EP0110106B1 - Stable, aqueous detergents and process for their preparation - Google Patents

Abstract

Stable, aqueous cleaning agents containing (a) anionic and/or nonionic surfactants, optionally chlorine-stable, (b) an abrasive component and/or (c) an active-chlorine-releasing compound and, optionally, (d) dyes and (e) fragrances, characterized in (f) a further content of amorphous calcium aluminum silicates precipitated in situ; and the process of their preparation wherein the various ingredients are mixed and the amorphous calcium aluminum silicates are formed by precipitation therein.

Description

The present invention relates to aqueous, storage- and action-stable liquid or pasty cleaning agents containing in particular chlorine-stable surfactants, an abrasive component and / or active chlorine-releasing compound, colorants and fragrances and calcium aluminum silicate precipitated in situ.

Large amounts of abrasives are used to clean heavily soiled, mechanically resistant surfaces in the home and business. Powdered abrasives with and without bleaching effects are offered on the market, about half each. Non-bleaching scouring powders are currently being increasingly replaced by liquid scouring agents. So far, however, there is no real, liquid and bleaching abrasive on the market. The reason should be seen in the difficulty of assembling such products in a storage-stable form, both with regard to the suspension and the bleaching agent stability.

Bleaching detergents or abrasives should have this effect in the shortest possible time, namely during their use and at room temperature. Compounds which release active chlorine are known as technically available bleaching agents for such liquid compositions which meet these conditions and whose loss of action can be tolerated in aqueous solution. For the production of a liquid cleaning agent or scouring agent, in particular based on these compounds, the task now was to find a medium which is particularly resistant to aqueous solutions containing active chlorine and which, on the one hand, is capable of suspending abrasive particles, if necessary, on storage, and on the other hand should have surface-active properties, so that the liquid cleaning or scouring agent, in addition to the pure scouring and / or bleaching performance, also has the cleaning effect expected by the consumer against greasy soiling.

In US-A-4248728 pasty abrasives containing crystalline Na-Al-silicate and optionally active chlorine-containing compounds and / or mineral abrasives are already described. The abrasive-containing examples produced according to the teaching of this US patent with the addition of swellable Mg-Al-silicate result in paste-like abrasives, but despite contrary but unspecific statements, the abrasives settle irreversibly to a solid sediment after storage. This means that the product is no longer operational.

EP-A-0003625 also teaches that swellable clays are used to stabilize the suspension of hypochlorite-containing liquid abrasives. However, they have the disadvantage that they have such a strong thickening effect that they can only be used in small quantities and only for the stabilization of the suspension of specifically light abrasives, namely from there preferred and exclusively used expanded perlites, but not for the stabilization of those also mentioned there and usually in real ones Abrasives that are used, specifically heavy abrasives such as quartz or marble powder, are suitable in amounts required for sufficient abrasion performance. These sediment even through thixotropic pastes and form an irreversible sediment. Another disadvantage is the fact that these swellable clays usually contain small amounts of impurities due to their natural origin, which accelerate the decomposition of active chlorine-containing compounds in aqueous solution via catalytic reactions and thus worsen their long-term effectiveness in the liquid cleaning or abrasive agents.

Also known from EP-A-0009942 are pourable liquid active chlorine-containing abrasives which contain a combination of anionic and nonionic or ampholytic surfactants and an electrolyte. However, the chlorine stability of these abrasive suspensions is not sufficient for sales products.

It has now been found that aqueous, storage- and action-stable liquid or pasty, cleaning or abrasives containing anionic and / or nonionic, in particular chlorine-stable surfactants and an abrasive component and / or an active chlorine-releasing compound are obtained if they are amorphous Calcium aluminum silicates are added, which are precipitated in situ, if appropriate in the presence of the abrasives which are preferably present.

