EP1123372A1 - Non-ionic surfactant mixtures - Google Patents

Non-ionic surfactant mixtures

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Publication number
EP1123372A1
EP1123372A1 EP99952555A EP99952555A EP1123372A1 EP 1123372 A1 EP1123372 A1 EP 1123372A1 EP 99952555 A EP99952555 A EP 99952555A EP 99952555 A EP99952555 A EP 99952555A EP 1123372 A1 EP1123372 A1 EP 1123372A1
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EP
European Patent Office
Prior art keywords
acid
weight
mixtures
radical
contain
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP99952555A
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German (de)
French (fr)
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EP1123372B1 (en
Inventor
Karl-Heinz Schmid
Rainer Eskuchen
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BASF Personal Care and Nutrition GmbH
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Cognis Deutschland GmbH and Co KG
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Publication of EP1123372A1 publication Critical patent/EP1123372A1/en
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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
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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

Definitions

  • the invention is in the detergent sector and relates to mixtures of alkyl glucosides of different chain lengths and their use for the production of detergents.
  • Alkyl oligoglucosides are nonionic surfactants that are produced by acidic acetalization of glucose or starch degradation products with primary alcohols. By choosing the process conditions, the average degree of polymerization, i.e. control the distribution of acetalized mono-, di-, tri- and oligoglucosides. If you also vary the chain length of the alcohol component or even use mixtures of different alcohols, countless types of alkyl oligoglucosides are available, which differ in their primary detergent properties - washing, emulsifying, foaming, wetting - more or less clearly.
  • Alkyl oligoglucosides are characterized by their foaming power, which clearly exceeds that of conventional nonionic surfactants and is more similar to anionic surfactants. This is undoubtedly an advantage for use in the area of manual dishwashing detergents or hair shampoos, whereas in the area of detergents, the opposite behavior, namely low foam, is desired in order to prevent the washing machine from overflowing or to keep the amount of defoamer required as low as possible .
  • Another problem is that the commercially available alkyl oligoglucosides, especially with regard to cosmetic soiling, show a rather average cleaning ability. This explains why alkyl oligoglucosides have so far only been used in modest amounts in detergent formulations. In this connection, reference is made to the two German patent applications DE-A1 4319699 and DE-A1 4319700, from which mild alkyl oligoglucoside mixtures with defined chain lengths and DP are known.
  • the complex object of the invention was therefore to provide new alkyl oligoglucosides which, with reduced foaming, should be distinguished by improved washability, in particular in relation to cosmetic soiling.
  • the invention relates to a nonionic surfactant mixture consisting of (a) alkyl oligoglucosides of the formula (I),
  • R 1 is a dodecyl / tetradecyl radical
  • G is a glucose radical
  • p1 is a number in the range from 1 to 3
  • R 2 is a hexadecyl radical
  • G is a glucose radical
  • p2 is a number in the range from 1 to 3, with the proviso that the weight ratio of the two components in the range from 45: 55 to 55: 45 and the average degree of polymerization in Range from 1, 4 to 1, 5 is.
  • the mixtures compared to conventional commercial products with reduced foaming, are distinguished by improved washing performance, in particular by cosmetic soiling.
  • Alkyl oligoglucosides are known nonionic surfactants which are usually prepared by acid-catalyzed acetalization of glucose or degraded starch syrup with primary alcohols; the catalyst is then neutralized and excess alcohol is distilled off.
  • Representative of the extensive literature here is the review by Biermann et al. in Starch /force 45, 281 (1993), B.Salka in Cosm.Toil. 108, 89 (1993) and J.Kahre et al. in S ⁇ FW- Journal issue 8, 598 (1995).
  • the DP ie the average degree of polymerization
  • the index number p1 or p2 for the individual, to a certain extent, chain-pure alkyl glucosides can be in the range from 1 to 3, since in the sense of the invention it is only important that the mixture has a DP of 1.4 to 1.5 having. This can be important, for example, if the surfactant mixtures are produced by mixing the individual glucosides.
  • the surfactant mixtures preferably contain those alkyl oligoglucosides of the formula (I) which have the dodecyl and tetradecyl glucosides in a weight ratio of 25:75 to 75:25, preferably 40:60 to 60:40.
  • the alkyl oligoglucosides are obtained in the form of aqueous pastes with a solids content in the range from 30 to 50% by weight and can be used directly in this form, in particular if they are to be incorporated into liquid detergents.
  • glucosides for example by spray drying, steam drying or simultaneous drying and granulation in a horizontal thin-film evaporator (flash dryer), and then adding powder detergents as dry powders or granules.
  • flash dryer horizontal thin-film evaporator
  • another object of the invention is their use for the production of detergents, in particular liquid detergents, in which they are present in amounts of 5 to 50, preferably 10 to 30 and in particular 15 to 25% by weight .-% - based on the I - may be included.
  • the liquid detergents obtainable for the purposes of the invention using the nonionic surfactant mixtures can have a nonaqueous fraction in the range from 5 to 50 and preferably 15 to 35% by weight. In the simplest case, these are aqueous solutions of the surfactant mixtures mentioned.
  • the liquid detergents can, however, also be essentially water-free detergents. In the context of this invention, “essentially anhydrous” means that the agent preferably does not contain any free water which is not bound as water of crystallization or in a comparable form. it contains. In some cases, small amounts of free water are tolerable, especially in amounts up to 5% by weight.
  • liquid detergents may also have other typical ingredients, such as, for example, solvents, hydrotropes, bleaches, builders, viscosity regulators, enzymes, enzyme stabilizers, optical brighteners, soil repellants, foam inhibitors, inorganic salts and fragrances and colorants, provided that these are sufficiently stable in an aqueous environment.
  • solvents such as, for example, solvents, hydrotropes, bleaches, builders, viscosity regulators, enzymes, enzyme stabilizers, optical brighteners, soil repellants, foam inhibitors, inorganic salts and fragrances and colorants, provided that these are sufficiently stable in an aqueous environment.
  • suitable organic solvents are monofunctional and / or polyfunctional alcohols having 1 to 6 carbon atoms, preferably having 1 to 4 carbon atoms.
  • Preferred alcohols are ethanol, 1, 2-propanediol, glycerol and mixtures thereof.
  • the compositions preferably contain 2 to 20% by weight and in particular 5 to 15% by weight of ethanol or any mixture of ethanol and 1, 2-propanediol or in particular of ethanol and glycerol. It is also possible that the preparations either contain, in addition to the mono- and / or polyfunctional alcohols having 1 to 6 carbon atoms or solely polyethylene glycol with a relative molecular weight between 200 and 2000, preferably up to 600, in amounts of 2 to 17% by weight .
  • toluenesulfonate, xylenesulfonate, cumene sulfonate or mixtures thereof can be used as hydrotropes.
  • bleaching agents are, for example, peroxy carbonate, citrate perhydrates and salts of peracids, such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight.
  • nathumperborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred. Due to its ability to bind free water with the formation of the tetrahydrate, it contributes to increasing the stability of the agent. However, the preparations are preferably free from such bleaching agents.
  • Suitable builders are ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids, e.g. the neutral reacting sodium salts of 1-hydroxyethane-1, 1, - diphosphonate, which can be present in amounts of 0.5 to 5, preferably 1 to 2 wt .-%.
  • Viscosity regulators which can be used are, for example, hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium - And titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used.
  • the latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular special copolymers of acrylic acid with maleic acid, preferably those from 50% to 10% maleic acid.
  • the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably between 50,000 to 120,000, based on the free acid.
  • Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above one million are also particularly suitable. Examples of this are the polymers with thickening action available under the name Carbopol® 940 and 941.
  • the crosslinked polyacrylates are preferably used in amounts of not more than 1% by weight, preferably in amounts of 0.2 to OJ% by weight.
  • the agents can additionally contain about 5 to 20% by weight of a partially esterified copolymer, as described in European patent application EP-A1 0367049.
  • These partially esterified polymers are obtained by copolymerizing (a) at least one C 4 -C28 olefin or mixtures of at least one C 4 -C28 olefin with up to 20 mol% of C 1 -C 2 -alkyl vinyl ethers and (b) ethylenically unsaturated dicarboxylic acid anhydrides 4 to 8 carbon atoms in a molar ratio of 1: 1 to copolymers with K values from 6 to 100 and subsequent partial esterification of the copolymers with reaction products such as C 1 -C 3 alcohols, C 8 -C 22 fatty acids, C 1 -C 2 -alkylphenols, secondary C2-C 30 amines or their mixtures with at least one C2-C-alkylene oxide or tetrahydrofuran and hydrolysis of the an
  • Preferred copolymers contain maleic anhydride as the ethylenically unsaturated dicarboxylic anhydride.
  • the partially esterified copolymers can be present either in the form of the free acid or preferably in partially or completely neutralized form.
  • the copolymers are advantageously used in the form of an aqueous solution, in particular in the form of a 40 to 50% strength by weight solution.
  • the copolymers not only contribute to the primary and secondary washing performance of the liquid washing and cleaning agent, but also bring about a desired reduction in the viscosity of the concentrated liquid washing agent.
