EP0555258A1 - Enzymatic liquid detergent. - Google Patents

Enzymatic liquid detergent.

Info

Publication number
EP0555258A1
EP0555258A1 EP91918230A EP91918230A EP0555258A1 EP 0555258 A1 EP0555258 A1 EP 0555258A1 EP 91918230 A EP91918230 A EP 91918230A EP 91918230 A EP91918230 A EP 91918230A EP 0555258 A1 EP0555258 A1 EP 0555258A1
Authority
EP
European Patent Office
Prior art keywords
weight
fatty
mixture
saturated
composition according
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.)
Granted
Application number
EP91918230A
Other languages
German (de)
French (fr)
Other versions
EP0555258B1 (en
Inventor
Karl Schwadtke
Eric Sung
Eduard Smulders
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0555258A1 publication Critical patent/EP0555258A1/en
Application granted granted Critical
Publication of EP0555258B1 publication Critical patent/EP0555258B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663—Stabilised liquid enzyme compositions
    • 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

Definitions

  • the invention relates to a liquid detergent which contains enzymes and is largely composed of surfactants which are obtained from native raw materials.
  • liquid detergents which contain alkyl polyglycosides as nonionic surfactants, enzymes and as solvents water and lower monofunctional alcohols with 1 to 3 carbon atoms or glycols such as 1,2-propanediol.
  • the alcoholic solvent component acts as an enzyme stabilizer.
  • Liquid detergents with enzymes are known from German patent application 31 25 533, polyols and boric acid or their boron equivalent being used as enzyme stabilizers.
  • Suitable polyols are diols, such as 1,2-propanediol or ethylene glycol, and glycerin.
  • German patent application 3910947 describes an enzymatic liquid detergent which contains anionic surfactants such as fatty alkyl sulfate and soap and, as a solvent, water and a mixture of mono- and polyfunctional alcohols.
  • the monofunctional alcohol consists of ethanol, while 1,2-propanediol is used as the polyfunctional alcohol.
  • the invention accordingly relates to an enzymatic liquid detergent, the anionic surfactants and water and as a solvent contains a mixture of mono- and polyfunctional alcohols and is characterized in that it contains fatty alkyl sulfates as anionic surfactants in the form of the sodium salts and soaps, consisting of salts of ethylenically unsaturated C12 to Cig fatty acids and saturated (2- to Cj ⁇ fatty acids in the Weight ratio of 3: 1 to 1: 3, as an organic solvent contains a mixture of ethanol and glycerol and enzymes from the group of proteases, aylases, lipases and mixtures of these.
  • Suitable fatty alkyl sulfates are the sulfuric acid monoesters of (42- to Ci8-fatty alcohols such as lauryl, myristyl or cetyl alcohol) and the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil and tallow, which also contain proportions of unsaturated alcohols, e.g. Mixtures in which the proportions of the alkyl radicals are 50 to 70% by weight up to (42, 18 to 30% by weight up to (44, 5 to 15% by weight). -% on (46, less than 3% by weight on (40 and less than 10% by weight on CQ.
  • the proportion of fatty alkyl sulfates in the compositions is preferably 3 to 20% by weight and in particular 5 to 16% by weight. - 5 -
  • the soaps are the salts of saturated and unsaturated fatty acids with ( 42 to Ci ⁇ chain lengths in the form of their mixtures.
  • a preferred soap mixture is formed from sodium oleate and the sodium salts of the saturated Ci2-Ci5 fatty acid mixtures.
  • the proportion of Ci2-i4 Fatty acids in the saturated soap component is expediently at least 60% by weight, preferably at least 75% by weight (calculated as fatty acid) .
  • Coconut fatty acids of which the proportions of 10 and Fewer carbon atoms are largely separated off
  • oleic acid and coconut fatty acid can still contain certain proportions of stearic acid, but their proportion, based on soap-forming fatty acids, should not exceed 25% by weight preferably less than 20% by weight, and a mixture of sodium oleate and the sodium salt of lauric acid is also preferred
  • the ratio of unsaturated soaps to saturated soaps is preferably 2: 1 to 1: 2 and in particular 1: 1 to 1: 1.5.
  • the arrival part of the soaps in the compositions is preferably 10 to 25% by weight and in particular 12 to 20% by weight.
