WO2007077088A1 - Produit liquide de lavage ou de nettoyage contenant un agent blanchissant a base de peracide sous forme de particules - Google Patents

Produit liquide de lavage ou de nettoyage contenant un agent blanchissant a base de peracide sous forme de particules Download PDF

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WO2007077088A1
WO2007077088A1 PCT/EP2006/069384 EP2006069384W WO2007077088A1 WO 2007077088 A1 WO2007077088 A1 WO 2007077088A1 EP 2006069384 W EP2006069384 W EP 2006069384W WO 2007077088 A1 WO2007077088 A1 WO 2007077088A1
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Prior art keywords
acid
composition according
weight
surfactants
acids
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PCT/EP2006/069384
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German (de)
English (en)
Inventor
Peter Schmiedel
Luca Bellomi
Wolfgang Von Rybinski
Bernhard Orlich
Hermann Jonke
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Henkel Kommanditgesellschaft Auf Aktien
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Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to JP2008547932A priority Critical patent/JP2009522386A/ja
Priority to ES06819915T priority patent/ES2382388T3/es
Priority to EP06819915A priority patent/EP1979453B1/fr
Priority to AT06819915T priority patent/ATE548442T1/de
Priority to PL06819915T priority patent/PL1979453T3/pl
Priority to US12/159,676 priority patent/US20090018045A1/en
Publication of WO2007077088A1 publication Critical patent/WO2007077088A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds

