EP0746599B1 - Produit de lavage a adjuvants au silicate amorphes - Google Patents

Produit de lavage a adjuvants au silicate amorphes Download PDF

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Publication number
EP0746599B1
EP0746599B1 EP95910477A EP95910477A EP0746599B1 EP 0746599 B1 EP0746599 B1 EP 0746599B1 EP 95910477 A EP95910477 A EP 95910477A EP 95910477 A EP95910477 A EP 95910477A EP 0746599 B1 EP0746599 B1 EP 0746599B1
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EP
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Prior art keywords
weight
detergent
carbonate
silicate
content
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EP95910477A
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German (de)
English (en)
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EP0746599A1 (fr
Inventor
Beatrix Kottwitz
Jörg Poethkow
Horst Upadek
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D3/08—Silicates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O

Definitions

  • the invention relates to a detergent, the amorphous silicate builder substances contains and both excellent primary and secondary Has washing properties.
  • the invention accordingly relates to a detergent containing surfactants from the Group of anionic, nonionic, cationic, amphoteric and zwitterionic Surfactants, silicate builder substances as well as carbonates and possibly others
  • Ingredients of detergents, the agent being amorphous alkali silicates and alkali carbonates contains in the form of a compound, which consists of about 40 to 80 wt .-% alkali carbonate, about 10 to 40 wt .-% alkali silicate, with the proviso that the alkali carbonate content is always greater is than the alkali silicate content, and consists of a maximum of 25% by weight of water and one inhomogeneous surface, which can be seen macroscopically also by a certain roughness distinguished, has and proportionately almost spherical granules and proportionately contains cylindrical and / or splinter-like granules.
  • alkali carbonates are also understood to mean bicarbonates, however, the use of dialkali metal carbonates is preferred. Particularly preferred are sodium carbonate, potassium carbonate or mixtures of these, mostly Sodium carbonate is used.
  • the preferred amorphous alkali silicates include, in particular, sodium silicates with a Na 2 O: SiO 2 molar ratio of 1: 1 to 1: 3.5, molar ratios between 1: 2 and 1: 3 being particularly preferred.
  • Compounds which contain disilicates have proven to be particularly advantageous.
  • the compounds can be produced by any process that allows inhomogeneous Generate surfaces and grain spectra. For example, it is possible that such Compounds are spray dried and / or granulated and then part of them Compounds is crushed. It is also possible that mixtures of carbonates and silicates or even spray-dried and / or granulated compounds Roll compaction or extrusion are supplied, the emerging strand optionally cut after a previous drying and / or cooling. Final roundings are not made to ensure the inhomogeneity of the Surface that is macroscopically characterized by a certain roughness, and not to destroy the grain spectrum.
  • the compounds consist partly of almost spherical (granules, while other parts are cylindrical and / or can be splinter-like with pointed corners and edges.
  • the size the individual particles are in a wide range. However it is preferred that a maximum of 20% by weight of the grains and in particular a maximum of 10 Wt .-% a smaller length diameter than 250 microns and a maximum of 15 wt .-% the grains, in particular a maximum of 10% by weight of a larger length diameter have than 1.5 mm.
  • the carbonate-silicate compounds used according to the invention have a bulk density of between approximately 600 and 1100 g / l, in particular between 700 and 1000 g / l.
  • the carbonate content preferably sodium carbonate
  • advantageous carbonate-silicate compounds have a silicate content, preferably a content of sodium silicate and in particular sodium disilicate, of 15 to 40% by weight and with particular advantages of 20 to 35% by weight, the water content being 22% by weight and in particular should not exceed 20% by weight.
  • Particularly advantageous embodiments of the carbonate-silicate compounds have weight ratios of carbonate to silicate, in each case based on the sodium salts, of 2.2: 1 to 1.8: 1.
  • a carbonate-silicate compound that meets all of these requirements is, for example, Gransil (R) , which is commercially available from Colin Stewart, Minchem (Great Britain).
  • the carbonate-silicate compounds mentioned can be used as a partial substitute or as a full substitute for conventional builder substances. Their content in the detergents according to the invention can therefore be about 2 to 50% by weight, but preferably 5 to 40% by weight and in particular 10 to about 35% by weight. In a preferred embodiment of the invention, the detergents are free of zeolite. However, if the compositions contain a combination of zeolite and the carbonate-silicate compounds mentioned, a preferred embodiment has zeolite and carbonate-silicate compounds in a weight ratio of 3: 1 to 1: 3, in particular 2: 1 to 1: 2 on. The carbonate-silicate compound content of the agents according to the invention preferably does not exceed 30% by weight.