  • the preferably builder-free agents contain water and a mixture of ethanol and glycerol as solvents.
  • the proportion of organic solvents is preferably 5 to 20% by weight and in particular 7 to 17% by weight.
  • the weight ratio of ethanol to glycerol is preferably 3: 1 to 1: 3 and in particular 2: 1 to 1: 1.5.
  • a mixture of ethanol and glycerin with a given weight ratio ethanol: glycerin has a higher enzyme stability than equal amounts of a mixture of ethanol and 1,2-propanediol with the same, given weight ratio ethanol: 1,2-propanediol.
  • glycerin is obtained from native and not from petrochemical raw materials.
  • glycerin in the liquid detergent according to the invention therefore also appears to be particularly advantageous from an ecological point of view.
  • the proportion of water is chosen so that non-gelling solutions are formed which are stable against segregation, for which 45-55% by weight of water are generally sufficient.
  • a greater dilution of the agents with water has no advantages because of the greater packaging requirement.
  • Preferred enzymes are proteases, in particular mixtures of protease and amylase, the weight ratio protease: amylase advantageously being between 15: 1 and 5: 1.
  • the total proportion of the enzymes is preferably 0.2 to 1% by weight and in particular 0.2 to 0.8% by weight.
  • the liquid detergents according to the invention can contain nonionic surfactants as further constituents.
  • Particularly preferred embodiments contain 1 to 10% by weight of alkyl glucosides of the general formula R0 (G) x , where R is a fatty alkyl radical, G is a glucose unit and x is a number between 1 and 10.
  • Suitable fatty alkyl glucosides are glucosides with a Cg to C22 alkyl radical.
  • the higher fatty alcohols are preferably obtained by reducing natural fats, so that within the scope of this disclosure the term alkyl in alkyl glucoside includes saturated and ethylenically unsaturated residues and their mixtures, including those with different chain lengths in the mixture.
  • a preferred alkyl radical is an im essentially from (42 to Cjg existing alkyl radical, which is derived from lauryl, myristyl, cetyl and stearyl alcohol and from technical fractions, which preferably contain saturated alcohols.
  • Particularly preferred is the use of alkyl glucosides, the alkyl radical of 50-70 wt % (42 and 18-30% by weight (44.
  • the index number x is any number between 1 and 10; it indicates the degree of oligo erization, ie the distribution of monoglucosides and oligoglucosides.
  • the average degree of oligomerization is preferred x has a value of 1.1-3.0 and in particular of significantly less than 1.5. A degree of oligomerization between 1.1 and 1.4 is particularly preferred.
  • the clear liquid agents can contain further non-ionic surfactants of the type of the adducts of 1-10 mol ethylene oxide with primary (42 to cig fatty alcohols and their mixtures such as coconut, tallow or oleyl alcohols.
  • Oxo alcohols according to The alcohols produced by the oxosynthesis or hydroformylation method are likewise suitable, but are less preferred on account of their origin from fossil raw materials, and the proportion of the fatty alcohol ethoxylates in the compositions can be 0-17% by weight, preferably up to 14% by weight .
  • the pH of the agents according to the invention is generally 7 to 10.5, preferably 7 to 9.5.
  • the agents can contain small amounts of free sodium hydroxide solution, which are required to set higher pH values between 8.5 and 10.5.
  • the detergents can contain known additives commonly used in detergents, for example salts of citric acid in amounts of 0.1-2, preferably 0.3-1% by weight (calculated as free acid), salts of polyphosphonic acids, optical brighteners, further enzyme stabilizers, filler salts and colorants and fragrances.
  • the salts of optionally present polyphosphonic acids are preferably the neutral reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and diethylenetriamine pentamethylene phosphonate in amounts of 0.1-1.5% by weight.
  • the total phosphorus content in the compositions is preferably less than 0.5%.
  • the agents can contain further enzyme stabilizers.
  • enzyme stabilizers for example, 0.5 to 1% by weight sodium formate can be used.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably 1.2% by weight, based on the enzyme.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of different foam inhibitors can also advantageously be used, eg. B. from silicone, paraffins or waxes.