  • the use of these partially esterified copolymers gives concentrated aqueous liquid detergents which are flowable under the sole influence of gravity and without the action of other shear forces.
  • the concentrated aqueous liquid detergents preferably contain partially esterified copolymers in amounts of 5 to 15% by weight and in particular in amounts of 8 to 12% by weight.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Their proportion can be about 0.2 to about 2% by weight. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. In addition to the mono- and polyfunctional alcohols and the phospho- Phonates can contain other enzyme stabilizers.
  • sodium formate 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 B ⁇ 3), metaboric acid (HBO2) and pyrobic acid (tetraboric acid H2B40), is particularly advantageous.
  • Suitable soil repellants are substances which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10.
  • the molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100.
  • the polymers are characterized by an average molecular weight of approximately 5000 to 200,000 and can have a block, but preferably a random structure
  • Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20.
  • Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).
  • foam inhibitors When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents.
  • Soaps of natural or synthetic origin with a high content of Ci8-C24 fatty acids are suitable.
  • 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 different foam inhibitors are also used with advantages, e.g. those made of silicone, 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 pH of the concentrated agents according to the invention is generally 7 to 10.5, preferably 7 to 9.5 and in particular 7 to 8.5. Higher pH values, for example above 9, can be set by using small amounts of sodium hydroxide solution or alkaline salts such as sodium carbonate or sodium silicate.
  • the liquid detergents according to the invention generally have viscosities between 150 and 10,000 mPas (Brookfield viscometer, spindle 1, 20 revolutions per minute, 20 ° C.). The essentially anhydrous Preferred viscosities between 150 and 5000 mPas.
  • the viscosity of the aqueous compositions is preferably below 2000 mPas and in particular between 150 and 1000 mPas.
  • the surfactants mentioned can, in addition to the surfactants mentioned, include other typical ingredients, such as, for example, builders, bleaches, bleach activators, detergency boosters, enzymes, enzyme stabilizers, graying inhibitors, optical brighteners, soil repellants, foam inhibitors, inorganic salts as well as fragrances and dyes.
  • builders for example, bleaches, bleach activators, detergency boosters, enzymes, enzyme stabilizers, graying inhibitors, optical brighteners, soil repellants, foam inhibitors, inorganic salts as well as fragrances and dyes.
  • finely crystalline, synthetic and bound water-containing zeolite such as zeolite NaA in detergent quality is used as the solid builder.
  • zeolite NaX and mixtures of NaA and NaX are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated Ci2-Ci8 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.
  • Suitable substitutes or partial substitutes for zeolites are crystalline, layered sodium silicates of the general formula NaMSi x ⁇ 2x + ryH2 ⁇ , 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 preferred values for x is 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A1 0164514.
  • Preferred crystalline layered silicates are those in which M in the general formula stands for sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na ⁇ Si ⁇ C y ⁇ O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171.
  • the powder detergents according to the invention preferably contain 10 to 60% by weight of zeolite and / or crystalline layered silicates as solid builders, mixtures of zeolite and crystalline layered silicates in any ratio being particularly advantageous.
  • the agents contain 20 to 50% by weight of zeolite and / or crystalline layered silicates.
  • Particularly preferred agents contain up to 40% by weight of zeolite and in particular up to 35% by weight of zeolite, in each case based on anhydrous active substance.
  • Other suitable ingredients of the agents are water-soluble amorphous silicates; they are preferably used in combination with zeolite and / or crystalline layered silicates.
  • Means which are preferred are particularly preferred all sodium silicate with a molar ratio (module) Na 2 0: SiÜ2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, contain.
  • the content of amorphous sodium silicates in the agents is preferably up to 15% by weight and preferably between 2 and 8% by weight.
  • Phosphates such as tripolyphosphates, pyrophosphates and orthophosphates can also be present in small amounts in the compositions.
  • the content of the phosphates in the compositions is preferably up to 15% by weight, but in particular 0 to 10% by weight.
  • the agents can also contain layered silicates of natural and synthetic origin. Layered silicates of this type are known, for example, from patent applications DE-C1 2334899, EP-A1 0026529 and DE-A1 3526405. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable layered silicates, which belong to the group of water-swellable smectites, are, for example, those of the general formulas
  • the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca 2+ .
  • the amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing.
  • Useful layer silicates are known, for example, from US 3,966,629, US 4,062,647, EP-A 0026529 and EP-A 0028432.
  • Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
  • Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrotriesriacetic acid (NTA), provided that such use is not objectionable for ecological reasons. and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of 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 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 to be particularly suitable.
  • Their relative molecular weight, 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. The use of polymeric polycarboxylates is not absolutely necessary.
  • polymeric polycarboxylates preference is given to those which are biodegradable Polymers, for example terpolymers, which contain, as monomers, acrylic acid and maleic acid or their salts and also vinyl alcohol or vinyl alcohol derivatives or which, as monomers, contain acrylic acid and 2-alkylallylsulfonic acid or their salts and sugar derivatives.
  • terpolymers which are obtained according to the teaching of German patent applications DE-A1 4221381 and DE-A1 4300772 are particularly preferred.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A1 0280223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with hydrogen peroxide, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
  • Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing 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 of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which are used instead of Morpholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) - diphenyls, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used.
  • Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also in small amounts, for example Contain 10- 6 to 10- 3 wt .-%, preferably by 10- 5 wt .-%, of a blue dye.
  • a particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).
  • the bulk density of the detergents is generally 300 to 1200 g / l, in particular 500 to 1100 g / l.
  • They can be produced by any of the known processes such as mixing, spray drying, granulating and extruding. Processes in which several partial components, for example spray-dried components and granulated and / or extruded components, are mixed with one another are particularly suitable. It is also possible for spray-dried or granulated components to be subsequently treated, for example with nonionic surfactants, in particular ethoxylated fatty alcohols, by the customary processes.
  • the anionic surfactants which may be present in the form of a spray-dried, granulated or extruded compound, either as an additive component in the process or as an additive to other granules.
  • the preferred heavier granules with bulk densities above 600 g / l preferably contain components which improve the flushing behavior and / or the dissolving behavior of the granules.
  • Alkoxylated fatty alcohols with 12 to 80 moles of ethylene oxide per mole of alcohol for example tallow fatty alcohol with 14 EO, 30 EO or 40 EO, and polyethylene glycols with a relative molecular weight between 200 and 12000, preferably between 200 and 600, are advantageously used for this purpose.
  • Suitable surface modifiers are known from the prior art.
  • finely divided zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts, for example calcium stearate are in particular however, mixtures of zeolite and silica or zeolite and calcium stearate are particularly preferred.

Abstract

The invention relates to non-ionic surfactant mixtures comprised of: (a) alkyl oligoglucosides of formula (I) R<1>O(G)p1, in which R<1> represents a dodecyl/tetradecyl radical, G represents a glucose radical and p1 represents a number ranging from 1 to 3; and (b) alkyl oligoglucosides of formula (II) R<2>O(G)p2, in which R<2> represents a hexadecyl radical, G represents a glucose radical and p2 represents a number ranging from 1 to 3, with the provision that the weight ratio of both constituents ranges from 45:55 to 55:55 and the average degree of polymerization ranges from 1.4 to 1.5. The mixtures are characterized by having an improved washing efficiency with reduced foaming.

Description

Nichtionische TensidmischungenNonionic surfactant mixtures
Gebiet der ErfindungField of the Invention
Die Erfindung befindet sich auf dem Waschmittelsektor und betrifft Gemische von Alkylglucosiden unterschiedlicher Kettenlänge sowie deren Verwendung zur Herstellung von Waschmitteln.The invention is in the detergent sector and relates to mixtures of alkyl glucosides of different chain lengths and their use for the production of detergents.
Stand der TechnikState of the art
Alkyloligoglucoside stellen nichtionische Tenside dar, die durch saure Acetalisierung von Glucose oder Stärkeabbauprodukten mit primären Alkoholen hergestellt werden. Durch Wahl der Prozeßbedingungen läßt sich der durchschnittliche Polymerisationsgrad, d.h. die Verteilung der acetalisierten Mono-, Di-, Tri- und Oligoglucosiden, steuern. Variiert man zusätzlich die Kettenlänge der Alkoholkomponente oder setzt gar Mischungen verschiedener Alkohole ein, sind unzählige Typen von Alkyloligoglucosiden zugänglich, die sich in ihren primären Detergenseigenschaften - Waschen, Emulgieren, Schäumen, Netzen - mehr oder weniger deutlich unterscheiden. Für den Fachmann besteht nun die Aufgabe, das für eine bestimmte Aufgabe geeignetste Alkylglucosid zur Verfügung zu stellen, was bei der großen Zahl möglicher Spezies umfangreiche Testprogramme erforderlich macht, zumal die Strukturparameter nicht alle stets in die gleiche Richtung laufen und Voraussagen über das Verhalten eines definierten Gluco- sids in einer Anwendung daher praktisch nicht möglich ist. Die Entwicklung von Alkyloligoglucosiden mit besonderen Eigenschaften erfolgt daher zwangsläufig nach dem Motto „trial and error".Alkyl oligoglucosides are nonionic surfactants that are produced by acidic acetalization of glucose or starch degradation products with primary alcohols. By choosing the process conditions, the average degree of polymerization, i.e. control the distribution of acetalized mono-, di-, tri- and oligoglucosides. If you also vary the chain length of the alcohol component or even use mixtures of different alcohols, countless types of alkyl oligoglucosides are available, which differ in their primary detergent properties - washing, emulsifying, foaming, wetting - more or less clearly. It is now the task of the person skilled in the art to provide the most suitable alkyl glucoside for a specific task, which makes extensive test programs necessary given the large number of possible species, especially since the structural parameters do not always run in the same direction and predictions about the behavior of a defined one are made Glucosids is therefore practically impossible in one application. The development of alkyl oligoglucosides with special properties is therefore necessarily based on the motto "trial and error".
