EP0160873B1 - Softening washing agent - Google Patents

Description

Frequent washing in drum washing machines adversely affects particularly soft and fluffy laundry items with a pleasant handle; the handle becomes harder, especially if drying is carried out repeatedly while hanging quietly. This is attributed to a fiber bond that occurs during drying, the so-called water rigidity.

This effect can be counteracted by using anti-aging agents. For this purpose, cationic surfactants, in particular quaternary ammonium compounds, are preferably used. As a rule, the softening also has an antistatic effect on the tissue. In the following, "softening" means this softening effect on the textiles and not, for example, softening of the water by complexing the calcium and magnesium ions causing the water hardness.

The cationic surfactants are incompatible with the anionic surfactants usually used in detergents, since poorly soluble precipitates result which lead to a partial loss of softening cationic surfactants and detergent-active anionic surfactants in the wash liquor and thus to a reduced effectiveness of the detergent. It is therefore known to use cationic reagents in a separate rinse cycle.

On the other hand, softening detergents are already known, which have a cleaning and softening effect in one operation. DE-PS 23 34 899 describes the use of clay minerals, namely saponites, hectorites or montmorrillonites as softening agents Active ingredients in detergent formulations. For the same purpose, DE-OS 33 12 774 bentonites are added to detergents.
It is also known to incorporate smectites into softening detergents in the presence of softening ammonium compounds (cationic surfactants) and / or amines (for example EP 00 76 572, US Pat. No. 4,375,416). This is intended to achieve a softening and antistatic effect, especially in laundry tumblers. Since the cationic surfactants are embedded in the smectites (crystalline alkali layer silicates), they are also effective in the presence of anionic surfactants.
Smectites are clay minerals that carry a grid charge and expand when solvated with water and alcohol. Montmorillonite belongs to the Smectite group



{(Al¹, ₆₇Mg₀, ₃₃) (OH) ₂ [Si₄O₁₀]} Na₀, ₃₃,

the hectorite



{(Mg₂, ₆₇Li₀, ₃₃) (OH, F) ₂ [Si₄O₁₀]} Na₀, ₃₃

and possibly the saponite



{(Mg₃ _-x Al _x ) (OH) ₂ [Si₄ _-y Al _y O₁₀]} Na _z .




Bentonites are certain clay minerals containing montmorrillonite.

With the above Clays are usually natural minerals that are more or less colored due to the inclusion of impurities; this is disadvantageous for use in detergents. Although synthetic clays can be produced, they cannot be used economically for cost reasons.

The task was to find softening active ingredients that overcome the disadvantages mentioned.

Surprisingly, it was found that crystalline layered silicates of the composition



M₂Si _x O₂ _x ₊₁. y H₂O;



x>7; in particular 7.5-23; y = 0-25; M = Na, K, H

have excellent anti-static properties that improve grip. The compounds are colorless, economically producible and free from alkaline earth and aluminum ions. Their molecular structure differs fundamentally from that of the above-mentioned clays; The layered silicates to be used according to the invention can be assigned to the group of phyllosilicates and contain adhesive and / or water of crystallization.

M is preferably sodium, but depending on the respective pH, it can also be partially replaced by protons.

The ion exchange capacity of the crystalline layered silicates is 130 - 400 mmol M ⁺ / 100 g anhydrous substance. In the X-ray diffraction diagram, the silicates have one or more reflections in the range of the d values of 3.0 - 4.0 x 10⁻⁸ cm, which cannot be assigned to quartz, tridymite and cristobalite.

Both natural and synthetic alkali silicates can be used in the context of the invention. Natural alkali silicates are e.g. Magadiite Na₂Si₁₄O₂₉. 11 H₂O and Kenyait Na₂Si₂₂O₄₅. 10 H₂O (H.P. Eugster, Science, 157, pp. 1177-1180 (1967)).

Synthetic products have, for example, the composition Na₂Si₈O₁₇, K₂Si₈O₁₇ or Na₂Si₁₄O₂₉ (RK Iler, J. Colloid Sci. 19, pp. 648-657 (1964); DE-PS 27 42 912; G. Lagaly et al., Am. Mineral. 60, pp. 642-649 (1975)).