  • the compositions contain 5 to 15% by weight of fatty alkyl sulfate, 10 to 20% by weight of soaps, consisting of the salt of 01-acid and the salt of saturated C42- bis (45-fatty acids or mixtures thereof in the weight ratio of oleate to saturated soap such as 2: 1 to 1: 2, 1 to 5% by weight of fatty alkyl glucoside, 12 to 17% by weight of ethanol and glycerol, 0.5 to 1% by weight of protease and 0.2 to 1% by weight. -% salt of citric acid (based on free acid).
  • Liquid detergents which contain 3 to 8% by weight of fatty alkyl sulfate, 12 to 20% by weight of soaps and consist of sodium oleate and the sodium salt of saturated (42- to (46-fatty acids or mixtures thereof) are particularly advantageous in the weight ratio of oleate to saturated soap such as 2: 1 to 1: 2, 0 to 3 wt .-% fatty alkyl glucoside, 8 to 14 wt .-% fatty alcohol with 1 to 10 moles of ethylene oxide per mole of fatty alcohol, 8 to 12 wt .-% ethanol and glycerol in a weight ratio of 2: 1 to 1: 1.5, 0.5 to 1% by weight of protease or a mixture of protease and amylase and 0 to 1% by weight of salt of citric acid (based on free acid) contain.
  • oleate to saturated soap such as 2: 1 to 1: 2, 0 to 3 wt .-% fatty alkyl glucoside
  • soaps consisting of sodium oleate and the sodium salt of saturated (42 to Cjo fatty acids or their mixtures in the weight ratio of oleate to saturated soap such as 2: 1 to 1: 1, 1 to 4% by weight of fatty alkyl glucoside, 2 to 5% by
  • the agents are notable for easy assembly, storage stability, especially at low temperatures between + 5 ° C. and -5 ° C., and easy miscibility with water. When used in mechanical washing processes, they also show good washing-in behavior.
  • the liquid detergents can be produced in a manner known per se.
  • the oleic acid and the C42 bis (46 fatty acid or the Ci2-Ci6 fatty acid mixture and optionally citric acid are first dissolved in a preheated mixture to 50-80 ° C., which contains water, sodium hydroxide and glycerol, and stirred in
  • the remaining constituents of the liquid detergent can be added in any order.
  • alkyl sulfate is added before the addition of alkyl glucoside and fatty alcohol ethoxylate.
  • the enzyme or the enzyme mixture is added as the last component, preferably at room temperature Liquid detergent stirred in. Examples
  • Liquid detergents according to the invention can be composed of the components listed in Table 1, where in particular means:
  • the fatty acid mixture (B1 + B2) contained a total of 10% by weight of stearic acid, based on the fatty acid mixture; Industrial oleic acid consisted of 12% by weight of palmitic acid.
  • the agents were prepared by first heating a mixture of water, sodium hydroxide (D) and glycerol (F2) to 70 ° C.
  • the fatty acids (B1) and (B2) and optionally citric acid (G) were stirred into the warm solution.
  • Fatty alkyl sulfate (A), alkyl glucoside (C) and fatty alcohol ethoxylate (E) were added in the order given with constant stirring.
  • ethanol (Fl) was added to the clear solution.
  • the enzyme and colorants and fragrances which belong to the remaining constituents, were added. 9
  • fatty alkyl sulfate in the above composition is partly or wholly by lauryl, myristyl or cetyl sulfate, by the sulfation product of oleyl alcohol or by the sulfation products of fatty alcohol mixtures obtained from palm and palm kernel oil and tallow, and by mixtures is replaced by these.
  • soap-forming saturated fatty acids (B2) specified in the above composition are partially or completely replaced by lauric, myristic or palmitic acid or by natural fatty acid mixtures such as hydrogenated tallow and by mixtures of these.
  • fatty alcohol ethoxylate used in the above agents is wholly or partly by pure C ⁇ 2 ⁇ C14, Ci6, saturated and unsaturated C ⁇ g fatty alcohol with 1-10 ethylene oxide groups (E0) or other native fatty alcohol - 3 mixtures, which are obtained, for example, from palm oil, palm kernel oil or dough fat, by means of Ci2-Ci4 fatty alcohol with 3 EO, Ci2-Ci4 fatty alcohol with 4 EO, Ci2-Ci8 fatty alcohol with 3 EO, Ci2-Ci8 fatty alcohol with 5 EO, by a mixture of Ci2-C ⁇ 8 fatty alcohol with 5 EO and Ci2-Ci4-fatty alcohol with 3 EO, by cetyloleyl alcohol (iodine number 50 - 55) with 2 EO, cetyloleyl alcohol (iodine number 50 - 55) with 7 EO, cetyloleyl alcohol (Iodine number 50-55) with 50% E0, by a mixture
  • the agents according to the invention are distinguished by a skin-friendly surfactant combination which is very readily biodegradable.