Alkyloligoglucoside zeichnen sich durch ein Schaumvermögen aus, welches das üblicher nichtionischer Tenside deutlich übersteigt und mehr dem anionischer Tenside ähnelt. Für die Anwendung im Bereich manueller Geschirrspülmittel oder Haarshampoos stellt dies zweifellos einen Vorteil dar, während im Bereich der Waschmittel gerade das umgekehrte Verhalten, nämlich Schaumarmut, gewünscht wird, um ein Überlaufen der Waschmaschine zu verhindern bzw. die erforderliche Menge an Entschäumer möglichst gering zu halten. Ein weiteres Problem besteht darin, daß die handelsüblichen Alkyloligoglucoside insbesondere gegenüber kosmetischen Anschmutzungen ein eher durchschnittliches Reinigungsvermögen zeigen. Dies erklärt, weshalb Alkyloligoglucoside in Waschmittelformulierungen bislang nur eher in bescheidenen Mengen Eingang gefunden haben. In diesem Zusammenhang sei auf die beiden deutschen Patentanmeldungen DE-A1 4319699 und DE- A1 4319700 verwiesen, aus der milde Alkyloligoglucosidmischungen mit definierten Kettenlängen und DP bekannt sind.Alkyl oligoglucosides are characterized by their foaming power, which clearly exceeds that of conventional nonionic surfactants and is more similar to anionic surfactants. This is undoubtedly an advantage for use in the area of manual dishwashing detergents or hair shampoos, whereas in the area of detergents, the opposite behavior, namely low foam, is desired in order to prevent the washing machine from overflowing or to keep the amount of defoamer required as low as possible . Another problem is that the commercially available alkyl oligoglucosides, especially with regard to cosmetic soiling, show a rather average cleaning ability. This explains why alkyl oligoglucosides have so far only been used in modest amounts in detergent formulations. In this connection, reference is made to the two German patent applications DE-A1 4319699 and DE-A1 4319700, from which mild alkyl oligoglucoside mixtures with defined chain lengths and DP are known.
Die komplexe Aufgabe der Erfindung hat daher darin bestanden, neue Alkyloligoglucoside zur Verfügung zu stellen, welche sich bei verminderter Schaumentwicklung durch ein verbessertes Waschvermögen, insbesondere gegenüber kosmetischen Anschmutzungen, auszeichnen sollten.The complex object of the invention was therefore to provide new alkyl oligoglucosides which, with reduced foaming, should be distinguished by improved washability, in particular in relation to cosmetic soiling.
Beschreibung der ErfindungDescription of the invention
Gegenstand der Erfindung sind nichtionische Tensidmischung, bestehend aus (a) Alkyloligoglucosiden der Formel (I),The invention relates to a nonionic surfactant mixture consisting of (a) alkyl oligoglucosides of the formula (I),
R10(G)P1 (I)R10 (G) P 1 (I)
in der R1 für einen Dodecyl/Tetradecylrest, G für einen Glucoserest und p1 für eine Zahl im Bereich von 1 bis 3 steht, und (b) Alkyloligoglucosiden der Formel (II),in which R 1 is a dodecyl / tetradecyl radical, G is a glucose radical and p1 is a number in the range from 1 to 3, and (b) alkyl oligoglucosides of the formula (II),
R20(G)P2 (II)R 2 0 (G) P 2 (II)
in der R2 für einen Hexadecylrest, G für einen Glucoserest und p2 für eine Zahl im Bereich von 1 bis 3 steht, mit der Maßgabe, daß das Gewichtsverhältnis der beiden Komponenten im Bereich von 45 : 55 bis 55 : 45 und der durchschnittliche Polymerisationsgrad im Bereich von 1 ,4 bis 1 ,5 liegt.in which R 2 is a hexadecyl radical, G is a glucose radical and p2 is a number in the range from 1 to 3, with the proviso that the weight ratio of the two components in the range from 45: 55 to 55: 45 and the average degree of polymerization in Range from 1, 4 to 1, 5 is.
Überraschenderweise wurde gefunden, daß die Mischungen sich gegenüber konventionellen Produkten des Handels bei verminderter Schaumentwicklung durch verbesserte Waschleistung, insbesondere gegenüber kosmetischen Anschmutzungen auszeichnen.Surprisingly, it has been found that the mixtures, compared to conventional commercial products with reduced foaming, are distinguished by improved washing performance, in particular by cosmetic soiling.
AlkyloligoglucosideAlkyl oligoglucosides
Alkyloligoglucoside stellen bekannte nichtionische Tenside dar, die üblicherweise durch säurekatalysierte Acetalisierung von Glucose oder abgebautem Stärkesirup mit primären Alkoholen hergestellt werden; im Anschluß wird der Katalysator neutralisiert und überschüssiger Alkohol abdestilliert. Stellvertretend für das umfangreiche Schrifttum sei hier auf die Übersichtsarbeit von Biermann et al. in Starch/Stärke 45, 281 (1993), B.Salka in Cosm.Toil. 108, 89 (1993) sowie J.Kahre et al. in SÖFW- Journal Heft 8, 598 (1995) verwiesen. Durch die Wahl der Reaktionsbedingungen, insbesondere des Alkoholüberschusses, läßt sich der DP, d.h. der durchschnittliche Polymerisationsgrad einstellen, der eine Maßzahl dafür ist, wieviele Zuckermoleküle unter den Bedingungen der Acetalisierung kondensieren, ehe sie sich mit dem Alkohol verbinden. Bezogen auf die erfindungsgemäße Mischung kann die Indexzahl p1 bzw. p2 für die einzelnen, gewissermaßen kettenreinen Alkylglucoside im Bereich von 1 bis 3 liegen, da es im Sinne der Erfindung nur darauf ankommt, daß die Mischung einen DP von 1 ,4 bis 1 ,5 aufweist. Dies kann beispielsweise dann von Bedeutung sein, wenn die Tensidmischungen durch Ausmischen der Einzelglucoside hergestellt werden. Üblicherweise erfolgt die Herstellung jedoch dergestalt, daß man eine entsprechende Alkoholmischung in die Acetalisierung einsetzt und die Reaktion so steuert, daß sich der gewünschte DP unmittelbar einstellt. Vorzugsweise sind in den Tensidmischungen solche Alkyloligoglucoside der Formel (I) enthalten, die die Dodecyl- und Tetradecylglucoside im Gewichtsverhältnis 25 : 75 bis 75 : 25, vorzugsweise 40 : 60 bis 60 : 40 aufweisen. Die Alkyloligoglucoside fallen nach der Herstellung in Form wäßriger Pasten mit einem Feststoffgehalt im Bereich von 30 bis 50 Gew.-% an und können in dieser Form direkt eingesetzt werden, insbesondere dann, wenn sie in Flüssigwaschmittel eingearbeitet werden sollen. Es ist jedoch ebenfalls möglich, die Gluco- side beispielsweise durch Sprühtrocknung, Wasserdampftrockung oder gleichzeitige Trocknung und Granulierung in einem horizontalen Dünnschichtverdampfer (Flash Dryer) zu entwässern und dann als trockene Pulver oder Granulate Pulverwaschmitteln zuzumischen.Alkyl oligoglucosides are known nonionic surfactants which are usually prepared by acid-catalyzed acetalization of glucose or degraded starch syrup with primary alcohols; the catalyst is then neutralized and excess alcohol is distilled off. Representative of the extensive literature here is the review by Biermann et al. in Starch /force 45, 281 (1993), B.Salka in Cosm.Toil. 108, 89 (1993) and J.Kahre et al. in SÖFW- Journal issue 8, 598 (1995). By choosing the reaction conditions, in particular the excess of alcohol, the DP, ie the average degree of polymerization, can be set, which is a measure of how many sugar molecules condense under the conditions of acetalization before they combine with the alcohol. Based on the mixture according to the invention, the index number p1 or p2 for the individual, to a certain extent, chain-pure alkyl glucosides can be in the range from 1 to 3, since in the sense of the invention it is only important that the mixture has a DP of 1.4 to 1.5 having. This can be important, for example, if the surfactant mixtures are produced by mixing the individual glucosides. Usually, however, the preparation takes place in such a way that an appropriate alcohol mixture is used in the acetalization and the reaction is controlled in such a way that the desired DP is established immediately. The surfactant mixtures preferably contain those alkyl oligoglucosides of the formula (I) which have the dodecyl and tetradecyl glucosides in a weight ratio of 25:75 to 75:25, preferably 40:60 to 60:40. The alkyl oligoglucosides are obtained in the form of aqueous pastes with a solids content in the range from 30 to 50% by weight and can be used directly in this form, in particular if they are to be incorporated into liquid detergents. However, it is also possible to dewater the glucosides, for example by spray drying, steam drying or simultaneous drying and granulation in a horizontal thin-film evaporator (flash dryer), and then adding powder detergents as dry powders or granules.
