EP0929621B1 - Aqueous washing-up agents - Google Patents

Aqueous washing-up agents Download PDF

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Publication number
EP0929621B1
EP0929621B1 EP97944788A EP97944788A EP0929621B1 EP 0929621 B1 EP0929621 B1 EP 0929621B1 EP 97944788 A EP97944788 A EP 97944788A EP 97944788 A EP97944788 A EP 97944788A EP 0929621 B1 EP0929621 B1 EP 0929621B1
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EP
European Patent Office
Prior art keywords
detergents
sulfates
alkyl
surfactants
monoglyceride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP97944788A
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German (de)
French (fr)
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EP0929621A1 (en
Inventor
Bernd Fabry
Manfred Weuthen
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BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the invention relates to aqueous hand dishwashing detergents containing monoglyceride (ether) sulfates and other surfactants and the use of these mixtures for the production of manual Hand dishwashing liquid.
  • DE-A-44 38 221 describes the use of monoglyceride sulfates as foam stabilizers in aqueous surfactant compositions.
  • the surfactants to be stabilized in the foam are anionic, nonionic, cationic, zwitterionic or amphoteric surfactants. In contrast to the agents according to the invention, however, no combination of the surfactants is described.
  • WO-A-95/06702 describes detergent mixtures with improved washing, rinsing, foaming and cleaning properties, which contain alkyl and / or alkylene oligoglucosides and other nonionic and / or anionic surfactants, for example monoglyceride (etehr) sulfates.
  • the agents according to the invention are also highly concentrated are flowable, have a low cloud point, largely independent of the concentration are not irritating to the skin and at the same time are voluminous, even with high fat levels stable foam and excellent dishwashing capacity.
  • the invention includes the discovery that mixtures of coconut fatty acid monoglyceride sulfate salts are included Alkyl sulfates, alkyl ether sulfates, sulfosuccinates, alkyl oligoglucosides and / or betaines to another Leads to improvement of the desired properties.
  • Monoglyceride sulfates and monoglyceride ether sulfates are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry.
  • the usual starting point for their preparation is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized.
  • suitable sulfating agents preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. EP-B1 0 561 825, EP-B1 0 561 999 (Henkel)].
  • the neutralized substances can be subjected to ultrafiltration in order to reduce the electrolyte content to a desired level [DE-A1 42 04 700 (Henkel)].
  • Overviews of the chemistry of the monoglyceride sulfates are, for example, by AKBiswas et al. in J.Am.Oil.Chem.Soc. 37 , 171 (1960) and FUAhmed J.Am.Oil.Chem.Soc. 67 , 8 (1990) .
  • Automatic dishwashing detergents containing short-chain alkyl ether sulfates and possibly monoglyceride sulfates are the subject of German design specification DE-AS 26 13 283 (Procter & Gamble).
  • the monoglyceride (ether) sulfates to be used in accordance with the invention follow the formula (I) in which R 1 CO stands for a linear or branched acyl radical with 6 to 22 carbon atoms, x, y and z in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and X stands for an alkali or alkaline earth metal.
  • Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride as well as their ethylene oxide adducts or their formulated with sulfuric acid trioxide.
  • Monoglyceride sulfates of the formula (I) are preferably used in which R 1 CO represents a linear acyl radical having 8 to 18 carbon atoms.
  • anionic surfactants which can be considered as component (b) are soaps, Alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, Sulfo fatty acids, alkyl sulfates, alkyl ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, Fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, Sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, Fatty acid sarcosinates, fatty acid taurides, N-acylamino
  • the Containing anionic surfactants polyglycol ether chains these can be conventional, preferably however, have a narrow homolog distribution.
  • Alkyl sulfates, alkyl ether sulfates are preferred and / or sulfosuccinates used.
  • the agents according to the invention can be the components (a) and (b) in a weight ratio of 90:10 to 10:90, preferably 75:25 to 15:85 and in particular 60: 40 to 25: 75 included.
  • nonionic surfactants that can be considered as component (d) are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, alk (en) yl oligoglycosides, fatty acid (N-protein) vegetable glucamides Wheat base), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaine.
  • Fatty alcohol polyglycol ethers, alkyl oligoglucosides, fatty acid N-alkyl glucamides and / or betaines are preferably used.
  • the agents according to the invention may contain components (a) and (c) or (d) in a weight ratio of 90:10 to 10:90, preferably 75:25 to 25:75 and in particular 60:40 to 40:60 and components (a ), (b) and (c) or (d) in the weight ratio (10 to 90): (5 to 85): (5 to 85) and in particular (20 to 80): (10 to 50): (10 to 50) included, with the proviso that the weight details add up to 100% by weight.
  • Another object of the invention relates to the use of the surfactant mixtures according to the invention for the production of hand dishwashing detergents.
  • the mixtures can be used in this context in minor amounts, other usual auxiliaries and additives, such as Have foam boosters, fragrances, etc.
  • the agents usually have an active substance or Proportion of surfactant - based on components (a), (b), (c) and optionally (d) - from 10 to 50 and preferably 15 to 35% by weight.
  • the foaming power was determined by the Ross Miles method using 1% by weight surfactant solutions at 20 ° C. in the presence of 1 g / l of dispersed olive oil. The base foam and the foam height are given after 5 minutes.
  • the determination of the dishwashing capacity was carried out with the help of the dish test [Fette, Seifen, Anstrichmitt ., 74 , 163 (1972)] .
  • plates with a diameter of 14 cm were soiled with 2 cm 3 of beef tallow (acid number 9-10) and stored for 24 hours at room temperature. The plates were then rinsed at 50 ° C. with 5 liters of tap water with a hardness of 16 ° d.
  • test mixtures were used at a dosage of 0.15 g active substance / l.
  • the rinsing attempt was stopped as soon as the foam had completely disappeared.
  • the skin tolerance of the comparison formulation R9 was selected as the standard according to the zeintest and all the information related to it.
  • the formulas R7 and R8 are according to the invention, the formulas R1 to R6 and R9 and R10 are used for comparison. The results are summarized in Table 1.