  • the protease activity of agents 1 to 4 was determined after 1 hour at 50 ° C. by absorbance measurement (Cenco autoanalyzer) at 420 nm relative to a known standard.
  • the absolute activity of the standard was determined by a second method ("For determining the proteolytic activity in enzyme concentrates and detergents, detergents and cleaning agents containing enzymes", HG van Raay, H. Saran, H. Verbeek, Tenside Detergents , 7th year, pages 125 to 132, 1 * 970).
  • the protease activity of agents i to 4_ was between 79 and 83% after 1 hour, in each case based on the initial value.
  • agents VI to V4 were measured, which differed from I to 1 only in that they contained (F2) 1,2-propanediol instead of glycerol.
  • the protease activity in means VI to V4 after 1 hour was between 68 and 73%, in each case based on the initial value.
  • the enzyme stability in the agents i to 1 according to the invention is therefore significantly higher than in the comparison agents VI to V4.

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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)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)

Abstract

Enzymatic detergents containing fatty alkyl sulphate and soap are more strongly stabilised by glycerine than by 1,2 propane diol. The soap consists of a mixture of salts of ethylenically unsaturated C12? to C18?-fatty acids and saturated C12? ot C18?-fatty acids in a proportion by weight of 3:1 to 1:3.

Description

"Enzvmatisches Flüssiowaschmittel" "Envmatic liquid detergent"
Die Erfindung betrifft ein Flüssigwaschmittel, das Enzyme enthält und weitgehend aus Tensiden aufgebaut ist, die aus nativen Rohstoffen gewonnen werden.The invention relates to a liquid detergent which contains enzymes and is largely composed of surfactants which are obtained from native raw materials.
Die Stabilisierung von Enzymen in Flüssigwaschmitteln stellt ein Problem dar, das bisher nicht generell gelöst werden konnte. Unbestritten ist je¬ doch, daß die Wahl des Lösungsmittels einen wesentlichen Faktor darstellt. So beschreibt die internationale Patentanmeldung WO 86/05187 Flüssigwasch¬ mittel, die Alkylpolyglykoside als nichtionische Tenside, Enzyme sowie als Lösungsmittel Wasser und niedere monofunktionelle Alkohole mit 1 bis 3 C-Atomen oder Glykole wie 1,2-Propandiol enthalten. Dabei wirkt die alko¬ holische Lösungsmittelkomponente als Enzymstabilisator.The stabilization of enzymes in liquid detergents is a problem that has not yet been generally solved. However, it is undisputed that the choice of solvent represents an essential factor. International patent application WO 86/05187 describes liquid detergents which contain alkyl polyglycosides as nonionic surfactants, enzymes and as solvents water and lower monofunctional alcohols with 1 to 3 carbon atoms or glycols such as 1,2-propanediol. The alcoholic solvent component acts as an enzyme stabilizer.
Aus der deutschen Patentanmeldung 31 25 533 sind Flüssigwaschmittel mit Enzymen bekannt, wobei als Enzymstabilisatoren Polyole und Borsäure oder deren Boräquivalent eingesetzt werden. Geeignete Polyole sind Diole, wie 1,2-Propandiol oder Ethylenglykol, und Glycerin.Liquid detergents with enzymes are known from German patent application 31 25 533, polyols and boric acid or their boron equivalent being used as enzyme stabilizers. Suitable polyols are diols, such as 1,2-propanediol or ethylene glycol, and glycerin.
