EP0160873A2 - Softening washing agent - Google Patents

Softening washing agent Download PDF

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Publication number
EP0160873A2
EP0160873A2 EP85104833A EP85104833A EP0160873A2 EP 0160873 A2 EP0160873 A2 EP 0160873A2 EP 85104833 A EP85104833 A EP 85104833A EP 85104833 A EP85104833 A EP 85104833A EP 0160873 A2 EP0160873 A2 EP 0160873A2
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EP
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Prior art keywords
crystalline layered
softening
weight
acid
alkali
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EP85104833A
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German (de)
French (fr)
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EP0160873A3 (en
EP0160873B1 (en
Inventor
Hans-Peter Dr. Rieck
Jürgen Dr. Grosse
Werner Gohla
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Clariant Produkte Deutschland GmbH
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Hoechst AG
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads

Definitions

  • 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.
  • DE-PS 23 34 899 describes the use of clay minerals, namely saponites, hectorites or montmorrillonites, as soft active ingredients in detergent formulations.
  • DE-OS 33 12 774 bentonites are added to detergents.
  • smectites are clay minerals that carry a grid charge and expand when solvated with water and alcohol. Montmorillonite belongs to the Smectite group the hectorite and possibly the saponite
  • Bentonites are understood to mean certain montmorrillonite-containing clay minerals.
  • 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.
  • 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.
  • 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.
  • Natural alkali silicates are, for example, magadiite Na 2 Si 14 O 29 .11 H 2 0 and Ken y ait Na 2 Si 22 0 45 . 10 H 2 0 (HP Eugster, Science, 157, pp. 1177-1180 (1967)).
  • Synthetic products have, for example, the composition Na 2 Si 8 O 17 , K 2 Si 8 O 17 or Na 2 Si 14 O 29 (RK Iler, J. Colloid Sci. 29, pp. 648-657 (1964); DE-PS 27 42 912; G. Lagaly et al. Am. Mineral. 60, pp. 642-649 (1975)).
  • 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.
  • 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 metal 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 are the water-soluble salts - higher fatty acids or resin acids, such as sodium or potassium soaps from coconut, palm kernel or turnip oil as well as from tallow and To understand mixtures of them.
  • Nonionic surfactants are understood to mean those compounds which have an organic, hydrophobic group and a hydrophilic radical, e.g. 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 of ethylene diamine and propylene oxide, and long-chain tertiary amine oxides
  • 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-reacting salts are, for example, the bicarbonates, carbonates or silicates of the alkalis, and also mono-, di- or trialkali orthophosphates.
  • the weakly acidic metaphosphates and the "alkaline polyphosphates; in particular the 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, polyalk -N-polycarboxylic acids and other known organic complexing agents, it also being possible to use combinations of different complexing agents.
  • Washing aids 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.
  • the bleaching agents specifically include sodium perborate mono- or tetrahydrate, the alkali salts of peroxomono- or peroxodisulfuric acid, the alkali salts of peroxodiphosphoric acid (H 4 P 2 O 8 ).
  • water-soluble, precipitated magnesium silicate acts as a stabilizer for these bleaches.
  • 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, and optical brighteners, disinfectants and / or proteolytic enzymes additional components of the softening detergent.
  • Detergent A is a commercially available detergent which, according to the invention, had been mixed in the mixer with the layered crystalline sodium silicate of the formula Na 2 Si 22 0 45 (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.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Das weichmachende Waschmittel der Erfindung mit 5 bis 70 Gew% mindestens eines Tensids, 0,5 bis 50 Gew% mindestens eines Gerüststoffes, 1 bis 20 Gew% mindestens einer kristallinen Schichtkieselsäure und/oder eines entsprechenden Alkalisilikats sowie üblichen Waschhilfsstoffen ist dadurch gekennzeichnet, daß die kristalline Schichtkieselsäure oder deren Alkalisalz die allgemeine Formal M2Six02x+1·yH20 hat, worin ×>7,0; M = Na, K oder H und y = 0 bis 25 bedeuten, und im Röntgenbeugungsdiagramm im Bereich der d-Werte von 3,0 bis 4,0 · 10<-><8> cm einen oder mehrere Reflexe aufweist, die nicht Quarz, Tridymit und Cristobalit zugeordnet werden können. Die Erfindung betrifft weiterhin die Verwendung der kristallinen Schichtkieselsäure oder deren Alkalisalze zum Weichspülen von Textilien.The softening detergent of the invention with 5 to 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 silica and / or a corresponding alkali silicate and conventional washing aids is characterized in that the crystalline layered silica or its alkali salt has the general formula M2Six02x + 1 · yH20, where ×> 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 one or more reflections that are not quartz , Tridymite and cristobalite can be assigned. The invention further relates to the use of crystalline layered silica or its alkali salts for fabric softening.

