WO1996029390A1 - Detergents et nettoyants pulverulents a granulaires - Google Patents

Detergents et nettoyants pulverulents a granulaires Download PDF

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Publication number
WO1996029390A1
WO1996029390A1 PCT/EP1996/001038 EP9601038W WO9629390A1 WO 1996029390 A1 WO1996029390 A1 WO 1996029390A1 EP 9601038 W EP9601038 W EP 9601038W WO 9629390 A1 WO9629390 A1 WO 9629390A1
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Prior art keywords
surfactant
surfactants
compound
weight
cleaning agent
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PCT/EP1996/001038
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German (de)
English (en)
Inventor
Thomas Förster
Peter Sandkühler
Wolfgang Seiter
Hubert Pawelczyk
Ansgar Behler
Horst-Dieter Speckmann
Dieter Nickel
Monika Böcker
Amerigo Pastura
Manfred Greger
Paul Schulz
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
PFLÜGER-SCHULZ, Brigitte
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Application filed by Henkel Kommanditgesellschaft Auf Aktien, PFLÜGER-SCHULZ, Brigitte filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1996029390A1 publication Critical patent/WO1996029390A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads

Definitions

  • the invention relates in particular to heavy powdery to granular detergents or cleaning agents with bulk densities of at least 500 g / l, which are characterized by no or a considerably reduced tendency to form gels when dissolved in water.
  • the invention also relates to a method for producing detergents or cleaning agents of this type.
  • the increasing bulk density of commercial detergent granules is mainly achieved by an increasingly compact grain structure of the granules, whereby the porosity of the granules decreases to an almost complete elimination of the connected pore system.
  • the decrease in porosity is generally associated with an undesired delay in dissolution, which can lead to deposits of detergent granules on textiles.
  • Gels are understood to mean dispersions which, in addition to a reduction in viscosity due to shear, also show a reduction and build-up of binding forces between molecules or particles depending on the shear time. Only when the gel phase is destroyed, for example by prolonged shear, that is to say the binding forces are broken, does the viscosity decrease again and the mixture reaches a flowable state again.
  • the gel break limit can be determined directly.
  • the length of the linear viscoelastic area indicates from which mechanical stress (strain) the gel breaks.
  • a number of both solid and liquid substances which are hydrophilic, water-soluble or water-dispersible are known as gel formation inhibitors or structure breakers. Some of them are mentioned, for example, in international patent application WO-A-93/02176. These include, for example, lower polyalkylene glycols which are derived from straight-chain or branched glycols having 2 to 6 carbon atoms, preferably polyethylene glycol or polypropylene glycol, and have a relative molecular weight between 200 and 12,000, in particular up to 2000.
  • Further gel formation preventers or structure breakers are the sulfates and in particular the disulfates of lower polyalkylene glycol ethers and in particular of polyethylene glycol and 1,2-polypropylene glycol with a relative molecular weight between 600 and 6000.
  • the disulfates generally originate from this from polyglycol ethers, such as those caused by slight traces of water in the alkoxylation of alcoholic components.
  • Another group of known gelation preventers consists of the water-soluble salts of mono- and / or disulfosuccinates of the lower polyalkylene glycol ethers.
  • anionically modified polyalkylene glycol ethers can be used in the form of any salts, in particular as sodium and potassium salts.
  • the addition products of about 20 to about 80 moles of alkylene oxide, in particular ethylene oxide, to 1 mole of an aliphatic alcohol with essentially 8 to 20 carbon atoms can serve as gelation inhibitors or structure breakers and thus improve the dissolution rates of the heavy detergents or cleaning agents to lead.
  • the addition products of 20 to 60 mol of ethylene oxide with primary alcohols, such as, for example, with coconut fatty alcohol or tallow fatty alcohol, with oleyl alcohols, with oxo alcohols, or with secondary alcohols with 8 to 18 carbon atoms, are particularly important here. Selected examples of this are tallow fatty alcohol with 30 E0 or 40 E0.