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  • Chemical & Material Sciences (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)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Abstract

A water-based manual dishwashing detergent composition containing(a) monoglyceride sulfates or monoglyceride ether sulfates corresponding to formula (I):in which R1CO is a linear or branched acyl group containing 6 to 22 carbon atoms, x, y and z together stand for 0 or a number from 1 to 30 and X is an alkali metal or alkaline earth metal cation,(b) anionic surfactants other than component (a), and(c) amphoteric or zwitterionic surfactants and optionally(d) nonionic surfactants.

Description

Gebiet der ErfindungField of the Invention

Die Erfindung betrifft wäßrige Handgeschirrspülmittel mit einem Gehalt an Monoglycerid(ether)sulfaten und weiteren Tensiden sowie die Verwendung dieser Mischungen zur Herstellung von manuellen Handgeschirrspülmitteln.The invention relates to aqueous hand dishwashing detergents containing monoglyceride (ether) sulfates and other surfactants and the use of these mixtures for the production of manual Hand dishwashing liquid.

Stand der TechnikState of the art

Zur manuellen Reinigung von verschmutztem Geschirr werden üblicherweise konzentrierte Tensidlösungen verwendet, an die heutzutage eine ganze Reihe teils sehr unterschiedlicher Anforderungen gestellt werden. Die Mittel sollen

  • einen möglichst hohen Aktivsubstanzgehalt aufweisen,
  • dabei flüssig oder zumindest fließfähig sein
  • einen möglichst niedrigen Kältetrübungspunkt besitzen,
  • auch in konzentrierter Form dermatologisch unbedenklich, d. h. nicht hautreizend sein,
  • auch bei hoher Fettbelastung der Flotte noch einen kräftigen, beständigen Schaum entwickeln und gleichzeitig natürlich
  • über ein hohes Tellerspülvermögen verfügen.
Concentrated surfactant solutions are usually used for the manual cleaning of dirty dishes, to which a whole series of very different requirements are made today. The funds should
  • have the highest possible active substance content,
  • be liquid or at least flowable
  • have the lowest possible cloud point,
  • also in a concentrated form dermatologically harmless, ie not irritating to the skin,
  • Develop a strong, stable foam even at high fat levels in the liquor and at the same time naturally
  • have a high dishwashing capacity.