Description

Durch oftmaliges Waschen in Trommelwaschmaschinen-werden besonders weiche und flauschige Wäschestücke mit angenehmem Griff nachteilig beeinflußt; der Griff wird härter, vor allem, wenn wiederholt ruhig hängend getrocknet wird. Dies wird zurückgeführt auf eine beim Trocknen entstehende Faserverklebung, die sogenannte Wasserstarre.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.

Diesem Effekt kann durch Einsatz von Avivagemitteln entgegengewirkt werden. Dazu werden bevorzugt kationische Tenside, insbesondere quaternäre Ammoniumverbindungen, eingesetzt. In der Regel ist mit der weichmachenden auch eine antistatische Wirkung auf das Gewebe verbunden. Im folgenden ist unter "Weichmachen" diese Avivage-Wirkung auf die Textilien und nicht etwa ein Weichmachen des Wassers durch Komplexierung der die Wasserhärte verursachenden Calcium- und Magnesiumionen zu verstehen.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.

Die kationischen Tenside sind mit den üblicherweise in Waschmitteln eingesetzten anionischen Tensiden nicht verträglich, da schwerlösliche Ausfällungen resultieren, die zu einem teilweisen Verlust von weichmachenden Kationentensiden und waschaktiven Anionentensiden in der Waschflotte und somit zu verringerter Wirksamkeit des Waschmittels führen. Es ist daher bekannt, kationische Reagenzien in einem separaten Spülgang einzusetzen.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.

Andererseits sind auch bereits weichmachende Waschmittel bekannt, welche in einem Arbeitsgang reinigende und weichmachende Wirkung entfalten. So beschreibt die DE-PS 23 34 899 den Einsatz von Tonmineralien, und zwar von Saponiten, Hectoriten oder Montmorrilloniten als weichmachende Wirkstoffe in Waschmittelformulierungen. Für den gleichen Zweck werden in der DE-OS 33 12 774 Bentonite zu Waschmitteln zugesetzt.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 soft active ingredients in detergent formulations. For the same purpose, DE-OS 33 12 774 bentonites are added to detergents.

Es ist ebenfalls bekannt, Smectite in Gegenwart von weichmachenden Ammoniumverbindungen (kationische Tenside) und/ oder Aminen (z.B. EP 00 76 572, US-PS 4 375 416) in weichmachende Waschmittel einzuarbeiten. Hierdurch soll besonders in Wäschetumblern eine weichmachende und antistatische Wirkung erzielt werden. Da die kationischen Tenside in die Smectite (kristalline Alkalischichtsilikate) eingelagert werden, sind sie auch in Gegenwart anionischer Tenside wirksam. Smectite sind Tonmineralien, die eine Gitterladung tragen, und sich ausdehnen, wenn sie mit Wasser und Alkohol solvatisiert werden. Zur Gruppe der Smectite gehören der Montmorillonit

Figure imgb0001
der Hectorit
Figure imgb0002
und ggf. der Saponit
Figure imgb0003
 It is also known to incorporate smectites into softening detergents in the presence of softening ammonium compounds (cationic surfactants) and / or amines (eg 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
Figure imgb0001
 the hectorite
Figure imgb0002
 and possibly the saponite
Figure imgb0003

Unter Bentoniten versteht man bestimmte montmorrillonithaltige Tonmineralien.Bentonites are understood to mean certain montmorrillonite-containing clay minerals.

