EP0395970A1 - Washing and cleaning compositions - Google Patents

Washing and cleaning compositions Download PDF

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Publication number
EP0395970A1
EP0395970A1 EP90107599A EP90107599A EP0395970A1 EP 0395970 A1 EP0395970 A1 EP 0395970A1 EP 90107599 A EP90107599 A EP 90107599A EP 90107599 A EP90107599 A EP 90107599A EP 0395970 A1 EP0395970 A1 EP 0395970A1
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EP
European Patent Office
Prior art keywords
lactobionic acid
compositions
washing
builder
compositions according
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Granted
Application number
EP90107599A
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German (de)
French (fr)
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EP0395970B1 (en
Inventor
Klaus-Günter Gerling
Detlef Wilke
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Kali Chemie AG
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Kali Chemie AG
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/221Mono, di- or trisaccharides or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3942Inorganic per-compounds

Definitions

  • the invention relates to compositions for washing and cleaning applications which contain biodegradable and ecologically compatible builder substances, to the use of these builder substances and to a method for washing and / or cleaning.
  • Builders are of central importance for the course of the washing and cleaning process.
  • the function of the builders is mainly that they are partly from water, partly from dirt or e.g. To eliminate calcium and magnesium ions from textiles by complex formation or ion exchange from the washing or cleaning process and to support the surfactant effect.
  • Modern builders therefore have to meet a number of eligibility criteria.
  • builders should have a certain primary washing or cleaning action. This means, for example, a good specific washing and cleaning action against pigments and fats or, for example, a good washing action against certain textile fibers, the improvement of the surfactant properties and a favorable influence on the foaming behavior.
  • they should make a major contribution to dispersing dirt in washing and cleaning liquors. In this way, for example, graying and yellowing of the textiles to be washed pushed back, which is very important for good washing results.
  • builders should have good dirt-carrying capacity and e.g. prevent incrustation on textiles. In addition, they should also prevent appropriate deposits in washing machines and cheap, i.e. show no correspondence behavior.
  • the builder substances should continue to be chemically stable, easy to process technically, not hygroscopic, stable in storage and compatible with the other detergents and cleaning agents. They should also have perfect color and smell qualities and be based on a secure raw material basis.
  • the builder substances should also be harmless to the environment, be biodegradable and, last but not least, also meet economic requirements.
  • Builder substances known in the prior art are e.g. certain washing alkalis (such as soda, sodium silicate or sodium monophosphate), complexing agents (such as e.g. sodium diphosphate, sodium triphosphate, phosphonic acid derivatives, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), citric acid, O- (carboxymethyl) malic acid) or ion exchangers (e.g. zeolite exchanger).
  • washing alkalis such as soda, sodium silicate or sodium monophosphate
  • complexing agents such as e.g. sodium diphosphate, sodium triphosphate, phosphonic acid derivatives, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), citric acid, O- (carboxymethyl) malic acid
  • ion exchangers e.g. zeolite exchanger
  • Alkaline detergents such as soda or monophosphate are now considered technically obsolete, since they form precipitates with the calcium and magnesium salts (so-called hardening agents) of service water, which settle on laundry and appliances as undesirable and annoying deposits.
  • the builder substances currently used no longer precipitate the hardness formers of the water, but instead eliminate them through complex formation or ion exchange.
  • the phosphates used as complexing agents contribute Eutrophication of standing or slowly flowing waters. The ecological side effect of the phosphates is undesirable and has led to an intensive search worldwide for suitable substitutes.
  • the object was therefore to provide washing and cleaning agent compositions which avoid or at least reduce the disadvantages of the prior art with regard to the builder substances contained in the compositions.
  • Another task was to specify builders which can be used in compositions for washing and cleaning purposes or in washing and cleaning processes and which, in addition to having sufficiently good calcium binding capacity, ecological compatibility and biodegradability, are characterized above all by very good dispersing behavior, which is necessary to achieve a good washing and cleaning effect is required.
  • the invention proposes detergent compositions which contain surfactants and, if appropriate, further constituents customary in detergents and cleaners, and also lactobionic acid and / or lactobionic acid salts in the presence of a boron oxygen compound as builder substances.
  • Lactobionic acid (4- (beta-D-galactosido) -D-gluconic acid) is already known as such and can be obtained, for example, by oxidation of lactose. So far, the lactobionic acid in the form of the calcium salt has been used pharmaceutically in the so-called calcium preparations for the prevention and therapy of calcium deficiency states. The use as a builder in detergents and cleaning agents, however, has not been described so far.
  • both the free lactobionic acid itself and its salts with environmentally compatible, non-hardness-forming metal cations or mixtures of these substances can be used as builder substance in the compositions according to the invention.
  • Alkali metal lactobionates, in particular sodium and potassium lactobionate, are preferably used here.
  • lactobionic acid and / or lactobionic acid salts can be contained in the compositions according to the invention in amounts which are conventional per se for builder substances.
  • the lactobionic acid and its salts can then be present in the detergent and cleaning agent compositions in an amount based on the total composition of up to 40% by weight.
  • the amount of builder substances contained in the compositions according to the invention is preferably up to 35% by weight.
  • these compositions contain a further component which consists of one or more boron oxygen compounds consists.
  • the builder action of lactobionic acid or its salts is increased in an unexpected and surprising manner by the presence of the boron oxygen compound.
  • the boron oxygen compounds are generally present in the compositions in an amount such that at least 1 mol of boron is contained for 1 mol of lactobionic acid and / or lactobionic acid salt.
  • boron oxygen compounds are suitable for this purpose, for example conventional borates known in the prior art, such as sodium borate, sodium metaborate, borax, pentaborate, etc., or mixtures thereof. Boron oxygen compounds of the aforementioned type are contained in particular in compositions which contain no bleaching agent or no perborate bleaching agent.
  • Peroxy group-containing boron oxygen compounds can also be used as boron oxygen compounds, e.g. those perborates known per se in the prior art, which are usually contained as bleaching agents in detergent and cleaning agent compositions.
  • the perborates are used in the washing and cleaning compositions in conventional amounts per se for bleaching agents and therefore in this case no further addition of boron oxygen compounds of the type described above (i.e. borates etc.) is required.
  • lactobionic acid and its salts per se can be used as builders for any detergent and cleaning agent compositions, for example also in liquid detergents and cleaning agents (for example liquid detergents), but the advantages which can be achieved with these builder substances are particularly evident in powdered detergents. and detergent compositions, for example in so-called powdered universal detergents, or in hand and machine dishwashing detergents.
  • lactobionic acid and / or their salts as cobuilders in combination with further organic and / or inorganic builders customary in the prior art in the detergent and cleaning agent compositions.
  • Typical examples of customary builders known in the prior art which may be present in the compositions as builders with the builders used according to the invention are sodium aluminosilicates (e.g. zeolites), sodium citrate or salts of aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid.
  • lactobionic acid and / or its salts can also be present in combination with lactobionic acid and / or its salts in detergent and cleaning agent compositions.
  • Lactobionic acid and / or its salts are present as cobuilders in the abovementioned compositions in amounts of up to 25% by weight, based on the total composition.
  • compositions of the invention can contain any bleaching agent or bleaching agent mixture customary in the art, for example chlorine bleaching agent or peroxygen bleaching agent.
  • the bleaching agent is a peroxygen bleaching agent, such as, for example, persulfate, percarbonate or perborates.
  • perborates such as sodium perborate tetrahydrate or sodium perborate monohydrate are particularly preferred.
  • compositions according to the invention can be formulated in a manner known per se.
  • all the usual materials that are usually used for the formulation of washing and cleaning agent compositions per se can be used in the compositions according to the invention usual amounts are used.
  • the compositions according to the invention contain surfactants as an essential constituent and, if appropriate, other customary auxiliaries.
  • compositions according to the invention can contain any surface-active organic compounds, such as anionic, cationic, ampholytic or non-ionic surfactants or mixtures thereof, as surfactants.
  • Anionic surfactants are e.g. synthetic surface-active compounds with one or more functional groups that ionize in aqueous solution to form negatively charged ions.
  • Suitable anionic surfactants are, for example, alkali metal, ammonium or alkanolamine salts of alkylbenzenesulfonates with 10 to 18 carbon atoms in the alkyl group; Alkyl and alkyl ether sulfates with 10 to 24 carbon atoms in the alkyl group and with 1 to 5 ethylene oxide groups; C10- to C12- ⁇ -olefin sulfonates, ⁇ -sulfo fatty acid esters.
  • Cationic surfactants are surfactants with one or more functional groups that ionize in aqueous solution to form positively charged organic ions.
  • cationic surfactants are aliphatic or aromatic higher-alkyl-di-lower-alkyl-ammonium halides, for example dialkyl-dimethylammonium chlorides such as distearyl-dime thylammonium chloride; Alkyl dimethyl benzyl ammonium chloride; Imidazolinium salts.
  • ampholytic (zwitterionic) surfactants include derivatives of straight-chain or branched aliphatic compounds with usually 8 to 24 carbon atoms, which contain aliphatic quaternary ammonium, phosphonium or sulfonium groups and at least one anionic water-soluble group and optionally also other substituents.
  • Examples are C12- to C18-alkyl betaines of the formula R-N+ (CH3) 2CH2-COO ⁇ and C12- to C18-alkyl sulfobetaines of the formula R-N+ (CH3) 2-SO3 ⁇ .
  • Non-ionic surfactants are usually cocondensates of ethylene oxide or propylene oxide with hydrocarbons which carry reactive groups such as hydroxyl, carboxyl or amino groups.
  • Examples are alkylphenol polyglycol ethers with C8-C12 alkyl radicals and 5 to 10 ethylene glycol units; Alkyl polyglycol ethers such as fatty alcohol polyethylene glycol ether and oxo alcohol polyethylene glycol ether; Fatty acid alkanolamides, e.g. of the fatty acid ethanolamide type.
  • non-ionic surfactants are the semi-polar non-ionic surfactants, e.g. water-soluble amine oxides with alkyl or hydroxyalkyl units with 8 to 28 C atoms, it being possible for two of these alkyl or hydroxyalkyl units to be linked to form a ring structure with 1 to 3 C atoms.
  • the detergent and cleaning agent compositions of the present invention can contain further customary auxiliaries for the formulation of detergents and cleaning agents.
  • auxiliaries include enhancers, detergent enzymes, enzyme stabilizers, soil carriers and / or compatibilizers, complexing agents and chelating agents, soap foam regulators and additives such as optical brighteners, opacifying agents, corrosion inhibitors, Antistatic agents, dyes, bactericides, bleach activators, peracid bleach precursors.
  • the invention also relates to compositions for washing and cleaning purposes or for bleaching purposes in washing and cleaning processes which contain lactobionic acid and / or lactobionic acid salts as builder substances, but which in themselves are not yet complete washing and cleaning agent compositions in the sense described above, since they contain only a part of the ingredients usually contained in a complete detergent and cleaning composition suitable for use.
  • Such partial compositions according to the invention can be used on the one hand for the industrial production of complete detergent and cleaning agent compositions.
  • the partial compositions are well suited as components for so-called modular detergent and cleaning agent systems.
  • the constituents are not already mixed with one another as in conventional (complete) detergent and cleaning agent compositions, but instead lie as separate system components, for example as a surfactant, bleach and builder component. in front.
  • the individual components are only coordinated with one another by the user depending on the individual requirements (such as the type of material to be washed or cleaned; type of washing or cleaning process, e.g. cottons or delicates, etc .; water hardness etc.).
  • the components can either be mixed with one another before use or metered separately into the wash water.
  • compositions of this variant of the invention i.e. for the partial compositions, it is not imperative that the lactobionic acid and / or the lactiobionic acid salts are already present in the presence of a boron oxygen compound, provided that it is ensured that when using such partial compositions for the industrial production of complete detergent and cleaning agent compositions, boron oxygen compounds (as described above for the Complete detergent and cleaning agent compositions described) are added, or that when assembling and using the components of modular detergent and cleaning agent systems, the components containing lactobionic acid and / or lactobionic acid salts are combined with another component containing boron oxygen in the manner according to the invention.
  • the partial compositions contain the lactobionic acid and / or lactobionic acid salts as builder substances, however, already in the presence of a boron oxygen compound.
  • the explanations given above for the detergent and cleaning agent compositions apply analogously to the boron oxygen compound present in the partial compositions.
  • the boron oxygen compound contained therein can be a peroxygen bleach, in analogy to that described above in connection with the washing and cleaning compositions.
  • Preferred peroxygen bleaches are perborates.
  • Such partial compositions for example in the form of powders or granules which contain lactobionic acid and / or lactobionic acid salts in the presence of perborate, are suitable, for example, for use as so-called dry bleach in washing and cleaning processes.
  • the invention further relates to the use of lactobionic acid and / or lactobionic acid salts as builder substances in compositions for washing and cleaning purposes.
  • lactobionic acid and / or lactobionic acid salts as builder substances in compositions for washing and cleaning purposes.
  • Both the free lactobionic acid itself and its salts with environmentally compatible, non-hardness-forming metal cations or mixtures of these substances can be used as builder substances in the manner described above for compositions according to the invention.
  • preference is given in particular to using the sodium or potassium salt of lactobionic acid.
  • the invention further relates to a method for washing and cleaning, which is characterized in that lactobionic acid and / or lactobionic acid salts are used as builder substances in the presence of boron oxygen compounds.
  • compositions according to the invention, the use according to the invention and the method according to the invention offer a surprising and problem-free solution to the widespread desire for suitable environmentally compatible and biodegradable builder substances which, in addition to good calcium binding capacity, in particular show very good dispersion behavior.
  • the very good dispersing power of lactobionic acid and its salts counteracts were a boron oxygen compound to suppress graying and yellowing. This property is of the utmost importance for washing and cleaning processes and is excellently fulfilled by lactobionic acid and its salts.
  • incrustations for example on textiles or in washing machines, are prevented to an unexpectedly favorable extent.
  • Lactobionic acid and its salts also show the so-called threshold effect, i.e. they are able to delay, reduce or at least cause the precipitation of insoluble salts even when using substoichiometric amounts of builders, or to cause the insoluble salts to occur predominantly in amorphous form and that Formation of sharp-edged, fiber-damaging crystals (eg calcite crystals) is largely suppressed.
  • the compounds are chemically stable, not hygroscopic, stable in storage and easy to process technically. Furthermore, they are well compatible with common detergent and cleaning agent ingredients. The compounds can easily be obtained from lactose by oxidation on the basis of a secure raw material base and are also economically advantageous. The biological origin and complete biodegradability of the substances guarantee harmlessness to humans and favorable environmental behavior.
  • the lime binding capacity of lactobionic acid in the presence of boron oxygen compounds (2.13 g borax and / or 2 g sodium perborate in 100 ml solution) was determined at pH 10 by mixing 100 ml of an aqueous solution of 1% by weight lactobionic acid, 0.4% by weight .-% sodium carbonate and optionally 0.1 wt .-% TAED as bleach activator with an aqueous 0.1 N calcium chloride solution until occurrence a permanent turbidity titrated. Under these test conditions, the lactobionic acid is present as the sodium salt in the test solution.
  • the measurement number for the lime binding capacity is the gram number of calcium ions which can be kept in solution per 100 g of lactobionic acid as builder substance under the aforementioned conditions.
  • aqueous dispersions were prepared from 0.1% by weight of the builder substance to be tested and 4% by weight powder graphite as dispersa by weighing the substances into a 100 ml shaking measuring cylinder, making up to 100 ml with water and shook vigorously for a minute.
  • the sedimentation volume of the graphite particles was determined as a measure of the dispersing capacity and, for additional tests, a sample was additionally taken from the dispersion at the level of the 70 ml measuring mark of the shaking measuring cylinder and sent to a photometric test.
  • the transmission of the samples was measured here in comparison to corresponding blank samples without graphite (transmission 100%), with smaller transmission values indicating better dispersibility.
  • lactobionic acid behaves equally well in terms of perborate stability as prior art builders.
  • the washing performance was determined by washing tests on test fabrics in two standard washing machines (type: Miele W 180). For this purpose, 2 kg of test fabric was washed with 155 g of detergent in the short program (washing time 1 h). A standardized heavy-duty detergent formulation was used as the detergent, which contained 30% by weight of the builder system to be tested.
  • composition of the standardized heavy-duty detergent formulation 30.0% by weight builder system (see table) 11.9% by weight of dodecylbenzenesulfonate 4.0% by weight of tallow fatty alcohol ethoxylate with 11 moles of ethylene oxide 4.0% by weight of sebum soap 4.0% by weight sodium silicate 32.9% by weight sodium perborate tetrahydrate 11.9% by weight sodium sulfate 1.3 wt% tylose.
  • the tests were carried out at pH 10 and 18 ° dH at 30 and 60 ° C.
  • the fleet ratio was 1:12.
  • the washing performance was determined by measuring the lightening of soiled test fabrics (cotton fabric and cotton blend fabric) as the reflectance difference (reflectance of the dry test fabric after the washing test minus the reflectance test fabric before the washing test) at 530 nm. The larger remission difference indicates the better washing performance.
  • Lactobionic acid alone, lactobionic acid with zeolite (in a 1: 1 ratio) and STPP as a comparison were used as builder systems in the heavy-duty detergent formulations. No.
  • lactobionic acid as builder substance prevents the graying of textiles
  • washing tests were carried out on bleached test fabrics without artificial soiling and without optical brighteners.
  • the test fabrics were allowed to run through a total of 25 washing cycles analogous to the washing conditions given in Example 4 at 60 ° C. in the normal program (soaking process, 2 h).
  • the graying of the test fabrics was then determined by measuring the reflectance at 530 nm.
  • Lactobionic acid was used as the builder in the standardized heavy-duty detergent formulation (see Example 4) and STPP as a comparison. The remission is indirectly proportional to the graying. No.
  • Example 4 To determine the inorganic incrustation, washing tests were carried out on test fabrics. For this purpose, the test fabrics were run through a total of 25 washing cycles analogous to the washing conditions specified in Example 4. After completion of the washing cycles, the test fabrics were ashed according to standard conditions known per se and the remaining ash content in% by weight (based on the test fabric used) was determined as a measure of the inorganic incrustation. Lactobionic acid was used as the builder in the standardized heavy-duty detergent formulation (see Example 4) and STPP as a comparison. The smaller the remaining ash content, the lower the incrustation. No. Builder Test fabric WFK Ash content in% 40 Lactobionic acid Cotton (type: 10 C) 0.19 41 STPP Cotton (type: 10 C) 0.20 42 Lactobionic acid Terrycloth 0.44 43 STPP Terrycloth 0.55