  • a further known group of yellowing inhibitors consists of alkylene glycol monoalkyl ethers of the general formula R0 (CH2CH2) nH, in which R represents a radical with 2 to 8 carbon atoms and n represents a number from 1 to 8. Examples of this group are ethylene glycol monoethyl ether and diethylene glycol monobutyl ether.
  • one class of nonionic surfactants is alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533, are known to have little or no tendency to gel.
  • the object of the invention was therefore to provide heavy detergents or cleaners, in particular those which contain surfactant mixtures, which have no or only a very slight and therefore negligible tendency to gel when dissolved in water.
  • Another object was to provide a general process by which heavy detergents or cleaning agents, which in particular contain surfactant mixtures, can be obtained which, when dissolved in the wash liquor, have no or only a very slight tendency to gel, in particular to Formation of low-viscosity gels with relatively weak binding forces and therefore have an improved dissolution rate in the liquor.
  • the invention relates in a first embodiment to a powdery to granular detergent or cleaning agent, in particular with bulk densities of at least 500 g / l, containing anionic and / or nonionic surfactants and other customary ingredients of detergents or cleaning agents, wherein the washing or cleaning agent contains at least 2 different types of surfactants, of which
  • At least one surfactant as raw material and at least one surfactant in one compound with more than two different surfactants at least one surfactant as raw material and at least one surfactant in at least one compound, or
  • granular agents are also understood to mean those which have been obtained, for example, by roller compaction or extrusion, so that the definition "powdery to granular” includes all solid agents which are obtained by spray drying, granulation, various known types of compacting and mixing the raw materials or individual compounds produced by these methods.
  • the yield point is in each case even less than 5 Pa and / or the gel break limit is in each case less than 2% strain.
  • the invention opens up the possibility of also using those surfactants which are normally able to form gels under certain conditions, but now, owing to the specific use of these surfactants according to the invention, the formation of gels when the agents dissolve in water is largely suppressed.
  • anionic surfactants nonionic surfactants, but also cationic surfactants, amphoteric surfactants and zwitterionic surfactants can be used as surfactants, provided that their form of use and thus also the entire detergent or cleaning agent obey the above-mentioned physicochemical conditions.
  • anionic and / or nonionic surfactants are used in the agents according to the invention.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Preferred surfactants of the sulfonate type are Cg-Ci3-alkylbenzenesulfonates, olefin sulfonates, i.e. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from Ci2-Ci8 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkane sulfonates which are obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, and their disalts, which can be obtained, for example, by saponification of the ester group.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example the Capron acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. If one starts from fats and oils, that is to say natural mixtures of different fatty acid glycerol esters, it is necessary to largely saturate the starting products with hydrogen in a manner known per se, ie to harden them to iodine numbers less than 5, advantageously less than 2.
  • Suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, rapeseed oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or lard. Due to their high natural content of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow.
  • the sulfonation of the saturated fatty acids with 6 to 22 carbon atoms or the mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, such as it is specified in international patent application WO-A-91/09009.
  • the sulfonation products are a complex mixture containing mono-, di- and triglyceride sulfonates with an ⁇ -position and / or internal sulfonic acid grouping.
  • Sulfonated fatty acid salts, glyceride sulfates, glycerol sulfates, glycerol and soaps are formed as by-products. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the ⁇ -sulfonated fatty acid disalts can be up to about 60% by weight, depending on the procedure.
  • Suitable sulfate-type surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • Alk (en) yl sulfates are the alkali metal and especially sodium salts of the sulfuric acid semiesters of C ⁇ -Ci ⁇ - ⁇ ⁇ 0 etta be - 10 ⁇ for example, alcohol from Kokosfett ⁇ , tallow fatty alcohol, lauryl, myristyl, cetyl or Stearyl alcohol or the C ⁇ o-C2 ⁇ -oxo alcohols and (1 those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petroche-based, straight-chain alkyl radical which have an analogous degradation behavior as the adequate connections based on oleochemical raw materials.
  • C15-C18-alk (en) yl sulfates are particularly preferred for reasons of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use Ci6-Cj8-alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize.