The suspension-stabilizing effect of Ca-AI silicate precipitated in situ has hitherto not been known and could not have been foreseen by the person skilled in the art. The Ca-AI silicate is obtained in X-ray amorphous form, has no swellability in water and, of course, no complexing effect against hardness-forming ions in the tap water. Because of these properties, there is no analogy to other silicates known as components of cleaning agents.

In addition to the chemical differences between the silicates known and proven from literature and practice and the claimed Ca-Al silicate, it is an essential feature of the present invention that the Ca-Al silicate is produced in situ, preferably in the presence of abrasives. If it is manufactured separately and subsequently added to the liquid cleaning agent or abrasive, the suspension stabilization is significantly lower. Scanning electron micrographs show that, for example, CaC0 ₃ particles used as abrasives in abrasives according to the invention are coated with a uniform layer of smaller solid particles in the case of Ca-Al silicate precipitated in situ. In contrast, the CaC0 ₃ particles are otherwise the same composition with a subsequently added equal amount of precipitated Ca-Al silicate, or Zu given a corresponding amount of commercially available hectorite clay (Na-Mg silicate), unchanged as a mixture with the finer solid particles.

In a particular embodiment, the agents according to the invention can also contain colorants and fragrances, which may have to be chlorine-stable.

• a) 1-10, vorzugsweise 2-6 Gew.-%, gegebenenfalls chlorstabilen anionischen und/oder nichtionischen Tensiden,
• b) 0-10, vorzugsweise 0,1-2 Gew.-% Aktivchlor,
• c) 0-60, vorzugsweise 10-50 Gew.-% einer Abrasivkomponente mit einer Korngrösse von 1-200 µm,
• d) 5-20, vorzugsweise 5-15 Gew.-%, gegebenenfalls in Gegenwart der Abrasivkomponente, in situ gefälltem Calcium-Aluminium-Silikat,
• e) Rest auf 100 Gew.-% vollentsalztes Wasser sowie gegebenenfalls Farb- und Duftstoffen, wobei wenigstens einer der Bestandteile b) oder c) vorhanden sein muss.

The present invention thus relates to aqueous storage or active ingredient-stable liquid or pasty cleaning or abrasive products containing

• a) 1-10, preferably 2-6% by weight, optionally chlorine-stable anionic and / or nonionic surfactants,
• b) 0-10, preferably 0.1-2% by weight of active chlorine,
• c) 0-60, preferably 10-50% by weight of an abrasive component with a grain size of 1-200 µm,
• d) 5-20, preferably 5-15% by weight, optionally in the presence of the abrasive component, calcium aluminum silicate precipitated in situ,
• e) the remainder to 100% by weight of demineralized water and, if appropriate, colorants and fragrances, at least one of the constituents b) or c) being present.

Furthermore, the invention relates to a process for the preparation of aqueous storage-stable and action-stable liquid or pasty cleaning or abrasive agents with a content of optionally chlorine-stable anionic and / or nonionic surfactants, an abrasive component and / or an active chlorine-releasing compound, and optionally colorants and fragrances, which is characterized in that the abrasive component is optionally stirred into an aqueous solution of the surfactants and optionally the dyes at room temperature and, with further stirring, a calcium chloride solution, then an aluminum hydroxide solution, then a water glass solution and optionally the chlorine solution and the fragrance are added.

If a certain pH value of the end product is to be set, which, however, should not be below 11.5 in the case of chlorine-containing cleaning agents for the known reasons of chlorine stability, this can be between the addition of the aluminate solution and the water glass solution with a chlorine-stable acid such as e.g. Hydrochloric acid, phosphoric acid or phosphonobutane tricarboxylic acid can be set.

Although the actual use of the present invention lies in the suspension stabilization of abrasives with grain sizes up to 200 μm in liquid abrasives, a cleaning agent without abrasives can also be produced with the Ca-AI silicate according to the invention. A thickened, thixotropic, preferably chlorine-containing cleaning agent is then obtained with only an extremely weak abrasive effect. Compared to conventional abrasive-free chlorine-containing liquid cleaners, such a product has the advantage of adhering better to vertical surfaces, which has a positive effect on the quality of the bleaching effect. Such agents are known for example from DE-A-2810187.

