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WO2004027009A1 - Produits de lavage ou de nettoyage comprimes sous l'effet d'une pression - Google Patents

Produits de lavage ou de nettoyage comprimes sous l'effet d'une pression Download PDF

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Publication number
WO2004027009A1
WO2004027009A1 PCT/EP2003/009983 EP0309983W WO2004027009A1 WO 2004027009 A1 WO2004027009 A1 WO 2004027009A1 EP 0309983 W EP0309983 W EP 0309983W WO 2004027009 A1 WO2004027009 A1 WO 2004027009A1
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WO
WIPO (PCT)
Prior art keywords
acid
water
weight
salts
composition according
Prior art date
Application number
PCT/EP2003/009983
Other languages
German (de)
English (en)
Inventor
Volker Blank
Henriette Weber
Kathrin Schnepp-Hentrich
Wilfried Rähse
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP03750500A priority Critical patent/EP1537199A1/fr
Priority to AU2003270156A priority patent/AU2003270156A1/en
Publication of WO2004027009A1 publication Critical patent/WO2004027009A1/fr
Priority to US11/079,046 priority patent/US20050187132A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids

Definitions

  • the present invention relates to a washing or cleaning agent compacted, in particular extruded, under mechanical pressure, which contains organic polycarboxylic acids and predominantly water-soluble builder substances and has a pH of less than 10.5, and a process for the preparation of these agents.
  • the processes for the production of heavy detergents or cleaning agents have been optimized in recent years in such a way that more and more concentrated agents with even higher bulk densities have resulted.
  • the extrusion process for example according to European patent EP 0486592 B1, is an example of this.
  • extruded washing or cleaning agents which preferably have a bulk density above 750 g / l, values of 950 to 980 g / l also being achieved.
  • the increase in the bulk density and, in particular, the higher concentration of the detergent or cleaning agent in the agent was generally bought by a subjectively poorer solubility from the point of view of the consumer, which is reflected in a slower dissolution rate of the agent used. From the point of view of the consumer, it is therefore also desirable that products with lower bulk densities are offered.
  • extruded washing or cleaning agents with bulk densities of 750 g / l to 1000 g / l are obtained.
  • the solubility problem could be solved by carrying out the extrusion almost water-free, the premix containing no free water and bound water only in certain amounts.
  • Raw materials or compounds are used as binders with simultaneous lubricant and adhesive functions, which have a solid character at a pressure of 1 bar and temperatures below 45 ° C and only soften or melt above this temperature, but are in liquid form under the processing conditions.
  • the alone or can be used in a mixture with other binders polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols are mentioned.
  • the modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12000 and in particular between 1000 and 4000.
  • Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which in turn have relative molecular weights have between 600 and 6000, preferably between 1000 and 4000.
  • polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C 3 -C 5 glycols and glycerol and mixtures of these as starting molecules. Ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included.
  • the preferably used polyethylene glycols can have a linear or branched structure, linear polyethylene glycols being preferred in particular.
  • binders reference is expressly made here to the disclosure of international patent application WO 98/12299.
  • Extruded detergents or cleaning agents produced in this way contain, as surfactants, above all anionic surfactants, which are introduced into the premix in solid form, inorganic and / or organic builder substances and further conventional ingredients of detergents or cleaning agents.
  • aluminosilicates of the zeolite type are mentioned as inorganic builder substances. In the formulations disclosed, these zeolites represent the main constituent of the builder substances contained overall.
  • organic builder substances are primarily (co) polymeric polycarboxylates, but also the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which have more than one acid function.
  • polycarboxylic acids themselves can also be used in principle since, in addition to their builder action, they also have an acidifying component and can therefore also contribute to the setting of a lower and milder pH of detergents or cleaning agents.
  • the pH value of detergents or cleaning agents is usually above 10.5, depending on the recipe, but especially in the case of powerful universal detergents or machine dishwashing detergents, values up to 11.5 also being found.
  • polycarboxylic acids themselves are either admixed subsequently or are used in the premix in anhydrous form, the subsequent admixing being the customary procedure.
  • solid premixes which contain polycarboxylic acids cannot be found in the disclosure, nor can there be any indications of how the other builder substances in the premix may have to be matched to this acidic component.
  • Detergents or cleaning agents which, according to the teachings of European patent EP 0486592 B1 or international patent application WO 98/12299, have - in addition to their application properties - also a high level of consumer acceptance due to their relatively uniform appearance.
  • extrudates produced by the process of international patent application WO 98/12299 and which contain a builder system which has zeolite as the main constituent have a desired amount of less than 750 if already small amounts of polycarboxylic acids are used in the premix g / l may have a reduced bulk density, but at the same time have an unacceptably changed fragrance.
  • the invention therefore relates in a first embodiment to a detergent or cleaning agent or compound compacted under pressure, in particular extruded therefor, which contains organic polycarboxylic acids and / or their salts, but not more than 5% by weight of non-water-soluble builder substances, where the pH of a 1% solution of the agent in water at 20 ° C is below 10.5.
  • compositions contain organic polycarboxylic acids and / or their salts, the use of organic polycarboxylic acids in the preparation of the compositions being not absolutely necessary, but being preferred, and the use of both organic polycarboxylic acids and their salts being particularly advantageous and therefore particularly preferred in the preparation is.
  • organic polycarboxylic acids in the preparation of the compositions being not absolutely necessary, but being preferred, and the use of both organic polycarboxylic acids and their salts being particularly advantageous and therefore particularly preferred in the preparation is.
  • the description of the agents at some points speaks of organic polycarboxylic acids contained in the agent, in order to be able to distinguish between salts originally used and salts contained in the process by neutralization.
  • organic polycarboxylic acids on average that is, the amounts of salt which are produced in the preparation of the agents by neutralization of the organic polycarboxylic acids, and any residues of unneutralized acid.
  • Useful organic polycarboxylic acids and / or their salts are, for example, those which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic acid, sugar acids and mixtures of these are preferred.
  • the salts are preferably used as alkali metal salts and in particular as sodium salts.
  • a combination of 2 or more acids and / or their salts from the above group is used as the organic polycarboxylic acid and / or its salt, it being particularly preferred that an agent is an organic polycarboxylic acid (which in the Production of the agent was at least partially neutralized as set out above) and contains a salt of an organic polycarboxylic acid.
  • the content of the agents in organic polycarboxylic acids and / or their salts, based on the sum of the water-soluble builder substances is at least 30% by weight and in particular at least 35% by weight, for example 40% by weight or even more than 50% by weight.
  • compositions preferably contain 5 to 35% by weight, in particular 10 to 30% by weight and, with very particular preference, up to 25% by weight of salts of organic polycarboxylic acids, which were also originally used as salts in the preparation of the compositions were.