Gewerbliche AnwendbarkeitIndustrial applicability
Nachdem sich die erfindungsgemäßen Tensidgemische durch verbesserte Reinigungsleistung bei verminderter Schaumentwicklung auszeichnen, besteht ein weiterer Gegenstand der Erfindung in ihrer Verwendung zur Herstellung von Waschmitteln, insbesondere Flüssigwaschmitteln, in denen sie in Mengen von 5 bis 50, vorzugsweise 10 bis 30 und insbesondere 15 bis 25 Gew.-% - bezogen auf die I - enthalten sein können.After the surfactant mixtures according to the invention are distinguished by improved cleaning performance with reduced foaming, another object of the invention is their use for the production of detergents, in particular liquid detergents, in which they are present in amounts of 5 to 50, preferably 10 to 30 and in particular 15 to 25% by weight .-% - based on the I - may be included.
FlüssigwaschmittelLiquid detergent
Die im Sinne der Erfindung unter Verwendung der nichtionischen Tensidgemische erhältlichen Flüssigwaschmittel können einen nicht wäßrigen Anteil im Bereich von 5 bis 50 und vorzugsweise 15 bis 35 Gew.-% aufweisen. Im einfachsten Fall handelt es sich um wäßrige Lösungen der genannten Tensidmischungen. Bei den Flüssigwaschmitteln kann es sich aber auch um im wesentlichen wasserfreie Mittel handeln. Dabei bedeutet "im wesentlichen wasserfrei" im Rahmen dieser Erfindung, daß das Mittel vorzugsweise kein freies, nicht als Kristallwasser oder in vergleichbarer Form gebundenes Was- ser enthält. In einigen Fällen sind geringe Menge an freiem Wasser tolerierbar, insbesondere in Mengen bis zu 5 Gew.-%.The liquid detergents obtainable for the purposes of the invention using the nonionic surfactant mixtures can have a nonaqueous fraction in the range from 5 to 50 and preferably 15 to 35% by weight. In the simplest case, these are aqueous solutions of the surfactant mixtures mentioned. The liquid detergents can, however, also be essentially water-free detergents. In the context of this invention, “essentially anhydrous” means that the agent preferably does not contain any free water which is not bound as water of crystallization or in a comparable form. it contains. In some cases, small amounts of free water are tolerable, especially in amounts up to 5% by weight.
Die Flüssigwaschmittel können neben den genannten Tensiden noch weitere typische Inhaltsstoffe, wie beispielsweise Lösungsmittel, Hydrotrope, Bleichmittel, Builder, Viskositätsregulatoren, Enzyme, Enzymstabilisatoren, optische Aufheller, Soil repellants, Schauminhibitoren, anorganische Salze sowie Duft- und Farbstoffe aufweisen, unter der Voraussetzung, daß diese im wäßrigen Milieu hinreichend lagerstabil sind.In addition to the surfactants mentioned, the liquid detergents may also have other typical ingredients, such as, for example, solvents, hydrotropes, bleaches, builders, viscosity regulators, enzymes, enzyme stabilizers, optical brighteners, soil repellants, foam inhibitors, inorganic salts and fragrances and colorants, provided that these are sufficiently stable in an aqueous environment.
Als organische Lösungsmittel kommen beispielsweise mono- und/oder polyfunktionelle Alkohole mit 1 bis 6 Kohlenstoffatomen, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in Frage. Bevorzugte Alkohole sind Ethanol, 1 ,2-Propandiol, Glycerin sowie deren Gemische. Die Mittel enthalten vorzugsweise 2 bis 20 Gew.-% und insbesondere 5 bis 15 Gew.-% Ethanol oder ein beliebiges Gemisch aus Ethanol und 1 ,2-Propandiol oder insbesondere aus Ethanol und Glycerin. Ebenso ist es möglich, daß die Zubereitungen entweder zusätzlich zu den mono- und/oder polyfunktionellen Alkoholen mit 1 bis 6 Kohlenstoffatomen oder allein Polyethylenglykol mit einer relativen Molekülmasse zwischen 200 und 2000, vorzugsweise bis 600 in Mengen von 2 bis 17 Gew.-% enthalten. Als Hydrotrope können beispielsweise Toluolsulfonat, Xylolsulfonat, Cumolsulfonat oder deren Mischungen eingesetzt werden.Examples of suitable organic solvents are monofunctional and / or polyfunctional alcohols having 1 to 6 carbon atoms, preferably having 1 to 4 carbon atoms. Preferred alcohols are ethanol, 1, 2-propanediol, glycerol and mixtures thereof. The compositions preferably contain 2 to 20% by weight and in particular 5 to 15% by weight of ethanol or any mixture of ethanol and 1, 2-propanediol or in particular of ethanol and glycerol. It is also possible that the preparations either contain, in addition to the mono- and / or polyfunctional alcohols having 1 to 6 carbon atoms or solely polyethylene glycol with a relative molecular weight between 200 and 2000, preferably up to 600, in amounts of 2 to 17% by weight . For example, toluenesulfonate, xylenesulfonate, cumene sulfonate or mixtures thereof can be used as hydrotropes.
Unter den als Bleichmittel dienenden, in Wasser Wasserstoffperoxid liefernden Verbindungen haben das Natriumperborat-Tetrahydrat und das Nat umperborat-Monohydrat eine besondere Bedeutung. Weitere Bleichmittel sind beispielsweise Peroxycarbonat, Citratperhydrate sowie Salze der Persäuren, wie Perbenzoate, Peroxyphthalate oder Diperoxydodecandisäure. Sie werden üblicherweise in Mengen von 8 bis 25 Gew.-% eingesetzt. Bevorzugt ist der Einsatz von Nathumperborat-Monohydrat in Mengen von 10 bis 20 Gew.-% und insbesondere von 10 bis 15 Gew.-%. Durch seine Fähigkeit, unter Ausbildung des Tetrahydrats freies Wasser binden zu können, trägt es zur Erhöhung der Stabilität des Mittels bei. Vorzugsweise sind die Zubereitungen jedoch frei von derartigen Bleichmitteln.Among the compounds which serve as bleaching agents and which supply hydrogen peroxide in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents are, for example, peroxy carbonate, citrate perhydrates and salts of peracids, such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight. The use of nathumperborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred. Due to its ability to bind free water with the formation of the tetrahydrate, it contributes to increasing the stability of the agent. However, the preparations are preferably free from such bleaching agents.
Geeignete Builder sind Ethylendiamintetraessigsäure, Nitrilotriessigsäure, Citronensäure sowie anorganische Phosphonsäuren, wie z.B. die neutral reagierenden Natriumsalze von 1-Hydroxyethan-1 ,1 ,- diphosphonat, die in Mengen von 0,5 bis 5, vorzugsweise 1 bis 2 Gew.-% zugegen sein können.Suitable builders are ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids, e.g. the neutral reacting sodium salts of 1-hydroxyethane-1, 1, - diphosphonate, which can be present in amounts of 0.5 to 5, preferably 1 to 2 wt .-%.