Crystalline layered silicas and their alkali metal salts which can be used according to the invention and processes for their preparation are also described in the older German DE-A-34 00 130 and 34 00 132.

The crystalline layered silicas or alkali layer silicates to be used in accordance with the invention can be incorporated into detergents by means of customary processes for the production of detergents, such as mixing, spray mixing processes and spray drying. However, they can also be used separately.

• a) x = 7,5 bis 23;
• b) die kristalline Schichtkieselsäure oder deren Alkalisalz im wasserfreien Zustand je 100 g ein Kationenausvermögen von 130 bis 400 mmol M⁺ aufweist;
• c) für M = H das Röntgenbeugungsdiagramm bei (3,42 ± 0,1) . 10⁻⁸ cm eine sehr starke erste Linie und bei (18 ± 4) . 10⁻⁸ cm eine weitere Linie aufweist, deren Intensität höchstens 75 % der Intensität der ersten Linie beträgt;
• d) für M = Na das Röntgenbeugungsdiagramm bis (3,42 ± 0,15) . 10⁻⁸ cm zumindest eine sehr starke Linie und bei (20 ± 2) . 10⁻⁸ cm eine weitere Linie aufweist, deren Intensität höchstens 75 % der Intensität der ersten Linie beträgt.

In particular, the invention now relates to a softening detergent with 5-70% by weight of at least one surfactant, 0.5 to 50% by weight of at least one builder, 1 to 20% by weight of at least one crystalline layered silicic acid and / or a corresponding alkali layered silicate and customary washing aids , which is characterized in that the crystalline layered silica or its alkali salt has the general formula M₂Si _x O₂ _x ₊₁. y has H₂O, where x>7.0; M = Na, K or H and y = 0 to 25, and in the X-ray diffraction pattern in the range of the d values from 3.0 to 4.0. 10⁻⁸ cm has one or more reflections that cannot be assigned to quartz, tridymite and cristobalite.
The softening detergent of the invention may further be preferred and optionally characterized in that

• a) x = 7.5 to 23;
• b) the crystalline layered silica or its alkali salt in the anhydrous state per 100 g has a cationic capacity of 130 to 400 mmol M⁺;
• c) for M = H the X-ray diffraction pattern at (3.42 ± 0.1). 10⁻⁸ cm a very strong first line and at (18 ± 4). 10⁻⁸ cm has another line, the intensity of which is at most 75% of the intensity of the first line;
• d) for M = Na the X-ray diffraction pattern up to (3.42 ± 0.15). 10⁻⁸ cm at least a very strong line and at (20 ± 2). 10⁻⁸ cm has another line, the intensity of which is at most 75% of the intensity of the first line.

The invention further relates to the use of a crystalline layered silica or its alkali salt for fabric softening, which is characterized in that the crystalline layered silica or its alkali salt is represented by the general formula M₂Si _x O₂ _x ₊₁. y H₂O, where x> 7.0, preferably 7.5 to 23; M = Na, K or H and y = 0 to 25, is characterized and in the X-ray diffraction diagram in the range of the d values from 3.0 to 4.0. 10⁻⁸ cm has one or more reflections that cannot be assigned to quartz, tridymite and cristobalite.

The softening detergent of the invention preferably contains 5-30% by weight of surfactants, 10-40% by weight of builders and 1-15% by weight of crystalline layered silicas or their alkali salts, the rest of the washing aids, provided that it is marketed in granules. If it is sold in liquid form, it preferably contains 10-55% by weight of surfactants, 0.5-25% by weight of builders and 1-15% by weight of crystalline layered silicas or their alkali salts, the rest of the washing aids. Very good washing results are achieved with the softening detergent of the invention. The softening detergent of the invention preferably contains such anionic, zwitterionic (ampholytic) or nonionic in nature as surfactants.

