EP0448581B1 - Washing agent containing bleach, in liquid to paste form - Google Patents

Washing agent containing bleach, in liquid to paste form Download PDF

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Publication number
EP0448581B1
EP0448581B1 EP90900135A EP90900135A EP0448581B1 EP 0448581 B1 EP0448581 B1 EP 0448581B1 EP 90900135 A EP90900135 A EP 90900135A EP 90900135 A EP90900135 A EP 90900135A EP 0448581 B1 EP0448581 B1 EP 0448581B1
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EP
European Patent Office
Prior art keywords
weight
detergent
component
salts
liquid
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EP90900135A
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German (de)
French (fr)
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EP0448581A1 (en
Inventor
Uwe Trabitzsch
Günther Amberg
Paul Schulz
Jean-Marie Paillau
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT90900135T priority Critical patent/ATE93890T1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C11D1/831—Mixtures of non-ionic with anionic compounds of sulfonates with ethers of polyoxyalkylenes without phosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to a phosphate-free, liquid to pasty detergent, which is primarily intended for use in general laundries due to its special surfactant composition, a strongly alkaline, phosphate-free builder component and a bleach content.
  • Pasty essentially water-free detergents containing bleaching per compounds are known.
  • DE-B-12 79 878 (GB-A-12 05 711) describes a pasty agent whose liquid phase consists of nonionic surfactants and lower alcohols.
  • Sodium tripolyphosphate (TPP) and soda are used as skeleton salts and sodium perborate monohydrate as bleaching agent.
  • TPP Sodium tripolyphosphate
  • soda soda
  • the solids are finely ground and suspension stabilizers in the form of finely divided silica are also added to the agent.
  • DE-A-22 33 771 discloses washing pastes which contain mixtures of nonionic surfactants and polyols as the liquid phase and phosphates, citrate and nitrilotriacetate as the structural salts.
  • Perborate can be used as a per-compound.
  • EP-A-30 096 teaches that the solids, consisting of skeleton salts and persalts, have to be ground to particle sizes below 10 ⁇ m in order to avoid segregation of the pastes during storage.
  • the skeleton salts consist essentially of polyphosphates. Metasilicates and organic builder salts can also be present, but no further details are given.
  • the surfactant component consists exclusively of liquid non-ionic surfactants. Anionic surfactants are not included in the pastes. The means are unsatisfactory for the high requirements in commercial laundries with regard to perfect washing results compared to the most varied stains with the shortest possible wash cycles in the interest of high utilization of the complex washing systems.
  • the present invention enables a substantial improvement here. It had to be taken into account that the detergents foam as little as possible during the washing process and also in the rinse cycle, since a high level of foaming not only leads to malfunctions due to escaping lye, but also delivers poorer washing results, since a high foam cushion dampens the necessary mechanical processing of the laundry. Furthermore, in the interest of minimal wastewater pollution, the aim is to be largely free of phosphates. P-free detergents, however, require a different overall concept compared to P-containing detergents in order to avoid a drop in cleaning power. With powder detergents, this development is already well advanced, while with paste-like detergents, the problems are much greater due to the limited choice with regard to the usable raw materials. In the commercial sector, however, liquid or pasty agents deserve preference because they can be dosed automatically.
  • Suitable constituents of the surfactant component (A1) are alkylbenzenesulfonates with a linear alkyl chain having 10 to 13 carbon atoms, alkanesulfonates with 12 dis 16 carbon atoms, as can be obtained by sulfochlorination or sulfoxidation of n-paraffins and subsequent conversion into the alkali metal salts , and in the alpha position sulfonated fatty acid esters and fatty acid salts derived from saturated C12118 fatty acids and from C1 ⁇ 4 alcohols, preferably methyl alcohol.
  • Preferred sulfonate surfactants are alkylbenzenesulfonates.
  • soaps of saturated or monounsaturated C12 ⁇ 22 fatty acids especially C12 ⁇ 18 fatty acids and fatty acid mixtures, for example coconut oil, tallow oil or rapeseed oil fatty acids.
  • the surfactants of group (A1) are present as alkali salts, preferably as sodium salts. Their proportion, based on the composition, is preferably 1.5 to 3% by weight. Mixtures of alkylbenzenesulfonate and soaps have proven to be particularly suitable, in which case the content of alkylbenzenesulfonate in the compositions is 1 to 2.8% by weight and soaps 0.2 to 1.5% by weight. Surprisingly, it has been shown that the alkylbenzenesulfonates, regardless of their small proportion in the total surfactant component, considerably increase the washing power of the compositions compared to a pure nonionic formulation. On the other hand, the presence of the sulfonate surfactants known to be very foam active does not lead to an undesirable increase in foaming when used.
  • Component (A2) consists of alkoxylated, preferably ethoxylated linear alcohols or alcohols branched in the 2-position methyl (oxo alcohols) having 10 to 18 carbon atoms, those with 18 carbon atoms preferably being predominantly monounsaturated, that is to say predominantly composed of Oleyl alcohol or mixtures thereof.
  • the number of ethylene glycol ether groups (E0) is usually 2 to 10, preferably 3 to 8 and should be matched with respect to the alcohol residue so that the ethoxylates or ethoxylate mixtures have a pour point of at most 10 ° C, preferably below 8 ° C .
  • Alcohol alkoxylates of the general formula R- (PO) x - (EO) y in which PO stands for a propylene glycol ether residue, x for the numbers 1 to 2 and y for the numbers 3 to 10, are also very useful.
  • Particularly suitable nonionics from this class are C10 ⁇ 14 coconut alcohols with 3 - 8 EO, oley alcohol with 5 - 10 EO, or with 1 - 2 PO and 4 - 8 EO, C10 ⁇ 14 oxo alcohols with 3 - 8 EO and C12 ⁇ 15-oxo alcohols with 3 - 7 EO, and their mixtures.
  • the proportion of the surfactant component (A2) is on average 16 to 34% by weight, preferably 18 to 30% by weight.
  • the total amount of surfactants is 20 to 35% by weight, preferably 22 to 33% by weight.
  • Component (B) consists of water-soluble or water-insoluble builder substances which are able to bind or sequester alkaline earth metal ions and possibly also heavy metal ions.
  • Hydrated, finely crystalline, synthetic zeolites of the NaA type are suitable as water-insoluble builder substance.
  • Suitable zeolites have practically no particles larger than 30 ⁇ m and preferably consist of at least 80% of particles smaller than 10 ⁇ m.
  • Their calcium binding capacity which is determined according to the information in DE-A-24 12 837, is in the range from 100 to 200 mg CaO / g.
  • the content of zeolites in the detergents should preferably not exceed 25% by weight and in particular 20% by weight in the interest of sufficient flowability of the paste.
  • Particularly suitable builder substances which are to be assigned to component (B) and are used either alone or in a mixture with the abovementioned zeolites are polyanionic, organic complexing agents, the proportion of which is preferably in total 10 to 20% by weight.
  • Nitrilotriacetic acid (NTA) and polyphosphonic acids in the form of the sodium salts such as ethylenediamine-tetramethylenephosphonic acid (EDTMP), diethylenetriamine-pentamethylenephosphonic acid (DTPMP), aminotrimethylenephosphonic acid (ADTMP) and in particular 1-hydroxyethane-1,1-diphosphonic acid (HED) are suitable.
  • the agent preferably contains 3 to 8% by weight of NTA (NA salt) and 0.5 to 4% by weight of HEDP (Na salt).
  • This component also includes polymeric or copolymeric carboxylic acids in the form of the sodium or potassium salts, the sodium salts being preferred. Suitable homopolymers are polyacrylic acid, polymethacrylic acid and polymaleic acid.
  • Suitable copolymers are those of acrylic acid with methacrylic acid or copolymers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether, furthermore with vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene.
  • vinyl ethers such as vinyl methyl ether or vinyl ethyl ether
  • vinyl esters such as vinyl acetate or vinyl propionate
  • acrylamide methacrylamide
  • ethylene, propylene or styrene ethylene, propylene or styrene.
  • the proportion thereof in the interest of sufficient water solubility is not more than 60 mole percent, preferably less than 50 mole percent.
  • Copolymers of acrylic acid or methacrylic acid with maleic acid such as are characterized, for example, in EP 25 551-B1 have proven to be particularly suitable.
  • copolymers which contain 50 to 90% by weight of acrylic acid or methacrylic acid and 50 to 10% by weight of maleic acid. Copolymers in which 60 to 85% by weight of acrylic acid and 40 to 15% by weight of maleic acid are present are particularly preferred.
  • the content of such (co) polymers in the compositions, based on sodium salts, is up to 10% by weight, preferably 3 to 8% by weight.
  • Component (C) consists of sodium metasilicate, which has a Na2O: SiO2 ratio of 1: 0.8 to 1: 1.5, preferably 1: 0.9 to 1: 1.1.
  • the sodium silicate is used as an anhydrous salt. Its proportion is preferably 20 to 35% by weight.
  • Possible components (D) are persalts or perhydrate salts, such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate.
  • Sodium perborate monohydrate is preferably used.
  • the content of the agents and such per-compounds is 8 to 25% by weight, preferably 10 to 20% by weight.
  • the component (E) comprises known nonionic or anionic polymers with graying-inhibiting action.
  • Cellulose ethers such as sodium carboxymethyl cellulose and mixtures thereof with other cellulose ethers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose or mixed ethers such as methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose or ethyl hydroxyethyl cellulose are particularly suitable.
  • Cellulose ethers and (co) polymers can advantageously be used together. Mixtures of carboxymethyl cellulose with methyl cellulose or methyl hydroxyethyl cellulose have proven to be particularly useful.
  • the graying inhibitor content of the agents is up to 3% by weight, preferably 0.5 to 2% by weight.
  • Enzymes, fragrances and customary optical brighteners come into question as cheerful non-surfactant components of component (E) which do not act as builders, in particular optical brighteners with substantivity for cellulose fibers (cotton) from the class of the substituted bis-triazinylstilbene disulfonic acids and sulfonated distyryle , which are usually used in proportions of 0.05 to 0.5% by weight.
  • agents for improving the flowability can also be added to the pastes.
  • hydrotropes such as alkylbenzosulfonates with 1 to 3 carbon atoms in one or two alkyl chains in the form of the sodium salts such as toluene, cumene or xylene sulfonate.
  • Solvents such as lower alcohols and ether alcohols and polyethylene glycols with a molecular weight of 200 to 1000 can also be used. The proportion of polyglycols can be up to 10% by weight. Alcohols can be used in the same amount, but they are less preferred.
  • the water content of the agents should be as low as possible, since free water increases the viscosity of the agents and thus complicates the processing and metering of the agents. Water contents of 2% by weight or less are therefore particularly preferred.
  • the agents are prepared by mixing and homogenizing the solid, finely divided constituents with the liquid nonionic surfactants (component A2), in particular with the liquid surfactant mixture (component A).
  • component A2 liquid nonionic surfactants
  • component A liquid surfactant mixture
  • the solid alkylbenzenesulfonates behave about half of their content as a liquid component and thus favor the incorporation of high solids contents.
  • the mixture is then expediently ground, for example in a colloid mill or on a roller mill, so that the grain size of the suspended solids is between 5 and 80 ⁇ m, preferably 10 to 50 ⁇ m.
  • the proportion of coarse particles (over 80 ⁇ m) should preferably be less than 20, in particular less than 5,% by weight.
  • the agents are generally used in a concentration of 4 to 12 g / l, preferably 5 to 10 g / l, suitably softened, i.e. water softened to a degree of hardness of less than 2 ° dH, in particular less than 1 ° dH, is used to prepare the wash liquor.
  • the agents are characterized by a high washing and bleaching capacity and a low, non-disturbing foam development during use. Surprisingly, it has been found that the agents are extremely stable against loss of oxygen and against segregation even under long-term storage under changing climatic conditions. They are suitable due to their favorable rheological properties Good for use in automatic dosing systems, since they are low-viscosity and easy to convey under the influence of shear effects, but are more viscous in the idle state and are therefore stable in storage.
  • the perborate was used in the form of the monohydrate.
  • the copolymer was composed of acrylic acid and maleic acid (3: 1) and had a molecular weight of approximately 70,000.
  • the cellulose ether consisted of a 2: 1 mixture of sodium carboxymethyl cellulose and methyl hydroxyethyl cellulose (hydroxyethyl content 0.8% by weight).
  • the Na salt of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid was used as the optical brightener .
  • the water came from the moisture content of the raw materials used.
  • Polydiol was a polyethylene glycol with a molecular weight of 400. The contents given in the table mean percentages by weight.
  • the foam development was low in all cases, i.e. the foam level was a maximum of 8 to 10 cm above the liquid level in the main wash cycle and 4 to 6 cm above the liquid level in the first rinse cycle. No foam development was visible in the third rinse cycle.