Die deutsche Patentanmeldung 3910947 beschreibt ein enzy atisches Flüs¬ sigwaschmittel, das anionische Tenside wie Fettalkylsulfat und Seife sowie als Lösungsmittel Wasser und eine Mischung aus mono- und polyfunktionellen Alkoholen enthält. Dabei besteht der monofunktionelle Alkohol aus Ethanol, während als polyfunktioneller Alkohol 1,2-Propandiol eingesetzt wird.German patent application 3910947 describes an enzymatic liquid detergent which contains anionic surfactants such as fatty alkyl sulfate and soap and, as a solvent, water and a mixture of mono- and polyfunctional alcohols. The monofunctional alcohol consists of ethanol, while 1,2-propanediol is used as the polyfunctional alcohol.
Überraschenderweise wurde nun festgestellt, daß Enzyme in einem Flüssig¬ waschmittel, das bestimmte Aniontenside enthält, durch Glycerin in stär¬ kerem Ausmaß stabilisiert werden als durch 1,2-Propandiol.Surprisingly, it has now been found that enzymes in a liquid detergent which contains certain anionic surfactants are stabilized to a greater extent by glycerol than by 1,2-propanediol.
Gegenstand der Erfindung ist dementsprechend ein enzymatisches Flüssig- Waschmittel, das anionische Tenside sowie als Lösungsmittel Wasser und eine Mischung aus mono- und polyfunktionellen Alkoholen enthält und das dadurch gekennzeichnet ist, daß es als Aniontenside Fettalkylsulfate in Form der Natriumsalze und Seifen, bestehend aus Salzen ethylenisch unge¬ sättigter C12- bis Cig-Fettsäuren und gesättigter ( 2- bis Cjβ- Fettsäuren im Gewichtsverhältnis von 3 : 1 bis 1 : 3, als organisches Lö¬ sungsmittel eine Mischung aus Ethanol und Glycerin und Enzyme aus der Gruppe der Proteasen, A ylasen, Lipasen und Gemische aus diesen enthält.The invention accordingly relates to an enzymatic liquid detergent, the anionic surfactants and water and as a solvent contains a mixture of mono- and polyfunctional alcohols and is characterized in that it contains fatty alkyl sulfates as anionic surfactants in the form of the sodium salts and soaps, consisting of salts of ethylenically unsaturated C12 to Cig fatty acids and saturated (2- to Cjβ fatty acids in the Weight ratio of 3: 1 to 1: 3, as an organic solvent contains a mixture of ethanol and glycerol and enzymes from the group of proteases, aylases, lipases and mixtures of these.
Als Fettalkylsulfate eignen sich die Schwefelsäuremonoester der (42- bis Ci8-Fettalkohole, wie Lauryl-, Myristyl- oder Cetylalkohol, und der aus Kokosöl, Palm- und Palmkernöl sowie Talg gewonnenen Fettalkoholgemische, die zusätzlich noch Anteile an ungesättigten Alkoholen, z. B. Qleylalko- hol, enthalten können. Eine bevorzugte Verwendung finden dabei Gemische, in denen die Anteile der Alkylreste zu 50 bis 70 Gew.-% auf (42, zu 18 bis 30 Gew.-% auf (44, zu 5 bis 15 Gew.-% auf (46, unter 3 Gew.-% auf (40 und unter 10 Gew.-% auf C Q verteilt sind. Der Anteil an FettalkylSulfaten in den Mitteln beträgt vorzugsweise 3 bis 20 Gew.-% und insbesondere 5 bis 16 Gew.-5-Suitable fatty alkyl sulfates are the sulfuric acid monoesters of (42- to Ci8-fatty alcohols such as lauryl, myristyl or cetyl alcohol) and the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil and tallow, which also contain proportions of unsaturated alcohols, e.g. Mixtures in which the proportions of the alkyl radicals are 50 to 70% by weight up to (42, 18 to 30% by weight up to (44, 5 to 15% by weight). -% on (46, less than 3% by weight on (40 and less than 10% by weight on CQ. The proportion of fatty alkyl sulfates in the compositions is preferably 3 to 20% by weight and in particular 5 to 16% by weight. - 5 -