  • the preferred content of organic polycarboxylic acids on the other hand is 1 to 10% by weight and in particular 1 to 5% by weight.
  • the sum of the total salts of organic polycarboxylates present can therefore be from 5 to 45% by weight in an advantageous embodiment, but is preferably from 8 to 30% by weight and in particular from 10 to 20% by weight.
  • the pH of the compositions is preferably at most 10.2 and in particular at most 10.0. Values from 9.0 to 9.9 are particularly preferred because of the mildness of the agents. It was surprising that such mild agents can be produced by compacting under pressure, which nevertheless had an acceptable value in the fragrance assessment and an unchanged fragrance note compared to agents with a higher pH.
  • the agents have a bulk density that is not above 750 g / l.
  • the agents according to the invention have bulk densities of between 500 and 700 g / l.
  • the preferred agents according to the invention thus combine several advantages: measured by their pH value, they are relatively mild and can therefore be subsequently mixed with other alkaline constituents without the alkaline value of the prepared agent being too high for use in the home, have one acceptable, compared to agents with higher pH values unchanged fragrance, a relatively low bulk density desired by the consumer and show in a further embodiment of the invention additionally a relatively uniform external appearance that the consumer of products manufactured by extrusion and under the Trademark Megaperls ® are distributed, known and valued.
  • the compositions as builder substances predominantly have those which are soluble in water.
  • these include further inorganic and / or organic builder substances.
  • agents are considered according to the invention which contain a builder system composed of organic and inorganic builder substances.
  • the water-soluble inorganic builder substances are selected primarily from the group of carbonates, amorphous alkali metal silicates, crystalline phyllosilicates, phosphates and mixtures of two, three, four or even more of the builder substances mentioned.
  • Both monoalkali metal salts and dialkali metal salts of carbonic acid as well as sesquicarbonates can be included in the compositions as carbonates.
  • Preferred alkali metal ions are sodium and / or potassium ions.
  • Compounds of, for example, carbonate, silicate and, if appropriate, further auxiliaries, such as, for example, anionic surfactants or other, in particular organic builder substances, can also be used in the preparation of the agents according to the invention.
  • 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 ones X-rays having a width of several degree units of the diffraction angle.
  • Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x 0 2 ⁇ + ⁇ ⁇ 2 0, 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.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 0 5 'yH 2 0 are suitable.
  • crystalline layered silicates are less preferred because they have a dissolving rate which is too slow and their processing in the extruder often leads to metal abrasion.
  • phosphates As builder substances, provided that such use should not be avoided for ecological reasons.
  • the aicali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry.
  • Aikalimetallphosphate is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 3 ) n and orthophosphoric acid H 3 P0 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and limescale deposits on the wash ware and also contribute to cleaning performance.
  • Suitable phosphates are sodium dihydrogen phosphate, NaH 2 P0, disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HP0 4 , trisodium phosphate, tertiary sodium phosphate, Na 3 P0 4 , tetrasodium dip osphate (sodium pyrophosphate), and Na P 2 0 7 the NaH 2 P0 4 and the KH 2 P0 4 result in higher molecular weight sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates.
  • agents which contain alkali metal carbonates and / or alkali metal bicarbonates, especially sodium carbonates and / or sodium bicarbonates, as inorganic water-soluble builder substances, agents which are particularly advantageous which comprise a combination of carbonate, especially sodium carbonate, and bicarbonate, especially sodium bicarbonate, and if desired have further inorganic and / or organic water-soluble builder substances.
  • the alkali metal carbonate and / or alkali metal bicarbonate and in particular alkali metal carbonate and alkali metal bicarbonate content of the agents according to the invention, based on the sum of the water-soluble builder substances, is preferably 10 to 80% by weight, in particular 20 to 60% by weight, recipes with less than 50 wt .-% and in particular with 20 to 40 wt .-% alkali metal carbonate and / or alkali metal bicarbonate, based on the sum of the water-soluble builder systems, may have application-related advantages, but are often less preferred for economic reasons.
  • the content of alkali metal carbonate and / or alkali metal bicarbonate and in particular of alkali metal carbonate and alkali metal bicarbonate, based on the agent according to the invention is preferably 1 to 30% by weight and in particular 1 to 20% by weight, contents of at least 5% by weight. % and in particular at least 10% by weight are particularly preferred.
  • the use of predominantly water-soluble builder systems, which in particular at least sodium carbonate and / or sodium bicarbonate on the one hand and organic polycarboxylic acid, in particular citric acid, does not lead to a deterioration in the dissolving behavior of the agents according to the invention, as has been the case with experiments with builder systems composed of water-insoluble and water-soluble builders in combination with organic Polycarboxylic acid would have been expected. Rather, the agents according to the invention have good dissolving behavior, which is comparable to the dissolving behavior of the extrudates based on zeolite produced according to WO 98/12299 as the main component of the builder system. Agents according to the invention thus have a solubility which, measured according to the L test given in the examples, has a value of 1 to 20% by weight and in particular 5 to 15% by weight.
  • the agents according to the invention have carbonate and / or bicarbonate and citric acid and / or citrate, the weight ratio of the sum of carbonate and / or bicarbonate to the sum of citric acid and / or citrate being between 3: 1 and 1 : 2, especially between 2: 1 and 1: 1.
  • the agents, compacted under pressure and, in particular, extruded contain no more than 5% by weight of non-water-soluble builder substances, which include, above all, aluminosilicates and, in particular, zeolites of this type in detergent quality.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • the zeolite is usually used as a spray-dried powder or as a compounded granulate.
  • Suitable finely divided powdered 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.
  • the agents according to the invention can be post-treated with solids and / or liquids.
  • the actual compacted and in particular extruded agent under pressure represents the core of the agent according to the invention which, in addition to this core, has at least one partial or complete shell which was subsequently applied.
  • the core of the agents according to the invention has less than 5% by weight, preferably a maximum of 3% by weight and in particular a maximum of 2% by weight of non-water-soluble builder substances.
  • Embodiments are very particularly preferred in which the core of the agents according to the invention is free of non-water-soluble builder substances and in particular free of aluminosilicates, such as, for example, zeolites.
  • the agent has at least one partial or complete shell made of one or more liquids, an aftertreatment advantageously being carried out on it with at least one, in particular finely divided, solid.
  • the core of the agents according to the invention, compacted under pressure and in particular extruded is first aftertreated with at least one, in particular finely divided, solid, whereupon a further aftertreatment with at least one liquid and, if desired, further aftertreatments with solids and liquids alternately. It is advantageous if the aftertreatment of the core is completed by powdering with a, in particular finely divided, solid.