• Als Tenside kommen alle für den Einsatz in Reinigungsmitteln bekannten üblichen anionischen und/oder nichtionischen Verbindungen in Betracht.
  • a) Als chlorstabile Tenside kommen z. B. C_$-C₂₂-, vorzugsweise C₁₀-C₁₈-Alkansulfonate, Cg-C_i5-, vorzugsweise C₁₀-C₁₃-Alkylbenzolsulfonate, C_f-C₁₈-, vorzugsweise C₁₂-C₁₆-Alkylsulfate, Betaine^- und C₁₀-C₁₈-Alkyldimethyl-aminoxide in Frage. Bevorzugt wird eine Mischung aus einem der genannten anionischen Tenside, insbesondere aus einem Alkansulfonat und einem Aminoxid, da derartige Mischungen in Gegenwart von Chlorbleichlauge bereits leicht viskose Lösungen bilden. Diese geringe Viskosität wirkt sich auf die Suspensionsstabilität der fertigen flüssigen chlorhaltigen Scheuermittel zusätzlich positiv aus, reicht jedoch keinesfalls allein aus, um die Abrasivstoffe ohne das erfindungsgemässe weitere Stabilisierungssystem in homogener Verteilung zu halten. Die gleiche vorteilhafte geringe Eigenviskosität einzelner Tensidkomponenten kann erreicht werden, wenn man ihnen geringe Mengen an bekannten Verdickungsmitteln vom Typ der Acrylat- bzw. Methacrylat-Copolymeren zusetzt.
  • b) Bekannte, in wässriger Lösung Hypochlorit bildende Aktivchlorverbindungen sind Na-, Li und Ca-Hypochlorit sowie organische Chlorträger wie Chloramin T und chlorierte Isocyanurate. Bevorzugt werden handelsübliche Chlorbleichlaugen mit einem Aktivchlor-Gehalt von 12-16 Gew.-%.
  • c) Als Abrasivstoffe können je nach gewünschter Scheuerwirkung solche mit relativ weichem Korn wie Marmormehl, Kieselgure und ähnliche oder solche mit hartem Korn wie Perlit-, Quarz-oder Cristobalitmehle eingesetzt werden. Eine Bevorzugung eines bestimmten Minerals ist nicht gegeben, jedoch muss es alkali- und gegebenenfalls chlorstabil sein, und es muss sichergestellt sein, dass die auf natürliche Fundstellen zurückgehenden Mineralmehle gegebenenfalls nur so geringe Mengen an Verunreinigungen enthalten, dass diese keine katalytische Zersetzung von Chlorbleichlauge fördern. Die Korngrösse richtet sich nach der gewünschten Scheuerleistung. Das Kornspektrum kann zwischen 1 bis 200 11m liegen. Für flüssige Scheuermittel, die für allgemeine Reinigungsaufgaben im Haushalt bestimmt sind, eignet sich besonders ein Kornspektrum von 1 bis 100 µm.
  • d) Das in situ zu fällende Ca-AI-Silikat kann aus preiswerten Rohstoffen erzeugt werden, die allerdings ebenfalls weitgehend frei von Schwermetallen und organischen Verunreinigungen sein müssen. Vorteilhaft geht man von den Rohstoffen Calciumchlorid, Aluminiumhydroxid und Wasserglas aus. Die Ausgangsstoffe werden in solchen Mengenverhältnissen untereinander eingesetzt, dass die Molverhältnisse von CaO:Al₂0₃:Si0₂ im Ansatz 1:1:2 betragen.
  • e) Die Auswahl von Farb- und Duftstoffen muss sich gegebenenfalls nach deren Beständigkeit in hypochlorithaltiger Lösung richten. Geeignete Farbstoffe sind dann zum Beispiel Cu-Phthalocyanine oder Ultramarinblau. Geeignete Duftstoffe werden beispielsweise in der US-A-3876551 beschrieben.

