WO2001027236A1

WO2001027236A1 - Thixotropic aqueous detergent

Info

Publication number: WO2001027236A1
Application number: PCT/EP2000/009543
Authority: WO
Inventors: Christian N. Kirsten; Oliver Schoss; Hermann Jonke
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1999-10-08
Filing date: 2000-09-29
Publication date: 2001-04-19
Also published as: DE19948859A1; AU7909900A; CA2323022A1

Abstract

The invention relates to a thixotropic aqueous detergent, containing one or more nanoparticulate inorganic compounds from the group of metal oxides, metal oxide hydrates, metal hydroxides, metal carbonates and metal phosphates, in addition to silicates. Said detergent can be used as a hand washing-up detergent, dishwasher detergent, bath or toilet cleaner, all-purpose cleaner, detergent, or as an aerosol cleaner.

Description

"Thixotropic aqueous cleaning agent"

The invention relates to a thixotropic aqueous cleaning agent which can be used for cleaning hard surfaces

Products for cleaning in the household sector, such as hand dishwashing detergents, machine dishwashing detergents, bathroom and toilet cleaners, all-purpose cleaners and detergents, are offered in different states, which are associated with special consumer-related benefits. For example, tablets facilitate the dosage and handling of a product can be applied specifically to soiling because they adhere to the surface to be cleaned for a longer period of time.However, low-viscosity products are used for large-area cleaning and are characterized by simple handling.For example, they are much easier to mix with water than viscous products or gels for thinning purposes

From a consumer point of view, it is worthwhile to use products in various areas of household cleaning that enable targeted concentrated as well as extensive, possibly diluted, cleaning and combine the advantages of a gel with those of a liquid

Commercial cleaning agents for toilet bowls, so-called toilet cleaners, for example, have a relatively high viscosity (zero shear viscosity) in the idle state, which ensures good adhesion on inclined, in particular vertical, surfaces.On the other hand, they have a relatively low viscosity under shear stress, so that they Can apply consumers with little effort from the bottle These theological properties are achieved by special polymeric thickeners such as xanthan gum

When using conventional polymeric thickeners, the achievable structural viscosity (dependence of the viscosity on the shear rate) or thixotropy (time-dependence of the viscosity) is limited, however, if a sufficiently high zero shear Viscosity or even a yield point (minimum shear stress that must be applied for a substance to flow) is no longer possible to liquefy, for example by shaking, with a force that is reasonable for the consumer, while the products that can be sufficiently liquefied by the shaker are acceptable and have a low zero shear viscosity exhibit.

The object of the present invention was to provide a cleaning agent which is in the rest state as a gel with a flow limit, can be liquefied reversibly by consumer-compatible effort, for example by shaking, and forms a gel again after a short time, for example a few minutes.

The invention relates to a thixotropic aqueous cleaning agent which contains one or more nanoparticulate inorganic compounds from the group of metal oxides, oxide hydrates, hydroxides, carbonates and phosphates, and sweetes.

A particular advantage of the agents according to the invention is their transparency, which - insofar as no pearlescent agents or the like. are contained - is not adversely affected by the nanoparticulate inorganic compounds.

Nanoparticulate Compounds

The content of one or more nanoparticulate inorganic compounds from the group of metal oxides, oxide hydrates, hydroxides, carbonates and phosphates and sweetes is usually from 0.1 to 20% by weight, preferably 0.5 to 10% by weight. %, in particular 1 to 8% by weight, particularly preferably 2 to 6% by weight, extremely preferably 3 to 5% by weight, for example 4% by weight.

The average particle size of the nanoparticulate compounds is usually 1 to 200 nm, preferably 5 to 100 nm, in particular 10 to 50 nm, the value relating to the particle diameter in the longitudinal direction, i.e. in the direction of the greatest expansion of the particles.