  • the core which is compacted and in particular extruded under mechanical pressure, has a water-soluble ingredient or a combination of two or more water-soluble ingredients, in particular from the group of amorphous silicates, sulfates, in particular sodium sulfates, fatty acid salts, in particular calcium stearates, alkali metal carbonates and powdered alkali metal bicarbonates.
  • amorphous silicates sulfates, in particular sodium sulfates, fatty acid salts, in particular calcium stearates, alkali metal carbonates and powdered alkali metal bicarbonates.
  • These ingredients which are also known as surface modifiers and / or flow aids, preferably have a particle size of less than 30 ⁇ m, with in a particularly preferred embodiment of the invention at least 90% of all particles having a maximum of 15 ⁇ m.
  • the core which is compacted and in particular extruded under mechanical pressure, with a non-water-soluble ingredient or a combination of two or more non-water-soluble ingredients, in particular from the group of fatty acids, aluminosilicates, in particular clays such as bentonites and smectites and zeolites, and powdered silicic acids, with aluminosilicates and in particular the zeolites of the type mentioned above being particularly preferred.
  • a non-water-soluble ingredient or a combination of two or more non-water-soluble ingredients in particular from the group of fatty acids, aluminosilicates, in particular clays such as bentonites and smectites and zeolites, and powdered silicic acids, with aluminosilicates and in particular the zeolites of the type mentioned above being particularly preferred.
  • aluminosilicates and silicas which are in particular hydrophobic, a mixture of 100 to 3 parts by weight of zeolite A, zeolite P and / or zeolite X per 1 part by weight of hydrophobic silica being particularly advantageous.
  • the preferred particle sizes for the non-water-soluble ingredients are the same as for water-soluble ingredients.
  • the means compacted and in particular extruded under mechanical pressure means the core produced accordingly, which is optionally post-treated as indicated above.
  • the water content of the agents according to the invention is relatively low compared to the water content of conventional spray-dried or granulated agents with comparable bulk densities. Despite the low water content, the agents are not hygroscopic and remain flowable and stable even after storage.
  • the agents according to the invention can contain, as further ingredients, additional further water-soluble builder substances, but also surfactants, if desired also bleaching agents, bleaching catalysts and / or bleach activators, soil-release and soil-repellent compounds, enzymes and Enzyme stabilizers, foam inhibitors, UV absorbers, optical brighteners, neutral filler salts and colorants and fragrances, all of which are already known from the prior art.
  • Polymeric polycarboxylates are suitable as further water-soluble builders; These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
  • GPC gel permeation chromatography
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
  • the molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1200 to 8000 g / mol, for example 4500 or 8000, may in turn be preferred from this group.
  • Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids, is generally 2,000 to 100,000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 g / mol.
  • the (co) polymeric polycarboxylates content of the particulate agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid
  • Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,
  • copolymers preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances.
  • Polyaspartic acids or their salts and derivatives are particularly preferred.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • 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.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • Ethylendiamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are those containing zeolite and / or particulate agents containing silicate between 3 to 15 wt .-%, based on the total agent.
  • IDS Iminodisuccinates
  • HDIS hydroxyiminodisuccinates
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may 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.
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of the neutral sodium salts, e.g. B.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C 12 -C 18 monoolefins with an end or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids esters of ⁇ -sulfofatty acids (ester sulfonates), 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 as well as their mixtures, as they are produced by esterification by a monoglycerol with 1 to 3 mols of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mols of glycerol be preserved.
  • alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 8 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 2 o-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.
  • C 6 -C 18 alk (en) yl sulfates are particularly preferred for washing technology reasons. It can also be particularly advantageous and particularly advantageous for machine washing agents to use C 16 -C 8 -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 12 -C 1 fatty alkyl sulfates or C 12 -C 18 fatty alkyl sulfates with C 16 -C 1a fatty alkyl sulfates and in particular C 12 -C 16 -Fatty alkyl sulfates with C ⁇ 6 - C 8 fatty alkyl sulfates.
  • not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 -C 18 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.
  • 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 C 8 to C 18 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).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Preferred anionic surfactant mixtures contain combinations of alcohol sulfates and alkylbenzenesulfonates, sulfated fatty acid glycerol esters and / or ⁇ -sulfofatty acid esters and / or sulfosuccinates.
  • Mixtures which contain, as anionic surfactants, alcohol sulfates and alkylbenzenesulfonates, alcohol sulfates and methyl ⁇ -sulfofatty acid and / or sulfated fatty acid glycerol esters are particularly preferred.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.2 to 2% 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, available.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the content of anionic surfactants in the agents according to the invention is preferably 5 to 35% by weight and in particular 10 to 30% by weight.
  • 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.
  • Preferred ethoxylated alcohols include, for example C12- ⁇ 4 -A! Alcohols with 3 EO or 4 EO, C 9 -C ⁇ alcohols containing 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 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 include tallow fatty alcohol with 14 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 alkylglycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, such as they are 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.
  • 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 alkanol amides 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 1 CO is an aliphatic acyl radical having 6 to 22 carbon atoms
  • R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the content of the agents in nonionic surfactants is preferably 1 to 15% by weight and in particular 2 to 10% by weight.
  • cationic surfactants are quaternary ammonium compounds, cationic polymers and emulsifiers, such as are used in hair care products and also in agents for textile finishing.
  • ester quats are particularly preferred here.
  • Agents according to the invention can contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all the enzymes established in the prior art for these purposes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are accordingly preferred. Agents according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 "6 to 5 percent by weight based on active protein.
  • the protein concentration can be determined using known methods, for example the BCA process (bicinchoninic acid; 2,2'-bichinolyl-4,4 '-dicarboxylic acid) or the biuret method can be determined.
  • the proteases those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and that which can no longer be assigned to the subtilisins in the narrow sense Proteases TW3 and TW7.
  • Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ® from Novozymes A / S, Bagsvasrd, Denmark.
  • the subtilisins 147 and 309 are sold under the trade names Esperase ®, or Savinase ® from Novozymes.
  • the protease from Bacillus lentus DSM 5483 is derived from the variants known as BLAP ® , which are described in particular in WO 92/21760, WO 95/23221 and in applications DE 10121463 and DE 10153792.
  • Other usable proteases from various Bacillus sp. and B. gibsonii emerge from the patent applications DE 10162727, DE 10163883, DE 10163884 and DE 10162728.
  • proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® by the company Genencor, which is sold under the trade name Protosol ® by Advanced Biochemicals Ltd., Thane, India, which is sold under the trade name Wuxi ® by Wuxi Snyder Bioproducts Ltd., China, and in the trade name Proleather ® and Protease P ® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermophilus and their further developments which are improved for use in detergents and cleaning agents.