Als Viskositätsregulatoren können beispielsweise gehärtetes Rizinusöl, Salze von langkettigen Fettsäuren, die vorzugsweise in Mengen von 0 bis 5 Gew.-% und insbesondere in Mengen von 0,5 bis 2 Gew.-%, beispielsweise Natrium-, Kalium-, Aluminium-, Magnesium- und Titanstearate oder die Natrium- und/oder Kaliumsalze der Behensäure, sowie weitere polymere Verbindungen eingesetzt werden. Zu den letzteren gehören bevorzugt Polyvinylpyrrolidon, Urethane und die Salze polymerer Polycar- boxylate, beispielsweise homopolymerer oder copolymerer Polyacrylate, Polymethacrylate und insbe- sondere Copolymere der Acrylsäure mit Maleinsäure, vorzugsweise solche aus 50 % bis 10 % Maleinsäure. Die relative Molekülmasse der Homopolymeren liegt im allgemeinen zwischen 1000 und 100000, die der Copolymeren zwischen 2000 und 200000, vorzugsweise zwischen 50000 bis 120000, bezogen auf die freie Säure. Insbesondere sind auch wasserlösliche Polyacrylate geeignet, die beispielsweise mit etwa 1 % eines Polyallylethers der Sucrose quervernetzt sind und die eine relative Molekülmasse oberhalb einer Million besitzen. Beispiele hierfür sind die unter dem Namen Carbopol® 940 und 941 erhältlichen Polymere mit verdickender Wirkung. Die quervernetzten Polyacrylate werden vorzugsweise in Mengen nicht über 1 Gew.-%, vorzugsweise in Mengen von 0,2 bis OJ Gew.-% eingesetzt. Die Mittel können zusätzlich etwa 5 bis 20 Gew.-% eines partiell veresterten Copolymerisats enthalten, wie es in der europäischen Patentanmeldung EP-A1 0367049 beschrieben ist. Diese partiell veresterten Polymere werden durch Copolymerisation von (a) mindestens einem C4-C28-Olefin oder Mischungen aus mindestens einem C4-C28-Olefin mit bis zu 20 Mol-% Cι-C2β-Alkylvinylethern und (b) ethylenisch ungesättigten Dicarbonsäureanhydriden mit 4 bis 8 Kohlenstoffatomen im Molverhältnis 1 : 1 zu Copoly- merisaten mit K-Werten von 6 bis 100 und anschließende partielle Veresterung der Copolymerisate mit Umsetzungsprodukten wie Cι-Cι3-Alkoholen, C8-C22-Fettsäuren, Cι-Ci2-Alkylphenolen, sekundären C2- C30-Aminen oder deren Mischungen mit mindestens einem C2-C -Alkylenoxid oder Tetrahydrofuran sowie Hydrolyse der Anhydridgruppen der Copolymerisate zu Carboxylgruppen erhalten, wobei die partielle Veresterung der Copolymerisate soweit geführt wird, daß 5 bis 50 % der Carboxylgruppen der Copolymerisate verestert sind. Bevorzugte Copolymerisate enthalten als ethylenisch ungesättigtes Dicar- bonsäureanhydrid Maleinsäureanhydrid. Die partiell veresterten Copolymerisate können entweder in Form der freien Säure oder vorzugsweise in partiell oder vollständig neutralisierter Form vorliegen. Vorteilhafterweise werden die Copolymerisate in Form einer wäßrigen Lösung, insbesondere in Form einer 40 bis 50 Gew.-%igen Lösung eingesetzt. Die Copolymerisate leisten nicht nur einen Beitrag zur Primär- und Sekundärwaschleistung des flüssigen Wasch- und Reinigungsmittels, sondern bewirken auch eine gewünschte Viskositätserniedrigung der konzentrierten flüssigen Waschmittel. Durch den Einsatz dieser partiell veresterten Copolymerisate werden konzentrierte wäßrige Flüssigwaschmittel erhalten, die unter dem alleinigen Einfluß der Schwerkraft und ohne Einwirkung sonstiger Scherkräfte fließfähig sind. Vorzugsweise beinhalten die konzentrierten wäßrigen Flüssigwaschmittel partiell vere- sterte Copolymerisate in Mengen von 5 bis 15 Gew.-% und insbesondere in Mengen von 8 bis 12 Gew.-%.Viscosity regulators which can be used are, for example, hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium - And titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used. The latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular special copolymers of acrylic acid with maleic acid, preferably those from 50% to 10% maleic acid. The relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably between 50,000 to 120,000, based on the free acid. Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above one million are also particularly suitable. Examples of this are the polymers with thickening action available under the name Carbopol® 940 and 941. The crosslinked polyacrylates are preferably used in amounts of not more than 1% by weight, preferably in amounts of 0.2 to OJ% by weight. The agents can additionally contain about 5 to 20% by weight of a partially esterified copolymer, as described in European patent application EP-A1 0367049. These partially esterified polymers are obtained by copolymerizing (a) at least one C 4 -C28 olefin or mixtures of at least one C 4 -C28 olefin with up to 20 mol% of C 1 -C 2 -alkyl vinyl ethers and (b) ethylenically unsaturated dicarboxylic acid anhydrides 4 to 8 carbon atoms in a molar ratio of 1: 1 to copolymers with K values from 6 to 100 and subsequent partial esterification of the copolymers with reaction products such as C 1 -C 3 alcohols, C 8 -C 22 fatty acids, C 1 -C 2 -alkylphenols, secondary C2-C 30 amines or their mixtures with at least one C2-C-alkylene oxide or tetrahydrofuran and hydrolysis of the anhydride groups of the copolymers to give carboxyl groups, the partial esterification of the copolymers being carried out to such an extent that 5 to 50% of the carboxyl groups of the copolymers are esterified . Preferred copolymers contain maleic anhydride as the ethylenically unsaturated dicarboxylic anhydride. The partially esterified copolymers can be present either in the form of the free acid or preferably in partially or completely neutralized form. The copolymers are advantageously used in the form of an aqueous solution, in particular in the form of a 40 to 50% strength by weight solution. The copolymers not only contribute to the primary and secondary washing performance of the liquid washing and cleaning agent, but also bring about a desired reduction in the viscosity of the concentrated liquid washing agent. The use of these partially esterified copolymers gives concentrated aqueous liquid detergents which are flowable under the sole influence of gravity and without the action of other shear forces. The concentrated aqueous liquid detergents preferably contain partially esterified copolymers in amounts of 5 to 15% by weight and in particular in amounts of 8 to 12% by weight.
Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen, Cellulasen bzw. deren Gemische in Frage. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus sub- tilis, Bacillus licheniformis und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Vorzugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Ihr Anteil kann etwa 0,2 bis etwa 2 Gew.-% betragen. Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen. Zusätzlich zu den mono- und polyfunktionellen Alkoholen und den Phos- phonaten können die Mittel weitere Enzymstabilisatoren enthalten. Beispielsweise können 0,5 bis 1 Gew.-% Natriumformiat eingesetzt werden. Möglich ist auch der Einsatz von Proteasen, die mit löslichen Caiciumsalzen und einem Caiciumgehalt von vorzugsweise etwa 1 ,2-Gew.-%, bezogen auf das Enzym, stabilisiert sind. Besonders vorteilhaft ist jedoch der Einsatz von Borverbindungen, beispielsweise von Borsäure, Boroxid, Borax und anderen Alkalimetallboraten wie den Salzen der Ortho- borsäure (H3Bθ3), der Metaborsäure (HBO2) und der Pyroborsäure (Tetraborsäure H2B40 ).Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Their proportion can be about 0.2 to about 2% by weight. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. In addition to the mono- and polyfunctional alcohols and the phospho- Phonates can contain other enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 Bθ3), metaboric acid (HBO2) and pyrobic acid (tetraboric acid H2B40), is particularly advantageous.
Als schmutzabweisenden Polymere („soil repellants") kommen solche Stoffe in Frage, die vorzugsweise Ethylenterephthalat- und/oder Polyethylenglycolterephthalatgruppen enthalten, wobei das Molverhältnis Ethylenterephthalat zu Polyethylenglycolterephthalat im Bereich von 50 : 50 bis 90 : 10 liegen kann. Das Molekulargewicht der verknüpfenden Polyethylenglycoleinheiten liegt insbesondere im Bereich von 750 bis 5000, d.h., der Ethoxylierungsgrad der Polyethylenglycolgruppenhaltigen Polymere kann ca. 15 bis 100 betragen. Die Polymeren zeichnen sich durch ein durchschnittliches Molekulargewicht von etwa 5000 bis 200.000 aus und können eine Block-, vorzugsweise aber eine Random- Struktur aufweisen. Bevorzugte Polymere sind solche mit Molverhältnissen Ethylenterephtha- lat/Polyethylenglycolterephthalat von etwa 65 : 35 bis etwa 90 : 10, vorzugsweise von etwa 70 : 30 bis 80 : 20. Weiterhin bevorzugt sind solche Polymeren, die verknüpfende Polyethylenglycoleinheiten mit einem Molekulargewicht von 750 bis 5000, vorzugsweise von 1000 bis etwa 3000 und ein Molekulargewicht des Polymeren von etwa 10.000 bis etwa 50.000 auf- weisen. Beispiele für handelsübliche Polymere sind die Produkte Milease® T (ICI) oder Repelotex® SRP 3 (Rhöne-Poulenc).Suitable soil repellants are substances which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10. The molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100. The polymers are characterized by an average molecular weight of approximately 5000 to 200,000 and can have a block, but preferably a random structure Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Also preferred are those polymers which have linking polyethylene glycol units with a molecular weight Not from 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of the polymer from about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).
Beim Einsatz in maschinellen Waschverfahren kann es von Vorteil sein, den Mitteln übliche Schauminhibitoren zuzusetzen. Hierfür eignen sich beispielsweise Seifen natürlicher oder synthetischer Herkunft, die einen hohen Anteil an Ci8-C24-Fettsäuren aufweisen. Geeignete nichttensidartige Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure oder Bistearylethylendiamid. Mit Vorteilen werden auch Gemische aus verschiedenen Schauminhibitoren verwendet, z.B. solche aus Silikonen, Paraffinen oder Wachsen. Vorzugsweise sind die Schauminhibitoren, insbesondere silikon- oder paraffinhaltige Schauminhibitoren, an eine granuläre, in Wasser lösliche bzw. dispergierbare Trägersubstanz gebunden. Insbesondere sind dabei Mischungen aus Paraffinen und Bistearylethylendiamiden bevorzugt.When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Soaps of natural or synthetic origin with a high content of Ci8-C24 fatty acids are suitable. 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 different foam inhibitors are also used with advantages, e.g. those made of silicone, 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.