  • the zeolite used is preferably NaA zeolite in detergent quality.
  • zeolite X or zeolite P and mixtures of A and X and P are also suitable, for example.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water.
  • the detergent contains crystalline layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH 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 Is 20 and are preferred values for x 2, 3 or 4, in combination with the carbonate-silicate compounds mentioned.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline sheet silicates of the above formula are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171 .
  • the combinations of crystalline layered sodium silicates and carbonate-silicate compounds can be used in a broad weight ratio of about 10: 1 to 1:10, but again weight ratios of 3: 1 to 1: 3 and in particular 2: 1 to 1: 2 are preferred.
  • the detergents contain carbonate-silicate compounds in combination with crystalline layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH 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 and are preferred values for x 2, 3 or 4, and additionally also zeolite.
  • Particularly advantageous detergents have a carbonate-silicate compound content of about 5 to 30% by weight, a crystalline layered sodium silicate content of about 2 to 15% by weight and a zeolite content also of about 2 to 15% by weight .-%, the weight information in all cases refer to the detergent.
  • the weight ratios between crystalline layered sodium silicates of the type mentioned and zeolite can vary in a range from 7.5: 1 to 1: 7.5, weight ratios above 1: 1 being particularly preferred.
  • Anionic, nonionic, cationic, amphoteric and / or zwitterionic surfactants can be mentioned as further ingredients of the detergents according to the invention.
  • Preferred anionic surfactants of the sulfonate type are the known C 9 -C 13 alkylbenzenesulfonates, ⁇ -olefin sulfonates and alkanesulfonates. Esters of ⁇ -sulfofatty acids or the disalts of ⁇ -sulfofatty acids are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol be preserved.
  • alk (en) yl sulfates used are the alkali metal salts, preferably the sodium salts, the sulfuric acid semiesters of the C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 10 -C 20 - Oxoalcohols, and those of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 16 -C 18 alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C 16 -C 18 -alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C.
  • the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C 12 -C 14 fatty alkyl sulfates or C 12 -C 18 fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates and in particular C 12 -C 16 -Fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates.
  • saturated alkyl sulfates not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
  • Mixtures of saturated sulfated fatty alcohols predominantly consisting of C 16 and unsaturated sulfated fatty alcohols predominantly consisting of C 18 are particularly preferred, for example those derived from solid or liquid HD-Ocenol (R) fatty alcohol mixtures (commercial product of the applicant) .
  • Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 2 to 4 EO are suitable. Due to their high foaming behavior, they are only used in relatively small amounts in detergents for machine washing.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, also known as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols represent. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or use their salts.
  • Saturated fatty acid soaps such as the salts of Lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid or behenic acid, and in particular from natural fatty acids, e.g. coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 24 fatty acid soaps.
  • the anionic surfactants and the soaps can be in the form of their alkali salts such as the sodium, potassium or ammonium salts and as soluble organic salts Bases, such as mono-, di- or triethanolamine, are present.
  • Bases such as mono-, di- or triethanolamine, are present.
  • the anionic surfactants and soaps in the form of their sodium or Potassium salts, especially in the form of the sodium salts.
  • the content of anionic surfactants in the detergents according to the invention is preferably 5 to 35% by weight, in particular 10 to 30% by weight, the use of fatty alk (en) yl sulfates and / or alkylbenzenesulfonate is preferred.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 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 can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohol 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 thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • the detergents according to the invention preferably contain 2 to 15% by weight of alkoxylated C 8 -C 18 alcohols and in particular 5 to 10% by weight of ethoxylated C 12 -C 18 fatty alcohols.