Suitable nanoparticulate oxides are, for example, magnesium oxide, aluminum oxide (Al ₂ 0 ₃ ), titanium dioxide, zirconium dioxide and zinc oxide and also silicon dioxide. A suitable nanoparticulate oxide hydrate is, for example, aluminum oxide hydrate (boehmite) and suitable nanoparticulate hydroxides are, for example, calcium hydroxide and aluminum hydroxide. Suitable nanoparticulate silicates are, for example, magnesium silicate and aluminum silicates such as zeolites. Nanoparticulate oxides, oxide hydrates or hydroxides can be produced by known processes, for example by EP-A-0 711 217 (Nanophase Technologies Corp.). Oxide hydrates and hydroxides can also be obtained in very fine distribution by hydrolysis of organometallic compounds.

Nanophase Technologies Corp. sells under the trade name NanoTelf. the nanoparticulate oxides NanoTelf Aluminum Oxide (average particle size 37 nm), NanoTelf Antimony Tin Oxide, NanoTelf Barium Titanate, NanoTelf Barium Strontium Titanate, NanoTelf Cerium Oxide (average particle size 11 nm), NanoTelf Copper Oxide, NanoTelf Indium Oxide, NanoTelf Indium Tin Oxide average particle size 14 nm), NanoTelf Iron Oxide (average particle size 26 nm), NanoTelf Iron Oxide, Black, NanoTelf Silicon Dioxide, NanoTelf Tin Oxide, NanoTelf Titanium Dioxide (average particle size 34 nm), NanoTelf Yttrium Oxide and NanoTelf Zinc Oxide (average particle size 36 nm) as well as NanoTelf Barium Oxide, NanoTelf Calcium Oxide, NanoTelf Chromium Oxide, NanoTelf Magnesium Oxide, NanoTelf Manganese Oxide, NanoTelf Molybdenum Oxide, NanoTelf Neodymium Oxide, NanoTelf Strontium Oxide and NanoTelf Strontium Titanate as well as the Nanoparticulate Silicate. Suitable silicates are available under the trade names Optigef from Süd-Chemie AG or Laponite ^® from Laporte Ltd. available.

Preferred silicates are the layer silicates (phyllosilicates), in particular bentonites (containing smectites, especially montmorillonite as main minerals), montmorillonites

(AI ₂ [(OH) ₂ / Si ₄ O ₁₀ ] ^■ n H ₂ O or AI ₂ O ₃ ^• 4 SiO ₂ ^■ H ₂ O ^• n H ₂ O, to the dioctahedral

Clay mineral belonging to smectites), kaolinite (AI ₂ [(OH) ₄ / Si ₂ O ₅ ] or

Al ₂ O ₃ ^• 2 SiO ₂ ^• 2 H ₂ O, triclinic two-layer clay mineral (1: 1 -phyllo-silicate)), talc

(hydrated magnesium silicate with the composition Mg ₃ [(OH) ₂ / Si ₄ O ₁₀ ] or 3 MgO ^• 4 SiO ₂ ^■ H ₂ O) and particularly preferably hectorite (M ⁺ ₀₃ (Mg ₂₇ l_i ₀₃ ) [Si ₄ O ₁₀ ( OH) ₂ ], M ⁺ mostly = Na ⁺ , monoclinic belonging to the smectites, similar to montmorillonite

Clay mineral).

A preferred carbonate is hydrotalcite (international name for dialuminium hexamagnesium carbonate hexadecahydroxide tetrahydrate, Al ₂ Mg ₆ (OH) ₁₆ CO ₃ ^• 4 H ₂ O).

Nanoparticulate boehmite (AIO (OH), aluminum oxide hydrate), which is available, for example, from Condea under the trade names DisperaP Sol P3 and Disperaf Sol P2, is particularly preferred. In a particular embodiment of the invention, nanoparticulate inorganic compounds with a specific surface area of more than 200 m ² / g are used. A preferred nanoparticulate compound of this type is magnesium silicate of the layered silicate type with a specific surface area of 200 to 500 m ² / g, in particular 300 to 400 m ² / g. This material is inexpensively available in large quantities. The product is available under the trade names Optigef SH (Süd-Chemie AG) and Laponite ^® XLG (Laporte Ltd.).

surface modification

In a further particular embodiment of the invention, the nanoparticulate inorganic compounds can be treated with one or more surface modification agents.

