EP0915962A2 - Additif pour produits de lavage ou de nettoyage, et procede de fabrication associe - Google Patents

Additif pour produits de lavage ou de nettoyage, et procede de fabrication associe

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Publication number
EP0915962A2
EP0915962A2 EP97930485A EP97930485A EP0915962A2 EP 0915962 A2 EP0915962 A2 EP 0915962A2 EP 97930485 A EP97930485 A EP 97930485A EP 97930485 A EP97930485 A EP 97930485A EP 0915962 A2 EP0915962 A2 EP 0915962A2
Authority
EP
European Patent Office
Prior art keywords
additive
weight
base granules
washing
acid
Prior art date
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.)
Withdrawn
Application number
EP97930485A
Other languages
German (de)
English (en)
Inventor
Hans-Friedrich Kruse
Volker Bauer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0915962A2 publication Critical patent/EP0915962A2/fr
Withdrawn legal-status Critical Current

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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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents 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
    • 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

Definitions

  • the invention relates to a detergent or cleaning agent additive which contains, in particular, customary admixing components of modern detergents or cleaning agents, a process for its preparation and the detergents or cleaning agents which can be obtained by admixing these additives.
  • modern washing or cleaning agents are understood to mean those which have bulk densities of at least 600 g / l.
  • Granular detergents or cleaning agents with bulk densities above 600 g / 1 are now part of the state of the art.
  • the products available on the market usually consist of at least one compound or several compounds, one basic granulate or several basic granules and other admixing components, which cannot be used in the manufacturing process of the basic granules either because of their temperature sensitivity or their water sensitivity or because of undesired interactions with other ingredients.
  • These are in particular solid ingredients such as bleach activators, so-called soil repellents, foam inhibitors, but also enzymes. These solids can be finely divided to granular.
  • the individually admixed components generally have a significantly lower bulk density than the basic granules or the basic granules and not only different grain sizes, but also different grain shapes and different surface properties than the basic granules. For this reason, the admixed components generally lead to a reduction in the bulk density of the finished product compared to the bulk density of the base granules or the base granules.
  • Another problem is the homogeneous distribution of the solid small components, that is to say those ingredients which are added to the base granules only in amounts of about 0.1 to 3% by weight.
  • the admixture and homogeneous distribution of these small components in the mixture is understandably fraught with a relatively high degree of error.
  • the invention was therefore based on the object of providing granular washing or cleaning agents with bulk densities of at least 600 g / l which do not have the disadvantages mentioned above.
  • the invention therefore relates in a first embodiment to a granular additive with a bulk density of at least 600 g / l, which is suitable for use in granular washing or cleaning agents with bulk densities of at least 600 g / l, this additive bleach activator and foam inhibitor and at least one contains further constituent usually contained in washing or cleaning agents.
  • the invention relates to a method for producing a granular additive with a bulk density of at least 600 g / l, which is suitable for use in granular detergents or cleaning agents with a bulk density of at least 600 g / l, wherein An additive which is uniform in composition, particle size and particle shape and which contains bleach activators and foam inhibitors and at least one further constituent which is usually present in washing or cleaning agents is produced by granulating, compacting or extruding.
  • Another object of the invention is a granular washing or cleaning agent with a bulk density of at least 600 g / l, which contains conventional ingredients including bleaching agents, bleach activators, foam inhibitors, the agent consisting of at least 2 granular compounds and one compound being an additive, which contains the blended activator, foam inhibitor and at least one further constituent usually contained in washing or cleaning agents.
  • the additive according to the invention is preferably not limited to a specific grain size, grain shape and certain surface properties and to a specific bulk density, but can be prepared in such a way that it constitutes (admixed) granules adapted to the base granules or the base granules in terms of bulk density, grain size and grain shape.
  • a common test for measuring the flow behavior is to fill 1 liter of the sample to be measured into a powder funnel, which is initially closed at its outlet direction, and then measure the outlet time of the samples compared to dry sea sand. The discharge time of the dry sea sand after the discharge opening has been released (13 seconds) is set to 100%. The flow behavior of the samples to be examined is given in%, based on 100% (measured on sea sand).
  • the flow behavior - determined according to the test described above - of the additive is set such that it does not differ from the flow behavior of the base granules or the sum of the base granules by more than 20% points 4, preferably not more than 10% points differs.
  • the additive according to the invention contains at least bleach activators, foam inhibitors (introduced in liquid or in solid form) and, preferably as constituents usually contained in washing or cleaning agents, enzymes, so-called soil repellents and / or surfactants, preferably alkyl sulfates (for a further description of possible surfactants, see below in the general description section).