Definitions

  • the present patent application relates to hydrous liquid detergents or cleaners which contain peroxycarboxylic acid particles.
  • phthalimidoperoxoalkanoic acids such as 6-phthalimidoperoxohexanoic acid (PAP) are highly efficient bleaches, but are chemically very unstable in conventional liquid detergent formulations. In most cases, they completely decompose in a few days. Even if these liquid agents are freed from possible reactants of the peroxycarboxylic acid, such as unsaturated compounds, aldehydes, amines, chloride, etc., they still decompose in the presence of the surfactants, even if they are not oxidatively attacked.
  • PAP 6-phthalimidoperoxohexanoic acid
  • phthalimidoperoxoalkanoic acids are stable as only slightly water-soluble solids, they dissolve in the presence of surfactants, are highly reactive in this form, and are soluble in solution both via a bimolecular reaction with elimination of singlet oxygen and through hydrolysis of phthalimidoalkanoic acid and H 2 O 2 decompose.
  • the latter is virtually not at low washing temperatures and in the concentrations occurring bleach active, so that in total the bleaching action of the agent is lost during storage.
  • a problem with such formulations with, for example, sodium sulfate is the phase stability and the storage stability, especially under climatic changing conditions. Under alternating climate, the solubility of the sodium sulfate changes very strongly, which can lead to precipitation and the growth of partially very large sulfate crystals in the liquid agents. In addition, the flow behavior of these agents is unsatisfactory and the preparation is complicated in practice, since even during the manufacturing process due to the hydrate formation of the sodium sulfate initially large crystals can form, which do not dissolve again in the thickened recipe.
  • Another approach to stabilize the bleaching agent is to coat it. It has been found, however, that the mere application of coating materials by no means always leads to an increase in the stability of the PAP. Coating, even with chemically inert materials such as paraffin in the systems under consideration, often even destabilizes the PAP. A coating that should be soluble in the application of the agent, usually in a water-containing product not completely diffusion-tight against water.
  • the present invention which aims to contribute to this, is an aqueous surfactant and bleach-containing liquid detergent or cleaning agent having a particulate peroxycarboxylic acid and characterized in that it contains magnesium sulfate.
  • Magnesium sulfate may, if desired, be present in agents according to the invention in amounts of up to 30% by weight. Preferably, amounts in the range of about 4 wt .-% to 20 wt .-%, in particular in the range of 6 wt .-% to 10 wt .-%. Magnesium sulfate may optionally also be used in mixtures with sodium and / or potassium sulfate.
  • compositions according to the invention is preferably between 2 and 6, in particular between 3 and 5.5 and more preferably between 3.5 and 5.
  • Water may, if desired, in amounts of up to 90% by weight, in particular 20% by weight, in agents according to the invention. -% to 75 wt .-%, be included; if necessary, however, these areas can also be exceeded or fallen short of.
  • the content of peroxycarboxylic acid in the compositions according to the invention is preferably 1% by weight to 25% by weight, in particular 2% by weight to 20% by weight and especially preferably 3% to 15% by weight. If the peroxycarboxylic acid is not in solid form at room temperature, it may have been formulated in a known manner using inert carrier materials in particulate form; However, a peroxycarboxylic acid which is solid at room temperature is preferably used in optionally coated form.
  • the peroxycarboxylic acid which may also be referred to as organic peracid, may carry aliphatic and / or cyclic, including heterocyclic and / or aromatic, radicals.
  • peroxo formic acid peroxoacetic acid, peroxo propionic acid, peroxohexanoic acid, peroxobenzoic acid and their substituted derivatives such as m-chloroperoxobenzoic acid, the mono- or di-peroxophthalic acids, 1,12-diperoxododecanedioic acid, nonylamidoperoxoadipic acid, 6-hydroxyperoxohexanoic acid, 4-phthalimidoperobutanoic acid , 5-phthalimidoperoxopentanoic acid, 6-phthalimidoperoxohexanoic acid, 7-phthalimidoperoxoheptanoic acid, N, N'-terephthaloyl-di-6-aminoperoxohexanoic acid and mixtures of these.
  • Preferred peracids include the phthalimidoperoxoalkanoic acids, especially 6-phthalimidoperoxohexanoic acid (P
  • the peroxycarbonic acid particles contained in the agent according to the invention may be coated. It is important that the coating material dissolves as little as possible in the liquid surrounding the coated Peroxocarbonklateilchen, but under the conditions of use of the agent (at higher temperature, by dilution with water changing pH, or the like) releases the coated peroxycarboxylic acid.
  • a preferred coating material is one which consists, at least in part, of saturated fatty acid. The chain length of the fatty acid is preferably greater than Ci 2 , particularly preferred is stearic acid. It has been found that, especially at low pH, the stability of PAP is very good, so that a coating for stabilizing the PAP is possibly unnecessary. However, it has been found that a coating of the peroxycarboxylic acid stabilizes enzymes when they are contained in an agent according to the invention. In particular, in the presence of enzymes, therefore, a PAP coating is advantageous.
  • a wrapping material if present, is preferably applied to the particulate peroxycarboxylic acid in amounts such that the coated peroxycarboxylic acid particles consist of from 5% to 50% by weight of the wrapping material.
  • the diameters of the coated PeroxocarbonTexreteilchen are preferably in Range from 100 ⁇ m to 1000 ⁇ m; Therefore, it starts from correspondingly finely divided Peroxocarbonchurematerial and covers it with the wrapping material.