Die DE-A-44 38 221 beschreibt die Verwendung von Monoglyceridsulfaten als Schaumstabilisator in wäßrigen Tensidzusammensetzungen. Dabei werden als Tenside, die im Schaum stabilisiert werden sollen, anionische, nichtionische, kationische, zwitterionische bzw. amphoterer Tenside genannt. Im Gegensatz zu den erfindungsgemäßen Mitteln ist jedoch keine Kombination der Tenside beschrieben. In der WO-A-95/06702 werden Detergenzmischungen mit verbessertem Wasch-, Spül-, Schaum- und Reinigungsvermögen beschrieben, die Alkyl- und/oder Alkylenoligoglucoside und weitere nichtionische und/oder anionische Tenside z.B. Monoglycerid(etehr)sulfate enthalten. DE-A-44 38 221 describes the use of monoglyceride sulfates as foam stabilizers in aqueous surfactant compositions. The surfactants to be stabilized in the foam are anionic, nonionic, cationic, zwitterionic or amphoteric surfactants. In contrast to the agents according to the invention, however, no combination of the surfactants is described. WO-A-95/06702 describes detergent mixtures with improved washing, rinsing, foaming and cleaning properties, which contain alkyl and / or alkylene oligoglucosides and other nonionic and / or anionic surfactants, for example monoglyceride (etehr) sulfates.

Auch wenn im Markt heute eine Vielzahl von Produkten vorhanden sind, besteht doch ein intensives Interesse sowohl von Seiten der Rohstofflieferanten und der Hersteller der Mittel als auch von Seiten der Kunden an Zubereitungen, die die geforderte komplexe Aufgabenstellung besser erfüllen als die Produkte des Stands der Technik. Die Aufgabe der Erfindung hat darin bestanden, diesem Bedürfnis Rechnung zu tragen.Even if there are a large number of products on the market today, there is an intensive one Interest from both the raw material suppliers and the manufacturers of the funds as well as from the side of preparations that better fulfill the required complex task than that State of the art products. The object of the invention was to meet this need To take into account.

Beschreibung der ErfindungDescription of the invention

Gegenstand der Erfindung sind wäßrige Handgeschirrspülmittel, enthaltend

  • (a) Monoglycerid(ether)sulfate der Formel (I)
    Figure 00020001
    in der R1CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen, x, y und z in Summe für 0 oder für Zahlen von 1 bis 30 und X für ein Alkali- oder Erdalkalimetall steht, und
  • (b) anionische Tenside und
  • (c) amphotere bzw. zwitterionische Tenside sowie ggf.
  • (d) nichtionische Tenside.
    • The invention relates to aqueous dishwashing detergents containing
  • (a) monoglyceride (ether) sulfates of the formula (I)
    Figure 00020001
    in which R 1 CO stands for a linear or branched acyl radical having 6 to 22 carbon atoms, x, y and z in total for 0 or for numbers from 1 to 30 and X for an alkali or alkaline earth metal, and
  • (b) anionic surfactants and
  • (c) amphoteric or zwitterionic surfactants and, if appropriate
  • (d) nonionic surfactants.