  • the enzyme from B. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar® ® ST. Development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®.
  • the ⁇ -amylase from ß. Amyloliquefaciens is sold by Novozymes under the name BAN ® , and derived variants from the ⁇ -amylase from ⁇ . stearothermophilus under the names BSG ® and Novamyl ® , also from Novozymes.
  • ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) described in the application PCT / EP01 / 13278 from ⁇ . highlight agaradherens (DSM 9948); further those belonging to the sequence space of ⁇ -amylases, which is defined in the application DE 10131441. Fusion products of the molecules mentioned can also be used, for example those from the application DE 10138753.
  • Agents according to the invention can contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors.
  • lipases or cutinases include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ® , Lipolase ® Ultra, LipoPrime ® , Lipozyme ® and Lipex ® .
  • the cutinases can be used, for example, which were originally isolated from Fusarium solani pisi and Humicola insolens.
  • lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp. Lipase ® , Lipase AP ® , Lipase M-AP ® and Lipase AML ® available.
  • the Genencor company can use the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • Agents according to the invention can contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement one another with regard to their various performance aspects.
  • These performance aspects include, in particular, contributions to the primary washing performance, to the secondary washing performance of the agent (anti-deposition effect or graying inhibition) and finish (tissue effect), up to the exertion of a “stone washed” effect.
  • EG endoglucanase
  • Novozymes A useful fungal, endoglucanase (EG) -rich cellulase preparation or its further developments are offered by the Novozymes company under the trade name Celluzyme ® .
  • the products Endolase ® and Carezyme ® also available from Novozymes, are based on the 50 kD-EG and the 43 kD-EG from H. insolens DSM 1800. Others possible commercial products from this company are Cellusoft ® and Renozyme ® .
  • the cellulases disclosed in application WO 97/14804 can also be used; For example, it revealed 20 kD EG Melanocarpus, available from AB Enzymes, Finland, under the trade names Ecostone® ® and Biotouch ®.
  • Suitable mannanases are available, for example under the name Gamanase ® and Pektinex AR ® from Novozymes, under the name Rohapec ® B1 L from AB Enzymes and under the name Pyrolase® ® from Diversa Corp., San Diego, CA, USA ,
  • a suitable ß-glucanase from a ß. alcalophilus can be found, for example, in application WO 99/06573.
  • the from ß. subtilis .beta.-glucanase obtained is available under the name Cereflo ® from Novozymes.
  • washing and cleaning agents according to the invention can contain oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain.
  • oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain.
  • Suitable commercial products are Denilite ® 1 and 2 from Novozymes.
  • organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of greatly different redox potentials between the oxidizing enzymes and the soiling.
  • the enzymes used in agents according to the invention either originate from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological processes known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.
  • the enzymes in question are advantageously purified by processes which are established per se, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, Microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
  • Agents according to the invention can be added to the enzymes in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers.
  • the enzymes can be encapsulated, for example by spray drying or extruding the enzyme solution together with a, preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed in a solidified gel or in a core-shell type , in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals.
  • Additional active ingredients for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers.
  • Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.
  • a protein and / or enzyme contained in an agent according to the invention can be protected, particularly during storage, against damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage.
  • the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases.
  • Agents according to the invention can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.
  • a group of stabilizers are reversible protease inhibitors.
  • Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used, including above all derivatives with aromatic groups, for example ortho-substituted, meta-substituted or para-substituted phenylboronic acids, or their salts or esters.
  • peptide aldehydes, ie oligopeptides with a reduced C-terminus are also disclosed.
  • Ovomucoid and leupeptin may be mentioned as peptide protease inhibitors; an additional option is the formation of fusion proteins from proteases and peptide inhibitors.
  • Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and their mixtures, aliphatic carboxylic acids up to C ⁇ 2 , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned, or end-capped fatty acid amide alkoxylates. Certain organic acids used as builders can additionally stabilize an enzyme contained.
  • Di-glycerol phosphate also protects against denaturation due to physical influences.
  • Calcium salts such as calcium acetate or calcium formate, and magnesium salts are also used.
  • Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation against physical influences, among other things.
  • Polymers containing polyamine-N-oxide act simultaneously as enzyme stabilizers and as color transfer inhibitors.
  • Other polymeric stabilizers are linear C 8 -C 18 polyoxyalkylenes.
  • the alkyl polyglycosides already mentioned can stabilize the enzymatic components of the agent according to the invention and even increase their performance.
  • Crosslinked N-containing compounds fulfill a double function as soil release agents and as enzyme stabilizers.
  • Reducing agents and antioxidants increase the stability of the enzymes against oxidative decay.
  • Sulfur-containing reducing agents are known, for example, from the patents EP 080748 and EP 080223.
  • Other examples are sodium sulfite and reducing sugars.
  • Combinations of stabilizers are preferably used, for example made of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.
  • the effect of peptide-aldehyde stabilizers is increased by the combination with boric acid and / or boric acid derivatives and polyols and is further enhanced by the additional use of divalent cations, such as calcium ions.
  • enzymes are excellently suited for being compacted and in particular extruded under pressure, it is preferred in a particular embodiment to prefabricate the enzymes and, if appropriate, mixtures of 2, 3 or more of the enzymes and enzyme stabilizers mentioned and then to prepare the agents according to the invention therewith ,
  • the enzyme and enzyme stabilizer content of the optionally prepared agents is preferably 0.5 up to 3% by weight, based on the agent according to the invention or on the agent that may be prepared.
  • the agents can also contain components which have a positive effect on the oil and fat washability from textiles. This effect is particularly evident when a textile is contaminated which 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, in each case 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 anionically and / or nonionically modified derivatives thereof.
  • 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, in each case based on the nonionic cellulose ether
  • foam inhibitors such as, for example, foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane. Mixtures of these active ingredients are also possible. Additives which are solid at room temperature, in particular in the case of the foam-inhibiting active substances mentioned, paraffin waxes, silicas, which can also be hydrophobicized in a known manner, and of C 2-7 diamines and C 12 . 22- carboxylic acid-derived bisamides in question.
  • Foam-inhibiting paraffin oils that can be used which may be present in a mixture with paraffin waxes, are generally complex substance mixtures without a sharp melting point.
  • the melting range is usually determined by differential thermal analysis (DTA), as in "The Analyst” 87 (1962), 420, and / or the freezing point. This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling.