  • the procedure is to spray a fluidized bed of the peroxycarboxylic acid particles to be coated with a solution or slurry, preferably an aqueous solution, or a melt of the coating material, if present, removing the solvent or slurry, preferably water, by evaporation or solidified melted wrapping material by cooling and discharges the coated PeroxocarbonTalkreteilchen in a conventional manner from the fluidized bed.
  • a solution or slurry preferably an aqueous solution, or a melt of the coating material, if present
  • removing the solvent or slurry preferably water
  • preference is given to melt-coating.
  • a liquid detergent or cleaning agent according to the invention may contain all conventional ingredients in such agents, such as solvents, builders, enzymes and other auxiliaries such as soil repellants, thickeners, dyes and perfumes or the like.
  • it contains nonionic surfactants and / or organic solvents and optionally anionic surfactants, cationic surfactants and / or amphoteric surfactants.
  • Surfactants of the sulfonate type, alk (en) ylsulfates, alkoxylated alk (en) ylsulfates, ester sulfonates and / or soaps are preferably used as anionic surfactants.
  • Suitable surfactants of the sulfonate type are preferably C 9 -Ci3 alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C 2 -C 8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of the C 10 -15 fatty alcohols, for example of coconut fatty alcohol, Taigfettalkohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 8 -C 2 O-oxo alcohols and those half-esters of secondary alcohols of this chain length is preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis.
  • Ci2-Ci6-alkyl sulfates and Ci2-Ci5-alkyl sulfates and Ci 4 -Ci 5 alkyl sulfates and Ci 4 -Ci 6 alkyl sulfates are particularly preferred.
  • 2,3-alkyl sulfates which may for example be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • sulfuric monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight-chain or branched C 7 -C 2I -AIkOhOIe such as 2-methyl-branched Cg-Cn alcohols having an average of 3.5 moles of ethylene oxide (EO) or Ci2-Ci8 fatty alcohols with 1 up to 4 EO, are suitable. Due to their high foaming behavior, they are usually used in detergents only in relatively small amounts, for example in amounts of from 0 to 5% by weight.
  • esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • anionic surfactants are particularly soaps 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 Taigfettklaren derived soap mixtures.
  • those soap mixtures are preferred which are composed of 50 to 100 wt .-% of saturated Ci 2 -C 24 fatty acid soaps and 0 to 50 wt .-% of oleic acid soap.
  • Ethercarbon Acid are water hardness insensitive and have excellent surfactant properties.
  • Cationic surfactants contain the surface activity of the high molecular weight hydrophobic residue upon dissociation in aqueous solution in the cation.
  • cationic surfactants are the quaternary ammonium compounds of the general formula: (R 1 R 2 R 3 R 4 N + ) X " where R 1 is C 1 -C 8 -alk (en) yl, R 2 to R 4 are each independently C n H 2n + i- p - ⁇ - (Y 1 (CO) R 5 ) p - (Y 2 H) x , where n is an integer without 0 and p and x are integers or 0.
  • Y 1 and Y 2 is independently of one another O, N or NH
  • R 5 denotes a C 3 -C 23 -alk (en) yl chain
  • X is a counterion which is preferably selected from the group of alkyl sulfates and alkyl carbonates. where the nitrogen group is substituted with two long acyl and two short alk (en) yl residues.
  • Amphoteric or ampholytic surfactants have a plurality of functional groups which can ionize in aqueous solution and thereby - depending on the conditions of the medium - give the compounds anionic or cationic character. Near the isoelectric point, the amphoteric surfactants form internal salts, rendering them difficult or insoluble in water. Amphoteric surfactants are subdivided into ampholytes and betaines, the latter being present in solution as zwitterions. Ampholytes are amphoteric electrolytes, d. H. Compounds that possess both acidic and basic hydrophilic groups and thus behave acidic or basic depending on the condition. Betaine refers to compounds with the atomic grouping
  • the nonionic surfactants used are preferably alkoxylated and / or propoxylated, in particular primary, alcohols having preferably 8 to 18 C atoms and on average 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles of propylene oxide (PO) per mole of alcohol.
  • EO ethylene oxide
  • PO propylene oxide
  • C 8 -C 16 -alkoxy alkoxylates advantageously ethoxylated and / or propoxylated C 10 -C 18 -alcohol alkoxylates, in particular C 12 -C 14 -alcohol alkoxylates, having a degree of ethoxylation of between 2 and 10, preferably between 3 and 8, and / or a degree of propoxylation between 1 and 6, preferably between 1.5 and 5.
  • the stated degrees of ethoxylation and propoxylation represent statistical averages which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates and propoxylates have a narrow homolog distribution (narrow ranks ethoxylates / propoxylates, NRE / NRP). additionally Fatty alcohols with more than 12 EO can also be used for these nonionic surfactants. Examples of these are (TaIg) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x , z. B. as compounds, especially with anionic surfactants, are used, in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol that represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.1 to 1.4.
  • 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, especially fatty acid methyl ester.
  • Particularly preferred are C12-C18 fatty acid methyl esters having an average of 3 to 15 EO, in particular having an average of 5 to 12 EO.
  • 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 usually a carbon chain, which should be long enough that the hydrophilic groups have enough distance 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. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates. End-capped dimeric and trimeric mixed ethers are particularly distinguished 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.