  • the agents therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of Ci2-Ci4-fatty alkyl sulfates or Ci2-Ci8 ⁇ fatty alkyl sulfates with Ci6-Ci8-fatty alkyl sulfates and in particular Ci2-Ci -Fatty alkyl sulfates with Ciss-Ci ⁇ fatty alkyl sulfates.
  • not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 1 to C 22 are used.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN ( R ), are also suitable anionic surfactants.
  • the Schwefelklasted Acidmonoester with 1 to 6 moles of ethylene ethoxylated linear or branched C7-C2i-alcohols such as 2-methyl-branched Cg-C j i-alcohols containing on average 3.5 moles of ethylene oxide (E0), or Ci2 ⁇ Ci8 fatty alcohols with 1 to 4 E0 are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain CQ ⁇ to Ci8 ⁇ fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, viewed in isolation, are nonionic surfactants (for a description, see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred.
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • isethionates, taurides or sarcosides can also be used.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.1 to 10% by weight, in particular 0.2 to 5% by weight, in each case based on the finished compositions.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures, as well as unsaturated fatty acid soaps, in particular salts of oleic acid or linoleic acid. In particular, however, those soap mixtures are preferred which are predominantly composed of saturated soaps.
  • the anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (E0) per mole of alcohol in which the alcohol radical has a methyl or linear branching, preferably in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 E0 per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 E0 or 4 E0, Cg-Cji alcohols with 7 E0, Ci3-Ci5 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, Ci2-Ci8- Alcohols with 3 E0, 5 E0 or 7 E0 and mixtures of these, such as mixtures of C12- Ci4 alcohol with 3 E0 and Ci2- i8 alcohol with 5 E0.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 E0 can also be used. Examples of this are tallow fatty alcohol with 14 E0, 25 E0, 30 E0 or 40 E0.
  • polyalkylene glycol amines for example coconut oil with about 2 to 10 E0
  • polyol ethers for example glycerol with about 3 to 10 E0
  • polyolamines for example triethanolamines with about 3 to 10 E0
  • alkyl glycosides of the general formula R0 (G), in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to, can also be used as further nonionic surfactants 18 means carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligo erization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkylglycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • polyalkylene glycol esters for example fatty acid polyethylene glycol esters, preferably coconut fatty acids with about 2 to 12 E0
  • polyalkylene glycol amides for example coconut fatty acid monoethanolamide with about 2 to 12 E0
  • polyol esters for example coconut fatty acid monoglyceride with about 2 to 12 EO
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • R 2 is C0 for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which are usually obtained by reductive amination of a reducing agent Sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride can be obtained.
  • Mono-, di- and / or triglycerides which may or may not be ethoxylated and may contain branched and / or unsaturated alkyl radicals, are also suitable nonionic surfactants.
  • the agents contain at least alkylbenzenesulfonates and / or alkylsulfates, advantageously alkylsulfates or alkylbenzenesulfonates and alkylsulfates, as anionic surfactants.
  • the agents preferably also contain nonionic surfactants such as ethoxylated and / or ethoxylated and propoxylated alcohols, in particular fatty alcohols, but also ethoxylated fatty acid esters, in particular ethoxylated fatty acid methyl esters.
  • Further preferred nonionic tenides are polyethylene glycol fatty acid esters, alkyl polyglycosides, in particular alkyl polyglucosides, and polyhydroxy fatty acid amides, in particular glucamides.
  • the distribution of the surfactants in the entire washing or cleaning agent is preferably heterogeneous. This means that all surfactants used, for example as raw material in a homogeneous mixture or - if the finished composition consists only of a single granulate - can be present together in a homogeneous distribution in these granules as long as the compositions correspond to the above-mentioned physicochemical conditions. However, it is preferred to introduce the surfactants into the washing or cleaning agent in various ways.
  • preferred embodiments of the invention provide that either at least one surfactant as raw material and at least one surfactant in one compound, with more than two different surfactants present, at least one surfactant as raw material and at least one surfactant in at least one compound or there are at least two different surfactant compounds. It can be particularly advantageous here if different surfactants are also strictly separated from one another, for example in different compounds or on the one hand in compounds and on the other hand as raw material or raw materials. Here is - 12 -
  • low-gelling surfactants such as ethoxylated fatty acid esters and gel-thickening surfactants such as polyalkylene glycol ethers is particularly advantageous.