Bei den o.g. Tonen handelt es sich üblicherweise um natürliche Mineralien, die durch Einschluß von Verunreinigungen mehr oder weniger gefärbt sind; dieser Umstand ist nachteilig für den Einsatz in Waschmitteln. Synthetische Tone können zwar hergestellt werden, sind aber aus Kostengründen nicht wirtschaftlich einsetzbar.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.

Es bestand die Aufgabe, weichmachende Wirkstoffe zu finden, die die genannten Nachteile überwinden.The task was to find softening active ingredients that overcome the disadvantages mentioned.

Überraschenderweise wurde gefunden, daß kristalline Schichtsilikate der Zusammensetzung

Figure imgb0004
x >7; insbesondere 7,5 - 23; y = 0 - 25; M = Na, K, H hervorragende, den Griff verbessernde, antistatische Wirkung aufweisen. Die Verbindungen sind farblos, wirtschaftlich herstellbar, sowie frei von Erdalkali- und Aluminiumionen. Ihr molekularer Aufbau unterscheidet sich grundlegend von dem der o.g. Tone; die erfindungsgemäß einzusetzenden Schichtsilikate können der Gruppe der Phyllosilikate zugerechnet werden und Haft- und/oder Kristallwasser enthalten.Surprisingly, it was found that crystalline layered silicates of the composition
Figure imgb0004
 x>7; in particular 7.5-23; y = 0-25; M = Na, K, H have excellent anti-static effects 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 ist bevorzugt Natrium, kann in Abhängigkeit des jeweiligen pH-Wertes jedoch auch teilweise durch Protonen ersetzt sein.M is preferably sodium, but depending on the respective pH, it can also be partially replaced by protons.

Das Ionenaustauschvermögen der kristallinen Schichtsilikate beträgt 130 - 400 mMol M+/100 g wasserfreie Substanz. Die Silikate haben im Röntgenbeugungsdiagramm einen oder mehrere Reflexe im Bereich der d-Werte von 3,0 - 4,0 x 10-8 cm, die nicht Quarz, Tridymit und Cristobalit zugeordnet werden können.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.

Im Rahmen der Erfindung können sowohl natürliche als auch synthetische Alkalisilikate eingesetzt werden. Natürliche Alkalisilikate sind z.B. Magadiit Na2Si14O29 · 11 H20 und Kenyait Na2Si22045 . 10 H20 (H.P. Eugster, Science, 157, S. 1177-1180 (1967)).Both natural and synthetic alkali silicates can be used in the context of the invention. Natural alkali silicates are, for example, magadiite Na 2 Si 14 O 29 .11 H 2 0 and Ken y ait Na 2 Si 22 0 45 . 10 H 2 0 (HP Eugster, Science, 157, pp. 1177-1180 (1967)).

Synthetische Produkte haben z.B. die Zusammensetzung Na2Si8O17, K2Si8O17 oder Na2Si14O29 (R.K. Iler, J. Colloid Sci. 29, S. 648-657 (1964); DE-PS 27 42 912; G. Lagaly et al.. Am. Mineral. 60, S. 642-649 (1975)).Synthetic products have, for example, the composition Na 2 Si 8 O 17 , K 2 Si 8 O 17 or Na 2 Si 14 O 29 (RK Iler, J. Colloid Sci. 29, pp. 648-657 (1964); DE-PS 27 42 912; G. Lagaly et al. Am. Mineral. 60, pp. 642-649 (1975)).

Erfindungsgemäß einsetzbare kristalline Schichtkieselsäuren und deren Alkalisalze sowie Verfahren zu ihrer Herstellung sind darüberhinaus in den älteren deutschen Patentanmeldungen P 34 00 130.1 und P 34 00 132.8 beschrieben.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 earlier German patent applications P 34 00 130.1 and P 34 00 132.8.

Die erfindungsgemäß einzusetzenden kristallinen Schichtkieselsäuren oder Alkalischichtsilikate können mittels üblicher Verfahren zur Waschmittelherstellung wie Mischen, Sprühnebelmischverfahren, Sprühtrocknen in Waschmittel eingearbeitet werden. Sie können aber auch getrennt angewendet werden.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.