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  • Engineering & Computer Science (AREA)
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Abstract

A phosphate-free washing agent in liquid to paste form contains (A) 20 to 35 wt.% of a tenside component composed of (A1) 1 to 4 wt.% of anionic tensides from the class of sulphonates and soaps and (A2) 16 to 34 wt.% of non-ionic tensides with a pour point of at least 10°C; (B) 10 to 35 wt.% of builder salts which form complexes or bind alkaline earth metal ions; (c) 15 to 40 wt.% of sodium metasilicate; (D) 8 to 25 wt.% of per-salts with a bleaching action; (E) up to 15 wt.% of other washing agent constituents; (F) less than 3 wt.% of water, provided that the sum of the components (B+C) = 30 to 60 wt.%. In each case, the content is expressed as a percentage of the weight of the washing agent.

Description

Die Erfindung betrifft ein phosphatfreies, flüssiges bis pastöses Waschmittel, das aufgrund seiner speziellen Tensidzusammensetzung, einer stark alkalischen, phosphatfreien Builderkomponente und einem Gehalt an Bleichmitteln in erster Linie zum Einsatz in generblichen Wäschereien bestimmt ist.The invention relates to a phosphate-free, liquid to pasty detergent, which is primarily intended for use in general laundries due to its special surfactant composition, a strongly alkaline, phosphate-free builder component and a bleach content.