  • the amount of surfactants present in the agents according to the invention is preferably 0.1% by weight to 50% by weight, in particular 10% by weight to 40% by weight, and particularly preferably 20% by weight to 70% by weight. -%.
  • Polydiols, ethers, alcohols, ketones, amides and / or esters in amounts of from 0 to 90% by weight, preferably 0.1 to 70% by weight, in particular 0.1 to 60% by weight, may preferably be used as organic solvents. %, in each case based on the amount of water available. Preference is given to low molecular weight polar substances, such as, for example, methanol, ethanol, propylene carbonate, acetone, acetonylacetone, diacetone alcohol, ethyl acetate, 2-propanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol, dipropylene glycol monomethyl ether and dimethylformamide or mixtures thereof.
  • polar substances such as, for example, methanol, ethanol, propylene carbonate, acetone, acetonylacetone, diacetone alcohol, ethyl acetate, 2-propanol, ethylene glycol, propylene glycol,
  • Suitable enzymes are, in particular, those from the class of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these Hydrolases in the wash contribute to the removal of entanglements, such as proteinaceous, fatty or starchy entanglements, and graying. Cellulases and other glycosyl hydrolases can contribute to color retention and increase the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer.
  • 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 ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and ß-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 proportion of enzymes or enzyme mixtures may be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 3 wt .-%. They are preferably used in preparations according to the invention in particulate form.
  • Further detergent ingredients may be builders, cobuilders, soil repellents, alkaline salts and also foam inhibitors, complexing agents, enzyme stabilizers, graying inhibitors, optical brighteners and UV absorbers.
  • a builder for example, fine crystalline, synthetic and bound water-containing zeolite can be used, preferably zeolite A and / or P.
  • zeolite P zeolite MAP ® commercial product from Crosfield
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • zeolite A and zeolite X which as VEGOBOND AX ® (a product of Condea) commercially available is.
  • the zeolite may preferably be used as a spray-dried powder.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , Ci 2 -Ci 4 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates can also be used as builders.
  • Suitable substitutes or sub-substituents for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x ⁇ 2 X + iy H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 is and preferred values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • the preferred builder substances also include amorphous sodium silicates with a Na 2 O: SiO 2 modulus of 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 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.
  • the term "amorphous" also This means that, in X-ray diffraction experiments, the silicates do not give sharp X-ray reflections typical of crystalline substances, but at best one or more maxima of the scattered X-rays, which have a width of several degrees of diffraction angle however, may well result in particularly good builder properties when the silica particles provide fuzzy or even sharp diffraction peaks in electron diffraction experiments, interpreted as having microcrystalline regions of size 10 to a few hundred nm, with values up to and including 50 nm in particular are preferred up to a maximum of 20 nm. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
  • Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.
  • Their content is generally not more than 25% by weight, preferably not more than 20% by weight, in each case based on the finished composition.
  • tripolyphosphates even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing power.
  • Preferred amounts of phosphates are below 10 wt .-%, especially at 0 wt .-%.
  • Suitable organic builder substances which are useful as co-builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and their derivatives and mixtures thereof.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • Further useable acidulants are known pH regulators, such as sodium bicarbonate and sodium hydrogen sulfate.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. 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 significantly higher than the molecular weights specified in this document.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 2,000 to 10,000 g / mol, and particularly preferably from 3,000 to 5,000 g / mol, may again be preferred from this group.
  • Suitable polymers may also include substances consisting partly or wholly of units of vinyl alcohol or its derivatives.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • 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 proven particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as an aqueous solution or, preferably, as a powder.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units for example those containing as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500 000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose which has a DE of 100.
  • DE dextrose equivalent
  • Both maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also yellow dextrins and white dextrins with relatively high molecular weights in the range from 2 000 to 30 000 g / mol are useful.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. These are products oxidized at C 6 and / or with ring opening at C 2 / C 3 of the saccharide ring. A product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • compositions may also contain components which positively influence the oil and grease washability from textiles, so-called soil repellents. This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component.
  • the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose having a proportion of methoxyl groups of 15 to 30% by weight and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, and known from the prior art polymers phthalic acid and / or terephthalic acid or their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