  • compounds are understood to mean both liquid and solid forms of use, in particular granular forms of use of surfactants, which, in addition to the surfactants and any impurities which may result from the preparation of the surfactants, also include other ingredients, in particular customary ingredients of Have washing or cleaning agents in substantial amounts or in which the surfactants have been converted into a granular structure by a special process.
  • the granular compounds can have been spray-dried, spray-granulated, granulated, roll-compacted, extruded or produced by any of the known other processes.
  • Such compounds are spray-dried compounds with contents of 5 to 30% by weight of anionic surfactants, for example alkyl sulfates and / or alkylbenzenesulfonates, which are usually used as so-called tower powders in detergents, but also in cleaning agents, and in addition to the surfactants, in particular contain special builder substances and inorganic salts.
  • anionic surfactants for example alkyl sulfates and / or alkylbenzenesulfonates
  • a further example would be a granulated and simultaneously dried surfactant granulate which advantageously has very high amounts of surfactants, for example between 40 and almost 100% by weight, based on the corresponding compound.
  • the latter granules can be obtained, for example, according to the teaching of international patent application WO-A-93/04162.
  • Another preferred embodiment for a compound is also a so-called carrier grain consisting of essentially inorganic constituents such as builder substances and inorganic salts, which has been aftertreated with surfactants and in particular with surfactants which are liquid to wax-like at the processing temperature.
  • the total surfactant content of the finished detergents or cleaning agents is in preferred embodiments 5 to 40% by weight, preferably 10 to 35% by weight and in particular 15 to 30% by weight.
  • the other ingredients of the washing or cleaning agents and the compounds include, in addition to the surfactants mentioned, in particular inorganic and / or organic builder substances, ingredients which sustainably increase the fat washability, the known and above-mentioned solubility improvers, alkaline salts, graying inhibitors (dirt carriers), foam inhibitors, bleaching agents and bleach activators, optical brighteners, enzymes, optionally textile-softening agents Substances, dyes and fragrances as well as neutral salts such as sulfates and chlorides in the form of their sodium or potassium salts.
  • Suitable inorganic builder substances are, in particular, zeolites, but also amorphous and / or crystalline silicates as well as carbonates, optionally in a mixture with silicates.
  • the fine crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality.
  • zeolite X and zeolite P and mixtures of A, X and / or P are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 8 -fatty alcohols with 2 to 5 ethylene oxide groups, Ci2-Ci4 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula (II) NaMSi x 02 ⁇ + ⁇ * yH20, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number is from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline sheet silicates of the formula (II) are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and fr-sodium disilicate Na2Si2 ⁇ 5 * yH2 ⁇ are preferred.
  • Suitable substitutes or partial substitutes for the zeolite are also sheet silicates of natural and synthetic origin, as are known, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here.
  • Amorphous silicates can also be used as inorganic builder substances.
  • the term “amorphous” is also understood to mean “x-ray orph”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degrees units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction axes in electron diffraction experiments.
  • the content of the inorganic builder substances in the finished compositions can vary within a wide range. In preferred embodiments it is 20 to 60% by weight, based on anhydrous active substance, mixtures of several inorganic builder substances such as zeolite and crystalline layered disilicates or zeolite and amorphous silicates or zeolite and soda-silicate compounds or amorphous silicates and crystalline layered disilicate or soda-silicate compounds and crystalline layered disilicate can be used.
  • inorganic builder substances such as zeolite and crystalline layered disilicates or zeolite and amorphous silicates or zeolite and soda-silicate compounds or amorphous silicates and crystalline layered disilicate or soda-silicate compounds and crystalline layered disilicate can be used.
  • 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, nitrilotriacetic 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.
  • Terpolymers are also particularly preferred, for example those which, according to DE-A-4300772, as salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or according to DE-C-4221 381 as monomers of acrylic acid and salts Contain 2-alkylallylsulfonic acid and sugar derivatives.