The individual components of the abrasives claimed can be characterized as follows:

• Suitable surfactants are all customary anionic and / or nonionic compounds known for use in cleaning agents.
  • a) As chlorine-stable surfactants such. B. C _$ -C ₂₂ -, preferably C ₁₀ -C ₁₈ alkanesulfonates, Cg-C _i5 -, preferably C ₁₀ -C ₁₃ alkylbenzenesulfonates, C _f -C ₁₈ -, preferably C ₁₂ -C ₁₆ alkyl sulfates, betaines ^- And C ₁₀ -C ₁₈ alkyl dimethyl amine oxides in question. A mixture of one of the anionic surfactants mentioned, in particular of an alkane sulfonate and an amine oxide, is preferred, since such mixtures already form slightly viscous solutions in the presence of chlorine bleach. This low viscosity additionally has a positive effect on the suspension stability of the finished liquid chlorine-containing abrasives, but is by no means sufficient to keep the abrasives in a homogeneous distribution without the further stabilization system according to the invention. The same advantageous low inherent viscosity of individual surfactant components can be achieved if small amounts of known thickeners of the acrylate or methacrylate copolymer type are added to them.
  • b) Known active chlorine compounds which form hypochlorite in aqueous solution are Na, Li and Ca hypochlorite and also organic chlorine carriers such as chloramine T and chlorinated isocyanurates. Commercial chlorine bleaches with an active chlorine content of 12-16% by weight are preferred.
  • c) Depending on the desired abrasive effect, those with relatively soft grain such as marble powder, diatomaceous earth and the like or those with hard grain such as pearlite, quartz or cristobalite powder can be used as abrasives. There is no preference for a particular mineral, but it must be stable to alkali and possibly chlorine, and it must be ensured that mineral flours attributed to natural sources may contain only small amounts of impurities that do not promote the catalytic decomposition of chlorine bleach. The grain size depends on the desired abrasion performance. The grain spectrum can be between 1 to 200 11m. For liquid abrasives that are intended for general household cleaning tasks, a grain size range of 1 to 100 µm is particularly suitable.
  • d) The Ca-AI silicate to be precipitated in situ can be produced from inexpensive raw materials, which, however, must also be largely free of heavy metals and organic impurities. The raw materials calcium chloride, aluminum hydroxide and water glass are advantageous. The starting materials are used in such proportions that the molar ratios of CaO: Al ₂ 0 ₃ : Si0 ₂ in the batch are 1: 1: 2.
  • e) The selection of colors and fragrances may have to be based on their resistance in hypochlorite-containing solution. Suitable dyes are then, for example, Cu phthalocyanines or ultramarine blue. Suitable fragrances are described for example in US-A-3876551.

The cleaning agents according to the invention are opaque, white suspensions which, even after prolonged storage, either do not separate at all or only so weakly that they can be homogenized again by gently shaking them before use.

The claimed agents are applied by pushing them out of soft plastic bottles or tubes.

example 1

• 6% Dimethyl-Kokosalkyl-aminoxid, 30% Aktivsubstanz, 4% sek.-Alkansulfonat, -Na-Salz, C₁₁-C₁₅, 60% Aktivsubstanz, 5% Chlorbleichlauge, 12-16% Aktivchlor, 25% Calciumcarbonat, Korngrösse 1-100 µm, 8,3% in situ gefälltes Calcium-Aluminium-Silikat, 0,01 % Cu-Phthalocyanin-Farbstoff, 0,2% Parfümöl, Rest Wasser, vollentsalzt.

Composition in% by weight:

• 6% dimethyl-cocoalkylamine oxide, 30% active substance, 4% sec-alkanesulfonate, -Na salt, C ₁₁ -C ₁₅ , 60% active substance, 5% chlorine bleach, 12-16% active chlorine, 25% calcium carbonate, grain size 1 -100 µm, 8.3% calcium aluminum silicate precipitated in situ, 0.01% Cu phthalocyanine dye, 0.2% perfume oil, remainder water, fully desalinated.