  • DTA differential thermal analysis
  • Paraffins with less than 17 carbon atoms cannot be used according to the invention, their proportion in the paraffin oil mixture should therefore be as low as possible and is preferably below the limit which is significantly measurable with customary analytical methods, for example gas chromatography. Paraffins which solidify in the range from 20 ° C. to 70 ° C. are preferably used.
  • paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin oils.
  • the liquid content is as high as possible at 40 ° C. without being 100% at this temperature.
  • Preferred paraffin wax mixtures have a liquid content of at least 50% by weight, in particular from 55% by weight to 80% by weight, at 40 ° C. and a liquid content of at least 60 ° C. 90% by weight. The consequence of this is that the paraffins are flowable and pumpable at temperatures down to at least 70 ° C., preferably down to at least 60 ° C. It is also important to ensure that the paraffins do not contain any volatile components.
  • Paraffin waxes contain less than 1% by weight, in particular less than 0.5% by weight, of parts which can be evaporated at 110 ° C. and normal pressure.
  • Paraffins which can be used according to the invention can be obtained, for example, under the trade names Lunaflex® from Guer and Deawax® from DEA Mineralöl AG.
  • the paraffin oils can contain bisamides which are solid at room temperature and which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18 C atoms and from alkylenediamines with 2 to 7 C atoms.
  • Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachic acid and behenic acid and mixtures thereof, as can be obtained from natural fats or hydrogenated oils, such as tallow or hydrogenated palm oil.
  • Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
  • Preferred diamines are ethylenediamine and hexamethylenediamine.
  • Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bispalmitoyl-ethylenediamine, bis-stearoyl-ethylenediamine and mixtures thereof, and the corresponding derivatives of hexamethylenediamine.
  • the agents can contain UV absorbers, which absorb onto the treated textiles and improve the lightfastness of the fibers and / or the lightfastness of the other formulation components.
  • UV absorbers are understood to mean organic substances (light protection filters) which are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, for example heat.
  • Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position.
  • Substituted benzotriazoles phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are also suitable.
  • UV-B absorbers as described in EP 0693471 B1; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene); Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenz
  • 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts
  • Sulfonic acid derivatives of 3-benzylidene camphor such as 4- (2-oxo-3-bornylidenemethyl) benzene-sulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and their salts.
  • UV-A filters -4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds as described in DE 19712033 A1 (BASF).
  • the UV-A and UV-B filters can of course also be used in mixtures.
  • insoluble light-protection pigments namely finely dispersed, preferably nanoized metal oxides or salts
  • suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
  • Silicates (talc), barium sulfate or zinc stearate can be used as salts.
  • the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm.
  • the pigments can also be surface-treated, ie hydrophilized or hydrophobicized.
  • Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones and, in particular, trialkoxyoctylsilanes or simethicones are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferably used. Further suitable UV light protection filters can be found in the overview by P.Finkel in S ⁇ FW-Journal 122, 543 (1996).
  • the UV absorbers are usually used in amounts of from 0.01% by weight to 5% by weight, preferably from 0.03% by weight to 1% by weight.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted type can also be used Diphenylstyryles may be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brighteners can also be used. It has been found that uniform white granules are obtained if the agents, in addition to the usual brighteners, are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight. also contain small amounts, for example 10 " to 10 " 3 % by weight, preferably around 10 "5 % by weight, of a blue dye. A particularly preferred dye is Tinolux ⁇ ) (commercial product from Ciba-Geigy).
  • the agents according to the invention compacted and in particular extruded under pressure preferably have a relatively uniform appearance, the grain spectrum being almost 100% by weight between 0.1 and 4 mm (including both values), in particular between 0.4 and 2.0 mm (including both values). Dust particles with particle sizes smaller than 0.1 mm are preferably completely excluded.
  • Another object of the invention relates to the production of the agents according to the invention.
  • a method according to the teaching of international patent application WO 98/12299 is used in particular. Reference is expressly made to the detailed description of the method in this document.
  • a method is preferred in which first a premix comprising individual raw materials and / or compounds which are in the form of a solid at room temperature and a pressure of 1 bar and which have a melting point or softening point not below 45 ° C., and optionally at temperatures below 45 ° C and a pressure of 1 bar liquid nonionic surfactants and preferably not more than 10 wt .-% of these at temperatures below 45 ° C and a pressure of 1 bar liquid nonionic surfactants, produced and using compression forces at temperatures of at least 45 ° C converted into a grain and, if necessary, subsequently processed or prepared.
  • the premix used has no free water and that the premix contains at least one raw material or compound which is in solid form at a pressure of 1 bar and temperatures below 45 ° C., but under the processing conditions is in the form of a melt, this melt serving as a polyfunctional, water-soluble binder which, in the preparation of the agents, performs both the function of a lubricant and an adhesive function for the solid detergent or cleaning agent compounds or raw materials when the agent is redissolved in aqueous fleet, however, has a disintegrating effect.
  • water can only be in chemically and / or physically bound form or as a component of the raw materials or compounds present as a solid at temperatures below 45 ° C at a pressure of 1 bar, but not as a liquid, solution or dispersion per se the process for the preparation of the premix are introduced.
  • a binder is used which is already completely in the form of a melt at temperatures of up to 130 ° C., preferably up to 100 ° C. and in particular up to 90 ° C.
  • the binder must therefore be selected depending on the process and process conditions, or the process conditions, in particular the process temperature, must - if a specific binder is desired - be adapted to the binder.
  • Preferred binders which can be used alone or in a mixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and also modified polyethylene glycols and polypropylene glycols.
  • the modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12000 and in particular between 1000 and 4000.
  • Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which in turn have relative molecular weights have between 600 and 6000, preferably between 1000 and 4000.
  • polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C 3 -C 5 glycols and glycerol and mixtures of these as starting molecules. Ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included.
  • the preferably used polyethylene glycols can have a linear or branched structure, linear polyethylene glycols being preferred in particular.
  • the particularly preferred polyethylene glycols include those with relative molecular weights between 1500 and 12000 (both values inclusive), advantageously around 1500 to 4000 (both values inclusive).
  • polyethylene glycols which are in the liquid state at room temperature and a pressure of 1 bar can also be used as binders; here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600.
  • these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C.
  • the modified polyethylene glycols also include polyethylene glycols which are end group-capped on one or more sides, the end groups preferably being CC 12 alkyl chains which can be linear or branched.
  • the end groups have the alkyl chains between Ci and C 6 , especially between ⁇ and C 4 , with isopropyl and isobutyl or tert-butyl also being possible alternatives.
  • binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights up to a maximum of 30,000. Relative molecular weight ranges between 3,000 and 30,000, for example around 10,000, are preferred here. Polyvinylpyrrolidones are preferably not used as the sole binder, but in combination with others, in particular in combination with Polyethylene glycols used.