Pastöse, im wesentlichen wasserfreie Waschmittel mit einem Gehalt an bleichend wirkenden Perverbindungen sind bekannt. In DE-B-12 79 878 (GB-A-12 05 711) ist ein pastöses Mittel beschrieben, dessen flüssige Phase aus nichtionischen Tensiden und niederer Alkoholen besteht. Als Gerüstsalze werden Natriumtripolyphosphat (TPP) und Soda, als Bleichmittel Natriumperborat-monohydrat eingesetzt. Um ein Entmischen der Pasten bei der Lagerung zu vermeiden, werden die Feststoffe fein gemahlen und dem Mittel zusätzlich Suspensionsstabilisaioren in Form feinteiliger Kieselsäure zugesetzt. Aus DE-A-22 33 771 (US-A-3 850 831) sind Waschpasten bekannt, die als flüssige Phase Gemische aus nichtionischen Tensiden und Polyolen und als Gerüstsalze Phosphate, Citrat und Nitrilotriacetat enthalten. Auch Wasserglas, d.h. ein schwach alkalisch reagierendes Silikat der Zusammensetzung Na20 : SiO₂ = 1 : 3,3, kann anwesend sein. Als Perverbindung kommt Perborat in Frage.Pasty, essentially water-free detergents containing bleaching per compounds are known. DE-B-12 79 878 (GB-A-12 05 711) describes a pasty agent whose liquid phase consists of nonionic surfactants and lower alcohols. Sodium tripolyphosphate (TPP) and soda are used as skeleton salts and sodium perborate monohydrate as bleaching agent. In order to avoid segregation of the pastes during storage, the solids are finely ground and suspension stabilizers in the form of finely divided silica are also added to the agent. DE-A-22 33 771 (US-A-3 850 831) discloses washing pastes which contain mixtures of nonionic surfactants and polyols as the liquid phase and phosphates, citrate and nitrilotriacetate as the structural salts. Water glass, ie a weakly alkaline-reacting silicate with the composition Na20: SiO₂ = 1: 3.3, can also be present. Perborate can be used as a per-compound.

EP-A-30 096 lehrt, daß man die Feststoffe, bestehend aus Gerüstsalzen und Persalzen, auf Korngrößen unter 10 µm vermahlen muß, um ein Entmischen der Pasten während der Lagerung zu vermeiden. Die Gerüstsalze bestehen im wesentlichen aus Polyphosphaten. Auch Metasilikate und organische Buildersalze können anwesend sein, jedoch werden hierzu keine näheren Angaben gemacht. Die Tensidkomponente besteht ausschließlich aus flüssigen nichtionischen Tensiden. Anionische Tenside sind in den Pasten nicht enthalten. Für die hohen Anforderungen in gewerblichen Wäschereien hinsichtlich einwandfreier Waschergebnisse gegenüber den unterschiedlichsten Anschmutzungen bei möglichst kurzen Waschzeiien im Interesse einer hohen Ausnutzung der aufwendigen Waschanlagen sind die Mittel unbefriedigend.EP-A-30 096 teaches that the solids, consisting of skeleton salts and persalts, have to be ground to particle sizes below 10 μm in order to avoid segregation of the pastes during storage. The skeleton salts consist essentially of polyphosphates. Metasilicates and organic builder salts can also be present, but no further details are given. The surfactant component consists exclusively of liquid non-ionic surfactants. Anionic surfactants are not included in the pastes. The means are unsatisfactory for the high requirements in commercial laundries with regard to perfect washing results compared to the most varied stains with the shortest possible wash cycles in the interest of high utilization of the complex washing systems.

Die vorliegende Erfindung ermöglicht hier eine wesentliche Verbesserung. Dabei war zu berücksichtigen, daß die Mittel während des Waschprozesses und auch im Nachspülgang möglichst wenig schäumen, da eine hohe Schaumentwicklung nicht nur zu Betriebsstörungen durch ausfließende Lauge führt, sondern auch schlechtere Waschergebnisse liefert, da ein hohes Schaumpolster die notwendige mechanische Bearbeitung des Waschgutes dämpft. Weiterhin ist im Interesse einer minimalen Abwasserbelastung eine weitgehende Phosphatfreiheit anzustreben. P-freie Waschmittel erfordern jedoch gegenüber P-haltigen Mitteln ein geändertes Gesamtkonzept um einen Abfall des Reinigungsvermögens zu vermeiden. Bei pulverförmigen Waschmitteln ist diese Entwicklung schon weit fortgeschritten während bei pastösen Mitteln die Probleme wegen der beschränkten Auswahlmöglichkeit hinsichtlich der brauchbaren Rohstoffe sehr viel größer sind. Im gewerblichen Bereich verdienen jedoch flüssige bzw. pastöse Mittel den Vorzug, da sie sich automatisch dosieren lassen.The present invention enables a substantial improvement here. It had to be taken into account that the detergents foam as little as possible during the washing process and also in the rinse cycle, since a high level of foaming not only leads to malfunctions due to escaping lye, but also delivers poorer washing results, since a high foam cushion dampens the necessary mechanical processing of the laundry. Furthermore, in the interest of minimal wastewater pollution, the aim is to be largely free of phosphates. P-free detergents, however, require a different overall concept compared to P-containing detergents in order to avoid a drop in cleaning power. With powder detergents, this development is already well advanced, while with paste-like detergents, the problems are much greater due to the limited choice with regard to the usable raw materials. In the commercial sector, however, liquid or pasty agents deserve preference because they can be dosed automatically.

Die nachfolgende Erfindung beschreibt einen Weg, wie sich die aufgezeigten Probleme vorteilhaft lösen lassen.The following invention describes a way in which the problems shown can be advantageously solved.

Gegenstand der Erfindung ist ein flüssiges bis pastöses, phosphatfreies Waschmittel mit einem jeweils auf das Waschmittel bezogenen Gehalt an

  • (A) 20 bis 35 Gew.-% einer Tensidkomponente der Zusammensetzung
    • (A1) 1 bis 4 Gew.-% an anionischen Tensiden aus der Klasse der Sulfonate und der Seifen, die als Alkalisalze vorliegen,
    • (A2) 16 bis 34 Gew.-% an nichtionischen Tensiden mit einem Stockpunkt von höchstens 10 °C, die alkoxylierte lineare Alkohole bzw. in 2-Stellung methylverzweigte Alkohole mit 10 bis 18 C-Atomen oder deren Gemische sind,
  • (B) 10 bis 35 Gew.-% an komplexierend wirkenden bzw. irdalkalimetallionen bindenden Buildersalzen,
  • (C) 15 bis 40 Gew.-% Natriummetasilikat,
  • (D) 8 bis 25 Gew.-% an bleichend wirkenden Persalzen,
  • (E) bis zu 15 Gew.-% an sonstigen Waschmittelbestandteilen,
  • (F) weniger als 3 Gew.-% Wasser, mit der Maßgabe, daß die Summe der Komponenten (B + C) = 30 bis 60 Gew.-% beträgt.
The invention relates to a liquid to pasty, phosphate-free detergent, each with a detergent content
  • (A) 20 to 35% by weight of a surfactant component of the composition
    • (A1) 1 to 4% by weight of anionic surfactants from the class of the sulfonates and the soaps, which are present as alkali salts,
    • (A2) 16 to 34% by weight of nonionic surfactants with a pour point of at most 10 ° C. which are alkoxylated linear alcohols or alcohols with methyl branching in the 2-position with 10 to 18 C atoms or mixtures thereof,
  • (B) 10 to 35% by weight of builder salts which have a complexing action or bind alkaline earth metal ions,
  • (C) 15 to 40% by weight sodium metasilicate,
  • (D) 8 to 25% by weight of bleaching persalts,
  • (E) up to 15% by weight of other detergent components,
  • (F) less than 3% by weight of water, with the proviso that the sum of the components (B + C) = 30 to 60% by weight.