Der pH-Wert der erfindungsgemäßen und insbesondere bevorzugten konzentrierten Mittel beträgt im allgemeinen 7 bis 10,5, vorzugsweise 7 bis 9,5 und insbesondere 7 bis 8,5. Die Einstellung höherer pH- Werte, beispielsweise oberhalb von 9, kann durch den Einsatz geringer Mengen an Natronlauge oder an alkalischen Salzen wie Nat umcarbonat oder Nat umsilicat erfolgen. Die erfindungsgemäßen Flüs- sigwaschmittei weisen im allgemeinen Viskositäten zwischen 150 und 10000 mPas (Brookfield-Viskosi- meter, Spindel 1 , 20 Umdrehungen pro Minute, 20°C). Dabei sind bei den im wesentlichen wasserfrei- en Mitteln Viskositäten zwischen 150 und 5000 mPas bevorzugt. Die Viskosität der wäßrigen Mittel liegt vorzugsweise unter 2000 mPas und liegt insbesondere zwischen 150 und 1000 mPas.The pH of the concentrated agents according to the invention, which are particularly preferred, is generally 7 to 10.5, preferably 7 to 9.5 and in particular 7 to 8.5. Higher pH values, for example above 9, can be set by using small amounts of sodium hydroxide solution or alkaline salts such as sodium carbonate or sodium silicate. The liquid detergents according to the invention generally have viscosities between 150 and 10,000 mPas (Brookfield viscometer, spindle 1, 20 revolutions per minute, 20 ° C.). The essentially anhydrous Preferred viscosities between 150 and 5000 mPas. The viscosity of the aqueous compositions is preferably below 2000 mPas and in particular between 150 and 1000 mPas.
PulverwaschmittelPowder detergent
Werden die erfindungsgemäßen Tensidgemische zur Herstellung von Pulverwaschmitteln verwendet, so können die neben den genannten Tensiden noch weitere typische Inhaltsstoffe, wie beispielsweise Builder, Bleichmittel, Bleichaktivatoren, Waschkraftverstärker, Enzyme, Enzymstabilisatoren, Vergrau- ungsinhibitoren, optische Aufheller, Soil repellants, Schauminhibitoren, anorganische Salze sowie Duft- und Farbstoffe enthalten. Eine Reihe dieser Stoffklassen wurde schon im Kapitel „Flüssigwaschmittel" erläutert.If the surfactant mixtures according to the invention are used to produce powder detergents, the surfactants mentioned can, in addition to the surfactants mentioned, include other typical ingredients, such as, for example, builders, bleaches, bleach activators, detergency boosters, enzymes, enzyme stabilizers, graying inhibitors, optical brighteners, soil repellants, foam inhibitors, inorganic salts as well as fragrances and dyes. A number of these classes of substances have already been explained in the chapter "Liquid detergents".
Als feste Builder wird insbesondere feinkristalliner, synthetisches und gebundenes Wasser enthaltender Zeolith wie Zeolith NaA in Waschmittelqualität eingesetzt. Geeignet sind jedoch auch Zeolith NaX sowie Mischungen aus NaA und NaX. Der Zeolith kann als sprühgetrocknetes Pulver oder auch als ungetrocknete, von ihrer Herstellung noch feuchte, stabilisierte Suspension zum Einsatz kommen. Für den Fall, daß der Zeolith als Suspension eingesetzt wird, kann diese geringe Zusätze an nichtionischen Tensiden als Stabilisatoren enthalten, beispielsweise 1 bis 3 Gew.-%, bezogen auf Zeolith, an ethoxylierten Ci2-Ci8-Fettalkoholen mit 2 bis 5 Ethylenoxidgruppen oder ethoxylierte Isotridecanole. Geeignete Zeolithe weisen eine mittlere Teilchengröße von weniger als 10 μm (Volumenverteilung; Meßmethode: Coulter Counter) auf und enthalten vorzugsweise 18 bis 22, insbesondere 20 bis 22 Gew.-% an gebundenem Wasser. Geeignete Substitute bzw. Teilsubstitute für Zeolithe sind kristalline, schichtförmige Natriumsilicate der allgemeinen Formel NaMSixθ2x+ryH2θ, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1 ,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Derartige kristalline Schichtsilicate werden beispielsweise in der europäischen Patentanmeldung EP-A1 0164514 beschrieben. Bevorzugte kristalline Schichtsilicate sind solche, in denen M in der allgemeinen Formel für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch γ-Natriumdisilicate Na∑Si∑C y^O bevorzugt, wobei ß-Natriumdisilicat beispielsweise nach dem Verfahren erhalten werden kann, das in der internationalen Patentanmeldung WO 91/08171 beschrieben ist. Die erfindungsgemäßen Pulverwaschmittel enthalten als feste Builder vorzugsweise 10 bis 60 Gew.-% Zeolith und/oder kristalline Schichtsilicate, wobei Mischungen von Zeolith und kristallinen Schichtsilicaten in einem beliebigen Verhältnis besonders vorteilhaft sein können. Insbesondere ist es bevorzugt, daß die Mittel 20 bis 50 Gew.-% Zeolith und/oder kristalline Schichtsilicate enthalten. Besonders bevorzugte Mittel enthalten bis 40 Gew.-% Zeolith und insbesondere bis 35 Gew.-% Zeolith, jeweils bezogen auf wasserfreie Aktivsubstanz. Weitere geeignete Inhaltsstoffe der Mittel sind wasserlösliche amorphe Silicate; vorzugsweise werden sie in Kombination mit Zeolith und/oder kristallinen Schichtsilicaten eingesetzt. Insbesondere bevorzugt sind dabei Mittel, welche vor allem Natriumsilicat mit einem molaren Verhältnis (Modul) Na20 : SiÜ2 von 1 :1 bis 1 :4,5, vorzugsweise von 1 :2 bis 1 :3,5, enthalten. Der Gehalt der Mittel an amorphen Natriumsilicaten beträgt dabei vorzugsweise bis 15 Gew.-% und vorzugsweise zwischen 2 und 8 Gew.-%. Auch Phosphate wie Tripolyphos- phate, Pyrophosphate und Orthophosphate können in geringen Mengen in den Mitteln enthalten sein. Vorzugsweise beträgt der Gehalt der Phosphate in den Mitteln bis 15 Gew.-%, jedoch insbesondere 0 bis 10 Gew.-%. Außerdem können die Mittel auch zusätzlich Schichtsilicate natürlichen und synthetischen Ursprungs enthalten. Derartige Schichtsilicate sind beispielsweise aus den Patent-anmeldungen DE-C1 2334899, EP-A1 0026529 und DE-A1 3526405 bekannt. Ihre Verwendbarkeit ist nicht auf eine spezielle Zusammensetzung bzw. Strukturformel beschränkt. Bevorzugt sind hier jedoch Smectite, insbesondere Bentonite. Geeignete Schichtsilicate, die zur Gruppe der mit Wasser quellfähigen Smectite zählen, sind z.B. solche der allgemeinen FormelnIn particular, finely crystalline, synthetic and bound water-containing zeolite such as zeolite NaA in detergent quality is used as the solid builder. However, zeolite NaX and mixtures of NaA and NaX are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated Ci2-Ci8 fatty alcohols with 2 to 5 ethylene oxide groups or ethoxylated Isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water. Suitable substitutes or partial substitutes for zeolites are crystalline, layered sodium silicates of the general formula NaMSi x θ2x + ryH2θ, 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 preferred values for x is 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A1 0164514. Preferred crystalline layered silicates are those in which M in the general formula stands for sodium and x assumes the values 2 or 3. In particular, both β- and γ-sodium disilicate Na ∑ Si ∑ C y ^ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171. The powder detergents according to the invention preferably contain 10 to 60% by weight of zeolite and / or crystalline layered silicates as solid builders, mixtures of zeolite and crystalline layered silicates in any ratio being particularly advantageous. In particular, it is preferred that the agents contain 20 to 50% by weight of zeolite and / or crystalline layered silicates. Particularly preferred agents contain up to 40% by weight of zeolite and in particular up to 35% by weight of zeolite, in each case based on anhydrous active substance. Other suitable ingredients of the agents are water-soluble amorphous silicates; they are preferably used in combination with zeolite and / or crystalline layered silicates. Means which are preferred are particularly preferred all sodium silicate with a molar ratio (module) Na 2 0: SiÜ2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, contain. The content of amorphous sodium silicates in the agents is preferably up to 15% by weight and preferably between 2 and 8% by weight. Phosphates such as tripolyphosphates, pyrophosphates and orthophosphates can also be present in small amounts in the compositions. The content of the phosphates in the compositions is preferably up to 15% by weight, but in particular 0 to 10% by weight. In addition, the agents can also contain layered silicates of natural and synthetic origin. Layered silicates of this type are known, for example, from patent applications DE-C1 2334899, EP-A1 0026529 and DE-A1 3526405. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable layered silicates, which belong to the group of water-swellable smectites, are, for example, those of the general formulas
(OH)4Si8-yAly(MgxAI4-x)θ2o Montmorrilonit (OH)4Si8-yAly(Mg6-zLiz)02Q Hectorit (OH)4Si8-yAly(Mg6-z Alz)O20 Saponit(OH) 4Si8-yAly (MgxAI 4 -x) θ2o montmorrilonite (OH) 4Si8- y Aly (Mg6- z Liz) 0 2 Q hectorite (OH) 4 Si8-yAly (Mg 6 - z Al z ) O 20 saponite