Anionic surfactants include the water-soluble salts of higher fatty acids or resin acids, such as sodium or potassium soaps from coconut, palm kernel or turnip oil, and from tallow and To understand mixtures of them. These also include higher alkyl-substituted aromatic sulfonates, such as alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl radical, alkylnaphthalenesulfonates, alkyltoluenesulfonates, alkylxylenesulfonates or alkylphenolsulfonates; Fatty alcohol sulfates (R-CH₂-O-SO₃Na; R = C₁₁₋₁₇) or fatty alcohol ether sulfates, such as alkali lauryl sulfate or alkali hexadecyl sulfate, triethanolamine lauryl sulfate, sodium or potassium oleyl sulfate, sodium or potassium salts of with 2 to 6 moles of ethylene sulfate ethoxylate ethoxylate. Other suitable anionic surfactants are secondary linear alkane sulfonates and α-olefin sulfonates with a chain length of 12-20 carbon atoms.

Schließlich umfassen Tenside mit zwitterionischem (ampholytischen) Charakter folgende Verbindungen:
Derivate von aliphatischen, sekundären und tertiären Aminen oder quaternären Ammoniumverbindungen mit 8 bis 18 C-Atomen und einer hydrophilen Gruppe im aliphatischen Rest, wie z.B. Natrium-3-dodecylaminopropionat, Natrium-3-dodecyl-aminopropansulfonat, 3-(N,N-Dimethyl-N-hexadecyl-amino)-propan-1-sulfonat oder Fettsäureaminoalkyl-N,N-dimethyl-acetobetain, wobei die Fettsäure 8 bis 18 C-Atome und der Alkylrest 1 - 3 C-Atome enthält.Nonionic surfactants are understood to mean those compounds which have an organic, hydrophobic group and a hydrophilic radical, for example the condensation products of alkylphenols or higher fatty alcohols with ethylene oxide, the condensation products of polypropylene glycol with ethylene oxide or propylene oxide, the condensation products of ethylene oxide with the reaction product from ethylenediamine and propylene oxide, as well as long-chain tertiary amine oxides

Finally, surfactants with a zwitterionic (ampholytic) character include the following compounds:
Derivatives of aliphatic, secondary and tertiary amines or quaternary ammonium compounds with 8 to 18 carbon atoms and a hydrophilic group in the aliphatic radical, such as sodium 3-dodecylaminopropionate, sodium 3-dodecylaminopropanesulfonate, 3- (N, N-dimethyl -N-hexadecyl-amino) -propane-1-sulfonate or fatty acid aminoalkyl-N, N-dimethyl-acetobetaine, where the fatty acid contains 8 to 18 carbon atoms and the alkyl radical contains 1 to 3 carbon atoms.

Suitable builders for the detergents according to the invention are weakly acidic, neutral or alkaline inorganic or organic salts, in particular inorganic or organic complexing agents.

Useful, weakly acidic, neutral or alkaline salts are, for example, the bicarbonates, carbonates or silicates of the alkalis, and also mono-, di- or trialkali orthophosphates. Di- or tetraalkali-pyrophosphates, metaphosphates known as complexing agents, alkali sulfates and the alkali salts of organic, non-capillary-active sulfonic acids containing 1 to 8 carbon atoms, carboxylic acids and sulfocarboxylic acids. These include, for example, water-soluble salts of benzene, toluene or xylene sulfonic acid, water-soluble salts of sulfoacetic acid, sulfobenzoic acid or salts of sulfodicarboxylic acids as well as the salts of acetic acid, lactic acid, citric acid, tartaric acid, oxydiacetic acid (HOOC-CH₂-O-CH₂-COOHeinsäure), oxydib , 1,2,3,4-cyclopentanetetracarboxylic acid, polyacrylic acid and polymaleic acid.