• Zuerst wurden folgende drei Lösungen bereitgestellt:
  • I. Aluminatlösung, hergestellt aus 19,7 Gew.-% Hydrargillit, technische Qualität, 88% AI (OH)₃, 53,6 Gew.-% NaOH-Lösung, 50%ig und 26,7 Gew.-% Wasser, vollentsalzt
  • II. CaC1₂-Lösung, hergestellt aus 24 Gew.-% CaCl₃-6 H₂O und 76 Gew.-% Wasser, vollentsalzt und
  • 111. Natronwasserglas, 34,5%ig, Molverhältnis SiO₂:Na₂O = 3,85.

Following the production process of the agents according to the invention, which was also claimed, the procedure was as follows:

• First three solutions were provided:
  • I. aluminate solution, prepared from 19.7% by weight of hydrargillite, technical quality, 88% Al (OH) ₃ , 53.6% by weight of NaOH solution, 50% and 26.7% by weight of water, fully desalinated
  • II. CaC1 ₂ solution, made from 24 wt .-% CaCl ₃ -6 H ₂ O and 76 wt .-% water, fully desalinated and
  • 111. Soda water glass, 34.5%, SiO ₂ : Na ₂ O molar ratio = 3.85.

Then the surfactants, the abrasive and the dye were stirred into water at room temperature. 10% by weight of solution II, 10% by weight of solution I, 5% by weight of solution III as well as the chlorine solution and the perfume oil were added successively to this homogeneous suspension.

The liquid abrasive obtained was thixotropic, had a relatively mild abrasive action and a very good bleaching action. After ¼ year storage at room temperature, the suspension was unchanged and the chlorine loss was only about 22%.

Without the addition of Ca-AI silicate precipitated in situ and without the addition of other stabilizers, the abrasive settled out after a short storage period, could be shaken up, but soon settled again. The end product was therefore completely uninteresting for commercial use.

The same applied if commercial hectorite (Na-Mg silicate) was added instead of this Ca-Al silicate.

It was also particularly surprising that a separately freshly precipitated Ca-AI silicate, when subsequently combined with the suspension of the other abrasive components, also led to a short-term phase separation.

Example 2 Composition:

2% Na-alkylbenzenesulfonate, C ₁₀ -C ₁₃ , 6% amine oxide, 30% as in example 1, 0.5% chloramine T, 10% expanded perlite, average particle diameter 7 µm, 5.6% in situ precipitated Ca Al silicate, remainder water, fully desalinated.

The preparation was carried out analogously to Example 1. It was a thixotropic abrasive paste with a weak abrasive effect. After 3 months of storage, the suspension remained homogeneous. The active chlorine content was practically retained.

Example 3 Composition:

4% alkanesulfonate Na salt, 60%, as in Example 1, 6% dimethyl-cocoalkylamine oxide, 30%, 5% chlorine bleach, 12-16% active chlorine, 25% cristobalite flour, particle size 1-100 µm, 8.3% Ca-AI silicate precipitated in situ, 0.1% fragrance, remainder water, fully desalinated.

The preparation was carried out analogously to Example 1.

It was a liquid abrasive with a strong abrasive effect. It was easy to store in terms of both suspension and chlorine stability. The active chlorine loss after 3 months was approx. 24%.

Example 4

2% alkanesulfonate Na salt, 60%, as in Example 1, 3% amine oxide, 30%, as in Example 1, 5% chlorine bleach, 12-16% active chlorine, 25% marble powder, grain size 1-100 µm, 13% Ca-AI silicate precipitated in situ, 0.1% fragrance, remainder water, fully desalinated.

The preparation was also carried out analogously to Example 1.

The liquid abrasive had properties similar to those of Example 1; the active chlorine loss after 3 months' storage at room temperature was only about 20%.