  • binders have been found to be raw materials which, as raw materials, have washing or cleaning properties per se, for example nonionic surfactants with melting points of at least 45 ° C. or mixtures of nonionic surfactants and other binders.
  • the preferred nonionic surfactants include alkoxylated fatty or oxo alcohols, in particular C 12 -C 18 alcohols. Degrees of alkoxylation, in particular degrees of ethoxylation, of on average 18 to 100 AO, in particular EO per mole of alcohol and mixtures thereof have proven to be particularly advantageous.
  • fatty alcohols with an average of 18 to 35 EO, in particular with an average of 20 to 25 EO show advantageous binder properties in the sense of the present invention.
  • Binder mixtures may optionally also contain ethoxylated alcohols with an average of fewer EO units per mole of alcohol, for example tallow fatty alcohol with 14 EO. However, it is preferred to use these relatively low ethoxylated alcohols only in a mixture with higher ethoxylated alcohols.
  • the binder content of these relatively low ethoxylated alcohols is advantageously less than 50% by weight, in particular less than 40% by weight, based on the total amount of binder used.
  • nonionic surfactants such as C 12 -C 18 alcohols with an average of 3 to 7 EO, which are usually used in detergents or cleaning agents and which are liquid per se at room temperature, are preferably only present in the binder mixtures in amounts that are less than 10 % By weight, in particular less than 8% by weight and advantageously less than 2% by weight, of these nonionic surfactants, in each case based on the end product of the process. As already described above, however, it is less preferred to use nonionic surfactants which are liquid at room temperature in the binder mixtures themselves.
  • nonionic surfactants are therefore not a constituent of the binder mixture, since they not only lower the softening point of the mixture, but can also contribute to the stickiness of the end product and, furthermore, also due to their tendency to cause gelling upon contact with water The requirement for rapid dissolution of the binder / partition in the end product often does not suffice to the desired extent.
  • anionic surfactants or their precursors the anionic surfactant acids, used in washing or cleaning agents are contained in the binder mixture.
  • nonionic surfactants that are suitable as binders are the non-gelling fatty acid methyl ester ethoxylates (for a more detailed description of this group of substances, see above), in particular those with an average of 10 to 25 EO, so that the representatives of this group of substances preferred as nonionic surfactants differ from those can distinguish preferred representatives as binders.
  • Particularly preferred representatives of this group of substances are predominantly methyl esters based on C 16 -cis fatty acids, for example hardened beef tallow methyl esters with an average of 12 EO or with an average of 20 EO.
  • ethoxylated fatty acids with 2 to 100 EO
  • the “fatty acid” residues of which can be linear or branched in the context of this invention.
  • Ethoxylates are particularly preferred which: have a narrowed homolog distribution (NRE) and / or a melting point above 50 ° C.
  • NRE narrowed homolog distribution
  • Such fatty acid ethoxylates can be used as the sole binder or in combination with other binders, while the non-ethoxylated sodium and potassium soaps are less preferred and only in combination with other binders can be used.
  • hydroxy mixed ethers which can be obtained according to the teaching of European patent application EP-A-0 754 667 (BASF) by ring opening of epoxides of unsaturated fatty acid esters, are also suitable as binders, in particular in combination with polyethylene glycols, the aforementioned fatty acid methyl ester ethoxylates or the fatty acid ethoxylates ,
  • water-free swollen polymers in particular starch disphosphate / glycerol, polyvinylpyrrolidone / glycerol and modified cellulose / glycerol, for example hydroxypropyl cellulose / glycerol, have also proven to be excellently usable binders. 5 to 20% by weight non-aqueous solutions of the polymers in glycerol, in particular about 10% by weight non-aqueous solutions, are particularly advantageous.
  • a mixture is used as the binder which contains C 12 -C 18 fatty alcohol based on coconut or tallow with an average of 20 EO and polyethylene glycol with a relative molecular weight of 400 to 4000.
  • a mixture is used as the binder which is predominantly methyl ester-based C 16 -C 8 fatty acids with an average of 10 to 25 EO, in particular hardened bovine methyl ester with an average of 12 EO or an average of 20 EO, and a C 2 - Contains C 18 fatty alcohol based on coconut or tallow with an average of 20 EO and / or polyethylene glycol with a relative molecular weight of 400 to 4000.
  • Binders which have proven to be particularly advantageous embodiments of the invention are either based solely on polyethylene glycols with a relative molecular mass of around 4000 or on a mixture of C 12 -C 18 fatty alcohol based on coconut or tallow with an average of 20 EO and one of the fatty acid methyl ester ethoxylates described above or based on a mixture of C 12 -C 18 fatty alcohol based on coconut or tallow with an average of 20 EO, one of the fatty acid methyl ester ethoxylates described above and a polyethylene glycol, in particular with a molecular weight of around 1500 to 4000.
  • binder mixtures in particular in a mixture with polyethylene glycols; however, they cannot be used as the sole binder, since they have a binding / adhesive function, but do not have a disintegrating effect.
  • alkyl glycosides of the general formula RO (G) x can also be used as further binders, alone or in combination with other binders.
  • Alkyl glycosides which have a degree of softening above 80 ° C. and a melting point above 140 ° C. are particularly suitable.
  • Highly concentrated compounds with contents of at least 70% by weight alkyl glycosides, preferably at least 80% by weight alkyl glycosides, are also suitable. Using high shear forces, the melt agglomeration and in particular the melt extrusion with such highly concentrated compounds can already be carried out at temperatures which are above the softening point but still below the melting temperature.
  • alkyl glycosides can also be used as the sole binder, it is preferred to use mixtures of alkyl glycosides and other binders.
  • mixtures of polyethylene glycols and alkyl glycosides advantageously in weight ratios from 25: 1 to 1: 5, with particular preference from 10: 1 to 2: 1.
  • binders in particular in combination with polyethylene glycols and / or alkyl glycosides, are polyhydroxy fatty acid amides of the type already described above.
  • the content of binder or binders in the premix is preferably at least 2% by weight, but less than 15% by weight, in particular less than 10% by weight, with particular preference from 3 to 6% by weight, in each case based on the premix.
  • the water-swollen polymers are used in amounts below 10% by weight, advantageously in amounts of 4 to 8% by weight, with preference of 5 to 6% by weight.
  • agents which have a bulk density of less than 600 g / l can also be produced by the process described in the preparation of agents according to the invention.
  • the agents nevertheless remain cutable when they emerge from the hole shape of the extruder and do not stick there.
  • organic polycarboxylic acids are used in the process according to the invention, preferably in amounts of 1 to 10% by weight and in particular in amounts of 1 to 5% by weight.