  • bleach activators which can be used according to the invention are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably polyacrylicized alkylenediamines such as N.N'-tetraacylated diamines, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, Hydrazides, triazoles, triazines, urazoles, ditopiperazines, sulfurylamides and cyanurates, also carboxylic acid esters such as p- (alkanoyloxy) benzenesulfonate, in particular sodium isononanoyloxybenzenesulfonate, and the p- (alkenoyloxy) benzenesulfonates, furthermore caprolactam anhydride derivatives such as carboxylic acid ester, carboxylic acid like glucose pentaacetate.
  • bleach activators are acetylated mixtures of sorbitol and mannitol, as described for example in European patent application EP-A-0 525 239, and acetylated pentaerythritol.
  • the bleach activator content of the additives according to the invention is in the usual range, preferably between 15 and 80% by weight and in particular between 20 and 60% by weight.
  • Bleach activators are particularly preferred NNN'.N'-tetraacetylethylenediamine (TAED), 1, 5-diacetyl-2,4-dioxo-hexahydro-1, 3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
  • TAED NNN'.N'-tetraacetylethylenediamine
  • DADHT 1, 5-diacetyl-2,4-dioxo-hexahydro-1, 3,5-triazine
  • the bleach activator can be coated with coating substances in a known manner or, if appropriate using auxiliaries, in particular methyl celluloses and / or carboxymethyl celluloses, may have been granulated or extruded / pelletized before use and, if desired, may contain further additives, for example dye. Such granules preferably contain more than 70% by weight, in particular 90 to 99% by weight, of bleach activator.
  • the additive according to the invention preferably contains a bleach activator which forms peracetic acid under washing conditions.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 12 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, possibly signed silica, and paraffins, waxes, microcrystalline waxes and their mixtures with signed 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 and / 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.
  • silicone oils and / or paraffin oils in solid and / or liquid to waxy form can be used to produce the granular additives according to the invention.
  • the content of these foam inhibitors in the additives according to the invention is preferably 1 to 10% by weight and in particular 2 to 5% by weight, calculated as the active substance.
  • Particularly suitable enzymes are those from the class of hydrolases, such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases, and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can help maintain color and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases, and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling
  • Enzymatic active substances 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.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • 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 in the granular additives according to the invention is preferably 5 to 30% by weight, in particular 8 to 20% by weight.
  • the other possible ingredients of the compounds according to the invention primarily include soil repellents, but also plasticizers and parts of the builder system, which are usually present in amounts up to a maximum of 10% by weight, preferably up to a maximum of 8% by weight and in particular in amounts below of 5% by weight, based in each case on the finished composition.
  • So-called soil repellents contain components that have a positive influence on the oil and fat washability from textiles. This effect becomes particularly clear 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, non-ionic 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, based in each case 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 anionically and / or nonionically modified derivatives of these. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • the additives according to the invention preferably contain such soil repellents, which are usually used in the finished agent in amounts of 0.2 to less than 5% by weight, in amounts of 1 to 8% by weight and in particular in amounts of 2 to 6% by weight .-%, calculated as active substance.
  • the flow agents which can be used to improve the flow behavior are, in particular, the known silicas, silicic acid derivatives, but aluminosilicates such as zeolite A and / or P. Their content in the additives is preferably not more than 3% by weight.
  • Organic constituents are particularly suitable as further ingredients of the additives according to the invention.
  • the additives advantageously contain dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000.
  • DE dextrose equivalent
  • Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used.
  • a preferred dextrin is described in British patent application 94 19 091, Bei The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO- A-92/18542, WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608.
  • a product oxidized to C ⁇ of the saccharide ring can be particularly advantageous.
  • Suitable builder substances are oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110 .
  • Oxidized oligosaccharides according to the older German patent application P 196 00 018.1 are also suitable.
  • the additives can also be oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate.
  • disuccinates preferably ethylenediamine disuccinate.
  • glycerol disuccinates and glycerol trisuccinates as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP-A-0 150 930 and Japanese Patent Application JP 93 / 339896.
  • Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such cobuilders are described, for example, in international patent application WO-A-95/20029.
  • Suitable poly ere 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 (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred; in the latter case they serve as granulation aids (see below).