Suitable surface modifiers for the nanoparticles are all mono- and polybasic carboxylic acids with 2 to 8 carbon atoms, e.g. Acetic acid, propionic acid, oxalic acid, glutaric acid, maleic acid, succinic acid, phthalic acid, adipic acid, suberic acid. The hydroxycarboxylic acids and fruit acids such as e.g. Glycolic acid, lactic acid, citric acid, malic acid, tartaric acid and gluconic acid. A hydroxycarboxylic acid from the group of lactic acid, citric acid, malic acid and tartaric acid is particularly preferably used as the carboxylic acid.

The surface modification of the inorganic nanoparticles is preferably carried out by treatment with an aqueous solution of a carboxylic or hydroxycarboxylic acid in such a way that the nanoparticles are treated with a solution of 0.05 to 0.5 mol of the carboxylic acid per mol of the nanoparticulate inorganic compound. This treatment is preferably carried out over a period of 1 to 24 hours at a temperature of at least 20 ° C, but preferably at the boiling point of the water at normal pressure (100 ° C). If pressure is applied, the treatment can also be carried out in a correspondingly shorter time at temperatures above 100 ° C.

The surface of the nanoparticles is modified by treatment with the carboxylic acids or hydroxycarboxylic acids. It is believed that the carboxylic acids or hydroxycarboxylic acids are bound to the surface of the nanoparticles in an ester-like manner.

The surface-modified nanoparticles are preferably isolated from the reaction mixture by dewatering. For this purpose, the dispersion preferably becomes one Freeze-dried. The solvent is sublimed at low temperature in a high vacuum.

Inorganic nanoparticles modified by this process contain between 1 and 30% by weight, preferably between 5 and 20% by weight, of the organic surface modifier based on the total weight of the surface-modified inorganic nanoparticles.

Functional silanes of the type (OR) _4-n SiR _n (R = organic residues with functional groups such as hydroxy, carboxy, ester, amine, epoxy, etc.), quaternary ammonium compounds or amino acids can also be used for the surface modification of the nanoparticles. Depending on the polarity of the modification agents, the modification described above is carried out in water or in organic solvents (alcohols, ethers, ketones, hydrocarbons, etc.), the reaction conditions being chosen analogously to those in water. Layered silicates such as hectorite can also be subjected to an ion exchange, with cations such as quaternary ammonium compounds being incorporated between the layers of the material. As a further surface modifier gelatin, starch, dextrin, dextran, pectin, gum ara- bicum, casein, gums, polyvinyl alcohols, polyethylene glycols, polyvinylpyrrolidone, polyvinyl for example lyvinylbutyrale, methylcellulose, carboxymethylcellulose, hydroxypropylcellulose suitable or emulsifiers such as fatty alcohol polyglycol ether, Fettalkoholpolyglycoside, fatty acid alkanolamides , Glycerol esters, sorbitan esters or alkoxylated esters and their derivatives.

PH value

The agent according to the invention can be made acidic, neutral or alkaline. Particularly suitable acids are formic acid, acetic acid, citric acid, amidosulfonic acid and the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof. Suitable bases are alkali, ammonia and airline.

In an acidic embodiment, the pH is preferably 1 to 4, in particular 1.5 to 3.5. surfactants

The agent according to the invention can contain one or more nonionic, anionic, amphoteric and / or cationic surfactants.

The agent according to the invention preferably contains one or more nonionic surfactants, for example alkyl polyglycosides and / or alkyl polyglycol ethers, or anionic surfactants, for example alkyl sulfates, alkyl ether sulfates, alkyl sulfonates and / or alkyl benzene sulfonates, in particular one or more nonionic and anionic surfactants.

Other ingredients

Depending on the design of the agent according to the invention, one or more other ingredients which are customary for the particular intended use of the agent may be present, in particular from the group of solvents (e.g. lower alcohols such as ethanol), electrolyte salts (e.g. NaCl, aluminum chlorohydrate) and the colorants and fragrances.

The agents according to the invention can be sprayed - both with a spray pump and as an aerosol. The invention therefore also relates to the use of the agent according to the invention as a spray cleaner.