  • non-ionic surfactants that either as the sole nonionic surfactant or in combination with others nonionic surfactants, especially together with alkoxylated Fatty alcohols used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as for example in the Japanese patent application JP-A-58/217598 are described or which are preferably according to the in the international patent application WO-A-90/13533 become.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • the content of alkylglycosides in the detergents is generally about 0 to 5% by weight and preferably 0.5 to 3% by weight.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may be suitable.
  • the amount of this nonionic Surfactants are preferably no more than that of the ethoxylated ones Fatty alcohols and the alkoxylated fatty acid alkyl esters, in particular not more than half of it.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in the R 2 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • organic builder substances can also be used.
  • Useful organic builder substances are preferred, for example polycarboxylic acids used in the form of their salts, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided such use ecological reasons are not objectionable, as well as mixtures of these.
  • Preferred salts are the sodium salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. Their content in detergents can generally 0 to 15 wt .-%.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain.
  • Their relative molecular mass, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • polymeric polycarboxylates also preferred terpolymers in the older German patent applications DE 42 21 381 and DE 43 00 722 are described.
  • the salary of the polymeric polycarboxylates and including the terpolymers preferably 2 to 7% by weight.
  • Suitable builder systems are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts as they described for example in the international patent application WO-A-93/08251 be or their production, for example, in the international Patent application WO-A-93/16110 or the older German patent application P 43 30 393.0 is described.
  • polyacetals which by reaction of dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and have at least 3 hydroxyl groups, for example as in European Patent application EP-A-0 280 223 can be obtained.
  • Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the detergents according to the invention can be used in addition to those Carbonate-silicate compounds still further amounts of carbonates and bicarbonates contain. Depending on the recipe, this may even be preferred his.
  • the detergents can contain other known additives commonly used in detergents, for example Bleaching agents and bleach activators, graying inhibitors, salts of polyphosphonic acids, Enzymes, enzyme stabilizers, small amounts of neutral Filling salts and, if necessary, colors and fragrances, opacifiers or Pearlescent agents and optical brighteners included.
  • Bleaching agents and bleach activators for example Bleaching agents and bleach activators, graying inhibitors, salts of polyphosphonic acids, Enzymes, enzyme stabilizers, small amounts of neutral Filling salts and, if necessary, colors and fragrances, opacifiers or Pearlescent agents and optical brighteners included.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate and / or percarbonate.
  • bleach activators are the N-acyl or O-acyl compounds which form H 2 O 2 organic peracids, preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate .
  • Particularly preferred bleach activators are N, N, N'N'-tetraacetylethylene diamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
  • the agents can also contain components that the oil and Influencing fat washability from textiles positively. This effect becomes particularly clear when a textile that is already soiled is soiled previously several times with a detergent according to the invention that this oil and contains fat-dissolving component, is washed.
  • nonionic cellulose ethers such as methyl cellulose and especially methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ether, as well as the polymers known from the prior art phthalic acid and / or terephthalic acid or their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates.
  • Graying inhibitors have the task of detaching from the fiber Keep dirt suspended in the fleet and prevent graying.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, Glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids Starch or the cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose.
  • soluble ones Use starch preparations and other starch products than those mentioned above, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
  • cellulose ethers such as carboxymethyl cellulose are preferred.