Als Bestandteile der Tensidkomponente (A1) eignen sich Alkylbenzolsulfonate mit linearer, 10 bis 13 C-Atome aufweisender Alkylkette, Alkansulfonate mit 12 Dis 16 C-Atomen, wie sie durch Sulfochlorierung bzw. Sulfoxidation von n-Paraffinen und anschließende Überführung in die Alkalisalze erhältlich sind, und in Alphastellung sulfonierte Fettsäureester und fettsaure Salze die sich von gesättigten C₁₂₋₁₈-Fettsäuren und von C₁₋₄-Alkoholen, vorzugsweise Methylalkohol, ableiten. Bevorzugte Sulfonattenside sind Alkylbenzolsulfonate.Suitable constituents of the surfactant component (A1) are alkylbenzenesulfonates with a linear alkyl chain having 10 to 13 carbon atoms, alkanesulfonates with 12 dis 16 carbon atoms, as can be obtained by sulfochlorination or sulfoxidation of n-paraffins and subsequent conversion into the alkali metal salts , and in the alpha position sulfonated fatty acid esters and fatty acid salts derived from saturated C₁₂₁₁₈ fatty acids and from C₁₋₄ alcohols, preferably methyl alcohol. Preferred sulfonate surfactants are alkylbenzenesulfonates.

Als weitere Bestandteile eignen sich Seifen von gesättigten bzw. einfach ungesättigten C₁₂₋₂₂-Fettsäuren, insbesondere C₁₂₋₁₈-Fettsäuren und Fettsäuregemischen, beispielsweise von Cocos-, Talg- oder Rübölfettsäuren.As further constituents are soaps of saturated or monounsaturated C₁₂₋₂₂ fatty acids, especially C₁₂₋₁₈ fatty acids and fatty acid mixtures, for example coconut oil, tallow oil or rapeseed oil fatty acids.

Die Tenside der Gruppe (A1) liegen als Alkalisalze, vorzugsweise als Natriumsalze vor. Ihr Anteil, bezogen auf das Mittel, beträgt vorzugsweise 1,5 bis 3 Gew.-%. Als besonders geeignet haben sich Gemische von Alkylbenzolsulfonat und Seifen erwiesen, wobei in diesem Falle der Gehalt der Mittel an Alkylbenzolsulfonat 1 bis 2,8 Gew.-% und an Seifen 0,2 bis 1,5 Gew.-% beträgt. Überraschend hat sich gezeigt, daß die Alkylbenzolsulfonate ungeachtet ihres geringen Anteils an der gesamten Tensidkomponente die Waschkraft der Mittel gegenüber einer reinen Nonionic-Formulierung ganz erheblich steigert. Andererseits führt die Anwesenheit der als sehr schaumaktiv bekannten Sulfonattenside nicht zu einer störenden Zunahme des Schäumens bei der Anwendung.The surfactants of group (A1) are present as alkali salts, preferably as sodium salts. Their proportion, based on the composition, is preferably 1.5 to 3% by weight. Mixtures of alkylbenzenesulfonate and soaps have proven to be particularly suitable, in which case the content of alkylbenzenesulfonate in the compositions is 1 to 2.8% by weight and soaps 0.2 to 1.5% by weight. Surprisingly, it has been shown that the alkylbenzenesulfonates, regardless of their small proportion in the total surfactant component, considerably increase the washing power of the compositions compared to a pure nonionic formulation. On the other hand, the presence of the sulfonate surfactants known to be very foam active does not lead to an undesirable increase in foaming when used.

Die Komponente (A2) besteht aus alkoxylierten, vorzugsweise ethoxylierten linearen Alkoholen bzw. in 2-Stellung methylverzweigten Alkoholen (Oxo-Alkoholen) mit 10 bis 18 C-Atomen, wobei solche mit 18 C-Atomen vorzugsweise überwiegend einfach ungesättigt sind, d.h. überwiegend aus Oleylalkohol bestehen oder deren Gemischen. Die Zahl des Ethylenglykolethergruppen (E0) beträgt in der Regel 2 bis 10, vorzugsweise 3 bis 8 und soll in Bezug auf den Alkoholrest so abgestimmt sein daß die Ethoxylate bzw. Ethoxylatgemische einen Stockpunkt von höchstens 10 °C, vorzuosweise von unter 8 °C aufweisen. Gut brauchbar sind auch Alkoholalkoxylate der allgemeinen Formel R-(PO)x-(EO)y, in der PO für einen Propylenglykoletherrest, x für die Zahlen 1 bis 2 und y für die Zahlen 3 bis 10 stehen. Besonders geeignete Nonionics aus dieser Klasse sind C₁₀₋₁₄-Cocosalkohole mit 3 - 8 EO, Oleylakohol mit 5 - 10 EO, bzw. mit 1 - 2 PO und 4 - 8 EO, C₁₀₋₁₄-Oxoalkohole mit 3 - 8 EO und C₁₂₋₁₅-Oxoalkohole mit 3 - 7 EO, sowie deren Gemische.Component (A2) consists of alkoxylated, preferably ethoxylated linear alcohols or alcohols branched in the 2-position methyl (oxo alcohols) having 10 to 18 carbon atoms, those with 18 carbon atoms preferably being predominantly monounsaturated, that is to say predominantly composed of Oleyl alcohol or mixtures thereof. The number of ethylene glycol ether groups (E0) is usually 2 to 10, preferably 3 to 8 and should be matched with respect to the alcohol residue so that the ethoxylates or ethoxylate mixtures have a pour point of at most 10 ° C, preferably below 8 ° C . Alcohol alkoxylates of the general formula R- (PO) x - (EO) y , in which PO stands for a propylene glycol ether residue, x for the numbers 1 to 2 and y for the numbers 3 to 10, are also very useful. Particularly suitable nonionics from this class are C₁₀₋₁₄ coconut alcohols with 3 - 8 EO, oley alcohol with 5 - 10 EO, or with 1 - 2 PO and 4 - 8 EO, C₁₀₋₁₄ oxo alcohols with 3 - 8 EO and C₁₂ ₋₁₅-oxo alcohols with 3 - 7 EO, and their mixtures.

Der Anteil der Tensidkomponente (A2) im Mittel beträgt 16 bis 34 Gew.-%, vorzugsweise 18 bis 30 Gew.-%. Die Gesamtmenge der Tenside beträgt 20 bis 35 Gew.-%, vorzugsweise 22 bis 33 Gew.-%.The proportion of the surfactant component (A2) is on average 16 to 34% by weight, preferably 18 to 30% by weight. The total amount of surfactants is 20 to 35% by weight, preferably 22 to 33% by weight.

Die Komponente (B) besteht aus wasserlöslichen oder auch wasserunlöslichen Buildersubstanzen, die Erdalkalimetallionen und ggf. auch Schwermetallionen zu binden bzw. zu sequestrieren vermögen.Component (B) consists of water-soluble or water-insoluble builder substances which are able to bind or sequester alkaline earth metal ions and possibly also heavy metal ions.