The agents according to the invention are suitable as hand dishwashing detergents, machine dishwashing detergents, bathroom and toilet cleaners, all-purpose cleaners and detergents. The invention therefore also relates to the use of the agent according to the invention as a hand dishwashing detergent, machine dishwashing detergent, bathroom and toilet cleaner, all-purpose cleaner and detergent.

The agents according to the invention can be produced by mixing the ingredients, if necessary using ultrasound.

B e i s p i e l e

Agents E1 to E17 according to the invention were produced. Tables 1 to 3 show their compositions in% by weight and mostly also the pH immediately after production and one day after production.

The agents E1 to E11 were first adjusted to a pH of about 11 to 11.5 with an aqueous NaOH solution of a concentration of 0.5 mol / l before the final pH adjustment.

The result was transparent gels that could be sprayed, liquefied by shaking, and converted back to a gel when they were at rest.

Table 1

Composition E1 E2 E3 E4 E5 E6

DisperaP Sol P3 ^a] 5 "5 ^[ 1 3 4 4 4

DisperaP Sol P ^b] - - - - - -

HCI - - 1, 8 - - -

Formic acid 1, 8 1, 8 1, 8 1, 8 - 0.8

Citric acid - 3.9 - - - -

Amidosulfonic acid - - - - 1, 8 1, 8

NaCI - - - - - 0.0175 ^[91

ACH solution (50% AS) ^M - - - - - -

APGf 220 UF∞ - - - - - -

Texapon ^® LS 3 & ^e] - - - - - -

Ethanol (96%) - - - - - -

Perfume - - - - - -

Water, fully desalinated ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 pH after preparation 1, 4 2.1 2.6 2.8 1, 6 1, 4 pH one day later - - - 3.2 2.4 1, 9

^[al nanoparticulate boehmite powder (Condea)

^[bl nanoparticulate boehmite powder (Condea)

^[cl aqueous 50% by weight solution of aluminum chlorohydrate (ACH)

^Idl C _8-10 alkyl-1,5-glucoside, 63% by weight, aqueous (Cognis Deutschland GmbH)

^[e] C ₁₂ . ₁₄ -fatty alcohol sulfate sodium salt, 35% by weight, aqueous (Cognis Germany

GmbH)

^[n Surface modified with lactic acid

^[gl used in the form of an aqueous NaCl solution with a concentration of 0.02 mol / l Table 2

Composition E7 E8 E9 E10 E11 E12

Disperaf * Sol P3P 4

Disperaf Sol P2 ^b] -

HCI -

Formic acid - 1.0 1.0 1.2 1.4

Citric acid -

Amidosulfonic acid 1.8 1.0 1.0 1.0 1.1 1.2

NaCI 1

ACH solution (50% AS) ^(C) - 10

APG ^® 220 UP ™ -

Texapon ^® LS 3 & ^e] -

Ethanol (96%) - 2 2 2

Perfume - 0.42 0.42 0.42

Water, fully desalinated ad 1C ad 100 ad 100 ad 100 ad 100 ad 100 pH after production 1.3 2.2 2.0 1.9 1.8 - pH one day later 2.2 3.0 3, 4 2.7 2.7

^{Ia el} s. Table 1

Table 3

Composition E13 E14 E15 E16 E17

Disperaf Sol P3 ^a] 4 - - - -

DisperaP Sol P ^b] - 3 4 4 4

HCI - - - - -

Formic acid - 1.76 3.85 1.2 1.0

Citric acid - 3.85 - - -

Amidosulfonic acid 1.4 - 1.76 1 0.25

NaCI - - - - -

ACH solution (50% AS) ^[C] - - - - -

APG ^® 220 UF ** 1 1 - 1 1

Texapori »LS 3 & ^el - 2.2 - - -

Ethanol (96%) 2 2 2 2 2

Perfume 0.42 0.42 0.42 0.42 0.42

Water, fully desalinated ad 100 ad 100 ad 100 ad 100 ad 100 pH after production 2.2 1.3 1.5 2.0 pH one day later 1.8 2.0 2.5

^Ia, - ^W s. Table 1 Agents E1 to E11 and E14 to E17 have been tested as toilet cleaners. Both sprayed out of a container and sprayed, they adhered to the surfaces much longer than conventional toilet cleaners. The cleaning performance was significantly higher than that of conventional toilet cleaners due to the long exposure time.