  • Suitable builder systems are oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts, as described, for example, in international patent application WO-A-93/08251 or their production, for example, in international patent application WO-A-93 / 16110.
  • polyaspartic acids or their salts and derivatives are also to be mentioned as further preferred builder substances.
  • 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-A-0 280 223 nen.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Organic builder substances are preferably contained in the compositions in amounts of 1 to 20% by weight, in particular in amounts of 2 to 15% by weight.
  • compounds containing anionic surfactants which additionally contain zeolite as builder substance but do not contain any of the known solubility improvers or structure breakers, contain either zeolite or anionic surfactants in a substantial excess, for example in a weight ratio of 2: 1 to 5 : 1 or from 1: 2 to 1: 5, but not by 1: 1, whereby the amounts of zeolite are always based on anhydrous active substance. It is particularly preferred that the weight ratio of zeolite to anionic surfactants in these compounds is more than 2.5: 1 or 1: 2.5 to 1: 4.
  • both zeolite as builder substance and known solubility improvers or structure breakers are used. It has been shown here that the weight ratio of zeolite to anionic surfactant can be particularly advantageous in areas above and around 1: 1. Surprisingly, the tendency to gel formation, including the zeolite, in particular the zeolite stabilized with nonionic surfactants, is changed by the addition of a non-surfactant solubility improver or structure breaker, preferably of polyethylene glycol, such that weight ratios of zeolite to anionic surfactant are now particularly attractive by 1 are, while weight ratios below 1: 2 can lead to very high moduli of elasticity and are therefore less preferred. Weight ratios of 3: 1 to 1: 1 are preferred here.
  • the agents can also contain components which have a positive influence on the oil and fat washability from textiles. This effect is particularly evident when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight. , each based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these.
  • solubility improvers and structure breakers which have already been described in detail above, can of course be used.
  • polyethylene glycol ethers with low molecular weights in particular between 200 and 2000
  • taig fat alcohols with 30 or 40 E0 taig fat alcohols with 30 or 40 E0. They can be used, for example, in amounts between 0.5 and 10% by weight.
  • Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these;
  • alkali carbonate and amorphous alkali silicate especially sodium silicate with a molar ratio Na2 ⁇ : Si ⁇ 2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used.
  • the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
  • soda-S 1-ic compounds are used as builder substances, it is possible that the carbonate content of the detergents is between 10 and 20% by weight at higher values.
  • the silicate content is then correspondingly high between 10 and 40% by weight.
  • alkali carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and, where appropriate, a further carboxyl and / or amino group and amino acids and / or their salts.
  • the alkali carbonates are partially or completely replaced by glycine or glycinate.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids providing H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborates or percarbonates being advantageously used.
  • bleach activators can be incorporated into the preparations.
  • Examples include N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • Further known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239.
  • the bleach activator content of the bleach-containing agents is 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'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-l, 3,5-triazine (DADHT) and acetylated sorbitol -Mannitol blends (S0RMAN).
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci8-C24 ⁇ fatty acids.
  • Suitable non-surfactant Like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular carrier substance which is soluble or dispersible in water. Mixtures of paraffins and bistearylethylene diamides are particularly preferred.
  • the neutral reacting sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate in amounts of 0.1 to 1.5% by weight are preferably used as salts of polyphosphonic acids.
  • Suitable enzymes are those from the class of proteases, lipases or lipolytically acting enzymes, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the above-mentioned salts of polyphosphonic acids are suitable as stabilizers, in particular for per-compounds and enzymes.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber 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 carboxyethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethy1ce11u1ose, methylhydroxypropylce11u1ose, methylcarboxymethylcellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight. %, based on the funds used.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar compounds, 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, e.g.
  • the bulk density of the preferred granular agents is generally 300 to 1200 g / 1, in particular 500 to 1100 g / 1.
  • They can be produced by any of the known processes, such as mixing, spray drying, granulating and / or extruding.
  • Particularly suitable methods according to the invention are those which allow partial components, for example spray-dried components and granulated and / or extruded components are mixed together.