The weakly acidic metaphosphates and the alkaline polyphosphates, in particular tripolyphosphate, are also suitable as complex-forming framework substances. They can be replaced in whole or in part by organic complexing agents. The organic complexing agents include, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, polyalkylene-polyamine-N-polycarboxylic acids and other known organic complexing agents, it also being possible to use combinations of different complexing agents.
Washing aids according to the invention include products such as the alkali or ammonium salts of sulfuric acid, silica, carbonic acid, boric acid, alkylene, hydroxyalkylene or aminoalkylenephosphonic acid as well as bleaching agents, stabilizers for peroxide compounds (bleaching agents) and water-soluble organic complexing agents.

In particular, the bleaching agents include sodium perborate mono- or tetrahydrate, the alkali salts of peroxomono- or peroxodisulfuric acid, the alkali salts of peroxodiphosphoric acid (H₄P₂O₈). A stabilizer for these bleaches is e.g. water-soluble, precipitated magnesium silicate. Organic complexing agents are the alkali salts of iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, methylenediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid and nitrilotrismethylenephosphonic acid.

Washing aids that increase the dirt-carrying capacity of washing liquors, such as carboxymethyl cellulose, carboxymethyl starch, methyl cellulose or copolymers of maleic anhydride with methyl vinyl ether, foam regulators, such as mono- and dialkyl phosphoric acid esters with 16 to 20 carbon atoms in the alkyl radical, as well as optical brighteners, disinfectants and / or proteolytic enzymes additional components of the softening detergent.

example

Terrycloth fabric was washed 5 times with one of the following two detergent compositions (in% by weight):

Detergent A is a commercially available detergent that had been mixed in the mixer according to the invention with the layered crystalline sodium silicate of the formula Na₂Si₂₂O₄₅ (loss on ignition 4% (5 h / 360 ° C)); Detergent B is a commercially available detergent that contains crystalline, layered alkali aluminum silicates and cationic surfactants and whose grip-improving effect is highlighted in advertising.

The grip assessment by a panel of experts showed a completely comparable grip-improving effect. Very good washing results were also achieved in both cases.

Claims (6)

1. A softening detergent composition comprising from 5 to 70 % by weight of at least one surfactant, from 0.5 to 50 % by weight of at least one builder, from 1 to 20 % by weight of at least one crystalline phyllosilicic acid and/or a corresponding alkali metal silicate and customary laundry aids, wherein the crystalline phyllosilicic acid or the alkali metal salt thereof has the formula M₂Si_xO₂_x₊₁ · yH₂O, where X > 7.0; M = Na, K or H; and y = 0-25, and shows one or more reflections in the X-ray diffraction diagram within the range of the d values of from 3.0 to 4.0 · 10⁻⁸ cm which cannot be assigned to quartz, tridymite or cristobalite.
2. The softening detergent composition of claim 1, wherein x is from 7.5 to 23.
3. The softening detergent composition of claim 1 or 2, wherein the crystalline phyllosilicic acid or the alkali metal salt thereof has in the anhydrous state a cation exchange capacity of from 130 to 400 mmol of M⁺ per 100 g.
4. The softening detergent composition of any one of the preceding claims, wherein for M = H the X-ray diffraction diagram has a very strong first line at (3.42 ± 0.1) · 10⁻⁸ cm and a further line at (18 ± 4) · 10⁻⁸ cm whose intensity is not more than 75 % of the intensity of the first line.
5. The softening detergent composition of any one of claims 1-3, wherein for M = Na the X-ray diffraction diagram has at least one very strong line at (3.42 ± 0.15) · 10⁻⁸ cm and a further line at (20 ± 2) · 10⁻⁸ cm whose intensity is not more than 75 % of the intensity of the first line.
6. The use of a crystalline phyllosilicic acid or the alkali metal salt thereof for softening textiles in the final rinse, wherein the crystalline phyllosilicic acid or the alkali metal salt thereof is characterized by the formula M₂Si_xO₂_x₊₁ · yH₂O, where x > 7.0, preferably from 7.5 to 23, M = Na, K or H; and y = 0-25, and shows one or more reflections in the X-ray diffraction diagram within the range of the d values of from 3.0 to 4.0 · 10⁻⁸ cm which cannot be assigned to quartz, tridymite or cristobalite.