Im einzelnen betrifft die Erfindung nunmehr ein weichmachendes Waschmittel mit 5-70 Gew% mindestens eines Tensids, 0,5 bis 50 Gew% mindestens eines Gerüststoffes, 1 bis'20 Gew% mindestens einer kristallinen Schichtkieselsäure und/ oder eines entsprechenden Alkali-Schichtsilikats sowie üblichen Waschhilfastoffen, welches dadurch gekennzeichnet ist, daß die kristalline Schichtkieselsäure oder deren Alkalisalz die allgemeine Formel M2SixO2 x+1 · y H 2 0 hat, worin x>7,0; M = Na, K oder H und y = 0 bis 25 bedeuten, und im Röntgenbeugungsdiagramm im Bereich der d-Werte von 3,0 bis 4,0 . 10-8 cm einen oder mehrere Reflexe aufweist, die nicht Quarz, Tridymit und Cristobalit zugeordnet werden können.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 conventional ones Open washing aid, which is characterized in that the crystalline layered silica or its alkali salt has the general formula M 2 Si x O 2 x + 1 · y H 2 0, 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.

Das weichmachende Waschmittel der Erfindung kann weiterhin bevorzugt und wahlweise dadurch gekennzeichnet sein, daß

  • 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.
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). 1 0 - 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). 1 0 - 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.

Die Erfindung betrifft weiterhin die Verwendung einer kristallinen Schichtkieselsäure oder deren Alkalisalz zum Weichspülen von Textilien, welche dadurch gekennzeichnet ist, daß die kristalline Schichtkieselsäure oder deren Alkalisalz durch die allgemeine Formel M2Six02 x+1 · y H 2 0, worin x>7,0, vorzugsweise 7,5 bis 23; M = Na, K oder H und y = 0 bis 25 bedeuten, charakterisiert ist und im Röntgenbeugungsdiagramm im Bereich der d-Werte von 3,0 bis 4,0 . 10-8 cm einen oder mehrere Reflexe aufweist, die nicht Quarz, Tridymit und Cristobalit zugeordnet werden können.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 M 2 Si x 0 2 x + 1 · y H 2 0, 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.

Das weichmachende Waschmittel der Erfindung enthält, sofern es granuliert in den Handel gelangt, bevorzugt 5-30 Gew% Tenside, 10-40 Gew% Gerüststoffe und 1-15 Gew% kristalline Schichtkieselsäuren bzw. deren Alkalisalze, Rest Waschhilfsstoffe. Kommt es flüssig in den Handel, so enthält es bevorzugt 10 - 55 Gew% Tenside, 0,5 - 25 Gew% Gerüststoffe und 1-15 Gew% kristalline Schichtkieselsäuren bzw. deren Alkalisalze, Rest Waschhilfsstoffe. Mit dem weichmachenden Waschmittel der Erfindung werden sehr gute Waschergebnisse erzielt. Das weichmachende Waschmittel der Erfindung enthält als Tenside bevorzugt solche anionischer, zwitterionischer (ampholytischer) oder nichtionischer Natur.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 metal 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.

Unter anionischen Tensiden sind die wasserlöslichen Salze - höherer Fettsäuren oder Harzsäuren, wie Natrium- oder Kaliumseifen von Kokos-, Palmkern- oder Rüböl sowie von Talg und Gemischen davon zu verstehen. Weiterhin zählen dazu höhere alkylsubstituierte, aromatische Sulfonate, wie Alkylbenzolsulfonate mit 9 bis 14 C-Atomen im Alkylrest, Alkylnaphthalinsulfonate, Alkyltoluolsulfonate, Alkylxylolsulfonate oder Alkylphenolsulfonate; Fettalkoholsulfate (R-CH2-O-SO3Na; R = C11-17) oder Fettalkoholethersulfate, wie Alkalilaurylsulfat oder Alkalihexadecylsulfat, Triethanolaminlaurylsulfat, Natrium- oder Kaliumoleylsulfat, Natrium- oder Kaliumsalze von mit 2 bis 6 Mol Ethylenoxid ethoxyliertem Laurylsulfat. Weitere geeignete anionische Tenside sind sekundäre lineare Alkansulfonate sowie α-Olefinsulfonate mit einer Kettenlänge von 12 - 20 C-Atomen.Among anionic surfactants are the water-soluble salts - higher fatty acids or resin acids, such as sodium or potassium soaps from coconut, palm kernel or turnip oil as well as 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-CH 2 -O-SO 3 Na; R = C 11-17 ) 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 lauryl ethoxylated with 2 to 6 moles of ethylene sulfate. Other suitable anionic surfactants are secondary linear alkane sulfonates and α-olefin sulfonates with a chain length of 12-20 carbon atoms.