Als wasserunlösliche Buildersubstanz eignen sich hydratisierte, feinkristalline, synthetische Zeolithe vom Typ NaA. Geeignete Zeolithe weisen praktisch kein Teilchen größer als 30 µm auf und bestehen vorzugsweise zu wenigstens 80 % aus Teilchen einer Größe kleiner als 10 µm. Ihr Calciumbindevermögen, das nach den Angaben in DE-A-24 12 837 bestimmt wird, liegt im Bereich von 100 bis 200 mg CaO/g. Der Gehalt der Mittel an Zeolithen soll im Interesse einer ausreichenden Fließfähigkeit der Paste vorzugsweise 25 Gew.-% und insbesondere 20 Gew.-% nicht überschreiten.Hydrated, finely crystalline, synthetic zeolites of the NaA type are suitable as water-insoluble builder substance. Suitable zeolites have practically no particles larger than 30 μm and preferably consist of at least 80% of particles smaller than 10 μm. Their calcium binding capacity, which is determined according to the information in DE-A-24 12 837, is in the range from 100 to 200 mg CaO / g. The content of zeolites in the detergents should preferably not exceed 25% by weight and in particular 20% by weight in the interest of sufficient flowability of the paste.

Besonders geeignete, der Komponente (B) zuzurechnende Buildersubstanzen, die entweder allein oder im Gemisch mit den vorgenannten Zeolithen eingesetzt werden, sind polyanionische, organische Komplexierungsmittel, deren Anteil vorzugsweise insgesamt 10 bis 20 Gew.-% beträgt. Geeignet sind Nitrilotriessigsäure (NTA) und Polyphosphonsäuren in Form der Natriumsalze, wie Ethylendiamin-tetramethylenphosphonsäure (EDTMP), Diethylentriamin-pentamethylenphosphonsäure (DTPMP), Aminotrimethylenphosphonsäure (ADTMP) und insbesondere der 1-Hydroxyethan-1,1-diphosphonsäure (HEDP). Vorzugsweise enthält das Mittel 3 bis 8 Gew.-% NTA (NA-Salz) und 0,5 bis 4 Gew.-% HEDP (Na-Salz). Weiterhin zählen zu dieser Komponente polymere bzw. copolymere Carbonsäuren in Form der Natrium- oder Kaliumsalze, wobei die Natriaumsalze bevorzugt sind. Geeignete Homopolymere sind Polyacrylsäure, Polymethacrylsäure und Polymaleinsäure. Geeignete Copolymere sind solche der Acrylsäure mit Methacrylsäure bzw. Copolymere der Acrylsäure, Methacrylsäure oder Maleinsäure mit Vinylethern, wie Vinylmethylether bzw. Vinylethylether, ferner mit Vinylestern, wie Vinylacetat oder Vinylpropionat, Acrylamid, Methacrylamid sowie mit Ethylen, Propylen oder Styrol. In solchen copolymeren Säuren, in denen eine der Komponenten keine Säurefunktion aufweist, beträgt deren Anteil im Interesse einer ausreichenden Wasserlöslichkeit nicht mehr als 60 Molprozent, vorzugsweise weniger als 50 Molprozent. Als besonders geeignet haben sich Copolymere der Acrylsäure bzw. Methacrylsäure mit Maleisäure erwiesen wie sie beilspielsweise in EP 25 551-B 1 charakterisiert sind. Es handelt sich dabei um Copolymerisate, die 50 bis 90 Gew.-% Acrylsäure bzw. Methacrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Besonders bevorzugt sind solche Copolymere, in denen 60 bis 85 Gew.-% Acrylsäure und 40 bis 15 Gew.-% Maleinsäure vorliegen. Der Gehalt der Mittel an derartigen (Co-)Polymeren beträgt, auf Natriumsalze bezogen, bis zu 10 Gew.-%, vorzugsweise 3 bis 8 Gew.-%.Particularly suitable builder substances which are to be assigned to component (B) and are used either alone or in a mixture with the abovementioned zeolites are polyanionic, organic complexing agents, the proportion of which is preferably in total 10 to 20% by weight. Nitrilotriacetic acid (NTA) and polyphosphonic acids in the form of the sodium salts, such as ethylenediamine-tetramethylenephosphonic acid (EDTMP), diethylenetriamine-pentamethylenephosphonic acid (DTPMP), aminotrimethylenephosphonic acid (ADTMP) and in particular 1-hydroxyethane-1,1-diphosphonic acid (HED) are suitable. The agent preferably contains 3 to 8% by weight of NTA (NA salt) and 0.5 to 4% by weight of HEDP (Na salt). This component also includes polymeric or copolymeric carboxylic acids in the form of the sodium or potassium salts, the sodium salts being preferred. Suitable homopolymers are polyacrylic acid, polymethacrylic acid and polymaleic acid. Suitable copolymers are those of acrylic acid with methacrylic acid or copolymers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether, furthermore with vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene. In those copolymeric acids in which one of the components has no acid function, the proportion thereof in the interest of sufficient water solubility is not more than 60 mole percent, preferably less than 50 mole percent. Copolymers of acrylic acid or methacrylic acid with maleic acid, such as are characterized, for example, in EP 25 551-B1 have proven to be particularly suitable. These are copolymers which contain 50 to 90% by weight of acrylic acid or methacrylic acid and 50 to 10% by weight of maleic acid. Copolymers in which 60 to 85% by weight of acrylic acid and 40 to 15% by weight of maleic acid are present are particularly preferred. The content of such (co) polymers in the compositions, based on sodium salts, is up to 10% by weight, preferably 3 to 8% by weight.

Die Komponente (C) besteht aus Natriummetasilikat, das ein Na₂O : SiO₂-Verhältnis von 1 : 0,8 bis 1 : 1,5, vorzugsweise 1 : 0,9 bis 1 : 1,1 aufweist. Das Natriumsilikat kommt als wasserfreies Salz zum Einsatz. Sein Anteil beträgt vorzugsweise 20 bis 35 Gew.-%.Component (C) consists of sodium metasilicate, which has a Na₂O: SiO₂ ratio of 1: 0.8 to 1: 1.5, preferably 1: 0.9 to 1: 1.1. The sodium silicate is used as an anhydrous salt. Its proportion is preferably 20 to 35% by weight.

Als Komponente (D) kommen Persalze bzw. Perhydratsalze in Frage, wie Natriumperborat-tetrahydrat, Natriumperborat-monohydrat und Natriumpercarbonat. Bevorzugt wird Natriumperborat-monohydrat eingesetzt. Der Gehalt der Mittel and derartigen Perverbindungen beträgt 8 bis 25 Gew.-%, vorzugsweise 10 bis 20 Gew.-%.Possible components (D) are persalts or perhydrate salts, such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate. Sodium perborate monohydrate is preferably used. The content of the agents and such per-compounds is 8 to 25% by weight, preferably 10 to 20% by weight.