  • Carboxymethyl cellulose (sodium salt), Methyl cellulose, methyl hydroxyethyl cellulose and their mixtures and polyvinyl pyrrolidone are preferred, for example in amounts of 0.1 to 5 % By weight, based on the detergent.
  • the agents can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed connections that instead the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present be, e.g.
  • Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. They are particularly well suited from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymatic Active ingredients. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used.
  • enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, in particular cellulase-containing and protease-containing mixtures of particular Interest.
  • (Per) oxidases can also be suitable.
  • the enzymes can adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition. It is also possible Use of proteases with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme, is stabilized are. Surprisingly, it was found that in particular the Effect of the enzymes through the use of the compounds mentioned above Use of conventional builder substances such as zeolite or crystalline layered sodium silicates could be significantly increased.
  • the salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and Diethylenetriaminepentamethylenephosphonate in amounts of 0.1 to 1.5% by weight used.
  • 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-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • the bulk density of the advantageously granular agents is preferably at least about 600 g / l, in particular 650 to 1100 g / l. It can however, means are also produced which are lower Have bulk density.
  • agent for example carbonates, citrate or Citric acid or other polycarboxylates or polycarboxylic acids, polymers Polycarboxylates, zeolite and / or layered silicates, for example layered crystalline ones Disilicates, subsequently spray-dried, granulated and / or extruded Components, if necessary, with nonionic surfactants and / or others in the Processing temperature are applied to liquid to waxy ingredients, be mixed in.
  • a method is preferred in which the surface of Partial components of the agent or the entire agent for reducing the stickiness of the granules rich in nonionic surfactants are subsequently treated.
  • Suitable Surface modifiers are known from the prior art. Among others finely divided zeolites, silicas, amorphous silicates, fatty acids or are suitable Fatty acid salts, for example calcium stearate, but especially mixtures of zeolite and silicas or zeolite and calcium stearate are particularly preferred.
  • a method is preferred in which a basic detergent is more common Composition is produced by conventional methods and a carbonate-silicate compound, which consists of about 40 to 80% by weight of alkali carbonate, about 10 to 40% by weight Alkali silicate, with the proviso that the alkali carbonate content is always greater than that Alkali silicate content, and consists of a maximum of 25 wt .-% water and an inhomogeneous Surface that is macroscopically characterized by a certain roughness, has and partly almost spherical granules and partly cylindrical and / or contains splinter-like granules, is subsequently mixed, optionally after the Adding the carbonate-silicate compound, further processing of the detergent, preferably with finely divided powder and / or liquid to pasty Detergent ingredients.
  • a carbonate-silicate compound which consists of about 40 to 80% by weight of alkali carbonate, about 10 to 40% by weight Alkali silicate, with the proviso that
  • Granular detergents of the compositions below were prepared. Due to the different raw materials, the funds had a different water content. The exchange took place over sodium sulfate.
  • a carbonate-silicate compound Gransil (R) from Colin Stewart, Minchem (Great Britain) was used, which contained 54% by weight sodium carbonate, 27% by weight amorphous sodium disilicate and 19% by weight water. The bulk density of this compound was above 800 g / l.
  • Comparative Example V1 instead of this compound, the same amount of zeolite NaA, based on anhydrous active substance, was used in Comparative Example V2, the same amount of crystalline layered ⁇ -sodium disilicate, which had been prepared according to the teaching of international patent application WO-A-91/08171.
  • the application test was carried out under practical conditions in Household washing machines.
  • the machines were cleaned with 3.0 kg Loaded laundry and 0.5 kg test fabric, the test fabric for testing of the primary detergent impregnated with usual test soiling was and consisted of white tissue to test the graying inhibition strips of standardized cotton fabric were used as the white test fabric (Krefeld laundry research institute, WFK), nettle (BN), knitwear (cotton jersey; B) and terry cloth (FT) used.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Catalysts (AREA)
  • Silicon Compounds (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)