  • the agents according to the invention compacted and in particular extruded under mechanical pressure can be offered and used directly as washing or cleaning agents.
  • the agents are prepared with further, separately and subsequently admixed components of washing or cleaning agents. This can be done in such a way that the finished, mixed washing or cleaning agents are obtained from a mixture of several different granules, of which the agents according to the invention, compacted and in particular extruded under mechanical pressure, form the main constituent.
  • compositions of different compositions, compacted under pressure and in particular extruded of which at least one is colored and serves as a speckle, for example.
  • further ingredients such as, for example, the enzymes already described above, but also bleaching agents, bleaching catalysts and / or bleach activators in the amounts customary for detergents or cleaning agents are subsequently added to the agents according to the invention which are compacted and in particular extruded under mechanical pressure.
  • the foaming behavior for detergents can be positively influenced if the foam inhibitor, for example organopolysiloxanes and their mixtures with microfine, optionally signed silica, and paraffins, waxes, Microcrystalline waxes and their mixtures with signed silica or bistearylethylenediamide, at least partly not extruded, but subsequently mixed with the extrudate.
  • the surface of the extrudate according to the invention is first covered, for example, with zeolite or a zeolite-containing mixture and then with a foam inhibitor.
  • zeolite or a zeolite-containing mixture and then with a foam inhibitor.
  • the finished washing or cleaning agents can contain antimicrobial agents.
  • antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenol mercuric acetate.
  • antimicrobial activity and antimicrobial active substance have the customary meaning which, for example, from KH Wall conference with "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene" (5th ed.
  • Suitable antimicrobial agents are preferably selected from the groups of alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes , Urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1, 2-dibromo-2,4-dicyanobutane, iodo-2-propynyl butyl carbamate , iodine, iodophores, peroxo compounds, halogen compounds and any mixtures of the foregoing.
  • the antimicrobial active ingredient can be selected from ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholinum acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylene-bis- (6-bromo-4-chlorophenol), 4,4'-dichloro-2'-hydroxydiphenyl ether (dichlosan), 2.4 , 4'-trichloro-2'-hydroxydiphenyl ether (trichlosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) urea, N.N'-Cl ⁇ O-decane-diyldi-l -pyridinyM
  • N 5 , N 5 ') hexane dihydrochloride le-DHNi.N ⁇ A ⁇ -trichlorophenyldiguanido-Ns.Ns ⁇ hexanetrahydrochloride, 1, 6-di- [N 1 , N' -alpha- (p-chlorophenyl) ethyldiguanido -N 5 , N 5 '] hexane dihydrochloride, omega: omega-di- (N 1 , N ⁇ '-p-chlorophenyldiguanido-N 5 , N 5 ') m-xylene-dihydrochloride, 1, 12-di- (N 1 , N ⁇ '-p-chlorophenyldiguanido-N 5 , N 5 ') dodecane dihydrochloride, 1, 10-di- (N 1 , N 1 '-phenyldiguanido-N 5 , N 5
  • nonylphenyl biguanide ethylene bis (phenyl biguanide), ethylene bis (N-butylphenyl biguanide), ethylene bis (2,5-diethoxyphenyl biguanide), ethylene bis (2,4-dimethylphenyl biguanide), ethylene bis (o - Diphenylbiguanid), ethylene-bis (mixed amyl naphthylbiguanid), N-butyl-ethylene-bis- (phenylbiguanid), trimethylene bis (o-tolylbiguanid), N-butyl-trimethyl-bis- (phenylbiguanide); and the corresponding salts such as acetates, gluconates, hydrochlorides, hydrobromides, citrates, bisulfites, fluorides, polymaleates, N-coconut alkyl sarcosinates, phosphites, hypophosphites, perfluorooctanoates, silicates,
  • Halogenated xylene and cresol derivatives such as p-chlorometacresol or p-chloro-meta-xylene, amphoterics and natural antimicrobial agents of plant origin (e.g. from spices or herbs), animal and microbial origin are also suitable.
  • antimicrobial surface-active quaternary compounds a natural antimicrobial agent of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent of plant origin from the group comprising caffeine, theobromine and theophylline as well as essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial active ingredient of animal origin from the group comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound with an ammonium, sulfonium, phosphonium, iodonium - Or arsonium group, peroxo compounds and chlorine compounds are used.
  • Substances of microbial origin so-called bacteriocins, can also be used.
  • Quaternary ammonium compounds (QAV) suitable as antimicrobial active substances have the general formula (R 3 ) (R 4 ) (R 5 ) (R 6 ) N + X " , in which R 3 to R s have the same or different CC 22 alkyl radicals, C 7 -C 2 s aralkyl radicals or heterocyclic radicals, two or, in the case of an aromatic integration, as in pyridine, even three radicals together with the nitrogen atom Form heterocycle, for example a pyridinium or imidazolinium compound, represent and X "are halide ions, sulfate ions, hydroxide ions or similar anions.
  • at least one of the radicals preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms on.
  • QAV are by reacting tertiary amines with alkylating agents such as Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide can be produced.
  • alkylating agents such as Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide can be produced.
  • alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly easy, and the quaternization of tertiary amines with two long radicals and one methyl group can also be carried out with the aid of methyl chloride under mild conditions.
  • Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are not very reactive and are preferably quaternized with dimethyl sulfate.
  • Suitable QAC are, for example, benzalkonium chloride (N-alkyl-N, N-dimethyl-benzyl-ammonium chloride, CAS No. 8001-54-5), benzalkon B (/ 77, p-dichlorobenzyl-dimethyl-C12-alkylammonium chloride, CAS No. 58390-78-6), benzoxonium chloride (benzyl-dodecyl-bis- (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No.
  • benzetonium chloride N, N-dimethyl-N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121- 54-0
  • dialkyldimethylammonium chloride such as di - /? - decyl-dimethyl-ammonium chloride (CAS No. 7173-51-5-5), didecyldi-methylammonium bromide (CAS No. 2390-68-3), dioctyl-dimethyl- ammoniumchloric, 1-cetylpyridinium chloride (CAS No.
  • QAV thiazoline iodide
  • Particularly preferred QAV are the benzalkonium chlorides with C 8 -C 18 -alkyl radicals, in particular C 12 -C 14 -alkyl-benzyl-dimethyl-ammonium chloride.
  • Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ® ex Lonza, Marquat® ® ex Mason, Variquat ® ex Witco / Sherex and Hyamine ® ex Lonza and as Bardac ® ex Lonza.