Abstract

Beschrieben werden Wasch- und Reinigungsmittelzusammensetzungen, die Tenside, ggf. Bleichmittel und weitere in Wasch- und Reinigungsmitten übliche Bestandteile, sowie als biologisch abbaubare und ökologisch verträgliche Waschmittelbuilder Lactobionsäure und/oder Lactobionsäure salze enthalten.Detergent and cleaning agent compositions are described which contain surfactants, optionally bleaching agents and other constituents customary in washing and cleaning agents, as well as lactobionic acid and / or lactobionic acid salts as biodegradable and ecologically compatible detergent builders.

Description

Die Erfindung bezieht sich auf Zusammensetzungen für Wasch- und Reinigungsanwendungen, die biologisch abbaubare und ökologisch verträgliche Buildersubstanzen enthalten, auf die Verwendung dieser Buildersubstanzen sowie auf ein Verfahren zum Waschen und/oder Reinigen.The invention relates to compositions for washing and cleaning applications which contain biodegradable and ecologically compatible builder substances, to the use of these builder substances and to a method for washing and / or cleaning.

Builder (Gerüststoffe, sogenannte Waschmittelver­stärker) besitzen für den Ablauf des Wasch- und Reini­gungsvorganges eine zentrale Bedeutung. Die Funktion der Builder besteht vorwiegend darin, die teils aus dem Wasser, teils aus Schmutz oder z.B. Textilien stammenden Calcium- und Magnesiumionen durch Komplexbildung oder Ionenaustausch aus dem Wasch- bzw. Reinigungsvorgang zu eliminieren und die Tensidwirkung zu unterstützen. Moderne Builder müssen daher eine Reihe von Eignungskriterien er­füllen.Builders (builders, so-called detergent boosters) are of central importance for the course of the washing and cleaning process. The function of the builders is mainly that they are partly from water, partly from dirt or e.g. To eliminate calcium and magnesium ions from textiles by complex formation or ion exchange from the washing or cleaning process and to support the surfactant effect. Modern builders therefore have to meet a number of eligibility criteria.

Außer der schon erwähnten Komplexierungs- oder Ionen­austauschfunktion für Erdalkaliionen sollten Builder eine gewisse Primärwasch- bzw. Reinigungswirkung aufweisen. Hierunter versteht man z.B. eine gute spezifische Wasch- und Reinigungswirkung gegenüber Pigmenten und Fetten oder z.B. eine gute Waschwirkung gegenüber bestimmten Textil­fasern, die Verbesserung der Tensideigenschaften und eine günstige Beeinflussung des Schaumverhaltens. Insbesondere sollten sie zusätzlich zu den genannten Funktionen in hohem Maße zu Dispergierung von Schmutz in Wasch- und Reinigungsflotten beitragen. Hierdurch werden z.B. Ver­grauungen und Vergilbungen der zu waschenden Textilien zurückgedrängt, was für einen guten Wascherfolg sehr wichtig ist.In addition to the complexing or ion exchange function for alkaline earth ions already mentioned, builders should have a certain primary washing or cleaning action. This means, for example, a good specific washing and cleaning action against pigments and fats or, for example, a good washing action against certain textile fibers, the improvement of the surfactant properties and a favorable influence on the foaming behavior. In particular, in addition to the functions mentioned, they should make a major contribution to dispersing dirt in washing and cleaning liquors. In this way, for example, graying and yellowing of the textiles to be washed pushed back, which is very important for good washing results.

Als Sekundäreigenschaften sollten Builder ein gutes Schmutztragevermögen zeigen und z.B. die Inkrustation auf Textilien verhindern. Darüber hinaus sollten sie auch ent­sprechende Ablagerungen in Waschmaschinen unterbinden und günstiges, d.h. kein Korrisonsverhalten zeigen.As secondary properties, builders should have good dirt-carrying capacity and e.g. prevent incrustation on textiles. In addition, they should also prevent appropriate deposits in washing machines and cheap, i.e. show no correspondence behavior.

Die Buildersubstanzen sollten weiterhin chemisch beständig, technisch gut zu verarbeiten, nicht hygrosko­pisch, lagerstabil und mit den anderen Wasch- und Reini­gungsmittelinhaltsstoffen verträglich sein. Auch sollten sie einwandfreie Farb- und Geruchsqualitäten aufweisen und auf einer gesicherten Rohstoffbasis beruhen.The builder substances should continue to be chemically stable, easy to process technically, not hygroscopic, stable in storage and compatible with the other detergents and cleaning agents. They should also have perfect color and smell qualities and be based on a secure raw material basis.