Der Bestandteil (E) umfaßt bekannte nichtionische oder anionische Polymere mit vergrauungsinhibierender Wirkung. Besonders geeignet sind Celluloseether, wie Na-Carboxymethylcellulose und deren Gemische mit anderen Celluloseethern, wie Methylcellulose, Ethylcellulose, Hydroxyethylcellulose, Hydroxypropylcellulose oder Mischether, wie Methyl-hydroxyethylcellulose, Methyl-carboxymethylcellulose oder Ethyl-hydroxyethylcellulose. Celluloseether und (Co-)Polymere können mit Vorteil gemeinsam verwendet werden. Als besonders brauchbar haben sich Gemische der Carboxymethylcellulose mit Methylcellulose oder Methyl-hydroxyethylcellulose erwiesen. Der Gehalt der Mittel an Vergrauungsinhibitoren beträgt bis zu 3 Gew.-%, vorzugsweise 0,5 bis 2 Gew.-%.The component (E) comprises known nonionic or anionic polymers with graying-inhibiting action. Cellulose ethers such as sodium carboxymethyl cellulose and mixtures thereof with other cellulose ethers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose or mixed ethers such as methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose or ethyl hydroxyethyl cellulose are particularly suitable. Cellulose ethers and (co) polymers can advantageously be used together. Mixtures of carboxymethyl cellulose with methyl cellulose or methyl hydroxyethyl cellulose have proven to be particularly useful. The graying inhibitor content of the agents is up to 3% by weight, preferably 0.5 to 2% by weight.

Als heitere nichttensidische bzw. nicht als Gerüststoff wirkende Bestandteile der Komponente (E) kommen Enzyme, Duftstoffe und übliche optische Aufheller in Frage, insbesondere optische Aufheller mit Substantivität für Cellulosefasern (Baumwolle) aus de Klasse der substituierten Bis-triazinylstilben-disulfonsäuren und der sulfonierten Distyryle, die üblicherweise in Anteilen von 0,05 bis 0,5 Gew.-% eingesetzt werden.Enzymes, fragrances and customary optical brighteners come into question as cheerful non-surfactant components of component (E) which do not act as builders, in particular optical brighteners with substantivity for cellulose fibers (cotton) from the class of the substituted bis-triazinylstilbene disulfonic acids and sulfonated distyryle , which are usually used in proportions of 0.05 to 0.5% by weight.

Darüber hinaus können den Pasten noch Mittel zur Verbesserung der Fließfähigkeit zugesetzt werden. Hierzu zählen bekannte Hydrotrope wie Alkylbenzosulfonate mit 1 bis 3 C-Atomen in einer oder zwei Alkylketten in Form der Natriumsalze wie Toluol-, Cumol- oder Xylolsulfonat. Brauchbar sind ferner Lösungsmittel, wie niedere Alkohole und Etheralkohole sowie Polyethylenglykole mit einem Molekulargewicht von 200 bis 1 000. Der Anteil an Polyglykolen kann bis 10 Gew.-% betragen. Alkohole können in gleicher Menge eingesetzt werden, sie sind jedoch weniger bevorzugt.In addition, agents for improving the flowability can also be added to the pastes. These include known hydrotropes such as alkylbenzosulfonates with 1 to 3 carbon atoms in one or two alkyl chains in the form of the sodium salts such as toluene, cumene or xylene sulfonate. Solvents such as lower alcohols and ether alcohols and polyethylene glycols with a molecular weight of 200 to 1000 can also be used. The proportion of polyglycols can be up to 10% by weight. Alcohols can be used in the same amount, but they are less preferred.

Der Wassergehalt der Mittel soll möglichst gering sein, da freies Wasser die Viskosität der Mittel erhöht und somit die Verarbeitung und die Dosierung der Mittel erschwert. Wassergehalte von 2 Gew.-% oder weniger sind daher besonders bevorzugt.The water content of the agents should be as low as possible, since free water increases the viscosity of the agents and thus complicates the processing and metering of the agents. Water contents of 2% by weight or less are therefore particularly preferred.

Die Herstellung der Mittel erfolgt durch Mischen und Homogenisieren der festen, feinteiligen Bestandteile mit den flüssigen nichtionischen Tensiden (Komponenten A2), insbesondere mit dem flüssigen Tensidgemisch (Komponente A). Überraschenderweise wurde festgestellt, daß auch die festen Alkylbenzolsulfonate etwa zur Hälfte ihres Anteils sich wie flüssige Bestandteil verhalten und somit das Einarbeiten hoher Feststoffanteile begünstigen. Zweckmäßigerweise wird das Gemisch anschließend vermahlen, beispielsweise in einer Kolloidmühle bzw. auf einem Walzenstuhl, so daß die Korngröße der suspendierten Feststoffe zwischen 5 und 80 µm, vorzugsweise 10 bis 50 µm liegt. Der Anteil grober Teilchen (über 80 µm) soll bevorzugt unter 20, insbesondere unter 5 Gew.-% liegen.The agents are prepared by mixing and homogenizing the solid, finely divided constituents with the liquid nonionic surfactants (component A2), in particular with the liquid surfactant mixture (component A). Surprisingly, it was found that the solid alkylbenzenesulfonates behave about half of their content as a liquid component and thus favor the incorporation of high solids contents. The mixture is then expediently ground, for example in a colloid mill or on a roller mill, so that the grain size of the suspended solids is between 5 and 80 μm, preferably 10 to 50 μm. The proportion of coarse particles (over 80 μm) should preferably be less than 20, in particular less than 5,% by weight.

Die Mittel werden im allgemeinen in einer Konzentration von 4 bis 12 g/l, vorzugsweise 5 bis 10 g/l eingesetzt, wobei zweckmäßigerweise enthärtetes, d.h. auf einen Härtegrad von weniger als 2 °dH, insbesondere weniger als 1 °dH enthärtetes Wasser, zum Ansetzen der Waschlauge verwendet wird.The agents are generally used in a concentration of 4 to 12 g / l, preferably 5 to 10 g / l, suitably softened, i.e. water softened to a degree of hardness of less than 2 ° dH, in particular less than 1 ° dH, is used to prepare the wash liquor.

Die Mittel zeichnen sich durch ein hohes Wasch- und Bleichvermögen und eine geringe, nicht störende Schaumentwicklung bei der Anwendung aus. Überraschend hat sich gezeigt, daß die Mittel auch bei langdauernder Lagerung unter wechselnden Klimabedingungen außerordentlich stabil gegen Sauerstoffverlust und gegen Entmischung sind. Sie eignen sich aufgrund ihrer günstigen rheologischen Eigenschaften gut zum Einsatz in automatischen Dosieranlagen, da sie unter Einwirkung von Scherwirkungen niedrigviskos und gut förderbar, im Ruhezustand jedoch höherviskos und damit lagerbeständig sind.The agents are characterized by a high washing and bleaching capacity and a low, non-disturbing foam development during use. Surprisingly, it has been found that the agents are extremely stable against loss of oxygen and against segregation even under long-term storage under changing climatic conditions. They are suitable due to their favorable rheological properties Good for use in automatic dosing systems, since they are low-viscosity and easy to convey under the influence of shear effects, but are more viscous in the idle state and are therefore stable in storage.