Unter nichtionischen Tensiden sind solche Verbindungen zu verstehen, die eine organische, hydrophobe Gruppe sowie einen hydrophilen Rest aufweisen, z.B. die Kondensationsprodukte von Alkylphenolen oder höheren Fettalkoholen mit Ethylenoxid, die Kondensationsprodukte von Polypropylenglykol mit Ethylenoxid oder Propylenoxid, die Kondensationsprodukte von Ethylenoxid mit dem Reaktionsprodukt aus Ethylendiamin und Propylenoxid, sowie langkettige tertiäre AminoxideNonionic surfactants are understood to mean those compounds which have an organic, hydrophobic group and a hydrophilic radical, e.g. 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 of ethylene diamine and propylene oxide, and long-chain tertiary amine oxides

Figure imgb0005
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.
Figure imgb0005
 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.

Als Gerüstsubstanzen für die Waschmittel gemäß der Erfindung eignen sich schwach sauer, neutral oder alkalisch reagierende anorganische oder organische Salze, insbesondere anorganische oder organische Komplexbildner.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.

Brauchbare, schwach sauer, neutral oder alkalisch reagierende Salze sind beispielsweise die Bicarbonate, Carbonate oder Silikate der Alkalien, weiterhin Mono-, Di- oder Trialkaliorthophosphate. Di- oder Tetraalkalipyrophosphate, als Komplexbildner bekannte Metaphosphate, Alkalisulfate sowie die Alkalisalze von organischen, nicht kapillaraktiven, 1 bis 8 C-Atome enthaltenden Sulfonsäuren, Carbonsäuren und Sulfocarbonsäuren: Hierzu gehören beispielsweise wasserlösliche,Salze der Benzol-, Toluol- oder Xylolsulfonsäure, wasserlösliche Salze der Sulfoessigsäure, Sulfobenzoesäure oder Salze von Sulfodicarbonsäuren sowie die Salze der Essigsäure, Milchsäure, Zitronensäure, Weinsäure, Oxydiessigsäure (HOOC-CH2-O-CH2-COOH), Oxydibernsteinsäure, 1,2,3,4-Cyclopentantetracarbonsäure, Polyacrylsäure und Polymaleinsäure.Useful, weakly acidic, neutral or alkaline-reacting 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, and water-soluble salts sulfoacetic acid, sulfobenzoic acid or salts of sulfodicarboxylic acids and the salts of acetic acid, lactic acid, citric acid, tartaric acid, oxydiacetic acid (HOOC-CH 2 -O-CH 2 -COOH), oxydisuccinic acid, 1,2,3,4-cyclopentantetracarboxylic acid, polyacrylic acid and polymaleic acid .

Als komplexbildende Gerüstsubstanzen eignen sich auch die schwach sauer reagierenden Metaphosphate sowie die" alkalisch reagierenden Polyphosphate; insbesondere das Tripolyphosphat. Sie können ganz oder teilweise durch organische Komplexbildner ersetzt werden. Zu den organischen Komplexbildnern gehören beispielsweise Nitrilotriessigsäure, Ethylendiamintetraessigsäure, N-Hydroxyethylethylendiamintriessigsäure, Polyalkylen-polyamin-N-polycarbonsäuren und andere bekannte organische Komplexbildner, wobei auch Kombinationen verschiedener Komplexbildner eingesetzt werden können.The weakly acidic metaphosphates and the "alkaline polyphosphates; in particular the 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, polyalk -N-polycarboxylic acids and other known organic complexing agents, it also being possible to use combinations of different complexing agents.