  • biodegradable polymers composed of more than two different monomer units, for example those which, according to DE-A-43 00 772, are salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, of which German Patent Application P 195 40 086.0 discloses that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • 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.
  • 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.
  • the additives can also include the polycarboxylic acids that can be used, for example, 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 contain this.
  • 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.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • the content of organic builder substances in the additives according to the invention is preferably 0.1 to 15% by weight.
  • Further ingredients are preferably phosphonates, which are usually used in finished products in amounts of 0.1 to normally not more than 2.5% by weight.
  • their content in the additives according to the invention is preferably more than 1% by weight and in particular 1.5 to 5% by weight.
  • the bulk density of the additives according to the invention is preferably in a range between 650 and 1000 g / l.
  • the bulk density of the additive according to the invention does not deviate by more than ⁇ 150 g / l, advantageously not more than ⁇ 100 g / l, from the bulk weight of the base granules or the base granules.
  • the additives according to the invention are preferably approximately in a spherical shape (pearl shape). In one embodiment of the invention, it is particularly advantageous if at least 95% by weight, in particular at least 99% by weight, of the additive has a grain size of 0.4 to 3.0 mm, in particular 0.6 to 2.0 mm exhibit.
  • Another particularly preferred exemplary embodiment consists in that the additives according to the invention deviate from the spherical shape by at most 20 area%, in particular at most 10 area%, the deviation being measured using the method of silhouette projection.
  • This measurement method can be carried out, for example, using the "Particle Size Counter 3" from Zeiss.
  • the deviation from the spherical shape is determined here by the percentage of the area outside a circle with the same total area as the projected image of the granulate.
  • the additives can also be provided with colorants and fragrances, but these are usually applied in liquid form.
  • the additives according to the invention contain bleach activators, foam inhibitors, enzymes and, if appropriate, the further components which are otherwise usually admixed in amounts of at least 30% by weight, in particular in amounts of 40 to 70% by weight.
  • surfactants preferably anionic surfactants, in particular sulfonates and / or organic sulfates (for a detailed description see below) can serve as “fillers”.
  • the water content of the additives is preferably below 10% by weight and in particular below 8% by weight. Particularly preferred - In some embodiments, the water content is even below 5% by weight, in particular below 3% by weight.
  • the additive according to the invention contains all components which are usually admixed in solid form to form a base granulate or a plurality of base granules, which in total up to 30% by weight, preferably up to 25% by weight and in particular at least 10% by weight. - Make up% of the finished detergent or cleaning agent.
  • Basic granules are understood to mean those compounds which, when used on their own, constitute a detergent and usually contain at least surfactants, builder substances and peroxy bleaching agents. These ingredients do not have to be contained in a single base granulate, but can also be present in different compounds. A detailed list of the preferred ingredients in the basic granules is given later.
  • the additive according to the invention is preferably prepared by batchwise or continuously granulating its ingredients, the latter being processed in a mixer / granulator with the addition of a small amount of granulating liquid to give a possibly moist granulate, which - if spherical or pearl shape is desired - in a rounder compacted and rounded and then optionally dried, especially in a fluidized bed.
  • Known apparatus for example granulators from Gebrüder Lödige, Paderborn, can be used as the mixer / granulator. Apparatus suitable for compacting and rounding are also known. An example is the rounder known under the name "Marumerizer ( R )". The mode of operation and the construction of this apparatus are described in GB-PS 1 517 713. Known rounding plates or rounding discs can also be used for rounding. In a particularly preferred embodiment of the invention, a rotating fluidized bed granulator, as described for example in Pietsch, "Size Enlargement by Agglomeration", John Wiley & Sons, 1990, p. 451, is used.
  • a large number of compounds can be used as granulation aids.
  • compounds from the class of water-soluble cellulose ethers, starch and starch ethers can be used.
  • Additives can also be used as granulation aids such as oxidation-stable complexing agents and stabilizers for per compounds and / or further constituents of detergents and cleaning agents are added or introduced via the aqueous granulating liquid. Examples of these are salts of polyphosphonic acids, such as 1-hydroxyethane-1,1-diphosphonate, ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate, each in the form of the sodium salt.
  • tallow alcohol sulfates and ethoxylated tallow alcohol sulfates are tallow alcohol sulfates and ethoxylated tallow alcohol sulfates (with up to 100 EO), starch phosphates, soaps and known emulsifying aids.
  • an aqueous solution of (co) polymeric polycarboxylates such as have already been described above, is used as the granulation aid.
  • copolymers of acrylic acid and maleic acid and biodegradable polymers of more than 2 monomer units have proven to be suitable.
  • the amount of water-containing granulating aid is advantageously such that no drying is required after the granulation.