    • Überraschenderweise wurde gefunden, daß die erfindungsgemäßen Mittel auch hochkonzentriert fließfähig sind, einen niedrigen Kältetrübungspunkt aufweisen, weitgehend unabhängig von der Konzentration nicht hautreizend sind und dabei gleichzeitig noch einen voluminösen, auch bei hoher Fettbelastung stabilen Schaum und ein ausgezeichnetes Tellerspülvermögen aufweisen. Die Erfindung schließt die Erkenntnis ein, daß Mischungen von Kokosfettsäuremonoglyceridsulfat-Salzen mit Alkylsulfaten, Alkylethersulfaten, Sulfosuccinaten, Alkyloligoglucosiden und/oder Betainen zu einer weiteren Verbesserung der gewünschten Eigenschaften führt.It has surprisingly been found that the agents according to the invention are also highly concentrated are flowable, have a low cloud point, largely independent of the concentration are not irritating to the skin and at the same time are voluminous, even with high fat levels stable foam and excellent dishwashing capacity. The invention includes the discovery that mixtures of coconut fatty acid monoglyceride sulfate salts are included Alkyl sulfates, alkyl ether sulfates, sulfosuccinates, alkyl oligoglucosides and / or betaines to another Leads to improvement of the desired properties.

    Monoglycerid(ether)sulfateMonoglyceride (ether) sulfates

    Monoglyceridsulfate und Monoglyceridethersulfate stellen bekannte anionische Tenside dar, die nach den einschlägigen Methoden der präparativen organischen Chemie erhalten werden können. Üblicherweise geht man zu ihrer Herstellung von Triglyceriden aus, die gegebenenfalls nach Ethoxylierung zu den Monoglyceriden umgeestert und nachfolgend sulfatiert und neutralisiert werden. Gleichfalls ist es möglich, die Partialglyceride mit geeigneten Sulfatierungsmitteln, vorzugsweise gasförmiges Schwefeltrioxid oder Chlorsulfonsäure umzusetzen [vgl. EP-B1 0 561 825, EP-B1 0 561 999 (Henkel)]. Die neutralisierten Stoffe können - falls gewünscht - einer Ultrafiltration unterworfen werden, um den Elektrolytgehalt auf ein gewünschtes Maß zu vermindern [DE-A1 42 04 700 (Henkel)]. Übersichten zur Chemie der Monoglyceridsulfate sind beispielsweise von A.K.Biswas et al. in J.Am.Oil.Chem.Soc. 37, 171 (1960) und F.U.Ahmed J.Am.Oil.Chem.Soc. 67, 8 (1990) erschienen. Maschinelle Geschirrspülmittel mit einem Gehalt an kurzkettigen Alkylethersulfaten und gegebenenfalls Monoglyceridsulfaten sind Gegenstand der deutschen Auslegeschrift DE-AS 26 13 283 (Procter & Gamble).Monoglyceride sulfates and monoglyceride ether sulfates are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry. The usual starting point for their preparation is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized. It is also possible to react the partial glycerides with suitable sulfating agents, preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. EP-B1 0 561 825, EP-B1 0 561 999 (Henkel)]. If desired, the neutralized substances can be subjected to ultrafiltration in order to reduce the electrolyte content to a desired level [DE-A1 42 04 700 (Henkel)]. Overviews of the chemistry of the monoglyceride sulfates are, for example, by AKBiswas et al. in J.Am.Oil.Chem.Soc. 37 , 171 (1960) and FUAhmed J.Am.Oil.Chem.Soc. 67 , 8 (1990) . Automatic dishwashing detergents containing short-chain alkyl ether sulfates and possibly monoglyceride sulfates are the subject of German design specification DE-AS 26 13 283 (Procter & Gamble).

    Die im Sinne der Erfindung einzusetzenden Monoglycerid(ether)sulfate folgen der Formel (I)