mit x = 0 bis 4, y = 0 bis 2, z = 0 bis 6. Zusätzlich kann in das Kristallgitter der Schichtsilicate gemäß den vorstehenden Formeln geringe Mengen an Eisen eingebaut sein. Ferner können die Schichtsilicate aufgrund ihrer ionenaustauschenden Eigenschaften Wasserstoff-, Alkali-, Erdalkaliionen, insbesondere Na+ und Ca2+ enthalten. Die Hydratwassermenge liegt meist im Bereich von 8 bis 20 Gew.-% und ist vom Quellzustand bzw. von der Art der Bearbeitung abhängig. Brauchbare Schichtsilicate sind beispielsweise aus US 3,966,629, US 4,062,647, EP-A 0026529 und EP-A 0028432 bekannt. Vorzugsweise werden Schichtsilicate verwendet, die aufgrund einer Alkalibehandlung weitgehend frei von Cal- ciumionen und stark färbenden Eisenionen sind. Brauchbare organische Gerüstsubstanzen sind beispielsweise die bevorzugt in Form ihrer Natriumsalze eingesetzten Polycarbonsäuren, wie Citronen- säure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren, Aminocarbonsäuren, Nitri- lotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citro- nensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren und Mischungen aus diesen. Geeignete polymere Polycarboxylate sind beispielsweise die Natriumsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 800 bis 150000 (auf Säure bezogen). Geeignete copolymere Polycarboxylate sind insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 5000 bis 200000, vorzugsweise 10000 bis 120000 und insbesondere 50000 bis 100000. Der Einsatz poiymerer Polycarboxylate ist nicht zwingend erforderlich. Falls jedoch polymere Polycarboxylate eingesetzt werden, so sind Mittel bevorzugt, welche biologisch abbaubare Polymere, beispielsweise Terpolymere, die als Monomere Acrylsäure und Maleinsäure bzw. deren Salze sowie Vinylalkohol bzw. Vinylalkohol-Derivate oder die als Monomere Acrylsäure und 2- Alkylallylsulfonsäure bzw. deren Salze sowie Zuckerderivate enthalten. Insbesondere sind Terpolymere bevorzugt, die nach der Lehre der deutschen Patentanmeldungen DE-A1 4221381 und DE-A1 4300772 erhalten werden. Weitere geeignete Buildersubstanzen sind Polyacetale, welche durch Umsetzung von Dialdehyden mit Polyolcarbonsäuren, welche 5 bis 7 Kohlenstoffatome und mindestens 3 Hydroxylgruppen aufweisen, beispielsweise wie in der europäischen Patentanmeldung EP-A1 0280223 beschrieben erhalten werden können. Bevorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutaraldehyd, Terephthalaldehyd sowie deren Gemischen und aus Polyolcarbonsäuren wie Glucon- säure und/oder Glucoheptonsäure erhalten.with x = 0 to 4, y = 0 to 2, z = 0 to 6. In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas. Furthermore, due to their ion-exchanging properties, the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca 2+ . The amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing. Useful layer silicates are known, for example, from US 3,966,629, US 4,062,647, EP-A 0026529 and EP-A 0028432. Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment. Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrotriesriacetic acid (NTA), provided that such use is not objectionable for ecological reasons. and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. Suitable polymeric polycarboxylates are, for example, the sodium salts of 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 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 to be particularly suitable. Their relative molecular weight, 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. The use of polymeric polycarboxylates is not absolutely necessary. However, if polymeric polycarboxylates are used, preference is given to those which are biodegradable Polymers, for example terpolymers, which contain, as monomers, acrylic acid and maleic acid or their salts and also vinyl alcohol or vinyl alcohol derivatives or which, as monomers, contain acrylic acid and 2-alkylallylsulfonic acid or their salts and sugar derivatives. Terpolymers which are obtained according to the teaching of German patent applications DE-A1 4221381 and DE-A1 4300772 are particularly preferred. Further suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A1 0280223. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.
Um beim Waschen bei Temperaturen von 60°C und darunter eine verbesserte Bleichwirkung zu erreichen, können Bleichaktivatoren in die Präparate eingearbeitet werden. Beispiele hierfür sind mit Wasserstoffperoxid organische Persäuren bildende N-Acyl- bzw. O-Acyl-Verbindungen, vorzugsweise N,N'- tetraacylierte Diamine, femer Carbonsäureanhydride und Ester von Polyolen wie Glucosepentaacetat. Der Gehalt der bleichmittelhaltigen Mittel an Bleichaktivatoren liegt in dem üblichen Bereich, vorzugsweise zwischen 1 und 10 Gew.-% und insbesondere zwischen 3 und 8 Gew.-%. Besonders bevorzugte Bleichaktivatoren sind N,N,N',N'-Tetraacetylethylendiamin und 1,5-Diacetyl-2,4-dioxo-hexahydro-1,3,5- triazin.In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples of these are N-acyl or O-acyl compounds which form organic peracids with hydrogen peroxide, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. The bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
Vergrauungsinhibitoren haben die Aufgabe, den von der Faser abgelösten Schmutz in der Flotte suspendiert zu halten und so das Vergrauen zu verhindern. Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise die wasserlöslichen Salze polymerer Carbonsäuren, Leim, Gelatine, Salze von Ethercarbonsäuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich lösliche Stärkepräparate und andere als die obengenannten Stärkeprodukte verwenden, z.B. abgebaute Stärke, Aldehydstärken usw.. Auch Polyvinylpyrrolidon ist brauchbar. Bevorzugt werden jedoch Celluloseether, wie Carboxymethylcellulose, Methylcellulose, Hydroxyalkylcellulose und Mischether, wie Methylhy- droxyethylcellulose, Methylhydroxypropylcellulose, Methylcarboxymethylcellulose und deren Gemische sowie Polyvinylpyrrolidon, beispielsweise in Mengen von 0,1 bis 5 Gew.-%, bezogen auf die Mittel.Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing 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 of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, preference is given to cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition.
Die Mittel können als optische Aufheller Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z.B. Salze der 4,4'-Bis(2-anilino-4-morpholino-1 ,3,5-triazinyl-6-ami- no)stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholino- Gruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilinogruppe oder eine 2-Meth- oxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ der substituierten Diphenylstyryle anwesend sein, z.B. die Alkalisalze des 4,4'-Bis(2-sulfostyryl)-diphenyls, 4,4'-Bis(4-chlor-3-sulfostyryl)- diphenyls, oder 4-(4-Chlorstyryl)-4'-(2-sulfostyryl)-diphenyls. Auch Gemische der vorgenannten Aufheller können verwendet werden. Einheitlich weiße Granulate werden erhalten, wenn die Mittel außer den üblichen Aufhellern in üblichen Mengen, beispielsweise zwischen 0,1 und 0,5 Gew.-%, vorzugsweise zwischen 0,1 und 0,3 Gew.-%, auch geringe Mengen, beispielsweise 10-6 bis 10-3 Gew.-%, vorzugsweise um 10-5 Gew.-%, eines blauen Farbstoffs enthalten. Ein besonders bevorzugter Farbstoff ist Tinolux® (Handelsprodukt der Ciba-Geigy).As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which are used instead of Morpholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) - diphenyls, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used. Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also in small amounts, for example Contain 10- 6 to 10- 3 wt .-%, preferably by 10- 5 wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).
HerstellverfahrenManufacturing process
Das Schüttgewicht der Waschmittel beträgt im allgemeinen 300 bis 1200 g/l, insbesondere 500 bis 1100 g/l. Ihre Herstellung kann nach jedem der bekannten Verfahren wie Mischen, Sprühtrocknung, Granulieren und Extrudieren erfolgen. Geeignet sind insbesondere solche Verfahren, in denen mehrere Teilkomponenten, beispielsweise sprühgetrocknete Komponenten und granulierte und/oder extrudierte Komponenten miteinander vermischt werden. Dabei ist es auch möglich, daß sprühgetrocknete oder granulierte Komponenten nachträglich in der Aufbereitung beispielsweise mit nichtionischen Tensiden, insbesondere ethoxylierten Fettalkoholen, nach den üblichen Verfahren beaufschlagt werden. Insbesondere in Granululations- und Extrusionsverfahren ist es bevorzugt, die gegebenenfalls vorhandenen Aniontenside in Form eines sprühgetrockneten, granulierten oder extrudierten Compounds entweder als Zumischkomponente in dem Verfahren oder als Additiv nachträglich zu anderen Granulaten einzusetzen. Insbesondere die bevorzugten schwereren Granulate mit Schüttgewichten oberhalb 600 g/l enthalten vorzugsweise Komponenten, welche das Einspülverhalten und/oder das Löseverhalten der Granulate verbessern. Vorteilhafterweise werden hierzu alkoxylierte Fettalkohole mit 12 bis 80 Mol Ethylenoxid pro Mol Alkohol, beispielsweise Taigfettalkohol mit 14 EO, 30 EO oder 40 EO, und Polye- thylenglykole mit einer relativen Molekülmasse zwischen 200 und 12000, vorzugsweise zwischen 200 und 600, eingesetzt.The bulk density of the detergents is generally 300 to 1200 g / l, in particular 500 to 1100 g / l. They can be produced by any of the known processes such as mixing, spray drying, granulating and extruding. Processes in which several partial components, for example spray-dried components and granulated and / or extruded components, are mixed with one another are particularly suitable. It is also possible for spray-dried or granulated components to be subsequently treated, for example with nonionic surfactants, in particular ethoxylated fatty alcohols, by the customary processes. In granulation and extrusion processes in particular, it is preferred to use the anionic surfactants which may be present in the form of a spray-dried, granulated or extruded compound, either as an additive component in the process or as an additive to other granules. In particular, the preferred heavier granules with bulk densities above 600 g / l preferably contain components which improve the flushing behavior and / or the dissolving behavior of the granules. Alkoxylated fatty alcohols with 12 to 80 moles of ethylene oxide per mole of alcohol, for example tallow fatty alcohol with 14 EO, 30 EO or 40 EO, and polyethylene glycols with a relative molecular weight between 200 and 12000, preferably between 200 and 600, are advantageously used for this purpose.