Neben humantoxikologischer Unbedenklichkeit sollten sich die Buildersubstanzen ferner gegenüber der Umwelt unschädlich verhalten, biologisch abbaubar sein und nicht zuletzt auch wirtschaftliche Anforderungen erfüllen.In addition to being harmless to human toxicology, the builder substances should also be harmless to the environment, be biodegradable and, last but not least, also meet economic requirements.

Im Stand der Technik bekannte Buildersubstanzen sind z.B. bestimmte Waschalkalien (wie Soda, Natriumsilikat oder Natriummonophosphat), Komplexbildner (wie z.B. Natriumdiphosphat, Natriumtriphosphat, Phosphonsäurederi­vate, Nitrilotriessigsäure (NTA), Ethylendiamintetraessig­säure (EDTA), Citronensäure, O-(Carboxymethyl)-äpfelsäure) oder Ionenaustauscher (z.B. Zeolithe).Builder substances known in the prior art are e.g. certain washing alkalis (such as soda, sodium silicate or sodium monophosphate), complexing agents (such as e.g. sodium diphosphate, sodium triphosphate, phosphonic acid derivatives, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), citric acid, O- (carboxymethyl) malic acid) or ion exchangers (e.g. zeolite exchanger).

Waschalkalien wie Soda oder Monophosphat gelten heute als technisch überholt, da sie mit den Calcium- und Magnesiumsalzen (sogenannte Härtebildner) von Gebrauchs­wasser Fällungen ergeben, die sich auf Wäsche und Geräten als unerwünschte und störende Ablagerungen festsetzen. Die zur Zeit verwendeten Buildersubstanzen fällen demgegenüber die Härtebildner des Wassers nicht mehr aus, sondern eli­minieren sie durch Komplexbildung oder Ionenaustausch. Die als Komplexbildner verwendeten Phosphate tragen jedoch zur Eutrophierung stehender oder langsam fließender Gewässer bei. Die ökologische Begleiterscheinung der Phosphate ist unerwünscht und führte weltweit zu einer intensiven Suche nach geeigneten Ersatzstoffen. Aber auch bekannte Ersatz­stoffe weisen noch eine Reihe von Nachteilen auf, da sie einerseits wie NTA oder EDTA z.B. schlecht biologisch ab­baubar sind oder andererseits wie Citronensäure oder O-(Carboxymethyl)-äpfelsäure vergleichsweise geringes Dispergiervermögen und nur mäßiges Primärwaschvermögen aufweisen. Ionenaustauscher wie Zeolithe wiederum zeigen sehr ausgeprägtes Ionenaustauschvermögen, welches im Hinblick auf Schwermetallionen jedoch unter ökologischen Gesichtspunkten bedenklich sein kann. Darüber hinaus ist es zur Unterstützung des in heterogener Phase stattfinden­den Ionenaustausches nötig, die Zeolithe in Kombination mit wasserlöslichen Komplexbildnern (z.B. den oben angege­benen, aber bedenklichen Komplexbildern wie NTA oder EDTA) oder Carboxylsäurepolymeren zu verwenden (Ausnutzung des sogenannten Carrier-Effektes). Nachteilig ist auch, daß Zeolithkristalle als Kondensationsboden für schwerlös­liche Verbindungen in der Wasch- bzw. Reinigungsflotte wirken können und daß sie kaum Dispergierverhalten zeigen.Alkaline detergents such as soda or monophosphate are now considered technically obsolete, since they form precipitates with the calcium and magnesium salts (so-called hardening agents) of service water, which settle on laundry and appliances as undesirable and annoying deposits. The builder substances currently used, on the other hand, no longer precipitate the hardness formers of the water, but instead eliminate them through complex formation or ion exchange. However, the phosphates used as complexing agents contribute Eutrophication of standing or slowly flowing waters. The ecological side effect of the phosphates is undesirable and has led to an intensive search worldwide for suitable substitutes. However, known substitutes also have a number of disadvantages, since on the one hand they are poorly biodegradable, such as NTA or EDTA, or on the other hand, such as citric acid or O- (carboxymethyl) malic acid, they have comparatively low dispersing power and only moderate primary washing power. Ion exchangers such as zeolites, on the other hand, show a very pronounced ion exchange capacity, which, however, can be of ecological concern with regard to heavy metal ions. In addition, to support the ion exchange taking place in the heterogeneous phase, it is necessary to use the zeolites in combination with water-soluble complexing agents (e.g. the above-mentioned but questionable complexing agents such as NTA or EDTA) or carboxylic acid polymers (exploitation of the so-called carrier effect). Another disadvantage is that zeolite crystals can act as condensation bottoms for poorly soluble compounds in the washing or cleaning liquor and that they hardly show any dispersion behavior.

Es bestand daher die Aufgabe, solche Wasch- und Reinigungsmittelzusammensetzungen zur Verfügung zu stel­len, die die Nachteile des Standes der Technik im Hinblick auf die in den Zusammensetzungen enthaltenen Buildersub­stanzen vermeiden bzw. wenigstens vermindern. Eine weitere Aufgabe bestand darin, in Zusammensetzungen für Wasch- und Reinigungszwecke bzw. in Wasch- und Reinigungsverfahren verwendbare Buildersubstanzen anzugeben, die sich außer durch ausreichend gutes Calciumbindevermögen, ökologische Verträglichkeit und biologische Abbaubarkeit vor allem durch ein sehr gutes Dispergierverhalten auszeichnen, welches zur Erzielung einer guten Wasch- und Reinigungs­wirkung erforderlich ist.The object was therefore to provide washing and cleaning agent compositions which avoid or at least reduce the disadvantages of the prior art with regard to the builder substances contained in the compositions. Another task was to specify builders which can be used in compositions for washing and cleaning purposes or in washing and cleaning processes and which, in addition to having sufficiently good calcium binding capacity, ecological compatibility and biodegradability, are characterized above all by very good dispersing behavior, which is necessary to achieve a good washing and cleaning effect is required.

Als Lösung dieser Aufgabe schlägt die Erfindung Wasch- und Reinigungsmittelzusammensetzungen vor, die Tenside und ggf. weitere in Wasch- und Reinigungsmitteln übliche Bestandteile, sowie als Buildersubstanzen Lacto­bionsäure und/oder Lactobionsäuresalze in Gegenwart einer Borsauerstoffverbindung enthalten.To achieve this object, the invention proposes detergent compositions which contain surfactants and, if appropriate, further constituents customary in detergents and cleaners, and also lactobionic acid and / or lactobionic acid salts in the presence of a boron oxygen compound as builder substances.

Lactobionsäure (4-(beta-D-Galactosido)-D-gluconsäure) ist als solche zwar bereits bekannt und kann beispiels­weise durch Oxidation von Lactose erhalten werden. Bisher fand die Lactobionsäure in Form des Calciumsalzes in den sogenannten Calciumpräparaten zur Vorbeugung und Therapie von Calciummangelzuständen pharmzeutische Verwendung. Der Einsatz als Builder in Wasch- und Reinigungsmitteln ist dagegen bisher nicht beschrieben.Lactobionic acid (4- (beta-D-galactosido) -D-gluconic acid) is already known as such and can be obtained, for example, by oxidation of lactose. So far, the lactobionic acid in the form of the calcium salt has been used pharmaceutically in the so-called calcium preparations for the prevention and therapy of calcium deficiency states. The use as a builder in detergents and cleaning agents, however, has not been described so far.

Prinzipiell können sowohl die freie Lactobionsäure selbst als auch deren Salze mit umweltverträglichen, nicht härtebildenden Metallkationen bzw. Gemische dieser Sub­stanzen in den erfindungsgemäßen Zusammensetzungen als Buildersubstanz eingesetzt werden. Bevorzugt werden hier­bei Alkalimetall-Lactobionate, insbesondere Natrium- und Kaliumlactobionat, eingesetzt.In principle, both the free lactobionic acid itself and its salts with environmentally compatible, non-hardness-forming metal cations or mixtures of these substances can be used as builder substance in the compositions according to the invention. Alkali metal lactobionates, in particular sodium and potassium lactobionate, are preferably used here.

Die Lactobionsäure und/oder Lactobionsäuresalze können in an sich für Buildersubstanzen üblichen Mengen in den erfindungsgemäßen Zusammensetzungen enthalten sein. Im allgemeinen können die Lactobionsäure und deren Salze dann in einer auf die Gesamtzusammensetzung bezogenen Menge bis 40 Gew.-% in den Wasch- und Reinigungsmittelzusammen­setzungen vorliegen. Vorzugsweise beträgt die Menge der erfindungsgemäß in den Zusammensetzungen enthaltenen Buildersubstanzen aber bis 35 Gew.-%.The lactobionic acid and / or lactobionic acid salts can be contained in the compositions according to the invention in amounts which are conventional per se for builder substances. In general, the lactobionic acid and its salts can then be present in the detergent and cleaning agent compositions in an amount based on the total composition of up to 40% by weight. However, the amount of builder substances contained in the compositions according to the invention is preferably up to 35% by weight.

Zusätzlich zur Lactobionsäure und/oder deren Salze, die als Buildersubstanzen in den erfindungsgemäßen Wasch- und Reinigungsmittelzusammensetzungen eingesetzt sind, enthalten diese Zusammensetzungen eine weitere Komponente, die aus einer oder mehreren Borsauerstoffverbindungen besteht. Durch die Gegenwart der Borsauerstoffverbindung wird die Builderwirkung der Lactobionsäure oder deren Salze in unerwarteter und überraschender Weise verstärkt. Die Borsauerstoffverbindungen liegen im allgemeinen in einer solchen Menge in den Zusammensetzungen vor, daß für 1 Mol Lactobionsäure und/oder Lactobionsäuresalz wenigstens 1 Mol Bor enthalten ist. Geeignet sind hierfür an sich beliebige Borsauerstoffverbindungen, z.B. übliche im Stand der Technik bekannte Borate wie Natriumborat, Natriummetaborat, Borax, Pentaborat usw. oder Gemische davon. Borsauerstoffverbindungen der vorgenannten Art sind insbesondere in solchen Zusammensetzungen enthalten, die kein Bleichmittel oder kein Perboratbleichmittel enthal­ten.In addition to lactobionic acid and / or its salts, which are used as builder substances in the washing and cleaning agent compositions according to the invention, these compositions contain a further component which consists of one or more boron oxygen compounds consists. The builder action of lactobionic acid or its salts is increased in an unexpected and surprising manner by the presence of the boron oxygen compound. The boron oxygen compounds are generally present in the compositions in an amount such that at least 1 mol of boron is contained for 1 mol of lactobionic acid and / or lactobionic acid salt. Any boron oxygen compounds are suitable for this purpose, for example conventional borates known in the prior art, such as sodium borate, sodium metaborate, borax, pentaborate, etc., or mixtures thereof. Boron oxygen compounds of the aforementioned type are contained in particular in compositions which contain no bleaching agent or no perborate bleaching agent.

Als Borsauerstoffverbindungen können weiterhin auch Peroxidgruppen enthaltende Borsauerstoffverbindungen (d.h. Bor-haltige Persauerstoffbleichmittel) eingesetzt werden, z.B. solche an sich im Stand der Technik bekannte Perborate, die üblicherweise als Bleichmittel in Wasch-und Reinigungsmittelzusammensetzungen enthalten sind. Die Perborate werden hierbei in für Bleichmittel an sich üblichen Mengen in den Wasch- und Reinigungszusammen­setzungen eingesetzt und es bedarf daher in diesem Falle keines weiteren Zusatzes von Borsauerstoffverbindungen der oben beschriebenen Art (d.h. Borate usw.).Peroxy group-containing boron oxygen compounds (i.e. boron-containing peroxygen bleach) can also be used as boron oxygen compounds, e.g. those perborates known per se in the prior art, which are usually contained as bleaching agents in detergent and cleaning agent compositions. The perborates are used in the washing and cleaning compositions in conventional amounts per se for bleaching agents and therefore in this case no further addition of boron oxygen compounds of the type described above (i.e. borates etc.) is required.