Waschhilfsstoffe gemäß der Erfindung umfassen Produkte wie die Alkali- oder Ammoniumsalze der Schwefelsäure, Kieselsäure, Kohlensäure, Borsäure, Alkylen-, Hydroxyalkylen-oder Aminoalkylenphosphonsäure sowie Bleichmittel, Stabilisatoren für Peroxidverbindungen (Bleichmittel) und wasserlösliche organische Komplexbildner.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.

Im einzelnen gehören zu den Bleichmitteln Natriumperboratmono- oder tetrahydrat, die Alkalisalze der Peroxomono-oder Peroxodischwefelsäure, die Alkalisalze der Peroxodiphosphorsäure (H4P2O8). Als Stabilisator für diese Bleichmittel fungiert z.B. wasserlösliches, gefälltes Magnesiumsilikat. Organische Komplexbildner sind die Alkalisalze der Iminodiessigsäure, Nitrilotriessigsäure, Ethylendiamintetraessigsäure, Methylendiphosphonsäure, 1-Hydroxyethan-1,1-diphosphonsäure und Nitrilotrismethylenphosphonsäure.The bleaching agents specifically include sodium perborate mono- or tetrahydrate, the alkali salts of peroxomono- or peroxodisulfuric acid, the alkali salts of peroxodiphosphoric acid (H 4 P 2 O 8 ). For example, water-soluble, precipitated magnesium silicate acts as a stabilizer for these bleaches. 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.

Waschhilfsstoffe, die das Schmutztragevermögen von Waschflotten erhöhen, wie Carboxymethylcellulose, Carboxymethylstärke, Methylcellulose oder Copolymere von Maleinsäureanhydrid mit Methylvinylether, Schaumregulatoren, wie Mono-und Dialkylphosphorsäureester mit 16 bis 20 C-Atomen im Alkylrest sowie optische Aufheller, Desinfizienzien und/ oder proteolytische Enzyme können ebenfalls zusätzliche Bestandteile des weichmachenden Waschmittels sein.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, and optical brighteners, disinfectants and / or proteolytic enzymes additional components of the softening detergent.

Beispielexample

Frotteegewebe wurde je 5x mit einer der beiden folgenden Waschmittelzusammensetzungen gewaschen (Angaben in Gew%):

Figure imgb0006
Figure imgb0007
 Terrycloth fabric was washed 5 times with one of the following two detergent compositions (in% by weight):
Figure imgb0006
Figure imgb0007

Bei Waschmittel A handelt es sich um ein handelsübliches Waschmittel, das im Mischer erfindungsgemäß mit dem schichtförmigen kristallinen Natriumsilikat der Formel Na2Si22045 (Glühverlust 4 % (5 h/360°C)) vermengt worden war; Waschmittel B ist ein handelsübliches Waschmittel, das kristalline, schichtförmige Alkalialuminiumsilikate und kationische Tenside enthält und dessen griffverbessernde Wirkung in der Werbung herausgestellt wird.Detergent A is a commercially available detergent which, according to the invention, had been mixed in the mixer with the layered crystalline sodium silicate of the formula Na 2 Si 22 0 45 (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.