Claims (11)

  1. Produit de lavage contenant un agent tensioactif choisi dans le groupe des agents tensioactifs anioniques, non ioniques, cationiques amphotères et zwitterioniques, des substances de structuration silicatées ainsi que des carbonates et le cas échéant d'autres ingrédients de produits de lavage,
    caractérisé en ce que
    le produit contient des silicates de métal alcalin amorphes et des carbonates de métal alcalin sous forme d'un composé qui consiste en environ 40 à 80 % en poids de carbonate de métal alcalin, environ 10 à 40 % en poids de silicate de métal alcalin, avec la restriction que la concentration en carbonate de métal alcalin est toujours plus grande que la concentration en silicate de métal alcalin, et en au maximum 25 % en poids d'eau, et qui possède une surface non homogène qui se caractérise, vue d'un point de vue macroscopique, aussi par un caractère rugueux certain et qui contient partiellement des granulés à peu près sphériques et partiellement des granulés de forme cylindrique et/ou du type copeaux.
  2. Produit selon la revendication 1,
    caractérisé en ce que
    le composé carbonate-silicate possède un spectre de grains dans lequel au maximum 20 % des grains, de préférence au maximum 10 % possèdent un diamètre longitudinal plus petit que 25 µm et qu'au maximum 15 % des grains, de préférence au maximum 10 %, possèdent un diamètre longitudinal plus grand que 1,5 mm.
  3. Produit selon l'une des revendications 1 ou 2,
    caractérisé en ce que
    le composé carbonate-silicate possède une teneur en carbonate, de préférence en carbonate de sodium, comprise entre 45 et 75 % en poids, en particulier entre 50 et 70 % en poids, et une teneur en silicate, de préférence en silicate de sodium et en particulier en disilicate de sodium, de 15 à 40 % et avec une préférence particulière de 20 à 25 % en poids, dans lequel la teneur en eau ne doit pas dépasser 22 % en poids et en particulier 20 % en poids.
  4. Produit selon l'une des revendications 1 à 3,
    caractérisé en ce qu'
    il contient environ 2 à 50 % en poids, de préférence cependant 5 à 40 % en poids et en particulier 10 à environ 75 % en poids du composé carbonate-silicate.
  5. Produit selon l'une des revendications 1 à 4,
    caractérisé en ce qu'
    il contient de la zéolite et les composés carbonate-silicate dans un rapport en poids allant de 3:1 à 1:3, de préférence de 2:1 à 1:2 dans lequel la teneur du produit en composé carbonate-silicate pour cela ne dépasse pas en particulier 30 % en poids.
  6. Produit selon l'une des revendications 1 à 4,
    caractérisé en ce qu'
    il ne renferme aucune zéolite.
  7. Produit selon l'une des revendications 1 à 4 ou selon la revendication 6,
    caractérisé en ce qu'
    il contient les composés carbonate-silicate en combinaison avec des silicates de sodium cristallins, lamellaires, de formule générale NaMSixO2x+1yH2O, dans laquelle M signifie du sodium ou de l'hydrogène, x est un nombre allant de 1,9 à 4 et y un nombre allant de 0 à 20 et des valeurs préférées pour x sont 2, 3 ou 4.
  8. Produit selon l'une des revendications 1 à 5,
    caractérisé en ce qu'
    il contient les composés carbonate-silicate en combinaison avec des silicates de sodium cristallins, lamellaires, de formule générale NaMSixO2x+1yH2O, dans laquelle M signifie du sodium ou de l'hydrogène, x est un nombre allant de 1,9 à 4 et y un nombre allant de 0 à 20 et des valeurs préférées de x sont 2, 3 ou 4, et de la zéolite dans lequel la teneur en composé carbonate-silicate, rapporté au produit de lavage, s'élève de préférence de 5 à 30 % en poids, la teneur en silicates de sodium cristallins, lamellaires rapporté au produit de lavage s'élève de 2 à 15 % en poids, et la teneur en zéolite rapporté au produit de lavage, s'élève également de 2 à 15 % en poids.
  9. Produit selon l'une des revendications 1 à 8,
    caractérisé en ce qu'
    il contient des enzymes choisis dans la classe des protéases, des lipases, des amylases, des cellulases ou leurs mélanges.
  10. Produit selon l'une des revendications 1 à 9,
    caractérisé en ce qu'
    il contient un agent de blanchiment péroxydique.
  11. Procédé de préparation d'un produit de blanchiment selon l'une des revendications 1 à 8,
    caractérisé en ce qu'
    on prépare un produit de lavage de base de composition habituelle, selon les procédés usuels, et en ce qu'on mélange ultérieurement un composé carbonate-silicate qui consiste en environ 40 à 80 % en poids de carbonate de métal alcalin, environ 10 à 40 % en poids de silicate de métal alcalin, avec la restriction que la teneur en carbonate de métal alcalin est toujours plus grande que la teneur en silicate de métal alcalin, et en au maximum 25 % en poids d'eau et qui possède une surface non homogène, qui se caractérise vue d'un point de vue macroscopique aussi par une rugosité certaine et renferme partiellement des granulés à peu près sphériques et partiellement des granulés de forme cylindrique et/ou du type copeaux, dans lequel le cas échéant, après addition du composé carbonate-silicate, un traitement supplémentaire du produit de lavage, de préférence avec des constituants de produits de lavage finement divisés, pulvérulents et/ou liquides à pâteux, se produit.
EP95910477A 1994-02-22 1995-02-13 Produit de lavage a adjuvants au silicate amorphes Expired - Lifetime EP0746599B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4405511 1994-02-22
DE4405511A DE4405511A1 (de) 1994-02-22 1994-02-22 Waschmittel mit amorphen silikatischen Buildersubstanzen
PCT/EP1995/000506 WO1995022592A1 (fr) 1994-02-22 1995-02-13 Produit de lavage a adjuvants au silicate amorphes