  • water-containing granulation aids are in particular not used in amounts above 5% by weight, with amounts between 0.1 and 2.5% by weight being particularly preferred.
  • the quantities are based on the total amount of the possibly moist and undried granules.
  • the granulation is carried out without water, that is to say with water-free granulation aids.
  • the nonionic surfactants that are liquid at the processing temperature (detailed list see below), especially ethoxylated (fatty) alcohols with a melting point below 40 ° C, but also polyethylene glycols with molecular weights between 200 and 100,000, the latter advantageously in combination with nonionic surfactants or in aqueous solution / dispersion.
  • the additives mentioned above in particular an aqueous solution of a granulating aid, or other ingredients of detergents and cleaning agents when rounding the moist granules can be added simultaneously, for. B. be injected. In an advantageous embodiment of the invention, however, no liquid is added in this process step.
  • the surface of the granules can also be finely divided up dusty parts are treated, whereby the flow behavior of the granules can be further improved.
  • Agents other than the fine grain fractions for the surface treatment are, for example, aluminosilicates such as amorphous and / or crystalline zeolite and / or calcium stearate and / or silicas.
  • the fine and / or Gro ⁇ banmaschine leads them to a comminution of the coarse fractions to granulation back.
  • a washing or cleaning agent is obtained in which the admixing components are evenly distributed and remain evenly distributed and which has an optically uniform appearance and can also have an increased bulk density .
  • An increased bulk density means that the bulk density of the agent according to the invention is higher than that of an agent with the same composition and the same basic granulate (s), but in which the admixing components are not added in compounded form.
  • the base granules contain in particular surfactants, especially anionic surfactants, nonionic surfactants, optionally also cationic surfactants, amphoteric surfactants and / or zwitterionic surfactants, and also builder substances, peroxy bleaching agents.
  • surfactants especially anionic surfactants, nonionic surfactants, optionally also cationic surfactants, amphoteric surfactants and / or zwitterionic surfactants, and also builder substances, peroxy bleaching agents.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Preferred surfactants of the sulfonate type are C9-C * i3-alkylbenzenesulfonates, olefin sulfonates, i.e. Mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from C * i2-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.
  • alkanesulfonates which are obtained from C- * 2-C- * 8-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids are also suitable, for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 Moles of glycerol can be obtained.
  • the sulfonation products are a complex mixture which contains mono-, di- and triglyceride sulfonates with an ⁇ -position and / or internal sulfonic acid grouping.
  • sulfonated fatty acid salts glyceride sulfates, glycerine sulfates, glycerin and soaps are formed. 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, depending on the procedure, be up to about 60% 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 represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C ⁇ - to Ci8 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • alk (en) yisulfates the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C * i2-Ci8 fatty alcohols are obtained, for example, from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C * io-C2o-oxo alcohols and 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, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • Ci6-C * i8-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 C * i6-Ci8-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 C-i2-Ci4-fatty alkyl sulfates or Ci2-Ci8-fatty alkyl sulfates with C-i ⁇ -C-ie fatty alkyl sulfates and in particular Ci2-Ci6-fatty alkyl sulfates with Ci6-C ⁇ -fatty alkyl sulfates.
  • not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C * 16 to C22 are used.
  • a preferred use is found in mixtures in which the proportion of the alkyl radicals is 15 to 40% by weight on C12, 5 to 15% by weight on C1, 15 to 25% by weight de, 30 to 60% by weight .-% on C * i8, and less than 1 wt .-% are distributed on C-io.
  • the total alk (en) yl sulfate content in the detergents is preferably 10 to 25% by weight.
  • 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 ( '), are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C7-C2 * ⁇ alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide (EO) or Ci2-C -i8 fatty alcohols with 1 to 4 EO 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.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.2 to 5% by weight.
  • Saturated fatty acid soaps are particularly 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.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also 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 (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Ci --- alcohols with 7 EO, Ci3-C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ⁇ 2 -C 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C-i2-C-i4 alcohol with 3 EO and Ci2-Ci8 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • 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 alkyl glycosides, 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.
  • Especially preferred are Ci2-C-
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N.N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic 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 CO stands 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
  • [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 preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical with 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred
  • [Z] represents a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this radical. [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • N-alkoxy- or N-aryloxy-substituted compounds can then, for example, according to the Teaching of international patent application WO-A-95/07331 can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are generally separated from one another by a so-called “spacer”. This spacer is generally a carbon chain which should be long enough that the hydrophilic groups are sufficiently far apart that they can act independently of one another. Such surfactants are distinguished generally due to an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water, but in exceptional cases the term gemini surfactants means not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE-A-43 21 022 or dimer alcohol bis and trimeral alcohol tris sulfates and ether sulfates according to older German patent application P 195 03 061.3.
  • End group-capped dimeric and trimeric mixed ethers according to the older German patent application P 195 13 391.9 are distinguished in particular by their bi- and multifunctionality.
  • the end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides can also be used, as described in international patent applications WO-A-95/1953, WO-A-95/19954 and WO95-A- / 19955.
  • Zeolites and / or silicates are preferably used as builder substances, in particular of an inorganic nature, but optionally also “and / or” conventional phosphates, especially tripolyphosphates.
  • the latter already contain amounts of up to 10% by weight, based on the entire agent, to significant improvements in washing performance when used in combination with zeolite and / or silicates.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • Zeolite P is zeolite MAP (R) (commercial product from Crosfield) and zeolite NaP (commercial product from Degus- sa) is particularly preferred.
  • zeolite X 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 in the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C-i2-C-i8 fatty alcohols with 2 to 5 ethylene oxide groups, C12-Ci4 fatty alcohols with 4 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% 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 aMSi x ⁇ 2 ⁇ + ⁇ yH2 ⁇ , 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 2, 3 or 4 are.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ - sodium disilicates a2Si2 ⁇ s yH2 ⁇ are preferred.
  • the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • 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 degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are used, for example, described in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the above-mentioned organic builder substances can of course also be contained in the base granules, at least in part.
  • bleaching agents are, for example, sodium percarbonate, peroxypyrophosphate, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.
  • 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 Na 2 O: S.O2 of 1: 1 to 1: 4.5, preferably of 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.
  • the content of normal sodium silicate (water glass) in the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • 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, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethyl cellulose, methylhydroxypro- pylcellulose, methylcarboxymethylcellulose 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 e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar compounds, instead of the morpholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type may be present, e.g.
  • the basic granules can be produced by any of the known processes such as spray drying, granulation, compacting (roller compacting, pelleting, extrusion). If a spray-dried base granulate is present, then this is mixed with another base granulate, which is produced in another way and contains the peroxy bleaching agent.
  • the washing or cleaning agents according to the invention preferably do not contain any base granules which have been produced by spray drying.
  • the washing or cleaning agent consists of a base granulate and an admixed additive according to the invention.
  • granulators which can consist of mixers with mixing tools rotating in a housing, although other technical designs of granulators are also possible and conceivable.
  • a method of this type is described, for example, in WO 93/23523 A1.
  • the base granules can also be produced by extrusion of a premix with subsequent shaping, as is described in more detail, for example, in WO-A-91/02047.
  • Table 1 The solid and liquid components listed in Table 1 were processed in a 51-ploughshare mixer from Gebr. Lödige, which was equipped with a horizontal rotating mixing shaft with mixing tools and a rotating cutter head, to form moist granules.
  • the parameters set are listed in Table 2.
  • the left-hand column in each example of Table 1 contains the values for the batch, and the right-hand column contains the composition for the dried granulated product.
  • FAS mean 80% by weight of fatty alcohol sulfate with a C chain length of 12 to 18 C-
  • soil repellent product from BASF
  • Sipernat 22 S amorphous precipitated silica product from Degussa
  • phosphonate solution instead of the phosphonate solution, it was also possible to use an aqueous solution of a copolymer of, for example, acrylic acid and maleic acid.
  • the moist granules obtained were compacted in a rounder of the type RM 700 (from H. Schlueter) and shaped into approximately spherical particles. 1.75 kg of the wet granules were rounded in each case at a rounding speed of 200 rpm for a period of 1 min (Examples 1 and 3) and 1.17 min (Example 2).
  • the product obtained was then dried in a WSG 5 fluidized bed dryer from Glatt at a product temperature of 67 ° C. (example 1), 66 ° C. (example 2) and 63 ° C. (example 3).
  • Example 1 Example 2
  • Example 3 Share 1.6 to 2.0 mm in% by weight (good product) 4.6 11 16.4 Share 1.0 to 1.6 mm in weight% (good product) 39. 0 44.6 47.4 0.8 to 1.0 mm in% by weight (good product) 25.1 21, 4 17.2 0.6 to 0.8 mm in% by weight (good product) 31, 3 23.0 19.0