Example 5 composition

4.0% alkanesulfonate Na salt, 60%, as in Example 1, 6.0% amine oxide, as in Example 1, 5.0% chlorine bleach, 12-16% active chlorine, 45.0% marble powder, average particle diameter 15 μm , 5.6% Ca-AI silicate precipitated in situ, 0.2% fragrance, remainder water, fully desalinated.

The preparation was carried out analogously to Example 1.

It was a scouring paste with a medium abrasive effect and good storage stability, also with regard to the active chlorine content. After 3 months at room temperature, the chlorine loss was about 27%.

Example 6 composition

4.0% alkanesulfonate Na salt, 60%, as in Example 1, 6.0% amine oxide, as in Example 1, 5.0% Chlorine bleach, 12-16% active chlorine, 13.0% Ca-AI silicate precipitated in situ, 0.2% fragrance, remainder water, fully desalinated.

This abrasive-free, active chlorine-containing thickened cleaning agent was also produced analogously to Example 1. This paste, which also adhered well to vertical surfaces, was still homogeneous even after 6 months of storage at room temperature and the chlorine loss was less than 50%.

Example 7 composition

2.5% alkanesulfonate Na salt, 60%, as in Example 1, 2.0% amine oxide, as in Example 1, 40.0% marble powder, grain size 1-100 μm, 5.0% Ca-AI precipitated in situ -Silicate, 0.2% fragrance, 0.2% formaldehyde, 30%, the rest water, fully desalinated. This abrasive-containing, active chlorine-free scouring agent was produced in accordance with the tasks in Example 1, but because of the lack of the active chlorine compound in the precipitation of the calcium aluminum silicate, before adding water glass, it was brought to a pH of approximately by slowly adding dilute hydrochloric acid 10 set. The suspension was still stable after 3 months.

Example 8

8% sec-alkanesulfonate, C ₁₁ -C ₁₅ , Na salt, 60% active substance, 2% methacrylic ethyl acrylate copolymer, 20% aqueous dispersion, 5% chlorine bleach, 12-16% active chlorine, 45% marble powder, medium Particle diameter 15 µm, 5% Ca-AI silicate precipitated in situ, 0.1% fragrance, remainder water, fully desalinated.

The preparation was carried out analogously to Example 1, the copolymer was added after the marble powder. Before adding the water glass, a pH of 12.5 was set with dilute hydrochloric acid, which did not change after the liquid abrasive was finished.

The pourable, bleaching abrasive showed similarly good storage results to both the suspension stability and the chlorine stability as the aforementioned examples.

Claims (3)

1. A stable aqueous cleaning preparation containing optionally chlorine-stable anionic and/or non-ionic surfactants, an abrasive component and/or an active chlorine compound and, optionally, dyes and perfumes, characterized in that they- contain amorphous calcium-aluminium silicates precipitated in situ.

2. A cleaning preparation as claimed in claim 1, consisting of

a) from 1 to 10% by weight and preferably from 2 to 6% by weight optionally chlorine-stable anionic and/or non-ionic surfactants,

b) from 0 to 10% by weight and preferably from 0.1 to 2 % by weight active chlorine,

c) from 0 to 60% by weight and preferably from 10 to 50% by weight of an abrasive component having a particle size of from 1 to 200 ₁1m,

d) from 5 to 20% by weight and preferably from 5 to 15% by weight calcium-aluminium silicate precipitated in situ, optionally in the presence of the abrasive component,

e) balance to 100% by weight fully deionized water and optionally dyes and perfumes, at least one of constituents b) or c) having to be present.

3. A process for the preparation of stable aqueous cleaning preparations containing optionally chlorine-stable anionic and/or non-ionic surfactants, an abrasive component and/or an active chlorine compound and, optionally, dyes and perfumes, characterized in that optionally the abrasive component is stirred at room temperature into an aqueous solution of the surfactants and, optionally, the dyes, after which a calcium chloride solution, then an aluminium hydroxide solution, then a waterglass solution and optionally the chlorine liquor and the perfume are added with continued stirring.