  • spray-dried or granulated components to be subsequently treated, for example with nonionic surfactants, in particular ethoxylated fatty alcohols, by the customary processes. Processes of this type are particularly advantageous in which washing or cleaning agents are obtained which bring about a heterogeneous distribution of the individual surfactants.
  • anionic surfactants 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.
  • anionic surfactant compounds if they contain zeolite at all, contain an excess of anionic surfactants compared to zeolite, again based on anhydrous active substance, zeolite to anionic surfactant weight ratios in particular from 1: 2.5 to 1: 4 are preferred.
  • 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.
  • zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts for example calcium stearate, but especially mixtures of zeolite and silicas or zeolite and calcium stearate are particularly preferred.
  • the finished washing or cleaning agents can also be constructed from several partial extrudates which contain the above-mentioned ingredients have and meet the physical conditions specified according to the invention.
  • the extrudates are processed with further ingredients of washing or cleaning agents. This can be such that the washing or cleaning agents are obtained by mixing several different granules, of which one extrudate or different partial extrudates form the main component and preferably more than 60% by weight, in particular more than 70% by weight. % turn off.
  • a method for producing extrudates with high density is known, a solid and free-flowing premix being extruded under pressure under pressure.
  • the solid and free-flowing premix contains a plasticizer and / or lubricant, which has the effect that the premix plastically softens under the pressure or the entry of specific work and thus becomes extrudable. After exiting the hole shape, the system is no longer subjected to shear forces and the viscosity of the system increases in such a way that the extruded strand can be cut to predeterminable extrudate dimensions.
  • a preferred embodiment of the invention now provides that the premix to be extruded is not completely homogenized, but rather that the premix is produced under conditions which are so gentle that there is heterogeneity in the distribution of the individual ingredients and in particular the surfactants both in the premix as well as in the finished extrudate. According to the invention, care must be taken to ensure that not only the extrudates or partial extrudates, but also the compounds used to prepare the heterogeneous premix, obey the above-mentioned physicochemical conditions. Examples
  • Example 1 Gel strength of surfactant mixtures in a salt solution containing 2.1% by weight sodium carbonate and 47.9% by weight water
  • Comparative example C3 has a viscosity which is in the range of the viscosities of examples according to the invention, such as examples 4 and 5.
  • the modulus of elasticity is also not the only decisive factor.
  • comparative example V3 also has a relatively low modulus of elasticity, which is lower than the module of example 4 or 5 according to the invention and the module of example 6 according to the invention is the same.
  • this example V3 has a very high gel breaking limit and thus a correspondingly high yield point. This achieves a gel strength that is no longer tolerable when using detergents in household washing machines.
  • Table 1 Gel strength of mixtures 1 to 8 according to the invention and typical comparative detergent gels VI to V3 (data in% by weight of active substance)
  • Breo ⁇ ( R ) is an ethoxylated and propoxylated block copolymer (E0: P0
  • PEG 400 is a polyethylene glycol with a molecular weight of
  • the viscosity Eta was measured at 25 ° C and a shear rate of 10 s _1 .
  • the elastic modulus G ' was measured at 25 ° C.
  • the gel break limit was also measured at 25 ° C as the length of the viscoelastic area in the oscillation test at 10 Hz; the yield point at 25 ° C results from the product of the elastic modulus and the gel break limit.
  • Example 2 Rheology of zeolite-Cg-Ci3-alkylbenzenesulfonate mixtures (data in% by weight) in water at 25 ° C.
  • Zeolite (based on 27.4 27.2 27.3 gene for water-free active substance)
  • the initial value without detergent (blank value) was subtracted from the measurement results and the percentage conductivity was calculated, the constant end value was set to 100%. From the representation of the time course of the conductivity, the time was interpolated in seconds at which 75% of the final value of the conductivity was reached.