Zwar können gemäß der Erfindung Lactobionsäure und deren Salze an sich für beliebige Wasch- und Reinigungs­mittelzusammensetzungen als Builder eingesetzt werden, z.B. auch in flüssigen Wasch- und Reinigungsmitteln (bspw. Flüssigwaschmittel), doch zeigen sich die mit diesen Buildersubstanzen erzielbaren Vorteile insbesondere in pulverförmigen Wasch- und Reinigungsmittelzusammensetzun­gen, z.B. in sogenannten pulverförmigen Universalwasch­mitteln, oder in Hand- und Maschinengeschirrspülmitteln.According to the invention, lactobionic acid and its salts per se can be used as builders for any detergent and cleaning agent compositions, for example also in liquid detergents and cleaning agents (for example liquid detergents), but the advantages which can be achieved with these builder substances are particularly evident in powdered detergents. and detergent compositions, for example in so-called powdered universal detergents, or in hand and machine dishwashing detergents.

In einer Abwandlung der Erfindung kann es darüber hinaus auch zweckmäßig sein, die erfindungsgemäßen Buildersubstanzen Lactobionsäure und/oder deren Salze als Cobuilder in Kombination mit weiteren, bisher im Stand der Technik üblichen organischen und/oder anorganischen Buildern in den Wasch- und Reinigungsmittelzusammen­setzungen einzusetzen. Dieses ist insbesondere für solche Anwendungen vorteilhaft, die nur einen begrenzten Ersatz der üblichen Buildersubstanzen erlauben oder wünschenswert erscheinen lassen. Typische Beispiele für übliche im Stand der Technik bekannte Builder, die mit den erfindungsgemäß eingesetzten Buildern als Cobuilder in den Zusammen­setzungen enthalten sein können sind Natriumaluminosili­kate (z.B. Zeolithe), Natriumcitrat oder Salze von Amino­polycarbonsäuren wie Nitrilotriessigsäure und Ethylendia­mintetraessigsäure. Aber auch andere bekannte Buildersub­stanzen können in Kombination mit Lactobionsäure und/oder deren Salze in Wasch- und Reinigungsmittelzusammensetzun­gen enthalten sein. In den vorgenannten Zusammensetzungen liegen Lactobionsäure und/oder deren Salze als Cobuilder in Mengen bis zu 25 Gew.-% vor, bezogen auf die Gesamtzusammensetzung.In a modification of the invention, it may also be expedient to use the builder substances according to the invention lactobionic acid and / or their salts as cobuilders in combination with further organic and / or inorganic builders customary in the prior art in the detergent and cleaning agent compositions. This is particularly advantageous for those applications which only allow a limited replacement of the usual builder substances or make them appear desirable. Typical examples of customary builders known in the prior art which may be present in the compositions as builders with the builders used according to the invention are sodium aluminosilicates (e.g. zeolites), sodium citrate or salts of aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid. However, other known builder substances can also be present in combination with lactobionic acid and / or its salts in detergent and cleaning agent compositions. Lactobionic acid and / or its salts are present as cobuilders in the abovementioned compositions in amounts of up to 25% by weight, based on the total composition.

Die Zusammensetzungen der Erfindung können außer den weiter ober bereits erwähnten Perboraten an sich belie­bige, im Stand der Technik übliche Bleichmittel oder Bleichmittelgemische enthalten, z.B. Chlorbleichmittel oder Persauerstoffbleichmittel. In bevorzugten erfin­dungsgemäßen Zusammensetzungen ist das Bleichmittel jedoch ein Persauerstoffbleichmittel, wie z.B. Persulfat, Percarbonat oder Perborate. In besonders günstiger Weise entfalten sich die vorteilhaften Wirkungen der in den er­findungsgemäßen Zusammensetzungen enthaltenen Buildersub­stanzen, wenn die Zusammensetzunngen als Bleichmittel ein Perborat enthalten. Bevorzugt sind dann insbesondere Per­borate wie Natriumperborat-Tetrahydrat oder Natriumper­borat-Monohydrat.In addition to the perborates already mentioned above, the compositions of the invention can contain any bleaching agent or bleaching agent mixture customary in the art, for example chlorine bleaching agent or peroxygen bleaching agent. In preferred compositions according to the invention, however, the bleaching agent is a peroxygen bleaching agent, such as, for example, persulfate, percarbonate or perborates. The advantageous effects of the builder substances contained in the compositions according to the invention develop particularly favorably if the compositions contain a perborate as the bleaching agent. Perborates such as sodium perborate tetrahydrate or sodium perborate monohydrate are particularly preferred.

Die erfindungsgemäßen Zusammensetzungen können in an sich bekannter Weise formuliert werden. Neben den bereits oben beschriebenen, in den Wasch- und Reinigungsmittelzu­sammensetzungen erfindungsgemäß enthaltenen Buildersub­stanzen und der Borsauerstoffverbindung oder dem ggf. an­wesenden Bleichmittel können in den erfindungsgemäßen Zu­sammensetzungen an sich alle gebräuchlichen Materialien, die üblicherweise zur Formulierung von Wasch- und Reini­gungsmittelzusammensetzungen Verwendung finden, in an sich üblichen Mengen eingesetzt werden. Insbesondere enthalten die erfindungsgemäßen Zusammensetzungen außer den genann­ten Komponenten als wesentlichen Bestandteil Tenside, sowie ggf. weitere übliche Hilfstoffe.The compositions according to the invention can be formulated in a manner known per se. In addition to the builder substances and the boron oxygen compound or the bleaching agent that may be present in the detergent and cleaning composition according to the invention already described above, all the usual materials that are usually used for the formulation of washing and cleaning agent compositions per se can be used in the compositions according to the invention usual amounts are used. In particular, in addition to the components mentioned, the compositions according to the invention contain surfactants as an essential constituent and, if appropriate, other customary auxiliaries.

Die erfindungsgemäßen Zusammensetzungen können als Tenside beliebige grenzflächenaktive organische Verbindun­gen, wie anionische, kationische, ampholytische oder nicht-ionische Tenside oder Mischungen davon enthalten.The compositions according to the invention can contain any surface-active organic compounds, such as anionic, cationic, ampholytic or non-ionic surfactants or mixtures thereof, as surfactants.

Anionische Tenside sind z.B. synthetische ober­flächenaktive Verbindungen mit einer oder mehreren funk­tionellen Gruppen, die in wäßriger Lösung unter Bildung negativ geladener Ionen ionisieren. Geeignete anionische Tenside sind beispielsweise Alkalimetall-, Ammonium- oder Alkanolaminsalze von Alkylbenzolsulfonaten mit 10 bis 18 C-Atomen in der Alkylgruppe; Alkyl- und Alkylethersulfate mit 10 bis 24 C-Atomen in der Alkylgruppe und mit 1 bis 5 Ethylenoxidgruppen; C₁₀- bis C₁₂-α-Olefinsulfonate, α-Sul­fo-Fettsäureester.Anionic surfactants are e.g. synthetic surface-active compounds with one or more functional groups that ionize in aqueous solution to form negatively charged ions. Suitable anionic surfactants are, for example, alkali metal, ammonium or alkanolamine salts of alkylbenzenesulfonates with 10 to 18 carbon atoms in the alkyl group; Alkyl and alkyl ether sulfates with 10 to 24 carbon atoms in the alkyl group and with 1 to 5 ethylene oxide groups; C₁₀- to C₁₂-α-olefin sulfonates, α-sulfo fatty acid esters.

Kationische Tenside sind Tenside mit einer oder meh­reren funktionellen Gruppen, die in wäßriger Lösung unter Bildung positiv geladener organischer Ionen ionisieren. Beispiele kationischer Tenside sind aliphatische oder aro­matische höher-Alkyl-di-niedrig-alkyl-ammoniumhalogenide, z.B. Dialkyl-dimethylammoniumchloride wie Distearyl-dime­ thylammoniumchlorid; Alkyl-dimethylbenzyl-ammoniumchlo­ride; Imidazolinium-salze.Cationic surfactants are surfactants with one or more functional groups that ionize in aqueous solution to form positively charged organic ions. Examples of cationic surfactants are aliphatic or aromatic higher-alkyl-di-lower-alkyl-ammonium halides, for example dialkyl-dimethylammonium chlorides such as distearyl-dime thylammonium chloride; Alkyl dimethyl benzyl ammonium chloride; Imidazolinium salts.

Zu den ampholytischen (zwitterionischen) Tensiden gehören Derivate von geradkettigen oder verzweigten ali­phatischen Verbindungen mit gewöhnlich 8 bis 24 C-Atomen, die aliphatische quartäre Ammonium-, Phosphonium- oder Sulfonium-Gruppen und wenigstens eine anionische wasser­lösliche Gruppe sowie gegebenenfalls noch andere Substi­tuenten enthalten. Beispiele sind C₁₂- bis C₁₈-Alkylbe­taine der Formel R-N⁺ (CH₃)₂CH₂-COO⁻ und C₁₂-bis C₁₈-Al­kyl-sulfobetaine der Formel R-N⁺ (CH₃)₂-SO₃⁻.The ampholytic (zwitterionic) surfactants include derivatives of straight-chain or branched aliphatic compounds with usually 8 to 24 carbon atoms, which contain aliphatic quaternary ammonium, phosphonium or sulfonium groups and at least one anionic water-soluble group and optionally also other substituents. Examples are C₁₂- to C₁₈-alkyl betaines of the formula R-N⁺ (CH₃) ₂CH₂-COO⁻ and C₁₂- to C₁₈-alkyl sulfobetaines of the formula R-N⁺ (CH₃) ₂-SO₃⁻.

Nicht-ionische Tenside sind gewöhnlich Cokondensate von Ethylenoxid oder Propylenoxid mit Kohlenwasserstoffen, die reaktive Gruppen wie Hydroxyl-, Carboxyl- oder Amino-­Gruppen tragen. Beispiele sind Alkylphenol-polyglykolether mit C₈-C₁₂-Alkylresten und 5 bis 10 Ethylenglykoleinhei­ten; Alkylpolyglykolether wie Fettalkohol-polyethylengly­kolether und Oxoalkohol-polyethylenglykolether; Fett­säure-alkanolamide, z.B. vom Typ der Fettsäure-ethanol­amide.Non-ionic surfactants are usually cocondensates of ethylene oxide or propylene oxide with hydrocarbons which carry reactive groups such as hydroxyl, carboxyl or amino groups. Examples are alkylphenol polyglycol ethers with C₈-C₁₂ alkyl radicals and 5 to 10 ethylene glycol units; Alkyl polyglycol ethers such as fatty alcohol polyethylene glycol ether and oxo alcohol polyethylene glycol ether; Fatty acid alkanolamides, e.g. of the fatty acid ethanolamide type.

Weitere nicht-ionische Tenside sind die semi-polaren nicht-ionischen Tenside, z.B. wasserlösliche Aminoxide mit Alkyl- oder Hydroxyalkyleinheiten mit 8 bis 28 C-Atomen, wobei zwei dieser Alkyl- oder Hydroxyalkyleinheiten gege­benenfalls zu einer Ringstruktur mit 1 bis 3 C-Atomen verknüpft sein können.Other non-ionic surfactants are the semi-polar non-ionic surfactants, e.g. water-soluble amine oxides with alkyl or hydroxyalkyl units with 8 to 28 C atoms, it being possible for two of these alkyl or hydroxyalkyl units to be linked to form a ring structure with 1 to 3 C atoms.