BeispieleExamples

Die Zusammensetzung der Mittel ist Tabelle 1 zu entnehmen. Es bedeuten:

ABS
= Natriumsalz einer linearen C₁₀₋₁₃-Alkylbenzolsulfonsäure (mittlere Alkylkettenlänge C11,8)
Seife
= Natriumseife aus hydrierten Talgfettsäuren
CA-3EO
= Cocosalkohol C₁₂₋₁₄ mit 3EO
OA-3EO
= Oxoalkohol C₁₂₋₁₅ mit 3EO
OA-6EO
= Oxoalkohol C₁₂₋₁₅ mit 6EO
OA-7EO
= Oxoalkohol C₁₂₋₁₅ mit 7EO
CO-1/6
= Cetyl-Oleylalkohol mit 55 % Anteil Oleylalkohol + 1 PO + 6EO
The composition of the agents is shown in Table 1. It means:
SECTION
= Sodium salt of a linear C₁₀₋₁₃ alkylbenzenesulfonic acid (average alkyl chain length C 11.8 )
Soap
= Sodium soap from hydrogenated tallow fatty acids
CA-3EO
= Coconut alcohol C₁₂₋₁₄ with 3EO
OA-3EO
= Oxo alcohol C₁₂₋₁₅ with 3EO
OA-6EO
= Oxo alcohol C₁₂₋₁₅ with 6EO
OA-7EO
= Oxo alcohol C₁₂₋₁₅ with 7EO
CO-1/6
= Cetyl oleyl alcohol with 55% oleyl alcohol + 1 PO + 6EO

Das Metasilikat wies die Zusammensetzung Na₂O:SiO₂ = 1:1 auf. Das Perborat wurde in Form des Monohydrats eingesetzt. Das Copolymere setzte sich aus Acrylsäure und Maleinsäure (3:1) zusammen und wies ein Molekulargewicht von ca. 70 000 auf. Der Celluloseether bestand aus einem 2:1-Gemisch aus Na-Carboxymethylcellulose und Methylhydroxyethylcellulose (Hydroxyethyl-Gehalt 0,8 Gew.-%). Als optische Aufheller kam das Na-Salz der 4,4'-Bis-(2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino)-stilben-2,2'-disulfonsäure zum Einsatz. Das Wasser entstammte dem Feuchtigkeitsgehalt der verwendeten Rohstoffe. Polydiol war ein Polyethylenglykol mit dem Molekulargewicht 400. Die in der Tabelle angegebenen Gehalte bedeuten Gewichtsprozente.

Figure imgb0001
The metasilicate had the composition Na₂O: SiO₂ = 1: 1. The perborate was used in the form of the monohydrate. The copolymer was composed of acrylic acid and maleic acid (3: 1) and had a molecular weight of approximately 70,000. The cellulose ether consisted of a 2: 1 mixture of sodium carboxymethyl cellulose and methyl hydroxyethyl cellulose (hydroxyethyl content 0.8% by weight). The Na salt of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid was used as the optical brightener . The water came from the moisture content of the raw materials used. Polydiol was a polyethylene glycol with a molecular weight of 400. The contents given in the table mean percentages by weight.
Figure imgb0001

Die Stabilität des Aktivsauerstoffs und die Entmischungstendenz wurden unter verschiedenen Lacerbedingungen getestet und zwar:

  • a) bei 22 °C Raumtemperatur,
  • b) in der Klimakammer bei 30 °C und 80 % relativer Luftfeuchtickeit,
  • c) im Wechselklima abwechselnd bei + 40 °C und - 10 °C.

In allen Fällen betrug der Aktivsauerstoffgehalt der getesteten Proben nach 8 Wochen noch 100 % des Ausgangswertes. Ein Entmischen hatte nicht stattgefunden.The stability of the active oxygen and the tendency to segregate were tested under different lacer conditions, namely:
  • a) at 22 ° C room temperature,
  • b) in the climatic chamber at 30 ° C and 80% relative humidity,
  • c) in an alternating climate alternately at + 40 ° C and - 10 ° C.

In all cases, the active oxygen content of the tested samples was still 100% of the initial value after 8 weeks. There had been no segregation.

WaschversucheWashing attempts

Eine Waschmaschine (Typ Frista (R)) wurde mit leicht verschmutzter Füllwäsche (einmal benutzte Bett- und Tischwäsche) und Testlappen mit folgenden Anschmutzungen beladen:

S1
Staub-Wollfett auf Baumwolle,
S2
Blut auf Baumwolle,
S3
Milchkakao auf Baumwolle,
S4
Staub-Hautfett auf veredelter Baumwolle,
S5
Staub-Hautfett auf Mischgewebe aus veredelter Baumwolle und Polyester,
S6
Staub-Wollfett auf Mischgewebe (wie S5),
S7
Rotwein auf Baumwolle,
S8
Tee auf Baumwolle.

Die Wäschemenge betrug 7,5 kg, die Wasserhärte 0 °dH, Normalprogramm (ohne Vorwäsche), Waschmittelkonzentration 4 g/l, 5 Minuten bei 40 °C und 15 Minuten bei 90 °C, dreimaliges Nachspülen.A washing machine (type Frista (R) ) was loaded with lightly soiled filling laundry (bed and table linen once used) and test rags with the following soiling:
S1
Dust-wool grease on cotton,
S2
Blood on cotton,
S3
Milk cocoa on cotton,
S4
Dust skin fat on refined cotton,
S5
Dust-skin fat on mixed fabrics made from refined cotton and polyester,
S6
Dust-wool grease on mixed fabrics (like S5),
S7
Red wine on cotton,
S8
Tea on cotton.

The amount of laundry was 7.5 kg, the water hardness 0 ° dH, normal program (without prewash), detergent concentration 4 g / l, 5 minutes at 40 ° C and 15 minutes at 90 ° C, rinsing three times.

Die prozentuale Remission (gegen Weißtandard) wurde photometrisch ausgewertet. Die Zahlenwerte sind Mittelwerte aus 3 Parallelbestimmungen (Streuung 2 %). Die Ergebnisse sind in der folgenden Tabelle 2 zusammengestellt. Zum Vergleich V wurde ein ähnlich zusammengesetztes, pastenförmiges Waschmittel des Handels getestet, das keine anionischen Tenside enthielt.

Figure imgb0002
The percentage remission (against white standard) was evaluated photometrically. The numerical values are mean values from 3 parallel determinations (spread 2%). The results are as follows Table 2 compiled. For comparison V, a similarly composed paste-like detergent from the trade was tested which did not contain any anionic surfactants.
Figure imgb0002

Die Schaumentwicklung war in allen Fällen gering, d.h. das Schaumniveau lag im Hauptwaschgang maximal 8 bis 10 cm über dem Flüssigkeitsniveau und im 1. Nachspülgang 4 bis 6 cm über dem Flüssigkeitsniveau. Im 3. Nachspülgang war keine Schaumentwicklung mehr sichtbar.The foam development was low in all cases, i.e. the foam level was a maximum of 8 to 10 cm above the liquid level in the main wash cycle and 4 to 6 cm above the liquid level in the first rinse cycle. No foam development was visible in the third rinse cycle.