Abstract

L'invention vise à mettre au point des détergents ou nettoyants lourds, notamment ceux qui contiennent des mélanges tensioactifs, et qui une fois dissous dans de l'eau, n'ont pas ou très peu tendance à la gélification, dans une mesure par conséquent négligeable. A cette fin, on utilise au moins deux différents types de tensioactifs, qui se présentent tous sous forme de matière brute ou sont en un seul composé ou dont au moins un tensioactif est sous forme de matière première et au moins un tensioactif est contenu en un seul composé, dans l'éventualité de plus de deux tensioactifs différents, au moins un tensioactif est sous forme de matière première et au moins un tensioactif est contenu en un seul composé, ou également dans l'éventualité de plus de deux tensioactifs différents, ces tensioactifs sont contenus dans au moins deux composés tensioactifs différents. Pour l'ensemble du détergent ou du nettoyant contenant des tensioactifs et chaque composé contenant des tensioactifs, se trouvant dans une solution saline contenant 50 % en poids du détergent ou du nettoyant ou du composé, 2,1 % en poids de carbonate de sodium et 47,9 % en poids d'eau, à 25 °C, la limite d'écoulement est inférieure à 10 Pa et la limite de rupture du gel est inférieure à 5 % de déformation.
PCT/EP1996/001038 1995-03-18 1996-03-11 Detergents et nettoyants pulverulents a granulaires WO1996029390A1 (fr)

Applications Claiming Priority (2)

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DE19509973.7 1995-03-18
DE1995109973 DE19509973A1 (de) 1995-03-18 1995-03-18 Pulverförmige bei granulare Wasch- oder Reinigungsmittel

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US20060252666A1 (en) 2005-05-09 2006-11-09 Dennis Sheirs Household cleaning composition

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2116200A (en) * 1982-03-01 1983-09-21 Procter & Gamble Granular detergent composition
EP0220024A2 (fr) * 1985-10-09 1987-04-29 The Procter & Gamble Company Compositions détergentes granulées à solubilité
EP0402112A2 (fr) * 1989-06-09 1990-12-12 The Procter & Gamble Company Formation de granules de détergent discrets à haute activité utilisant un système de neutralisation continu
EP0460925A2 (fr) * 1990-06-06 1991-12-11 Unilever Plc Compositions détergentes
WO1994003568A1 (fr) * 1992-08-01 1994-02-17 The Procter & Gamble Company Compositions detersives a faible niveau de gelification et procede de preparation
DE4319666A1 (de) * 1993-06-14 1994-12-15 Henkel Kgaa Verfahren zur Herstellung fester Wasch- oder Reinigungsmittel mit hohem Schüttgewicht und verbesserter Rheologie
EP0639637A1 (fr) * 1993-08-17 1995-02-22 The Procter & Gamble Company Compositions détergentes contenant des percarbonates comme agents de blanchiment
DE4335955A1 (de) * 1993-10-21 1995-04-27 Henkel Kgaa Verfahren zur Herstellung wasch- oder reinigungsaktiver Extrudate mit verbessertem Redispergiervermögen

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2116200A (en) * 1982-03-01 1983-09-21 Procter & Gamble Granular detergent composition
EP0220024A2 (fr) * 1985-10-09 1987-04-29 The Procter & Gamble Company Compositions détergentes granulées à solubilité
EP0402112A2 (fr) * 1989-06-09 1990-12-12 The Procter & Gamble Company Formation de granules de détergent discrets à haute activité utilisant un système de neutralisation continu
EP0460925A2 (fr) * 1990-06-06 1991-12-11 Unilever Plc Compositions détergentes
WO1994003568A1 (fr) * 1992-08-01 1994-02-17 The Procter & Gamble Company Compositions detersives a faible niveau de gelification et procede de preparation
DE4319666A1 (de) * 1993-06-14 1994-12-15 Henkel Kgaa Verfahren zur Herstellung fester Wasch- oder Reinigungsmittel mit hohem Schüttgewicht und verbesserter Rheologie
EP0639637A1 (fr) * 1993-08-17 1995-02-22 The Procter & Gamble Company Compositions détergentes contenant des percarbonates comme agents de blanchiment
DE4335955A1 (de) * 1993-10-21 1995-04-27 Henkel Kgaa Verfahren zur Herstellung wasch- oder reinigungsaktiver Extrudate mit verbessertem Redispergiervermögen

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