    Figure 00030001
    in der R1CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen, x, y und z in Summe für 0 oder für Zahlen von 1 bis 30, vorzugsweise 2 bis 10, und X für ein Alkali- oder Erdalkalimetall steht. Typische Beispiele für im Sinne der Erfindung geeignete Monoglycerid(ether)sulfate sind die Umsetzungsprodukte von Laurinsäuremonoglycerid, Kokosfettsäuremonoglycerid, Palmitinsäuremonoglycerid, Stearinsäuremonoglycerid, Ölsäuremonoglycerid und Talgfettsäuremonoglycerid sowie deren Ethylenoxidaddukte mit Schwefeltrioxid oder Chlorsulfonsäure in Form ihrer Natriumsalze. Vorzugsweise werden Monoglyceridsulfate der Formel (I) eingesetzt, in der R1CO für einen linearen Acylrest mit 8 bis 18 Kohlenstoffatomen steht.The monoglyceride (ether) sulfates to be used in accordance with the invention follow the formula (I)
    Figure 00030001
    in which R 1 CO stands for a linear or branched acyl radical with 6 to 22 carbon atoms, x, y and z in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and X stands for an alkali or alkaline earth metal. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride as well as their ethylene oxide adducts or their formulated with sulfuric acid trioxide. Monoglyceride sulfates of the formula (I) are preferably used in which R 1 CO represents a linear acyl radical having 8 to 18 carbon atoms.

    AniontensideAnionic surfactants

    Typische Beispiele für anionische Tenside, die als Komponente (b) in Betracht kommen, sind Seifen, Alkylbenzolsulfonate, Alkansulfonate, Olefinsulfonate, Alkylethersulfonate, Glycerinethersulfonate, α-Methylestersulfonate, Sulfofettsäuren, Alkylsulfate, Alkylethersulfate, Glycerinethersulfate, Hydroxymischethersulfate, Fettsäureamid(ether)sulfate, Mono- und Dialkylsulfosuccinate, Mono- und Dialkylsulfosuccinamate, Sulfotriglyceride, Amidseifen, Ethercarbonsäuren und deren Salze, Fettsäureisethionate, Fettsäuresarcosinate, Fettsäuretauride, N-Acylaminosäuren wie beispielsweise Acyllactylate, Acyltartrate, Acylglutamate und Acylaspartate, Alkyloligoglucosidsulfate, Proteinfettsäurekondensate (insbesondere pflanzliche Produkte auf Weizenbasis) und Alkyl(ether)phosphate. Sofem die anionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen. Vorzugsweise werden Alkylsulfate, Alkylethersulfate und/oder Sulfosuccinate eingesetzt. Die erfindungsgemäßen Mittel können die Komponenten (a) und (b) im Gewichtsverhältnis 90 : 10 bis 10 : 90, vorzugsweise 75 : 25 bis 15 : 85 und insbesondere 60 : 40 bis 25 : 75 enthalten.Typical examples of anionic surfactants which can be considered as component (b) are soaps, Alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, Sulfo fatty acids, alkyl sulfates, alkyl ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, Fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, Sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, Fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as, for example, acyl lactylates, Acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable products based on wheat) and alkyl (ether) phosphates. Sofem the Containing anionic surfactants polyglycol ether chains, these can be conventional, preferably however, have a narrow homolog distribution. Alkyl sulfates, alkyl ether sulfates are preferred and / or sulfosuccinates used. The agents according to the invention can be the components (a) and (b) in a weight ratio of 90:10 to 10:90, preferably 75:25 to 15:85 and in particular 60: 40 to 25: 75 included.

