)(R4)N+X-,

    R1, R2 et R3 étant choisis, indépendamment les uns des autres, parmi C1-C4-alkyle, C1-C4-hydroxyalkyle, benzyle et -(C2H4O)xH, x valant 2 à 5, et R4 représentant C8-C22-alkyle, et X- représentant un anion, de préférence un ion halogénure, méthosulfate, méthophosphate ou phosphate ainsi que leurs mélanges.
  8. Agent selon la revendication 6, caractérisé en ce qu'il s'agit d'un composé d'ammonium quaternaire selon la formule (II),

            (II)     R5R6 nR7 3-nN+X-

    R5 représentant C6-C24-alkyle ou C6-C24-alcényle, chaque R6 représentant indépendamment l'un de l'autre un groupe -(CnH2nO)xR8, n valant 1 à 4 et x valant 1 à 14, et R8 représentant méthyle, éthyle ou de préférence hydrogène, et chaque R7 représentant, indépendamment l'un de l'autre, un groupe C1-C12- alkyle ou C1-C12-alcényle, m valant 1 à 3, et X- représentant un anion, de préférence un ion halogénure, méthosulfate, méthophosphate ou phosphate ainsi que leurs mélanges.
  9. Agent selon la revendication 8, caractérisé en ce que R6 représente - CH2CH2OH, R7 représente, à chaque fois indépendamment, C1-C4-alkyle, m vaut 1 ou 2, et R5 représentant un groupe C6-C14-alkyle linéaire.
  10. Agent selon l'une quelconque des revendications 1 à 9, caractérisé en ce qu'il s'agit, pour l'agent tensioactif cationique, d'un composé de type C8-C16-alkyl-di(hydroxyéthyl)-méthylammonium, de préférence d'un composé de type C12-C14-alkyldi(hydroxyéthyl)-méthylammonium, et/ou d'un composé de type C8-C16-alkyl-(hydroxyéthyl)-diméthylammonium, de préférence d'un composé de type C12-C14-alkyl-(hydroxyéthyl)-diméthylammonium, en particulier des halogénures, des méthosulfates, des méthophosphates ou des phosphates respectifs ainsi que de leurs mélanges.
  11. Agent selon la revendication 1 ou 10, caractérisé en ce qu'il contient moins de 3% en poids d'aluminosilicate, il est en particulier totalement exempt d'aluminosilicate, par rapport à la totalité de l'agent de lavage ou de nettoyage.
  12. Utilisation d'un agent selon l'une quelconque des revendications 1 à 11 pour l'inhibition des incrustations sur des surfaces de substrats au moins partiellement hydrophobes ou hydrofugées, de préférence des textiles, en particulier dans le cadre d'un processus de lavage de textiles en machine.
EP04765743.2A 2003-11-21 2004-10-01 Systeme adjuvant soluble Not-in-force EP1685224B1 (fr)

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DE10354561A DE10354561A1 (de) 2003-11-21 2003-11-21 Lösliches Buildersystem
PCT/EP2004/010978 WO2005052105A1 (fr) 2003-11-21 2004-10-01 Systeme adjuvant soluble

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DE10354561A1 (de) 2005-07-14
WO2005052105A1 (fr) 2005-06-09
PL1685224T3 (pl) 2014-01-31
EP1685224A1 (fr) 2006-08-02
US20060281665A1 (en) 2006-12-14

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