Publications (2)

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EP0746599A1 EP0746599A1 (fr) 1996-12-11
EP0746599B1 true EP0746599B1 (fr) 2000-05-24

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US (1) US5798328A (fr)
EP (1) EP0746599B1 (fr)
JP (1) JPH09509204A (fr)
KR (1) KR970701256A (fr)
CN (1) CN1065268C (fr)
AT (1) ATE193315T1 (fr)
AU (1) AU1756895A (fr)
DE (2) DE4405511A1 (fr)
ES (1) ES2147843T3 (fr)
HU (1) HU219719B (fr)
PL (1) PL316846A1 (fr)
SK (1) SK107196A3 (fr)
WO (1) WO1995022592A1 (fr)

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DE10148354A1 (de) * 2001-09-29 2003-04-24 Henkel Kgaa Rückstandsfreie Waschmittel und Verfahren zu ihrer Herstellung
WO2014200656A1 (fr) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase provenant de streptomyces umbrinus
WO2014200658A1 (fr) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase issue de promicromonospora vindobonensis
WO2014200657A1 (fr) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase provenant destreptomyces xiamenensis
WO2014204596A1 (fr) 2013-06-17 2014-12-24 Danisco Us Inc. Alpha-amylase issue d'un membre de la famille des bacillaceae
WO2015050724A1 (fr) 2013-10-03 2015-04-09 Danisco Us Inc. Alpha-amylases faisant partie d'un sous-ensemble d'exiguobacterium, et procédés d'utilisation correspondants
WO2015050723A1 (fr) 2013-10-03 2015-04-09 Danisco Us Inc. Alpha-amylases provenant de exiguobacterium, méthodes d'utilisation de celles-ci
WO2015077126A1 (fr) 2013-11-20 2015-05-28 Danisco Us Inc. Variants d'alpha-amylases ayant une sensibilité réduite au clivage protéasique, et leurs procédés d'utilisation
WO2017173190A2 (fr) 2016-04-01 2017-10-05 Danisco Us Inc. Alpha-amylases, compositions et procédés
WO2017173324A2 (fr) 2016-04-01 2017-10-05 Danisco Us Inc. Alpha-amylases, compositions et procédés

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10148354A1 (de) * 2001-09-29 2003-04-24 Henkel Kgaa Rückstandsfreie Waschmittel und Verfahren zu ihrer Herstellung
DE10148354B4 (de) * 2001-09-29 2008-11-20 Henkel Ag & Co. Kgaa Rückstandsfreie Waschmittel und Verfahren zu ihrer Herstellung
WO2014200656A1 (fr) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase provenant de streptomyces umbrinus
WO2014200658A1 (fr) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase issue de promicromonospora vindobonensis
WO2014200657A1 (fr) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase provenant destreptomyces xiamenensis
WO2014204596A1 (fr) 2013-06-17 2014-12-24 Danisco Us Inc. Alpha-amylase issue d'un membre de la famille des bacillaceae
WO2015050724A1 (fr) 2013-10-03 2015-04-09 Danisco Us Inc. Alpha-amylases faisant partie d'un sous-ensemble d'exiguobacterium, et procédés d'utilisation correspondants
WO2015050723A1 (fr) 2013-10-03 2015-04-09 Danisco Us Inc. Alpha-amylases provenant de exiguobacterium, méthodes d'utilisation de celles-ci
WO2015077126A1 (fr) 2013-11-20 2015-05-28 Danisco Us Inc. Variants d'alpha-amylases ayant une sensibilité réduite au clivage protéasique, et leurs procédés d'utilisation
WO2017173190A2 (fr) 2016-04-01 2017-10-05 Danisco Us Inc. Alpha-amylases, compositions et procédés
WO2017173324A2 (fr) 2016-04-01 2017-10-05 Danisco Us Inc. Alpha-amylases, compositions et procédés

Also Published As

Publication number Publication date
AU1756895A (en) 1995-09-04
JPH09509204A (ja) 1997-09-16
EP0746599A1 (fr) 1996-12-11
CN1065268C (zh) 2001-05-02
DE59508395D1 (de) 2000-06-29
US5798328A (en) 1998-08-25
ES2147843T3 (es) 2000-10-01
HU219719B (hu) 2001-06-28
DE4405511A1 (de) 1995-08-24
WO1995022592A1 (fr) 1995-08-24
CN1142245A (zh) 1997-02-05
KR970701256A (ko) 1997-03-17
SK107196A3 (en) 1997-07-09
HU9602297D0 (en) 1996-10-28
PL316846A1 (en) 1997-02-17
HUT74605A (en) 1997-01-28
ATE193315T1 (de) 2000-06-15

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