  • Suitable 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. It is also advantageous to use mixtures of different foam inhibitors, for example those of silicones, paraffins or waxes.
  • the salts of polyphosphonic come into consideration.
  • the sodium salts of, for example, l-hydroxyethane-1,1-diphosphonate, but also diethylenetriamine penta-methylene phosphonate or ethylenediamine tetramethylene phosphonate in amounts of from 0.1% by weight to 5% by weight of the composition are preferably used. Preference is given to nitrogen-free complexing agents.
  • 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 (co) 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 carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, as well as polyvinylpyrrolidone, for example, in amounts of 0.1 to 5 wt .-%, based on the means used.
  • the funds can optical brighteners such.
  • brighteners of the substituted diphenylstyrene type may be present, e.g.
  • UV absorbers can also be used. These are compounds with pronounced ultraviolet radiation absorptivity which contribute to improving the light fastness of dyes and pigments as well as textile fibers as light stabilizers (UV stabilizers) and also protect the wearer's skin from textile exposure to UV radiation.
  • the compounds which are active by radiationless deactivation are derivatives of benzophenone whose substituents, such as hydroxyl and / or alkoxy groups, are usually in the 2- and / or 4-position.
  • substituted benzotriazoles are also suitable, furthermore in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic nickel complexes and natural products such as umbelliferone and the body's own urocanic acid.
  • the UV absorbers absorb UV-A and UV-B radiation and optionally UV-C radiation and radiate back with wavelengths of blue light, so that they additionally have the effect of an optical brightener.
  • Preferred UV absorbers are also triazine derivatives, for. B.
  • UV absorbers can also be used to absorb ultraviolet radiation pigments such as titanium dioxide.
  • compositions may contain further conventional thickeners and anti-settling agents and also viscosity regulators such as polyacrylates, polycarboxylic acids, polysaccharides and their derivatives, polyurethanes, polyvinylpyrrolidones, castor oil derivatives, polyamine derivatives such as quaternized and / or ethoxylated hexamethylenediamines and any desired mixtures thereof.
  • viscosity regulators such as polyacrylates, polycarboxylic acids, polysaccharides and their derivatives, polyurethanes, polyvinylpyrrolidones, castor oil derivatives, polyamine derivatives such as quaternized and / or ethoxylated hexamethylenediamines and any desired mixtures thereof.
  • viscosity regulators such as polyacrylates, polycarboxylic acids, polysaccharides and their derivatives, polyurethanes, polyvinylpyrrolidones, castor oil derivatives, polyamine derivatives such as
  • the agents may further typical detergents and detergent ingredients such as perfumes and / or dyestuffs, preference being given to those dyestuffs which have no or negligible coloring action on the textiles to be washed .
  • Preferred quantitative ranges of the totality of the dyestuffs used are less than 1% by weight, preferably less than 0.1% by weight, based on
  • the agent may optionally also contain white pigments such as TiO 2 .
  • Preferred agents have densities of 0.5 to 2.0 g / cm 3 , in particular 0.7 to 1.5 g / cm 3 , on.
  • the density difference between the PeroxocarbonTexreteilchen and the liquid phase of the composition is preferably not more than 10% of the density of the two and is particularly so low that the PeroxocarbonTexreteilchen and preferably also optionally other suspended in the funds solid particles float in the liquid phase.
  • Example 1 Preparation of an agent according to the invention
  • an agent El according to the invention with the following composition (percentages by weight) was prepared:
  • Fluidized bed system (Aeromatic) was produced.
  • An agent VI was otherwise prepared as in Example 1, but containing no magnesium sulfate (replaced by water).
  • Example 3 Comparative Example 2 An agent V2 was otherwise prepared as in Example 1, but magnesium sulfate was replaced with the same amount of sodium sulfate.
  • the agents of Examples 1 to 3 were evaluated for phase stability and bleach loss.
  • the characterization was carried out after a storage period of 1 week under changing climatic conditions (temperature cycles between 25 ° C and 40 0 C) and constant 35 ° C.
  • VI showed unacceptable bleach loss.
  • V2 showed crystal formation and phase instability under alternating climate storage conditions. The benefits of El outweigh.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un produit liquide aqueux de nettoyage ou de lavage contenant un agent blanchissant et un tensioactif, ledit produit contenant un acide peroxocarboxylique sous forme de particules et du sulfate de magnésium.
PCT/EP2006/069384 2005-12-30 2006-12-06 Produit liquide de lavage ou de nettoyage contenant un agent blanchissant a base de peracide sous forme de particules WO2007077088A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2008547932A JP2009522386A (ja) 2005-12-30 2006-12-06 粒状過酸漂白剤を含む液状洗剤組成物または洗浄剤組成物
ES06819915T ES2382388T3 (es) 2005-12-30 2006-12-06 Detergentes o productos de limpieza líquidos con blanqueante perácido dividido en partículas
EP06819915A EP1979453B1 (fr) 2005-12-30 2006-12-06 Produit liquide de lavage ou de nettoyage contenant un agent blanchissant a base de peracide sous forme de particules
AT06819915T ATE548442T1 (de) 2005-12-30 2006-12-06 Flüssiges wasch- oder reinigungsmittel mit teilchenförmigem persäure-bleichmittel
PL06819915T PL1979453T3 (pl) 2005-12-30 2006-12-06 Ciekły środek piorący lub czyszczący ze środkiem bielącym spośród kwasu nadtlenowego w postaci cząstek
US12/159,676 US20090018045A1 (en) 2005-12-30 2006-12-06 Liquid Washing or Cleaning Composition Comprising Particulate Peracid Bleach