Rheological properties

The theological properties of the means E12 and E13 were investigated with the shear rate-controlled rotary rheometer Paar Physica UDS 2000 (geometry: cone / plate with a diameter of 5 cm and an angle of 1 °) at 25 ° C.

The elasticity or storage modulus G ', the viscosity or loss modulus G ", the yield point τ _π and the zero shear viscosity η ₀ (Table 4) and the viscosity η as a function of the shear rate (Table 5) were determined, the viscosity at the Shear rates 1, 10, 30, 50 and 100 s ^{"1 were determined} both in the order of increasing shear rate (values in the columns labeled" on ") and in the order of decreasing shear rate (values in the columns labeled" ab ").

Table 4

(Pa) (Pa) (Pa) (Pa s)

E12 18 7 0.16 2.88 1140

E13 115 13 0.1 11, 5 1160

Table 5

In addition, the viscosity increased with a continuous increase or decrease in the shear rate (= speed gradient) as well as after shearing for 2.5 minutes at a shear rate of 10, 20, 30, 50 or 100 s ^"1 during a subsequent relaxation at a shear rate of only 10 ^"4 s ^{" 1} tracked.

Figure 1 shows the double logarithmic viscosity / shear rate diagram for E12 (measuring point symbol: triangle) and E13 (measuring point symbol: filled diamond) with two each - increasing (arrows pointing up and down right) and decreasing (arrows pointing up and left) Shear rate of measured curves.

Figure 2 shows the viscosity / time diagram for E12 with five curves for the five different feed rates, in which the viscosity is plotted logarithmically.

Figure 3 shows the viscosity / time diagram for E13 with five curves for the five different feed rates, in which the viscosity is plotted logarithmically.

The rheological studies provide impressive evidence of the pronounced structural viscosity (Table 5; slope of the curves in Figure 1) and thixotropy of E12 and E13 (difference between the "up and down" values in Table 5; hysteresis of the curves in Figure 1; Figures 2 and 3) The higher amidosulfonic acid content in E13 compared to E12 results in higher viscosities and an even higher structural viscosity and in particular thixotropy, while the zero shear viscosity is almost identical.

Figures 2 and 3 illustrate that E12 and E13 can be liquefied by shear stress, for example by shaking more vigorously, remain liquid for about 2.5 minutes after the shear stress has ended and then gel again with an almost sudden increase in viscosity (a Form gel).

Claims

Pate nta ns sp

1. Thixotropic aqueous cleaning agent, characterized in that it contains one or more nanoparticulate inorganic compounds from the group of metal oxides, oxide hydrates, hydroxides, carbonates and phosphates as well as sweetes.

2. Composition according to claim 1, characterized in that the average particle size of the nanoparticulate compounds is 1 to 200 nm, preferably 5 to 100 nm, in particular 10 to 50 nm.

3. Composition according to one of claims 1 or 2, characterized in that one or more nanoparticulate compounds in an amount of 0.1 to 20 wt .-%, preferably 0.5 to 10 wt .-%, in particular 1 to 8 wt .-%, particularly preferably 2 to 6 wt .-%, most preferably 3 to 5 wt .-%, contains.

4. Agent according to one of claims 1 to 3, characterized in that contains boehmite.

5. Agent according to one of the preceding claims, characterized in that it contains one or more acids or bases.

6. Agent according to one of the preceding claims, characterized in that it contains one or more surfactants.

7. Composition according to one of the preceding claims, characterized in that it contains one or more surfactants.

8. Use of an agent according to one of the preceding claims as a hand dishwashing detergent, machine dishwashing detergent, bathroom or toilet cleaner, all-purpose cleaner or detergent.

9. Use of an agent according to one of the preceding claims as a spray cleaner.