Ebenso ist es möglich und kann in Abhängigkeit von der Rezeptur von Vorteil sein, wenn weitere einzelne Bestandteile des Mittels, beispielsweise Citrat bzw. Citronensäure oder andere Polycarboxylate bzw. Polycarbonsäuren, polymere Polycarboxylate, Zeolith und/oder Schichtsilikate, die gegebenenfalls kristallin sein können, nachträglich zu sprühgetrockneten, granulierten und/oder extrudierten Komponenten, die gegebenenfalls mit nichtionischen Tensiden und/oder anderen bei der Verarbeitungstemperatur flüssigen bis wachsartigen Inhaltsstoffen beaufschlagt sind, hinzugemischt werden. Bevorzugt ist dabei ein Verfahren, bei dem die Oberfläche von Teilkomponenten des Mittels oder des gesamtem Mittels zur Reduzierung der Klebrigkeit der an Niotensiden reichen Granulate und/oder zu ihrer verbesserten Löslichkeit nachträglich behandelt wird. Geeignete Oberflächenmodifizierer sind dabei aus dem Stand der Technik bekannt. Neben weiteren geeigneten sind dabei feinteilige Zeolithe, Kieselsäuren, amorphe Silikate, Fettsäuren oder Fettsäuresalze, beispielsweise Calciumstearat, insbe- sondere jedoch Mischungen aus Zeolith und Kieselsäuren oder Zeolith und Caiciumstearat besonders bevorzugt. It is also possible and, depending on the recipe, to be advantageous if additional individual constituents of the agent, for example citrate or citric acid or other polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, zeolite and / or layered silicates, which can optionally be crystalline, subsequently to spray-dried, granulated and / or extruded components, which may have nonionic surfactants and / or other ingredients which are liquid to waxy at the processing temperature, mixed. A method is preferred in which the surface of partial components of the composition or of the entire composition is subsequently treated to reduce the stickiness of the granules rich in nonionic surfactants and / or to improve their solubility. Suitable surface modifiers are known from the prior art. In addition to other suitable ones, finely divided zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts, for example calcium stearate, are in particular however, mixtures of zeolite and silica or zeolite and calcium stearate are particularly preferred.
BeispieleExamples
Alkyloligoglucoside unterschiedlicher C-Kettenverteilung im Alkylrest und mit verschiedenen DP wurden hinsichtlich ihrer anwendungstechnischen Eigenschaften charakterisiert. Das Schaumvermögen wurden nach dem Ross-Miles Test in 1 Gew.-%iger Lösung bei 40°C in hartem Wasser (16°) untersucht. Bestimmt wurden Basisschaum und Schaumhöhe nach 20 min. Das Waschvermögen in einer Standard-Flüssigwaschmittelformulierung (Konzentration : 100 g/Waschgang) bei 40°C mit einer Koch/Buntwäsche wurde in Abhängigkeit verschiedener Anschmutzungen und Gewebe photometrisch gegen einen Bariumsulfat-Weißstandard bestimmt. Angegeben sind die Mittelwerte aus 5 Bestimmungen. Die Ergebnisse sind in Tabelle 1 zusammengefaßt. Beispiel 1 ist erfindungsgemäß, die Beispiele V1 bis V5 dienen zum Vergleich; V5 stellt dabei ein Alkyloligoglucosid des Handels dar.Alkyl oligoglucosides with different C chain distribution in the alkyl radical and with different DPs were characterized with regard to their application properties. The foaming power was investigated according to the Ross-Miles test in 1% by weight solution at 40 ° C. in hard water (16 °). Base foam and foam height were determined after 20 min. The washability in a standard liquid detergent formulation (concentration: 100 g / wash cycle) at 40 ° C. with a boil / colored wash was determined photometrically against a barium sulfate white standard depending on different soiling and fabrics. The mean values from 5 determinations are given. The results are summarized in Table 1. Example 1 is according to the invention, Examples V1 to V5 are used for comparison; V5 is a commercial alkyl oligoglucoside.
Tabelle 1Table 1
Schaumvermögen und WaschleistungFoaming power and washing performance

Claims

Patentansprüche claims
1. Nichtionische Tensidmischung, bestehend aus (a) Alkyloligoglucosiden der Formel (I),1. Nonionic surfactant mixture consisting of (a) alkyl oligoglucosides of the formula (I),
in der R1 für einen Dodecyl/Tetradecylrest, G für einen Glucoserest und p1 für eine Zahl im Bereich von 1 bis 3 steht, und (b) Alkyloligoglucosiden der Formel (II),in which R 1 is a dodecyl / tetradecyl radical, G is a glucose radical and p1 is a number in the range from 1 to 3, and (b) alkyl oligoglucosides of the formula (II),
R20(G)P2 (II)R 2 0 (G) P 2 (II)
in der R2 für einen Hexadecylrest, G für einen Glucoserest und p2 für eine Zahl im Bereich von 1 bis 3 steht, mit der Maßgabe, daß das Gewichtsverhältnis der beiden Komponenten im Bereich von 45 : 55 bis 55 : 45 und der durchschnittliche Polymerisationsgrad der Mischung im Bereich von 1 ,4 bis 1 ,5 liegt.in which R 2 is a hexadecyl radical, G is a glucose radical and p2 is a number in the range from 1 to 3, with the proviso that the weight ratio of the two components is in the range from 45:55 to 55:45 and the average degree of polymerization of the Mixture is in the range of 1.4 to 1.5.
2. Tensidmischungen nach Anspruch 1 , dadurch gekennzeichnet, daß sie Alkyloligoglucoside der Formel (I) enthalten, die Dodecyl- und Tetradecylglucoside im Gewichtsverhältnis 25 : 75 bis 75 : 25 enthalten.2. Surfactant mixtures according to claim 1, characterized in that they contain alkyl oligoglucosides of the formula (I) which contain dodecyl and tetradecyl glucosides in a weight ratio of 25:75 to 75:25.
3. Tensidmischungen nach den Ansprüchen 1 und/oder 2, dadurch gekennzeichnet, daß sie als wäßrige Pasten mit einem Feststoffgehalt im Bereich von 5 bis 50 Gew.-% vorliegen.3. surfactant mixtures according to claims 1 and / or 2, characterized in that they are present as aqueous pastes with a solids content in the range from 5 to 50 wt .-%.
4. Tensidmischungen nach den Ansprüchen 1 und/oder 2, dadurch gekennzeichnet, daß sie als wasserfreie Granulate vorliegen.4. surfactant mixtures according to claims 1 and / or 2, characterized in that they are present as anhydrous granules.
5. Verwendung von Tensidmischungen nach Anspruch 1 zur Herstellung von Waschmitteln.5. Use of surfactant mixtures according to claim 1 for the production of detergents.
6. Verwendung nach Anspruch 4, dadurch gekennzeichnet, daß man Flüssigwaschmittel herstellt. 6. Use according to claim 4, characterized in that one produces liquid detergents.
EP99952555A 1998-10-21 1999-10-12 Non-ionic surfactant mixtures Expired - Lifetime EP1123372B1 (en)

Applications Claiming Priority (3)

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DE19848550A DE19848550A1 (en) 1998-10-21 1998-10-21 Nonionic surfactant mixture useful for making laundry detergent, e.g. liquid detergent, consists of dodecyl-, tetradecyl- and hexadecyl-oligoglucosides with specified ratio and low average degree of polymerization
DE19848550 1998-10-21
PCT/EP1999/007659 WO2000023550A1 (en) 1998-10-21 1999-10-12 Non-ionic surfactant mixtures

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AU640786B2 (en) * 1990-06-22 1993-09-02 Colgate-Palmolive Company, The Toilet soap bar composition with alkyl polyglycoside surfactant
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FR2712595B1 (en) * 1993-11-19 1995-12-22 Seppic Sa A concentrate comprising alkyl glycosides and its uses.

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