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Abstract

L'invention concerne des additifs ayant une masse volumique apparente supérieure ou égale à 600 g/l, destinés à des produits de lavage ou de nettoyage ayant une masse volumique apparente supérieure ou égale à 600 g/l. Les additifs contiennent des activateurs de blanchiment et des agents anti-mousse, ainsi qu'au moins un autre composant normalement contenu dans les produits de lavage et de nettoyage. L'addition de ces additifs lourds aux granulés lourds de base, les additifs ayant approximativement la forme, la taille et la masse volumique apparente des granulés de base, permet de fabriquer des produits de lavage ou de nettoyage ayant une masse volumique apparente plus élevée et un aspect homogène, et n'ayant pas tendance à se séparer.
EP97930485A 1996-07-08 1997-07-02 Additif pour produits de lavage ou de nettoyage, et procede de fabrication associe Withdrawn EP0915962A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19627427 1996-07-08
DE1996127427 DE19627427A1 (de) 1996-07-08 1996-07-08 Wasch- oder Reinigungsmitteladditiv sowie ein Verfahren zu seiner Herstellung
PCT/EP1997/003471 WO1998001532A2 (fr) 1996-07-08 1997-07-02 Additif pour produits de lavage ou de nettoyage, et procede de fabrication associe

Publications (1)

Publication Number Publication Date
EP0915962A2 true EP0915962A2 (fr) 1999-05-19

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EP97930485A Withdrawn EP0915962A2 (fr) 1996-07-08 1997-07-02 Additif pour produits de lavage ou de nettoyage, et procede de fabrication associe

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EP (1) EP0915962A2 (fr)
JP (1) JP2000514121A (fr)
DE (1) DE19627427A1 (fr)
WO (1) WO1998001532A2 (fr)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8811447D0 (en) * 1988-05-13 1988-06-15 Procter & Gamble Granular laundry compositions
WO1991002047A1 (fr) * 1989-08-09 1991-02-21 Henkel Kommanditgesellschaft Auf Aktien Fabrication de granules comprimes pour produits de lavage
US5576277A (en) * 1992-03-10 1996-11-19 The Procter & Gamble Company Granular detergent compositions
DE4221736A1 (de) * 1992-07-02 1994-01-05 Henkel Kgaa Feste waschaktive Zubereitung mit verbessertem Einspülverhalten
EP0712437B1 (fr) * 1993-08-02 1997-10-08 Henkel Kommanditgesellschaft auf Aktien Granule regulateur du moussage et son procede de preparation
DE19521365A1 (de) * 1995-06-12 1996-12-19 Henkel Kgaa Feste und hochverdichtete waschaktive Zubereitungen mit verbesserter Löslichkeit auch schon bei niederen Flottentemperaturen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9801532A3 *

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WO1998001532A2 (fr) 1998-01-15
JP2000514121A (ja) 2000-10-24
DE19627427A1 (de) 1998-01-15

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