Claims (11)

  1. A liquid to paste-form phosphate-free detergent containing - based on the detergent -
    (A) 20 to 35% by weight of a surfactant component having the following composition:
    (A1) 1 to 4% by weight anionic surfactants from the class of sulfonates and soaps present as alkali metal salts,
    (A2) 16 to 34% by weight nonionic surfactant with a pour point of at most 10°C in the form of alkoxylated linear alcohols or 2-methyl-branched alcohols containing 10 to 18 carbon atoms or mixtures thereof,
    (B) 10 to 35% by weight builder salts which have a complexing effect of which bind alkaline earth metal ions,
    (C) 15 to 40% by weight sodium metasilicate,
    (D) 8 to 25% by weight bleaching per salts of perhydrate salts,
    (E) up to 15% by weight other detergent ingredients,
    (F) less than 3% by weight water,
    with the proviso that the sum of components (B + C) = 30 to 60% by weight.
  2. A detergent as claimed in claim 1, characterized in that it contains 1.5 to 3% by weight of component (A1).
  3. A detergent as claimed in claim 1 or 2, characterized in that component (A1) consists of 1 to 2.8% by weight C₁₀₋₁₃ alkyl benzenesulfonate and 0.2 to 1.5% by weight soaps of saturated or monounsaturated C₁₂₋₂₂ fatty acids.
  4. A detergent as claimed in one or more of claims 1 to 3, characterized in that component (A2) consists of alkoxylated, saturated of monounsaturated, linear of 2-methyl-branched C₁₀₋₁₈ alcohols containing 2 to 10 ethylene glycol ether groups or mixtures thereof and makes up 18 to 30% by weight of the detergent.
  5. A detergent as claimed in claim 4, characterized in that the pour point of component (A2) is below 8°C.
  6. A detergent as as claimed in one or more of claims 1 to 5, charaterized in that component (B) contains finely crystalline zeolites of the NaA type, of which the percentage content is not more than 25% by weight.
  7. A detergent as claimed in one or more of claims 1 to 6, characterized in that component (B) is the sodium salt of nitrilotriacetic acid (NTA) and/or the sodium salt of 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and/or the sodium salt of the copolymer of acrylic acid and maleic acid, of which the total percentage content is 10 to 20% by weight.
  8. A detergent as claimed in one or more of claims 1 to 7, characterized in that component (C) has the composition Na₂O:SiO₂ = 1:0.9 to 1:1.1, their percentage content being 20 to 35% by weight.
  9. A detergent as claimed in one or more of claims 1 to 8, characterized in that component (D) consists of sodium perborate monohydrate of which the percentage content is 10 to 20% by weight.
  10. A detergent as claimed in one or more of claims 1 to 9, characterized in that it has a water content of less than 2% by weight.
  11. A process for the production of the liquid to paste-form phosphate-free detergent claimed in claim 1, characterized in that the solids (B) to (E) are dispersed in the liquid component (A) and ground to a particle size of 5 to 80 µm and preferably 10 to 50 µm.
EP90900135A 1988-12-14 1989-12-05 Washing agent containing bleach, in liquid to paste form Expired - Lifetime EP0448581B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90900135T ATE93890T1 (en) 1988-12-14 1989-12-05 LIQUID TO PASTONES DETERGENT CONTAINING BLEACH.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3842007A DE3842007A1 (en) 1988-12-14 1988-12-14 FLUID TO PASTOESES, BLEACHING DETERGENT
DE3842007 1988-12-14

Publications (2)

Publication Number Publication Date
EP0448581A1 EP0448581A1 (en) 1991-10-02
EP0448581B1 true EP0448581B1 (en) 1993-09-01

Family

ID=6369101

Family Applications (2)

Application Number Title Priority Date Filing Date
EP90900135A Expired - Lifetime EP0448581B1 (en) 1988-12-14 1989-12-05 Washing agent containing bleach, in liquid to paste form
EP89122421A Withdrawn EP0373483A1 (en) 1988-12-14 1989-12-05 Liquid-to-pasty washing compositon containing a bleaching agent

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP89122421A Withdrawn EP0373483A1 (en) 1988-12-14 1989-12-05 Liquid-to-pasty washing compositon containing a bleaching agent

Country Status (13)

Country Link
US (1) US5456850A (en)
EP (2) EP0448581B1 (en)
JP (1) JPH04502338A (en)
KR (1) KR970002041B1 (en)
BR (1) BR8907821A (en)
DE (2) DE3842007A1 (en)
DK (1) DK112491A (en)
ES (1) ES2043353T3 (en)
FI (1) FI99142C (en)
IE (1) IE71938B1 (en)
PT (1) PT92544B (en)
TR (1) TR24156A (en)
WO (1) WO1990006986A1 (en)

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FR2677371B1 (en) * 1991-06-05 1993-10-15 Nln Sa CONCENTRATED LIQUID DETERGENT COMPOSITION CONTAINING A POLYPHOSPHONATE - SEQUENCING AGENT.
GB9124489D0 (en) * 1991-11-18 1992-01-08 Unilever Plc Liquid cleaning products
DE4216453A1 (en) * 1992-05-19 1993-11-25 Henkel Kgaa Process for the preparation of pasty detergents
WO1993024603A2 (en) * 1992-06-02 1993-12-09 Unilever N.V. Liquid cleaning products
DK0598170T3 (en) * 1992-11-16 1998-03-02 Procter & Gamble Cleansing and bleaching compositions
US6916596B2 (en) 1993-06-25 2005-07-12 Michael Wen-Chein Yang Laser imaged printing plates
US6194367B1 (en) 1995-03-01 2001-02-27 Charvid Limited Liability Co. Non-caustic cleaning composition comprising peroxygen compound and specific silicate and method of making the same in free-flowing, particulate form
US5898024A (en) * 1995-03-01 1999-04-27 Charvid Limited Liability Non-caustic cleaning composition comprising peroxygen compound and specific silicate, and method of making the same in free-flowing, particulate form
US6034048A (en) * 1995-03-01 2000-03-07 Charvid Limited Liability Co. Non-caustic cleaning composition using an alkali salt
US5663132A (en) * 1995-03-01 1997-09-02 Charvid Limited Liability Company Non-caustic composition comprising peroxygen compound and metasilicate and cleaning methods for using same
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US5869474A (en) * 1997-05-16 1999-02-09 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Low dosage treatment for cocaine craving and withdrawal
US5906215A (en) * 1997-11-20 1999-05-25 Reel Clean Corporation Fishing reel cleaning solution
DE19857687A1 (en) * 1998-12-15 2000-06-21 Henkel Ecolab Gmbh & Co Ohg Pasty detergent
US6225268B1 (en) * 1999-08-23 2001-05-01 Sinon Corporation Liquid detergent composition
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US20060178289A1 (en) * 2004-07-20 2006-08-10 Enrique Hernandez Multifunctional material compositions and methods
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US20100056404A1 (en) * 2008-08-29 2010-03-04 Micro Pure Solutions, Llc Method for treating hydrogen sulfide-containing fluids
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US11179377B2 (en) 2017-03-10 2021-11-23 Embera Neurotherapeutics, Inc. Pharmaceutical compositions and uses thereof

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Also Published As

Publication number Publication date
EP0448581A1 (en) 1991-10-02
IE71938B1 (en) 1997-03-12
FI99142C (en) 1997-10-10
ES2043353T3 (en) 1993-12-16
PT92544B (en) 1996-08-30
IE893981L (en) 1990-06-14
PT92544A (en) 1990-06-29
KR970002041B1 (en) 1997-02-21
TR24156A (en) 1991-04-26
DK112491A (en) 1991-08-05
FI99142B (en) 1997-06-30
BR8907821A (en) 1991-10-22
JPH04502338A (en) 1992-04-23
KR910700326A (en) 1991-03-14
EP0373483A1 (en) 1990-06-20
DK112491D0 (en) 1991-06-12
FI912464A0 (en) 1991-05-21
WO1990006986A1 (en) 1990-06-28
DE3842007A1 (en) 1990-06-21
US5456850A (en) 1995-10-10
DE58905488D1 (en) 1993-10-07

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