    Nichtionische und amphotere TensideNonionic and amphoteric surfactants

    Typische Beispiele für nichtionische Tenside, die als Komponente (d) in Betracht kommen, sind Fettalkoholpolyglycolether, Alkylphenolpolyglycolether, Fettsäurepolyglycolester, Fettsäureamidpolyglycolether, Fettaminpolyglycolether, alkoxylierte Triglyceride, Alk(en)yloligoglykoside, Fettsäure-N-alkyl-glucamide, Proteinhydrolysate (insbesondere pflanzliche Produkte auf Weizenbasis), Polyolfettsäureester, Zuckerester, Sorbitanester, Polysorbate und Aminoxide. Sofem die nichtionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen.
    Typische Beispiele für amphotere bzw. zwitterionische Tenside sind Alkylbetaine, Alkylamidobetaine, Aminopropionate, Aminoglycinate, Imidazoliniumbetaine und Sulfo-betaine. Vorzugsweise werden Fettalkoholpolyglycolether, Alkyloligoglucoside, Fettsäure-N-alkyl-glucamide und/oder Betaine eingesetzt. Die erfindungsgemäßen Mittel können die Komponenten (a) und (c) bzw. (d) im Gewichtsverhältnis 90 : 10 bis 10 : 90, vorzugsweise 75 : 25 bis 25 : 75 und insbesondere 60 : 40 bis 40 : 60 und die Komponenten (a), (b) und (c) bzw. (d) im Gewichtsverhältnis (10 bis 90) : (5 bis 85) : (5 bis 85) und insbesondere (20 bis 80) : (10 bis 50) : (10 bis 50) enthalten, mit der Maßgabe, daß sich die Gewichtsangaben zu 100 Gew.-% ergänzen.    Typical examples of nonionic surfactants that can be considered as component (d) are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, alk (en) yl oligoglycosides, fatty acid (N-protein) vegetable glucamides Wheat base), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
    Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaine. Fatty alcohol polyglycol ethers, alkyl oligoglucosides, fatty acid N-alkyl glucamides and / or betaines are preferably used. The agents according to the invention may contain components (a) and (c) or (d) in a weight ratio of 90:10 to 10:90, preferably 75:25 to 25:75 and in particular 60:40 to 40:60 and components (a ), (b) and (c) or (d) in the weight ratio (10 to 90): (5 to 85): (5 to 85) and in particular (20 to 80): (10 to 50): (10 to 50) included, with the proviso that the weight details add up to 100% by weight.

    Gewerbliche AnwendbarkeitIndustrial applicability

    Ein weiterer Gegenstand der Erfindung betrifft die Verwendung der erfindungsgemäßen Tensidmischungen zur Herstellung von Handgeschirrspülmitteln. Die Mischungen können in diesem Zusammenhang in untergeordneten Mengen weitere übliche Hilfs- und Zusatzstoffe, wie beispielsweise Schaumbooster, Duftstoffe etc. aufweisen. Üblicherweise besitzen die Mittel einen Aktivsubstanz- bzw. Tensidanteil - bezogen auf die Komponenten (a), (b), (c) und gegebenenfalls (d) - von 10 bis 50 und vorzugsweise 15 bis 35 Gew.-%. Another object of the invention relates to the use of the surfactant mixtures according to the invention for the production of hand dishwashing detergents. The mixtures can be used in this context in minor amounts, other usual auxiliaries and additives, such as Have foam boosters, fragrances, etc. The agents usually have an active substance or Proportion of surfactant - based on components (a), (b), (c) and optionally (d) - from 10 to 50 and preferably 15 to 35% by weight.