Die Griffbeurteilung durch ein Gremium von Experten ergab eine vollkommen vergleichbare griffverbessernde Wirkung. Auch wurden in beiden Fällen sehr gute Waschergebnisse erzielt.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. Weichmachendes Waschmittel mit 5 bis 7o Gew% mindestens eines Tensids, 0,5 bis 50 Gew% mindestens eines Gerüststoffes, 1 bis 20 Gew% mindestens einer kristallinen Schichtkieselsäure und/oder eines entsprechenden Alkalisilikats sowie üblichen Waschhilfsstoffen, dadurch gekennzeichnet, daß die kristalline Schichtkieselsäure oder deren Alkalisalz die allgemeine Formel M2SixO2x+1 · yH2O hat, worin x>7,0; M = Na, K oder H und y = 0 bis 25 bedeuten, und im Röntgenbeugungsdiagramm im Bereich der d-Werte von 3,0 bis 4, 0 · 10-8 cm einen oder mehrere Reflexe aufweist, die nicht Quarz, Tridymit und Cristobalit zugeordnet werden können.1. Softening detergent with 5 to 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 silica and / or a corresponding alkali silicate and conventional washing aids, characterized in that the crystalline Layered silica or its alkali salt has the general formula M 2 Si x O 2x + 1 .yH 2 O, 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 one or more reflections which are not quartz, tridymite and cristobalite can be assigned. 2. Weichmachendes Waschmittel gemäß Anspruch 1, dadurch gekennzeichnet, daß x = 7,5 bis 23 bedeutet.2. Softening detergent according to claim 1, characterized in that x = 7.5 to 23 means. 3. Weichmachendes Waschmittel gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß die kristalline Schichtkieselsäure oder deren Alkalisalz im wasserfreien Zustand je 100 g ein Kationenaustauschvermögen von 130 bis 400 mmol M+ aufweist.3. Softening detergent according to claim 1 or 2, characterized in that the crystalline layered silica or its alkali salt in the anhydrous state per 100 g has a cation exchange capacity of 130 to 400 mmol M + . 4. Weichmachendes Waschmittel gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß 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.4. Softening detergent according to one of the preceding claims, characterized in that for M = H the X-ray diffraction pattern at (3.42 + 0.1) · 10 -8 cm is 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. 5. Weichmachendes Wachmittel gemäß einem der Ansprüche 1 - 3, dadurch gekennzeichnet, daß für M = Na das Röntgenbeugungsdiagramm bei (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.5. Softening detergent according to one of claims 1-3, characterized in that for M = Na the X-ray diffraction pattern at (3.42 ± 0.15) · 10 -8 cm at least one 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. 6. Verwendung einer kristallinen Schichtkieselsäure oder deren Alkalisalz zum Weichspülen von Textilien, dadurch gekennzeichnet, daß die kristalline Schichtkieselsäure oder deren Alkalisalz durch die allgemeine Formel M2SixO2x+1 · yH20, worin x>7,0, vorzugsweise 7,5 bis 23; M = Na, K oder H und y = 0 bis 25 bedeuten, charakterisiert ist und im Röntgenbeugungsdiagramm im Bereich der d-Werte von 3,0 bis 4,0 · 10-8 cm einen oder mehrere Reflexe aufweist, die nicht Quarz, Tridymit und Cristobalit zugeordnet werden können.6. Use of a crystalline layered silica or its alkali salt for fabric softening, characterized in that the crystalline layered silica or its alkali salt by the general formula M 2 Si x O 2x + 1 · yH20, where x> 7.0, preferably 7.5 to 23; M = Na, K or H and y = 0 to 25, is characterized and has one or more reflections in the X-ray diffraction diagram in the range of the d values from 3.0 to 4.0 · 10 - 8 cm, which are not quartz, tridymite and cristobalite can be assigned.
EP85104833A 1984-05-05 1985-04-20 Softening washing agent Expired - Lifetime EP0160873B1 (en)

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EP0264615A1 (en) * 1986-09-22 1988-04-27 Henkel Kommanditgesellschaft auf Aktien Laundry agent having a reduced phosphate content containing N-alkoxylated fatty acid amides
EP0640683A2 (en) * 1993-08-25 1995-03-01 Hoechst Aktiengesellschaft Inhibitior for chemical damage of textile fibres
EP0653480A1 (en) * 1993-11-11 1995-05-17 The Procter & Gamble Company Softening through the wash compositions

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JPH02178398A (en) * 1988-12-29 1990-07-11 Lion Corp High-bulk density detergent composition
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EP0640683A2 (en) * 1993-08-25 1995-03-01 Hoechst Aktiengesellschaft Inhibitior for chemical damage of textile fibres
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EP0653480A1 (en) * 1993-11-11 1995-05-17 The Procter & Gamble Company Softening through the wash compositions

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US4728443A (en) 1988-03-01
DE3416669A1 (en) 1985-11-07
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DK166288B (en) 1993-03-29
DK166288C (en) 1993-08-23
CA1228205A (en) 1987-10-20
DK199685A (en) 1985-11-06
EP0160873B1 (en) 1991-06-26

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