Die Wasch- und Reinigungsmittelzusammensetzungen der vorliegenden Erfindung können weitere übliche Hilfsstoffe für die Formulierung von Wasch- und Reinigungsmitteln ent­halten. Zu solchen Hilfsstoffen gehören Verstärker, Wasch­mittelenzyme, Enzymstabilisatoren, Schmutzträger und/oder Kompatibilisierungsmittel, Komplex- und Chelatbildner, Seifenschaumregulatoren und Zusatzstoffe wie optische Auf­heller, Opazifizierungsmittel, Korrosionsinhibitoren, Antielektrostatika, Farbstoffe, Bakterizide, Bleichakti­vatoren, Persäurebleichmittelvorstufen.The detergent and cleaning agent compositions of the present invention can contain further customary auxiliaries for the formulation of detergents and cleaning agents. Such auxiliaries include enhancers, detergent enzymes, enzyme stabilizers, soil carriers and / or compatibilizers, complexing agents and chelating agents, soap foam regulators and additives such as optical brighteners, opacifying agents, corrosion inhibitors, Antistatic agents, dyes, bactericides, bleach activators, peracid bleach precursors.

So enthalten erfindungsgemäße Waschmittelzusammen­setzungen in typischer beispielhafter Zusammensetzung

  • a) wenigstens 5 Gew.-% eines Tensids oder Tensidge­misches,
  • b) bis 40 Gew.-% Lactobionsäure und/oder Lactobion­säuresalz als Builder, ggf. einschließlich des Anteils der in der Zusammensetzung enthaltenen weiteren Builder­substanzen,
  • c) bis 40 Gew.-% eines Natriumperborates und
  • d) weitere Bestandteile wie Hilfsstoffe etc. ad 100 Gew.-%.
So contain detergent compositions according to the invention in a typical exemplary composition
  • a) at least 5% by weight of a surfactant or surfactant mixture,
  • b) up to 40% by weight of lactobionic acid and / or lactobionic acid salt as a builder, if appropriate including the proportion of the further builder substances contained in the composition,
  • c) up to 40 wt .-% of a sodium perborate and
  • d) further components such as auxiliaries, etc. ad 100 wt .-%.

Die Erfindung betrifft in einer weiteren Variante auch solche Zusammensetzungen für Wasch- und Reinigungs­zwecke oder für Bleichzwecke in Wasch- und Reinigungsver­fahren, die Lactobionsäure und/oder Lactobionsäuresalze als Buildersubstanzen enthalten, aber an sich noch keine vollständigen Wasch- und Reinigungsmittelzusammensetzungen im vorstehend beschriebenen Sinne sind, da sie nur einen Teil der üblicherweise in einer vollständigen, für die Anwendung geeigneten Wasch- und Reinigungsmittelzusammen­setzung enthaltenen Bestandteile enthalten. Solche erfin­dungsgemäßen Teilzusammensetzungen können einerseits zur industriellen Herstellung vollständiger Wasch- und Reini­gungsmittelzusammensetzungen dienen. Andererseits sind die Teilzusammensetzungen als Komponenten für sogenannte Wasch- und Reinigungsmittel-Baukastensysteme gut geeignet. In solchen Baukastensystemen sind die Bestandteile nicht wie in herkömmlichen (vollständigen) Wasch- und Reini­gungsmittelzusammensetzungen bereits miteinander ver­mischt, sondern liegen als getrennte Systemkomponenten, z.B. als Tensid-, Bleichmittel- und Builderkomponente, vor. Die einzelnen Komponenten werden erst vom Anwender je nach den individuellen Erfordernissen (wie Art des zu waschenden oder zu reinigenden Materials; Art des Wasch- oder Reinigungsverfahrens, z.B. Koch- oder Feinwäsche etc.; Wasserhärte etc.) in ihrer Menge aufeinander abge­stimmt. Die Komponenten können dabei sowohl vor ihrem Ein­satz miteinander vermischt als auch getrennt dem Wasch­wasser zudosiert werden.In a further variant, the invention also relates to compositions for washing and cleaning purposes or for bleaching purposes in washing and cleaning processes which contain lactobionic acid and / or lactobionic acid salts as builder substances, but which in themselves are not yet complete washing and cleaning agent compositions in the sense described above, since they contain only a part of the ingredients usually contained in a complete detergent and cleaning composition suitable for use. Such partial compositions according to the invention can be used on the one hand for the industrial production of complete detergent and cleaning agent compositions. On the other hand, the partial compositions are well suited as components for so-called modular detergent and cleaning agent systems. In such modular systems, the constituents are not already mixed with one another as in conventional (complete) detergent and cleaning agent compositions, but instead lie as separate system components, for example as a surfactant, bleach and builder component. in front. The individual components are only coordinated with one another by the user depending on the individual requirements (such as the type of material to be washed or cleaned; type of washing or cleaning process, e.g. cottons or delicates, etc .; water hardness etc.). The components can either be mixed with one another before use or metered separately into the wash water.

Für die Zusammensetzungen dieser Variante der Erfin­dung, d.h. für die Teilzusammensetzungen, ist es nicht zwingend, daß die Lactobionsäure und/oder die Lactiobion­säuresalze bereits in Gegenwart einer Borsauerstoffverbin­dung vorliegen, sofern sichergestellt ist, daß bei der Verwendung solcher Teilzusammensetzungen für die industri­elle Herstellung vollständiger Wasch- und Reinigungs­mittelzusammensetzungen Borsauerstoffverbindungen (wie weiter oben für die vollständigen Wasch- und Reinigungs­mittelzusammensetzungen beschrieben) zugesetzt werden, oder daß bei der Zusammenstellung und Anwendung der Kompo­nenten von Wasch- und Reinigungsmittel-Baukastensystemen die Lactobionsäure und/oder Lactobionsäuresalze enthalten­den Komponenten mit einer weiteren, die Borsauerstoffver­bindung enthaltenden Komponente in erfindungsgemäßer Weise miteinander kombiniert werden.For the compositions of this variant of the invention, i.e. for the partial compositions, it is not imperative that the lactobionic acid and / or the lactiobionic acid salts are already present in the presence of a boron oxygen compound, provided that it is ensured that when using such partial compositions for the industrial production of complete detergent and cleaning agent compositions, boron oxygen compounds (as described above for the Complete detergent and cleaning agent compositions described) are added, or that when assembling and using the components of modular detergent and cleaning agent systems, the components containing lactobionic acid and / or lactobionic acid salts are combined with another component containing boron oxygen in the manner according to the invention.

In einer zweckmäßigen Ausgestaltung dieser Variante der Erfindung enthalten die Teilzusammensetzungen die Lac­tobionsäure und/oder Lactobionsäuresalze als Buildersub­stanzen jedoch bereits in Gegenwart einer Borsauerstoff­verbindung. Für die in den Teilzusammensetzungen anwesende Borsauerstoffverbindung gelten analog die weiter oben für die Wasch- und Reinigungsmittelzusammensetzungen gegebenen Erläuterungen.In an expedient embodiment of this variant of the invention, the partial compositions contain the lactobionic acid and / or lactobionic acid salts as builder substances, however, already in the presence of a boron oxygen compound. The explanations given above for the detergent and cleaning agent compositions apply analogously to the boron oxygen compound present in the partial compositions.

In einer vorteilhaften Ausgestaltung der erfin­dungsgemäßen Teilzusammensetzungen kann die darin ent­haltende Borsauerstoffverbindung ein Persauerstoffbleich­mittel sein, in Analogie wie dieses weiter oben im Zu­sammenhang mit den Wasch- und Reinigungszusammensetzungen beschrieben ist. Bevorzugte Persauerstoffbleichmittel sind Perborate. Solche Teilzusammensetzungen, beispielsweise in Form von Pulvern oder Granulaten, die Lactobionsäure und/ oder Lactobionsäuresalze in Gegenwart von Perborat enthalten, eignen sich z.B. für die Verwendung als soge­nannte Trockenbleiche in Wasch- und Reinigungsverfahren.In an advantageous embodiment of the partial compositions according to the invention, the boron oxygen compound contained therein can be a peroxygen bleach, in analogy to that described above in connection with the washing and cleaning compositions. Preferred peroxygen bleaches are perborates. Such partial compositions, for example in the form of powders or granules which contain lactobionic acid and / or lactobionic acid salts in the presence of perborate, are suitable, for example, for use as so-called dry bleach in washing and cleaning processes.

Die Erfindung betrifft weiterhin die Verwendung von Lactobionsäure und/oder Lactobionsäuresalzen als Builder­substanzen in Zusammensetzungen für Wasch- und Reinigungs­zwecke. Hierbei können sowohl die freie Lactobionsäure selbst als auch deren Salze mit umweltverträglichen, nicht härtebildenden Metallkationen bzw. Gemische dieser Sub­stanzen als Buildersubstanzen in der oben beschriebenen Weise für erfindungsgemäße Zusammensetzungen verwendet werden. Bevorzugt verwendet man aber insbesondere das Natrium- oder Kaliumsalz der Lactobionsäure.The invention further relates to the use of lactobionic acid and / or lactobionic acid salts as builder substances in compositions for washing and cleaning purposes. Both the free lactobionic acid itself and its salts with environmentally compatible, non-hardness-forming metal cations or mixtures of these substances can be used as builder substances in the manner described above for compositions according to the invention. However, preference is given in particular to using the sodium or potassium salt of lactobionic acid.

Die Erfindung betrifft ferner ein Verfahren zum Waschen und Reinigen, welches sich dadurch auszeichnet, daß Lactobionsäure und/oder Lactobionsäuresalze als Buildersubstanzen in Gegenwart von Borsauerstoffverbin­dungen eingesetzt werden.The invention further relates to a method for washing and cleaning, which is characterized in that lactobionic acid and / or lactobionic acid salts are used as builder substances in the presence of boron oxygen compounds.