    BeispieleExamples

    Das Schaumvermögen wurde nach der Ross-Miles-Methode unter Einsatz von 1 Gew.-%igen Tensidlösungen bei 20°C in Gegenwart von 1 g/l dispergiertem Olivenöl bestimmt. Angegeben ist der Basisschaum sowie die Schaumhöhe nach 5 min. Die Ermittlung des Tellerspülvermögens wurde mit Hilfe des Tellertestes [Fette, Seifen, Anstrichmitt., 74, 163 (1972)] durchgeführt. Hierzu wurden Teller mit einem Durchmesser von 14 cm mit je 2 cm3 Rindertalg (Säurezahl 9-10) angeschmutzt und 24 h bei Raumtemperatur gelagert. Anschließend wurden die Teller bei 50°C mit 5 l Leitungswasser der Härte 16°d gespült. Die Prüfmischungen wurden mit einer Dosierung von 0,15 g Aktivsubstanz/l eingesetzt. Der Spülversuch wurde abgebrochen, sobald der Schaum vollständig verschwunden war. Zur Bestimmung der hautkosmetischen Verträglichkeit wurde die Hautverträglichkeit der Vergleichsrezeptur R9 gemäß Zeintest als Standard gewählt und alle Angaben darauf bezogen. Die Rezepturen R7 und R8 sind erfindungsgemäß, die Rezepturen R1 bis R6 und R9 und R10 dienen dem Vergleich. Die Ergebnisse sind in Tabelle 1 zusammengefaßt. Eigenschaften von Tensidmischungen (Mengenangaben als Gew.-%) R1 R2 R3 R4 R5 R6 R7 R8 R9 R10 Kokosfettsäuremonoglyceridsulfat-Natriumsalz 15 15 15 15 - 12 12 12 - - Kokosfettalkohol+2EO-sulfat-Natriumsalz 15 - - - - 12 12 12 30 15 Laurylsulfat-Natriumsalz - 15 - - - - - - - - Di-n-octyl+2EO-sulfosuccinat-Natriumsalz - - 15 - - - - - - - Kokosalkyloligoglucosid - - - 15 - 6 - 3 - 15 Kokosfettsäurebetain - - - - 15 - 6 3 - - Wasser ad 100 Basisschaum [ml] 420 400 410 410 390 410 410 410 400 380 Schaumhöhe nach 5 min[ml] 380 380 380 380 380 380 390 390 370 350 Anzahl gespülter Teller 14 14 15 14 14 15 17 20 12 12 Kältetrübungspunkt [°C] < -3 < -3 < -3 < -3 < -3 < -3 < -3 < -3 0 0 Hautverträglichkeit [%-rel] 63 69 61 59 59 57 57 55 100 70 The foaming power was determined by the Ross Miles method using 1% by weight surfactant solutions at 20 ° C. in the presence of 1 g / l of dispersed olive oil. The base foam and the foam height are given after 5 minutes. The determination of the dishwashing capacity was carried out with the help of the dish test [Fette, Seifen, Anstrichmitt ., 74 , 163 (1972)] . For this purpose, plates with a diameter of 14 cm were soiled with 2 cm 3 of beef tallow (acid number 9-10) and stored for 24 hours at room temperature. The plates were then rinsed at 50 ° C. with 5 liters of tap water with a hardness of 16 ° d. The test mixtures were used at a dosage of 0.15 g active substance / l. The rinsing attempt was stopped as soon as the foam had completely disappeared. To determine the skin cosmetic tolerance, the skin tolerance of the comparison formulation R9 was selected as the standard according to the zeintest and all the information related to it. The formulas R7 and R8 are according to the invention, the formulas R1 to R6 and R9 and R10 are used for comparison. The results are summarized in Table 1. Properties of surfactant mixtures (quantities as% by weight) R1 R2 R3 R4 R5 R6 R7 R8 R9 R10 Coconut fatty acid monoglyceride sulfate sodium salt 15 15 15 15 - 12th 12th 12th - - Coconut fatty alcohol + 2EO sulfate sodium salt 15 - - - - 12th 12th 12th 30th 15 Lauryl sulfate sodium salt - 15 - - - - - - - - Di-n-octyl + 2EO sulfosuccinate sodium salt - - 15 - - - - - - - Coconut alkyl oligoglucoside - - - 15th - 6 - 3rd - 15th Coconut fatty acid betaine - - - - 15 - 6 3rd - - water ad 100 Base foam [ml] 420 400 410 410 390 410 410 410 400 380 Foam height after 5 min [ml] 380 380 380 380 380 380 390 390 370 350 Number of dishes washed 14 14 15 14 14 15 17th 20th 12th 12th Cold cloud point [° C] <-3 <-3 <-3 <-3 <-3 <-3 <-3 <-3 0 0 Skin tolerance [% -rel] 63 69 61 59 59 57 57 55 100 70

    Claims (7)