  • antimicrobial agents are N- (3-chloroallyl) hexaminium chloride such as Dowicide and Dowicil ® ® ex Dow, benzethonium chloride such as Hyamine ® 1622 ex Rohm & Haas, methylbenzethonium as Hyamine ® 10X ex Rohm & Haas, cetylpyridinium chloride such as Cepacol ex Merrell Labs ,
  • the antimicrobial substances can be compacted and, in particular, extruded under mechanical pressure; however, it is preferred to mix these substances subsequently and, if necessary, in compounded form with other substances.
  • bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 0 2 -supplying peracidic salts or peracids, such as perbenzoates, Peroxophthalate, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines especially tetraacetylethylene diamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- Acyiimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, ethylene glycol, 2.5 2,5-dihydrofuran and enol esters as well as acetylated sorbitol and mann
  • agent M1 according to the invention and comparative agent V1 were produced.
  • the recipes are given below.
  • the ingredients mentioned were extruded at an extrusion pressure of 77 bar (M1) or 102 bar (V1) and a cut-off temperature of 103 ° C (M1) or 109 ° C (V1) and immediately after the exit cut from the hole shape.
  • Polyethylene glycol 1500 was used as a binder and lubricant with a solid character at temperatures below 45 ° C.
  • the extrudates were then powdered with zeolite A under the same conditions in the fillet.
  • the bulk weights were 660 g / l (M1) and 780 g / l (V1).
  • the L test (see below) gave 10% for M1, but 19% for V1.
  • the grain spectrum of both M1 and V1 was 100% by weight in the range from 0.4 to 2.0 mm.
  • the pH value of M1 of significantly less than 10.5 (namely 9.5)
  • the fragrance assessment gave the value “acceptable”. There was no change in the fragrance grade compared to V1.
  • compositions (figures in% by weight): MI VI
  • agents V2 and V3 were produced, the formulations of which are given below. With the exception of 3.55% by weight of the spray-dried zeolite A, the ingredients mentioned were extruded at an extrusion pressure of 78 bar (V2) or 65 bar (V3) and cut immediately after they emerged from the hole mold. Polyethylene glycol 4000 was used as a binder and lubricant with a solid character at temperatures below 45 ° C. The extrudates V2 and V3 were then powdered with 3.55% by weight of spray-dried zeolite A under the same conditions and under comparable conditions as in Example 1.
  • V2 and V3 The grain spectrum of both V2 and V3 was 100% by weight in the range from 0.4 to 2 mm.
  • the value of the L-test for V2 with 8.6% as well as for V3 with 9.8% was in a comparable order of magnitude as for M1 and thus in the acceptable range.
  • the bulk density for V2 was 790 g / l, for V3 730 g / l.
  • the replacement of the citrate with citric acid also led to a reduction in the bulk density in agents containing zeolite. However, this is significantly lower than in Example 1.
  • V2 had a pH of 10.7, while the pH of V3 was 9.5 (measured in each case at 20%, 1% solution in water).
  • the fragrance rating of V2 gave the value “acceptable”, while V3 had an unconsciously changed, acidic smell that had to be rated “unacceptable”.
  • compositions (figures in% by weight): V2 V3
  • Zeolite A (calculated as anhydrous active substance) 38.7 38.7

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Abstract

L'invention concerne des produits ou des compositions de lavage ou de nettoyage comprimé(e)s sous l'effet d'une pression et en particulier extrudé(e)s, qui contiennent des acides polycarboxyliques organiques et/ou des sels de ces acides ainsi qu'une quantité inférieure ou égale à 5 % en poids d'adjuvants non hydrosolubles, et présentent un pH inférieur à 10,5. Le parfum de ces produits est jugé acceptable malgré leur faible teneur en acides polycarboxyliques organiques, qui sont partiellement ou intégralement neutralisés lors de la production desdits produits, et malgré leur faible pH.
PCT/EP2003/009983 2002-09-12 2003-09-09 Produits de lavage ou de nettoyage comprimes sous l'effet d'une pression WO2004027009A1 (fr)

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EP03750500A EP1537199A1 (fr) 2002-09-12 2003-09-09 Produits de lavage ou de nettoyage comprimes sous l'effet d'une pression
AU2003270156A AU2003270156A1 (en) 2002-09-12 2003-09-09 Detergent or cleaning agent that is compacted under pressure
US11/079,046 US20050187132A1 (en) 2002-09-12 2005-03-14 Detergent composition which has been compacted under pressure

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DE10242222.2 2002-09-12
DE2002142222 DE10242222A1 (de) 2002-09-12 2002-09-12 Unter Druck kompaktiertes Wasch- oder Reinigungsmittel

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EP2103679A3 (fr) * 2003-08-01 2009-11-25 Reckitt-Benckiser (UK) Limited Pastilles de detergent ou pastilles d'adoucissant d'eau et leur fabrication
EP2206767B1 (fr) 2007-05-04 2016-03-30 Ecolab INC. Compositions de nettoyage solides
US9862915B2 (en) 2007-10-18 2018-01-09 Ecolab Usa Inc. Pressed, self-solidifying, solid cleaning compositions and methods of making them

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WO1998012299A1 (fr) * 1996-09-20 1998-03-26 Henkel Kommanditgesellschaft Auf Aktien Procede de production d'un detergent ou nettoyant particulaire
DE19723616A1 (de) * 1997-06-05 1998-12-10 Henkel Kgaa Granulares Waschmittel
EP0918087A1 (fr) * 1997-11-20 1999-05-26 Henkel Kommanditgesellschaft auf Aktien Méthode de fabrication d'un co-adjuvant
WO1999032599A1 (fr) * 1997-12-19 1999-07-01 Manro Performance Chemicals Limited Procede de production de particules
EP1138756A2 (fr) * 2000-03-29 2001-10-04 Henkel Kommanditgesellschaft auf Aktien Détergents sous forme de comprimé comprenant des granules particuliers des agents tensioactifs

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2103679A3 (fr) * 2003-08-01 2009-11-25 Reckitt-Benckiser (UK) Limited Pastilles de detergent ou pastilles d'adoucissant d'eau et leur fabrication
EP2206767B1 (fr) 2007-05-04 2016-03-30 Ecolab INC. Compositions de nettoyage solides
US9862915B2 (en) 2007-10-18 2018-01-09 Ecolab Usa Inc. Pressed, self-solidifying, solid cleaning compositions and methods of making them
US11104869B2 (en) 2007-10-18 2021-08-31 Ecolab Usa Inc. Pressed, self-solidifying, solid cleaning compositions and methods of making them

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DE10242222A1 (de) 2004-03-25
EP1537199A1 (fr) 2005-06-08
AU2003270156A1 (en) 2004-04-08

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