Die erfindungsgemäßen Zusammensetzungen, die erfin­dungsgemäße Verwendung sowie das erfindungsgemäße Verfah­ren bieten eine überraschende und problemlose Lösung für den vielfach vorhandenen Wunsch nach geeigneten umwelt­verträglichen und biologisch abbaubaren Buildersubstanzen, die außer gutem Calciumbindevermögen insbesondere sehr gutes Dispergierverhalten zeigen. Neben der Eliminierung von störenden Kationen wie Calcium und Magnesium und neben einer guten Primärwaschwirkung führt das sehr gute Disper­giervermögen der Lactobionsäure und deren Salze in Gegen­ wart einer Borsauerstoffverbindung zur Zurückdrängung von Vergrauungen und Vergilbungen. Diese Eigenschaft ist für Wasch- und Reinigungsprozesse von höchster Bedeutung und wird von Lactobionsäure und deren Salze in hervorragender Weise erfüllt. Darüber hinaus werden auch Inkrustationen z.B. auf Textilien oder in Waschmaschinen in unerwartet günstigem Ausmaß unterbunden. Weiterhin zeigen Lactobion­säure und deren Salze auch den sogenannten Threshold-­Effekt, d.h. sie sind befähigt, die Ausfällung unlöslicher Salze auch bei Anwendung unterstöchiometrischer Mengen an Builder zu verzögern, zu vermindern oder zumindest zu be­wirken, daß die unlöslichen Salze vorwiegend in amorpher Form anfallen und die Bildung von scharfkantigen, faser­schädigenden Kristallen (z.B. Calcit-Kristalle) weitgehend zurückgedrängt wird. Die Verbindungen sind chemisch be­ständig, nicht hygroskopisch, lagerstabil und technisch gut zu verarbeiten. Weiterhin sind sie mit üblichen Wasch- und Reinigungsmittelinhaltsstoffen gut verträglich. Die Verbindungen können auf Grundlage einer gesicherten Roh­stoffbasis leicht aus Lactose durch Oxidation gewonnen werden und sind auch in wirtschaftlicher Hinsicht vorteil­haft. Die biologische Herkunft und vollständige biolo­gische Abbaubarkeit der Substanzen garantiert humantoxi­kologische Unbedenklichkeit und günstiges Umweltverhalten.The compositions according to the invention, the use according to the invention and the method according to the invention offer a surprising and problem-free solution to the widespread desire for suitable environmentally compatible and biodegradable builder substances which, in addition to good calcium binding capacity, in particular show very good dispersion behavior. In addition to the elimination of disruptive cations such as calcium and magnesium and a good primary washing action, the very good dispersing power of lactobionic acid and its salts counteracts were a boron oxygen compound to suppress graying and yellowing. This property is of the utmost importance for washing and cleaning processes and is excellently fulfilled by lactobionic acid and its salts. In addition, incrustations, for example on textiles or in washing machines, are prevented to an unexpectedly favorable extent. Lactobionic acid and its salts also show the so-called threshold effect, i.e. they are able to delay, reduce or at least cause the precipitation of insoluble salts even when using substoichiometric amounts of builders, or to cause the insoluble salts to occur predominantly in amorphous form and that Formation of sharp-edged, fiber-damaging crystals (eg calcite crystals) is largely suppressed. The compounds are chemically stable, not hygroscopic, stable in storage and easy to process technically. Furthermore, they are well compatible with common detergent and cleaning agent ingredients. The compounds can easily be obtained from lactose by oxidation on the basis of a secure raw material base and are also economically advantageous. The biological origin and complete biodegradability of the substances guarantee harmlessness to humans and favorable environmental behavior.

Die nachfolgenden Beispiele sollen die Erfindung weiter erläutern, ohne sie jedoch in ihrem Umfang zu be­grenzen.The following examples are intended to explain the invention further, but without restricting its scope.

Beispiel 1: Sequestriervermögen Example 1: Sequestrability

Das Kalkbindevermögen von Lactobionsäure in Gegenwart von Borsauerstoffverbindungen (2,13 g Borax und/oder 2 g Natriumperborat in 100 ml Lösung) wurde bei pH 10 ermit­telt, indem man 100 ml einer wässrigen Lösung aus 1 Gew.-% Lactobionsäure, 0,4 Gew.-% Natriumcarbonat und gegebenen­falls 0,1 Gew.-% TAED als Bleichaktivator mit einer wässrigen 0,1 N Calciumchloridlösung bis zum Auftreten einer bleibenden Trübung titrierte. Unter diesen Versuchs­bedingungen liegt die Lactobionsäure als Natriumsalz in der Testlösung vor. Als Meßzahl für das Kalkbindevermögen wird die Grammzahl der Calciumionen angegeben, die pro 100 g Lactobionsäure als Buildersubstanz unter den vorge­nannten Bedingungen in Lösung gehalten werden kann.The lime binding capacity of lactobionic acid in the presence of boron oxygen compounds (2.13 g borax and / or 2 g sodium perborate in 100 ml solution) was determined at pH 10 by mixing 100 ml of an aqueous solution of 1% by weight lactobionic acid, 0.4% by weight .-% sodium carbonate and optionally 0.1 wt .-% TAED as bleach activator with an aqueous 0.1 N calcium chloride solution until occurrence a permanent turbidity titrated. Under these test conditions, the lactobionic acid is present as the sodium salt in the test solution. The measurement number for the lime binding capacity is the gram number of calcium ions which can be kept in solution per 100 g of lactobionic acid as builder substance under the aforementioned conditions.

Die in der nachfolgenden Tabelle angegebenen Versuche wurden bei Raumtemperatur durchgeführt. Versuch-Nr. Buildersystem Kalkbindevermögen (g Ca/100 g Lactobionsäure) 1 Lactobionsäure + Borax 8,16 2 Lactobionsäure + Borax 8,8 3 Lactobionsäure + Borax 8,4 4 Lactobionsäure + Borax 8,44 5 Lactobionsäure + Borax 7,45 6 Lactobionsäure + Natriumperborat* + TAED 6,65 7 Lactobionsäure + Natriumperborat* + TAED + Borax 6,29 8 Lactobionsäure + Natriumperborat* + TAED + Borax 7,13 * in Form des Tetrahydrates Die Versuche zeigen, daß Buildersysteme mit Lactobionsäure deutliches Calciumbindevermögen, d.h. deutliches Sequestriervermögen, aufweisen.The tests given in the table below were carried out at room temperature. Trial no. Builder system Lime binding capacity (g Ca / 100 g lactobionic acid) 1 Lactobionic acid + borax 8.16 2nd Lactobionic acid + borax 8.8 3rd Lactobionic acid + borax 8.4 4th Lactobionic acid + borax 8.44 5 Lactobionic acid + borax 7.45 6 Lactobionic acid + sodium perborate * + TAED 6.65 7 Lactobionic acid + sodium perborate * + TAED + borax 6.29 8th Lactobionic acid + sodium perborate * + TAED + borax 7.13 * in the form of tetrahydrate The experiments show that builder systems with lactobionic acid have a clear calcium binding capacity, ie a clear ability to sequester.

Beispiel 2: Dispergiervermögen Example 2: Dispersibility

Das Dispergiervermögen von Lactobionsäure in Gegenwart von Borax als Borsauerstoffverbindung (0,21 g in 100 ml Lösung) wurde im Vergleich zu anderen Buildersubstanzen untersucht. Zur Bestimmung des Dispergiervermögens wurden hierzu wässrige Dispersionen aus 0,1 Gew.-% der zu prüfen­den Buildersubstanz und 4 Gew.-% Pudergraphit als Dispersa hergestellt, indem man die Substanzen in einen 100-ml-Schüttelmeßzylinder einwog, mit Wasser auf 100 ml auffüllte und eine Minute intensiv schüttelte. Als Maß für das Dispergiervermögen wurde nach 24 stündigem Stehen insbesondere das Sedimentationsvolumen der Graphitpartikel ermittelt und für ergänzende Untersuchungen zusätzlich eine Probe aus der Dispersion in Höhe der 70 ml-Meßmarke des Schüttelmeßzylinders entnommen und einer photo­metrischen Untersuchung zugeleitet. Gemessen wurde hierbei die Transmission der Proben im Vergleich zu entsprechenden Blindproben ohne Graphit (Transmission 100 %), wobei kleinere Transmissionswerte besseres Dispergiervermögen andeuten.The dispersibility of lactobionic acid in the presence of borax as boron oxygen compound (0.21 g in 100 ml solution) was investigated in comparison to other builder substances. To determine the dispersibility, aqueous dispersions were prepared from 0.1% by weight of the builder substance to be tested and 4% by weight powder graphite as dispersa by weighing the substances into a 100 ml shaking measuring cylinder, making up to 100 ml with water and shook vigorously for a minute. After 24 hours of standing, the sedimentation volume of the graphite particles, in particular, was determined as a measure of the dispersing capacity and, for additional tests, a sample was additionally taken from the dispersion at the level of the 70 ml measuring mark of the shaking measuring cylinder and sent to a photometric test. The transmission of the samples was measured here in comparison to corresponding blank samples without graphite (transmission 100%), with smaller transmission values indicating better dispersibility.

a) Untersuchungen an Proben ohne gesonderte pH-Wertein­stellung (Eigen-pH-Wert der Buildersubstanzen):a) Investigations on samples without a separate pH value setting (intrinsic pH value of the builder substances):

Versuch-Nr.Trial no. BuildersubstanzBuilder substance Transmission in % bei WellenlängeTransmission in% at wavelength Sedimentationsvolumen des Graphits in mlSedimentation volume of the graphite in ml 480 nm480 nm 700 nm700 nm 99 Lactobionsäure + BoraxLactobionic acid + borax 73,073.0 82,682.6 16,516.5 1010th CitronensäureCitric acid 93,393.3 93,893.8 2020th 1111 NTANTA 9090 91,291.2 2020th 1212 STPPSTPP 89,389.3 91,791.7 22,022.0

b) Untersuchung von Builderproben, die auf einen pH-Wert 10 (mit 5 N Natriumhydroxid) eingestellt waren:b) Examination of builder samples which were adjusted to a pH of 10 (with 5 N sodium hydroxide):

Versuch-Nr.Trial no. BuildersubstanzBuilder substance Transmission in % bei WellenlängeTransmission in% at wavelength Sedimentationsvolumen des Graphits in mlSedimentation volume of the graphite in ml 480 nm480 nm 700 nm700 nm 1313 Lactobionsäure + BoraxLactobionic acid + borax 78,678.6 84,384.3 18,518.5 1414 CitronensäureCitric acid 88,088.0 92,092.0 21,021.0 1515 NTANTA 87,387.3 92,692.6 21,521.5 1616 STPPSTPP 90,890.8 94,294.2 19,519.5

Die Versuche zeigen, daß bei erfindungsgemäßem Einsatz von Lactobionsäure als Buildersubstanz (Versuche Nr. 9 und 13) deutlich geringere Sedimentationsvolumina und kleinere Transmissionswerte als bei den Vergleichsversuchen 10 bis 12 und 14 bis 16 auftreten. Lactobionsäure als Buildersubstanz weist damit deutlich besseres Dispergier­vermögen als Buildersubstanzen des Standes der Technik auf.The experiments show that when lactobionic acid is used according to the invention as builder substance (Experiments Nos. 9 and 13), significantly lower sedimentation volumes and smaller transmission values than in the comparative experiments 10 to 12 and 14 to 16 occur. Lactobionic acid as builder substance thus has significantly better dispersing power than builder substances of the prior art.