    1. Water-based manual dishwashing detergents containing
      (a) monoglyceride (ether) sulfates corresponding to formula (I):
      Figure 00070001
      in which R1CO is a linear or branched acyl group containing 6 to 22 carbon atoms, x, y and z together stand for 0 or a number of 1 to 30 and X is an alkali metal or alkaline earth metal,
      (b) anionic surfactants,
      (c) amphoteric or zwitterionic surfactants and optionally
      (d) nonionic surfactants.
    2. Detergents as claimed in claim 1, characterized in that they contain anionic surfactants selected from the group consisting of alkyl sulfates, alkyl ether sulfates and sulfosuccinates.
    3. Detergents as claimed in claims 1 and 2, characterized in that they contain betaines as amphoteric or zwitterionic surfactants.
    4. Detergents as claimed in claims 1 to 3, characterized in that they contain nonionic surfactants selected from the group consisting of fatty alcohol polyglycol ethers, alkyl oligoglucosides and/or fatty acid-N-alkyl glucamides.
    5. Detergents as claimed in claims 1 to 3, characterized in that they contain components (a), (b) and (c) in a ratio by weight of (10 to 90) : (5 to 85) : (5 to 85), with the proviso that the percentages by weight add up to 100% by weight.
    6. Detergents as claimed in claims 1 to 5, characterized in that they have a percentage surfactant content - based on components (a), (b), (c) and optionally (d) - of 10 to 50% by weight.
    7. The use of the compositions claimed in claims 1 to 6 for the production of manual dishwashing detergents.
    EP97944788A 1996-09-02 1997-08-25 Aqueous washing-up agents Expired - Lifetime EP0929621B1 (en)

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    DE19635555A DE19635555C2 (en) 1996-09-02 1996-09-02 Aqueous hand dishwashing liquid
    DE19635555 1996-09-02
    PCT/EP1997/004619 WO1998010047A1 (en) 1996-09-02 1997-08-25 Aqueous washing-up agents

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    DE19717950A1 (en) * 1997-04-29 1998-11-05 Henkel Kgaa Mixtures of surfactants
    US20100311633A1 (en) * 2007-02-15 2010-12-09 Ecolab Usa Inc. Detergent composition for removing fish soil
    US8093200B2 (en) 2007-02-15 2012-01-10 Ecolab Usa Inc. Fast dissolving solid detergent
    DE102007032110A1 (en) * 2007-07-09 2009-01-15 Henkel Ag & Co. Kgaa Detergents or cleaning agents with surfactants based on renewable raw materials

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    JPS5852989B2 (en) 1973-10-30 1983-11-26 ワコウジユンヤクコウギヨウ カブシキガイシヤ Monoglyceride sulfate compound
    US4024078A (en) 1975-03-31 1977-05-17 The Procter & Gamble Company Liquid detergent composition
    DE4032909A1 (en) 1990-10-17 1992-04-23 Henkel Kgaa METHOD FOR PRODUCING ALKYL SULFATE PASTES WITH IMPROVED FLOWABILITY
    DE4038477A1 (en) 1990-12-03 1992-06-04 Henkel Kgaa METHOD FOR THE CONTINUOUS PRODUCTION OF PARTIAL GLYCERIDE SULFATES
    DE4038478A1 (en) 1990-12-03 1992-06-04 Henkel Kgaa METHOD FOR PRODUCING PARTIAL GLYCERIDE SULFATES
    DE4204700A1 (en) 1992-02-17 1993-08-19 Henkel Kgaa METHOD FOR SEPARATING INORGANIC SALTS
    DE4220423A1 (en) 1992-06-22 1993-12-23 Henkel Kgaa Detergents and cleaning agents in liquid to pasty form
    DE4236506A1 (en) * 1992-10-29 1994-05-05 Henkel Kgaa Process for the preparation of aqueous solutions of anionic surfactants with improved low-temperature stability
    DE4303176C2 (en) 1993-02-04 1997-07-31 Henkel Kgaa Solid washing, rinsing and cleaning agents
    GB2280682A (en) * 1993-06-30 1995-02-08 Procter & Gamble Effective control of ammonia odor in hexangonal phase detergent gels containing urea
    ES2112556T3 (en) 1993-09-02 1998-04-01 Henkel Kgaa AQUEOUS DETERGENT MIX.
    DE4438221A1 (en) 1994-10-26 1996-05-02 Henkel Kgaa Sodium mono:glyceride sulphate use as foam stabiliser for surfactant

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