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005063180A DE102005063180A1 (de) 2005-12-30 2005-12-30 Flüssiges Wasch- oder Reinigungsmittel mit teilchenförmigem Persäure-Bleichmittel
DE102005063180.0 2005-12-30

Publications (1)

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WO2007077088A1 true WO2007077088A1 (fr) 2007-07-12

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Country Status (7)

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EP (1) EP1979453B1 (fr)
JP (1) JP2009522386A (fr)
AT (1) ATE548442T1 (fr)
DE (1) DE102005063180A1 (fr)
ES (1) ES2382388T3 (fr)
PL (1) PL1979453T3 (fr)
WO (1) WO2007077088A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011005917A1 (fr) * 2009-07-09 2011-01-13 The Procter & Gamble Company Procédé de blanchissage de tissus à l'aide d'une composition liquide de détergent pour le linge
WO2020030517A1 (fr) * 2018-08-07 2020-02-13 Henkel Ag & Co. Kgaa Détergent ou agent de nettoyage liquide contenant un précurseur de blanchiment

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180362892A1 (en) * 2017-06-20 2018-12-20 The Procter & Gamble Company Systems comprising a bleaching agent and encapsulates

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0240481A1 (fr) * 1986-03-31 1987-10-07 The Procter & Gamble Company Agent de blanchiment liquide stable à base de diperoxyacides
EP0435379A2 (fr) * 1989-12-22 1991-07-03 Akzo Nobel N.V. Suspension, enrobage, agglomération et utilisation d'acides imidoperoxycarboxyliques
US5073285A (en) * 1989-06-12 1991-12-17 Lever Brothers Company, Division Of Conopco, Inc. Stably suspended organic peroxy bleach in a structured aqueous liquid
EP0504952A1 (fr) * 1991-02-15 1992-09-23 The Procter & Gamble Company Agent de blanchiment liquide stable à base d'acide peroxyamidique
GB2281744A (en) * 1993-06-30 1995-03-15 Procter & Gamble Stable pourable aqueous liquid detergent
EP0890635A2 (fr) * 1997-07-08 1999-01-13 Manitoba Italia S.p.A. Compositions basées sur des acides percarboxyliques comme agents de nettoyage et de désinfection

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0240481A1 (fr) * 1986-03-31 1987-10-07 The Procter & Gamble Company Agent de blanchiment liquide stable à base de diperoxyacides
US5073285A (en) * 1989-06-12 1991-12-17 Lever Brothers Company, Division Of Conopco, Inc. Stably suspended organic peroxy bleach in a structured aqueous liquid
EP0435379A2 (fr) * 1989-12-22 1991-07-03 Akzo Nobel N.V. Suspension, enrobage, agglomération et utilisation d'acides imidoperoxycarboxyliques
EP0504952A1 (fr) * 1991-02-15 1992-09-23 The Procter & Gamble Company Agent de blanchiment liquide stable à base d'acide peroxyamidique
GB2281744A (en) * 1993-06-30 1995-03-15 Procter & Gamble Stable pourable aqueous liquid detergent
EP0890635A2 (fr) * 1997-07-08 1999-01-13 Manitoba Italia S.p.A. Compositions basées sur des acides percarboxyliques comme agents de nettoyage et de désinfection

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011005917A1 (fr) * 2009-07-09 2011-01-13 The Procter & Gamble Company Procédé de blanchissage de tissus à l'aide d'une composition liquide de détergent pour le linge
WO2020030517A1 (fr) * 2018-08-07 2020-02-13 Henkel Ag & Co. Kgaa Détergent ou agent de nettoyage liquide contenant un précurseur de blanchiment

Also Published As

Publication number Publication date
PL1979453T3 (pl) 2012-08-31
DE102005063180A1 (de) 2007-07-05
EP1979453B1 (fr) 2012-03-07
JP2009522386A (ja) 2009-06-11
ES2382388T3 (es) 2012-06-07
ATE548442T1 (de) 2012-03-15
EP1979453A1 (fr) 2008-10-15

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