Beispiel 3: Perboratstabilität Example 3: Perborate stability


a) Zur Prüfung des Einflusses des Builders auf die Perboratstabilität wurden 250 ml einer auf pH = 10 (mit 5 N NaOH) eingestellten wässrigen Lösung, die 5 g Buildersubstanz, 5 g Natriumperborat-Tetrahydrat, 0,02 g Eisen(III)chlorid und ggf. 10,25 g Borax enthielt, im Wasserbad auf 90 °C erhitzt. Zur Bestimmung des Aktiv­sauerstoffgehaltes wurden jeweils nach 30, 90 und 150 Minuten Proben von 50 ml für eine jodometrische Titration entnommen. Hierzu wurde die Probe von 50 ml Lösung mit 10 ml 4 N Salzsäure und 3 g Kaliumjodid ver­setzt und 10 Minuten im Dunkeln stehen gelassen. Anschließend wurde mit 1 molarer Natriumthiosulfatlösung gegen Stärke als Indikator titriert. Der Aktivsauerstoff­gehalt der Proben in % bezieht sich auf jeweils gleich­behandelte Blindproben (100%) ohne Buildersubstanz, die ansonsten aber die gleiche Zusammensetzung wie die ent­sprechende Probe aufwiesen. Nr. Buildersystem Aktivsauerstoffgehalt in % nach 30 min 90 min 150 min 17 Lactobionsäure + Borax 10,6 8,3 7,3 18 STPP 10,3 8,6 8,2
b) Die Versuche wurden analog zu a) mit wässrigen Lösungen wiederholt, die außer den oben unter a) angegebenen Bestandteilen noch 0,25 g TAED als Bleichmittelaktivator in 250 ml Lösung enthielten. Nr. Buildersystem Aktivsauerstoffgehalt in % nach 30 min 90 min 150 min 19 Lactobionsäure + Borax 6,3 6,0 0 20 STPP 3,6 3,0 1,4

a) To test the influence of the builder on the perborate stability, 250 ml of an aqueous solution adjusted to pH = 10 (with 5 N NaOH), the 5 g builder substance, 5 g sodium perborate tetrahydrate, 0.02 g iron (III) chloride and optionally contained 10.25 g of borax, heated to 90 ° C. in a water bath. To determine the active oxygen content, 50 ml samples were taken for iodometric titration after 30, 90 and 150 minutes. For this purpose, the sample of 50 ml of solution was mixed with 10 ml of 4N hydrochloric acid and 3 g of potassium iodide and left to stand in the dark for 10 minutes. It was then titrated with 1 molar sodium thiosulfate solution against starch as an indicator. The active oxygen content of the samples in% relates to blank samples (100%) treated in the same way without builder substance, but which otherwise had the same composition as the corresponding sample. No. Builder system Active oxygen content in% 30 min 90 min 150 min 17th Lactobionic acid + borax 10.6 8.3 7.3 18th STPP 10.3 8.6 8.2
b) The experiments were repeated analogously to a) with aqueous solutions which, in addition to the constituents given above under a), also contained 0.25 g of TAED as bleach activator in 250 ml of solution. No. Builder system Active oxygen content in% 30 min 90 min 150 min 19th Lactobionic acid + borax 6.3 6.0 0 20th STPP 3.6 3.0 1.4

Wie der Vergleich mit dem bekannten Builder STPP (Vergleichsversuche Nr. 18 und 20) zeigt, wird durch den erfindungsgemäßen Einsatz von Lactobionsäure als Buildersubstanz (Versuche 17 und 19 dieses Beispiels) die Perboratstabilität nicht negativ beeinflußt. Lactobionsäure verhält sich hinsichtlich der Perboratstabilität gleichermaßen gut wie Builder im Stand der Technik.As the comparison with the known builder STPP (comparative experiments No. 18 and 20) shows, the use of lactobionic acid as builder substance according to the invention (experiments 17 and 19 of this example) does not adversely affect the perborate stability. Lactobionic acid behaves equally well in terms of perborate stability as prior art builders.

Außer durch die voranstehenden Laborversuche der Beispiele 1 bis 3 werden die hervorragenden Eigenschaften der Lactobionsäure bezüglich ihres Einsatzes als Buildersub­stanz in Wasch- und Reinigungsmittelzusammensetzungen insbesondere durch die Waschversuche der nachfolgenden Beispiele 4 bis 6 sehr deutlich.In addition to the laboratory tests of Examples 1 to 3 above, the excellent properties of lactobionic acid with regard to its use as builder in detergent and cleaning agent compositions are particularly evident from the washing tests of Examples 4 to 6 below.

Beispiel 4: Waschleistung Example 4: Washing performance

Die Waschleistung wurde durch Waschversuche an Testgeweben in zwei Standardwaschmaschinen (Typ: Miele W 180) bestimmt. Hierzu wurden 2 kg Testgewebe mit 155 g Wasch­mittel im Kurzprogramm (Waschdauer 1 h) gewaschen. Als Waschmittel wurde eine standardisierte Vollwaschmittel­formulierung eingesetzt, die 30 Gew.-% des zu testenden Buildersystems enthielt. Zusammensetzung der standardi­sierten Vollwaschmittelformulierung:
30,0 Gew.-% Buildersystem (siehe Tabelle)
11,9 Gew.-% Dodecylbenzolsulfonat
4,0 Gew.-% Talgfettalkoholethoxylat mit 11 Mol Ethylenoxid
4,0 Gew.-% Talgseife
4,0 Gew.-% Natriumsilikat
32,9 Gew.-% Natriumperborat-Tetrahydrat
11,9 Gew.-% Natriumsulfat
1,3 Gew.-% Tylose.
The washing performance was determined by washing tests on test fabrics in two standard washing machines (type: Miele W 180). For this purpose, 2 kg of test fabric was washed with 155 g of detergent in the short program (washing time 1 h). A standardized heavy-duty detergent formulation was used as the detergent, which contained 30% by weight of the builder system to be tested. Composition of the standardized heavy-duty detergent formulation:
30.0% by weight builder system (see table)
11.9% by weight of dodecylbenzenesulfonate
4.0% by weight of tallow fatty alcohol ethoxylate with 11 moles of ethylene oxide
4.0% by weight of sebum soap
4.0% by weight sodium silicate
32.9% by weight sodium perborate tetrahydrate
11.9% by weight sodium sulfate
1.3 wt% tylose.

Die Versuche wurden bei pH 10 und 18 °dH bei 30 und 60 °C ausgeführt. Das Flottenverhältnis lag bei 1:12. Die Waschleistung wurde durch Messung der Aufhellung von angeschmutzten Testgeweben (Baumwollgewebe und Baumwoll­mischgewebe) als Remissionsdifferenz (Remission des trockenen Testgewebes nach dem Waschversuch abzüglich der Remission Testgewebes vor dem Waschversuch) bei 530 nm ermittelt. Die größere Remissionsdifferenz gibt hierbei die bessere Waschleistung an. Als Buildersysteme in den Vollwaschmittelformulierungen wurden Lactobionsäure allein, Lactobionsäure mit Zeolith (im Verhältnis 1:1) und als Vergleich STPP eingesetzt. Nr. Buildersystem Testgewebe Waschtemperatur in °C Remissionsdifferenz in % * 21 Lactobionsäure WFK-Gewebe PE/BW (20 C) 30 21,67 22 Lactobionsäure + Zeolith WFK-Gewebe PE/BW (20 C) 30 20,44 23 STPP WFK-Gewebe PE/BW (20 C) 30 19,26 24 Lactobionsäure WFK-Gewebe PE/BW (20 C) 60 27,14 25 Lactobionsäure + Zeolith WFK-Gewebe PE/BW (20 C) 60 27,98 26 STPP WFK-Gewebe PE/BW (20 C) 60 24,08 27 Lactobionsäure WFK-Gewebe BW (10 C) 60 28,18 28 Lactobionsäure + Zeolith WFK-Gewebe BW (10 C) 60 23,76 29 STPP WFK-Gewebe BW (10 C) 60 22,38 30 Lactobionsäure EMPA-Gewebe PE/Bw (104) 60 29,30 31 Lactobionsäure + Zeolith EMPA-Gewebe PE/Bw (104) 60 29,20 32 STPP EMPA-Gewebe PE/Bw (104) 60 37,16 33 Lactobionsäure EMPA-Gewebe BW (101) 60 23,24 34 Lactobionsäure + Zeolith EMPA-Gewebe BW (101) 60 21,26 35 STPP EMPA-Gewebe BW (101) 60 29,53 * Mittelwerte aus zwei Waschversuchen The tests were carried out at pH 10 and 18 ° dH at 30 and 60 ° C. The fleet ratio was 1:12. The washing performance was determined by measuring the lightening of soiled test fabrics (cotton fabric and cotton blend fabric) as the reflectance difference (reflectance of the dry test fabric after the washing test minus the reflectance test fabric before the washing test) at 530 nm. The larger remission difference indicates the better washing performance. Lactobionic acid alone, lactobionic acid with zeolite (in a 1: 1 ratio) and STPP as a comparison were used as builder systems in the heavy-duty detergent formulations. No. Builder system Test fabric Wash temperature in ° C Remission difference in% * 21st Lactobionic acid WFK fabric PE / BW (20 C) 30th 21.67 22 Lactobionic acid + zeolite WFK fabric PE / BW (20 C) 30th 20.44 23 STPP WFK fabric PE / BW (20 C) 30th 19.26 24th Lactobionic acid WFK fabric PE / BW (20 C) 60 27.14 25th Lactobionic acid + zeolite WFK fabric PE / BW (20 C) 60 27.98 26 STPP WFK fabric PE / BW (20 C) 60 24.08 27th Lactobionic acid WFK fabric BW (10 C) 60 28.18 28 Lactobionic acid + zeolite WFK fabric BW (10 C) 60 23.76 29 STPP WFK fabric BW (10 C) 60 22.38 30th Lactobionic acid EMPA fabric PE / Bw (104) 60 29.30 31 Lactobionic acid + zeolite EMPA fabric PE / Bw (104) 60 29.20 32 STPP EMPA fabric PE / Bw (104) 60 37.16 33 Lactobionic acid EMPA fabric BW (101) 60 23.24 34 Lactobionic acid + zeolite EMPA fabric BW (101) 60 21.26 35 STPP EMPA fabric BW (101) 60 29.53 * Average values from two washing tests

Die erfindungsgemäßen Versuche dieses Beispiels (Nr. 21, 22, 24, 25, 27, 28, 30, 31, 33 und 34) zeigen, daß Buildersysteme mit Lactobionsäure je nach Gewebeart vergleichbare, z.T. sogar bessere Waschleistungen verglichen mit guten Buildern gemäß Stand der Technik (Vergleichsversuche Nr. 23, 26, 29, 32 und 35) aufweisen.The experiments according to the invention of this example (No. 21, 22, 24, 25, 27, 28, 30, 31, 33 and 34) show that builder systems with lactobionic acid, depending on the type of fabric, have comparable, in some cases even better washing performance compared to good builders according to the prior art Technique (comparative experiments No. 23, 26, 29, 32 and 35).

Beispiel 5: Vergrauung Example 5: Graying

Zur Verdeutlichung, inwieweit der Einsatz von Lactobionsäure als Buildersubstanz die Vergrauung von Textilien verhindert, wurden Waschversuche an gebleichten Testgeweben ohne künstliche Anschmutzung und ohne optische Aufheller durchgeführt. Hierzu ließ man die Testgewebe insgesamt 25 Waschzyklen analog zu den im Beispiel 4 angegebenen Waschbedingungen bei 60 °C im Normalprogramm (Einlaugenverfahren, 2 h) durchlaufen. Danach wurde die Vergrauung der Testgewebe (Baumwollgewebe, Frottee) durch Messung der Remission bei 530 nm ermittelt. Als Builder in der standardisierten Vollwaschmittelformulierung (siehe Beispiel 4) wurden Lactobionsäure und als Vergleich STPP eingesetzt. Die Remission ist indirekt proportional zur Vergrauung. Nr. Builder Testgewebe WFK Remission in % nach 0 Waschzyklen 25 Waschzyklen 36 Lactobionsäure Baumwolle (Typ 10 C) 91,69 92,60 37 STPP Baumwolle (Typ 10 C) 91,69 92,67 38 Lactobionsäure Frottee 92,25 93,55 39 STPP Frottee 92,25 92,61 To clarify to what extent the use of lactobionic acid as builder substance prevents the graying of textiles, washing tests were carried out on bleached test fabrics without artificial soiling and without optical brighteners. For this purpose, the test fabrics were allowed to run through a total of 25 washing cycles analogous to the washing conditions given in Example 4 at 60 ° C. in the normal program (soaking process, 2 h). The graying of the test fabrics (cotton fabric, terry cloth) was then determined by measuring the reflectance at 530 nm. Lactobionic acid was used as the builder in the standardized heavy-duty detergent formulation (see Example 4) and STPP as a comparison. The remission is indirectly proportional to the graying. No. Builder Test fabric WFK % Remission after 0 wash cycles 25 washing cycles 36 Lactobionic acid Cotton (type 10 C) 91.69 92.60 37 STPP Cotton (type 10 C) 91.69 92.67 38 Lactobionic acid Terrycloth 92.25 93.55 39 STPP Terrycloth 92.25 92.61

Die erfindungsgemäßen Versuche dieses Beispiels (Nr. 36 und 38) zeigen, daß bei Einsatz von Lactobionsäure als Buildersubstanz in Wasch- und Reinigungsmittelzusammen­setzungen die Vergrauung von Textilien ebenso hervorragend verhindert wird die durch bekanntermaßen gute Builder des Standes der Technik (Vergleichsversuche Nr. 37 und 39).The experiments according to the invention of this example (Nos. 36 and 38) show that when lactobionic acid is used as builder in detergent and cleaning agent compositions, the graying of textiles is also prevented in an outstanding manner by the known builders of the prior art (comparative experiments Nos. 37 and 39 ).

Beispiel 6: Inkrustierung Example 6: incrustation

Zur Bestimmung der anorganischen Inkrustierung wurden Waschversuche an Testgeweben durchgeführt. Hierzu ließ man die Testgewebe insgesamt 25 Waschzyklen analog zu den im Beispiel 4 angegebenen Waschbedingungen durchlaufen. Nach Beendigung der Waschzyklen wurden die Testgewebe nach an sich bekannten Standardbedingungen verascht und als Maß für die anorganische Inkrustierung der verbliebene Asche­gehalt in Gew.-% (bezogen auf eingesetztes Testgewebe) ermittelt. Als Builder in der standardisierten Vollwasch­mittelformulierung (siehe Beispiel 4) wurden Lactobion­säure und als Vergleich STPP eingesetzt. Je kleiner der verbliebene Aschegehalt ist, desto geringer ist die Inkrustierung. Nr. Builder Testgewebe WFK Aschegehalt in % 40 Lactobionsäure Baumwolle (Typ: 10 C) 0,19 41 STPP Baumwolle (Typ: 10 C) 0,20 42 Lactobionsäure Frottee 0,44 43 STPP Frottee 0,55 To determine the inorganic incrustation, washing tests were carried out on test fabrics. For this purpose, the test fabrics were run through a total of 25 washing cycles analogous to the washing conditions specified in Example 4. After completion of the washing cycles, the test fabrics were ashed according to standard conditions known per se and the remaining ash content in% by weight (based on the test fabric used) was determined as a measure of the inorganic incrustation. Lactobionic acid was used as the builder in the standardized heavy-duty detergent formulation (see Example 4) and STPP as a comparison. The smaller the remaining ash content, the lower the incrustation. No. Builder Test fabric WFK Ash content in% 40 Lactobionic acid Cotton (type: 10 C) 0.19 41 STPP Cotton (type: 10 C) 0.20 42 Lactobionic acid Terrycloth 0.44 43 STPP Terrycloth 0.55

Die erfindungsgemäßen Versuche dieses Beispiels (Nr. 40 und 42) zeigen, daß bei Einsatz von Lactobionsäure in Wasch- und Reinigungsmittelzusammensetzungen die Inkrustierung von Textilien je nach Gewebeart etwas (Baumwolle) oder sogar viel besser (Frottee) als durch bekanntermaßen gute Builder des Standes der Technik (Vergleichsversuche 41 und 43) verhindert wird.
Abkürzungen
WFK - Wäschereiforschung Krefeld
PE/BW (20 C) = Polyester/Baumwolle (Typ 20 C)
BW (10 C) = Baumwolle (Typ 10 C)
EMPA = Eidgenössische Materialprüfungsanstalt
PE/BW (104) = Polyester/Baumwolle (Typ 104)
BW (101) = Baumwolle (Typ 101)
STPP = Natriumtripolyphosphat bzw. Natriumtriphosphat
NTA = Nitrilotriessigsäure
TAED = Tetraacetylethylendiamin
The experiments according to the invention of this example (Nos. 40 and 42) show that when lactobionic acid is used in detergent and cleaning agent compositions, the incrustation of textiles, depending on the type of fabric, is somewhat (cotton) or even much better (terry cloth) than by known builders of the prior art Technology (comparative tests 41 and 43) is prevented.
Abbreviations
WFK - laundry research Krefeld
PE / BW (20 C) = polyester / cotton (type 20 C)
BW (10 C) = cotton (type 10 C)
EMPA = Federal Materials Testing Institute
PE / BW (104) = polyester / cotton (type 104)
BW (101) = cotton (type 101)
STPP = sodium tripolyphosphate or sodium triphosphate
NTA = nitrilotriacetic acid
TAED = tetraacetylethylenediamine

Claims (14)

1. Wasch- und Reinigungsmittelzusammensetzungen enthaltend Tenside und gegebenenfalls weitere in Wasch- und Reinigungsmitteln übliche Bestandteile, dadurch gekennzeichnet, daß sie Lactobionsäure und/oder Lactobion­säuresalze als Buildersubstanzen in Gegenwart einer Bor­sauerstoffverbindung enthalten.1. Detergent and detergent compositions containing surfactants and optionally other ingredients customary in detergents and cleaning agents, characterized in that they contain lactobionic acid and / or lactobionic acid salts as builder substances in the presence of a boron oxygen compound. 2. Zusammensetzungen gemäß Anspruch 1, dadurch gekennzeichnet, daß die Lactobionsäure und/oder Lactobion­säuresalze in Mengen bis 40 Gew.-% vorliegen, bezogen auf die Gesamtzusammensetzung.2. Compositions according to claim 1, characterized in that the lactobionic acid and / or lactobionic acid salts are present in amounts of up to 40% by weight, based on the total composition. 3. Zusammensetzungen gemäß Anspruch 1, dadurch gekennzeichnet, daß die Borsauerstoffverbindung in den Zusammensetzungen in einer solchen Menge vorliegen, daß für 1 Mol Lactobionsäure und/oder Lactobionsäuresalz wenigstens 1 Mol Bor enthalten ist.3. Compositions according to claim 1, characterized in that the boron oxygen compound is present in the compositions in such an amount that at least 1 mol of boron is contained for 1 mol of lactobionic acid and / or lactobionic acid salt. 4. Zusammensetzungen gemäß Anspruch 1, dadurch gekennzeichnet, daß die Borsauerstoffverbindung ein Per­sauerstoffbleichmittel ist.4. Compositions according to claim 1, characterized in that the boron oxygen compound is a peroxygen bleach. 5. Zusammensetzungen gemäß Anspruch 4, dadurch gekennzeichnet, daß das Persauerstoffbleichmittel ein Perborat ist.5. Compositions according to claim 4, characterized in that the peroxygen bleach is a perborate. 6. Zusammensetzungen gemäß Anspruch 1, dadurch gekennzeichnet, daß die Zusammensetzungen pulverförmige Wasch- und Reinigungsmittelzusammensetzungen sind.6. Compositions according to claim 1, characterized in that the compositions are powder detergent compositions. 7. Abwandlung der Zusammensetzungen gemäß Anspruch 1, dadurch gekennzeichnet, daß die Zusammensetzungen als Builderkomponente eine Kombination aus üblichen Buildersubstanzen und Lactobionsäure und/oder Lactobionsäuresalzen als Cobuilder enthalten.7. Modification of the compositions according to claim 1, characterized in that the compositions contain as a builder component a combination of conventional builder substances and lactobionic acid and / or lactobionic acid salts as cobuilders. 8. Zusammensetzungen gemäß Anspruch 7, dadurch gekennzeichnet, daß die üblichen Buildersubstanzen ausge­wählt sind aus der Gruppe Zeolithe, Natriumcitrat und Aminopolycarbonsäuren.8. Compositions according to claim 7, characterized in that the usual builder substances are selected from the group of zeolites, sodium citrate and aminopolycarboxylic acids. 9. Zusammensetzungen gemäß Anspruch 7, dadurch gekennzeichnet, daß die Lactobionsäure und/oder die Lactobionsäuresalze als Cobuilder in Mengen bis zu 25 Gew.-% vorliegen, bezogen auf die Gesamtzusammen­setzung.9. Compositions according to claim 7, characterized in that the lactobionic acid and / or the lactobionic acid salts are present as cobuilders in amounts of up to 25% by weight, based on the total composition. 10. Zusammensetzungen für Wasch-, Reinigungs- und Bleichzwecke, dadurch gekennzeichnet, daß sie Lactobion­säure und/oder Lactobionsäuresalze als Buildersubstanzen enthalten.10. Compositions for washing, cleaning and bleaching purposes, characterized in that they contain lactobionic acid and / or lactobionic acid salts as builder substances. 11. Zusammensetzungen nach Anspruch 10, dadurch ge­kennzeichnet, daß sie die Lactobionsäure und/oder die Lactobionsäuresalze in Gegenwart einer Borsauerstoffver­bindung enthalten.11. Compositions according to claim 10, characterized in that they contain the lactobionic acid and / or the lactobionic acid salts in the presence of a boron oxygen compound. 12. Zusammensetzungen nach Anspruch 11, dadurch ge­kennzeichnet, daß die Borsauerstoffverbindung ein Per­sauerstoffbleichmittel, vorzugsweise ein Perborat, ist.12. Compositions according to claim 11, characterized in that the boron oxygen compound is a peroxygen bleach, preferably a perborate. 13. Verwendung von Lactobionsäure und/oder Lactobion­säuresalzen als Buildersubstanzen in Zusammensetzungen für Wasch- und Reinigungszwecke.13. Use of lactobionic acid and / or lactobionic acid salts as builder substances in compositions for washing and cleaning purposes. 14. Verfahren zum Waschen oder Reinigen, dadurch gekennzeichnet, daß Lactobionsäure und/oder Lactobion­säuresalze als Buildersubstanzen in Gegenwart von Bor­sauerstoffverbindungen eingesetzt werden.14. A method for washing or cleaning, characterized in that lactobionic acid and / or lactobionic acid salts are used as builder substances in the presence of boron oxygen compounds.
EP90107599A 1989-04-29 1990-04-21 Washing and cleaning compositions Expired - Lifetime EP0395970B1 (en)

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WO1995018064A1 (en) * 1993-12-29 1995-07-06 Solvay Interox Gmbh Coated alkali metal peroxo salts and process for producing the same
EP0455522B1 (en) * 1990-03-23 1996-08-14 Roquette Frˬres Phosphate free detergent

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US5433883A (en) * 1993-11-04 1995-07-18 Lever Brothers Company, Division Of Conopco, Inc. Toilet bar compositions comprising nonionic glycolipid surfactants and polyalkylene glycol structurant
WO2006131503A2 (en) * 2005-06-10 2006-12-14 Novozymes A/S Detergents with enzymatic builder and bleach systems
PT3156475T (en) 2015-10-16 2018-10-19 Georg Hagleitner Hans Liquid cleaning concentrate
CN106496618B (en) * 2016-10-18 2022-02-08 浙江伟星实业发展股份有限公司 Laser hollow-out processing liquid for fruit buttons and laser hollow-out fruit buttons

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EP0455522B1 (en) * 1990-03-23 1996-08-14 Roquette Frˬres Phosphate free detergent
WO1995018064A1 (en) * 1993-12-29 1995-07-06 Solvay Interox Gmbh Coated alkali metal peroxo salts and process for producing the same
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EP0395970B1 (en) 1994-06-15
US5069808A (en) 1991-12-03
ES2057245T3 (en) 1994-10-16
DE3914293A1 (en) 1990-10-31
DE59006100D1 (en) 1994-07-21
DK0395970T3 (en) 1994-07-04
JPH02305899A (en) 1990-12-19
CA2012836A1 (en) 1990-10-29
JP2672175B2 (en) 1997-11-05
CA2012836C (en) 1999-06-29

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