Als Seifen sind die Salze von gesättigten und ungesättigten Fettsäuren mit (42- bis Ciβ-Kettenl ngen in Form ihrer Gemische geeignet. Ein bevorzugt verwendetes Seifengemisch wird aus Natriumoleat und den Natriumsalzen der gesättigten Ci2-Ci5-Fettsäuregemische gebildet. Der Anteil an Ci2- i4-Fett- säuren in der gesättigten Seifenkomponente beträgt zweckmäßigerweise min¬ destens 60 Gew.-%, vorzugsweise mindestens 75 Gew.-% (gerechnet als Fett¬ säure). Geeignet hierfür sind z. B. Kokosfettsäuren, von denen die Anteile mit 10 und weniger C-Atomen weitgehend abgetrennt sind. Wie bei tech¬ nischen Fettsäureschnitten üblich, können die Ölsäure sowie die Kokosfett¬ säure noch gewisse Anteile an Stearinsäure enthalten, jedoch soll deren Anteil, bezogen auf seifenbildende Fettsäuren, höchstens 25 Gew.-%, vor¬ zugsweise weniger als 20 Gew.-% betragen. Ebenso bevorzugt ist ein Sei¬ fengemisch aus Natriumoleat und dem Natriumsalz der Laurinsäure. Das Ge¬ wichtsverhältnis von ungesättigten Seifen zu gesättigten Seifen beträgt vorzugsweise 2 : 1 bis 1 : 2 und insbesondere 1 : 1 bis 1 : 1,5. Der An- teil der Seifen in den Mitteln beträgt vorzugsweise 10 bis 25 Gew.-% und insbesondere 12 bis 20 Gew.-%.The soaps are the salts of saturated and unsaturated fatty acids with ( 42 to Ciβ chain lengths in the form of their mixtures. A preferred soap mixture is formed from sodium oleate and the sodium salts of the saturated Ci2-Ci5 fatty acid mixtures. The proportion of Ci2-i4 Fatty acids in the saturated soap component is expediently at least 60% by weight, preferably at least 75% by weight (calculated as fatty acid) .Coconut fatty acids, of which the proportions of 10 and Fewer carbon atoms are largely separated off As is customary in technical fatty acid cuts, oleic acid and coconut fatty acid can still contain certain proportions of stearic acid, but their proportion, based on soap-forming fatty acids, should not exceed 25% by weight preferably less than 20% by weight, and a mixture of sodium oleate and the sodium salt of lauric acid is also preferred The ratio of unsaturated soaps to saturated soaps is preferably 2: 1 to 1: 2 and in particular 1: 1 to 1: 1.5. The arrival part of the soaps in the compositions is preferably 10 to 25% by weight and in particular 12 to 20% by weight.
Die vorzugsweise buildersubstanzfreien Mittel enthalten als Lösungsmittel Wasser und eine Mischung aus Ethanol und Glycerin. Der Anteil der orga¬ nischen Lösungsmittel beträgt vorzugsweise 5 bis 20 Gew.-% und insbeson¬ dere 7 bis 17 Gew.-%. Das Gewichtsverhältnis von Ethanol zu Glycerin be¬ trägt vorzugsweise 3 : 1 bis 1 : 3 und insbesondere 2 : 1 bis 1 : 1,5. Überraschenderweise bewirkt eine Mischung aus Ethanol und Glycerin mit einem vorgegebenen Gewichtsverhältnis Ethanol : Glycerin eine höhere Enzymstabilität als gleiche Mengen einer Mischung aus Ethanol und 1,2-Propandiol mit demselben, vorgegebenem GewichtsVerhältnis Ethanol : 1,2-Propandiol. Zudem wird Glycerin aus nativen und nicht aus petro- chemischen Rohstoffen gewonnen. Der Einsatz von Glycerin im erfindungsge¬ mäßen Flüssigwaschmittel erscheint daher auch aus ökologischer Sicht be¬ sonders vorteilhaft. Der Anteil des Wassers wird so gewählt, daß nicht-ge- lierende Lösungen entstehen, die stabil gegen Entmischung sind, wozu im allgemeinen 45 - 55 Gew.-% Wasser ausreichen. Ein stärkeres Verdünnen der Mittel mit Wasser bringt wegen des größeren Verpackungsbedarfs keine Vor¬ teile.The preferably builder-free agents contain water and a mixture of ethanol and glycerol as solvents. The proportion of organic solvents is preferably 5 to 20% by weight and in particular 7 to 17% by weight. The weight ratio of ethanol to glycerol is preferably 3: 1 to 1: 3 and in particular 2: 1 to 1: 1.5. Surprisingly, a mixture of ethanol and glycerin with a given weight ratio ethanol: glycerin has a higher enzyme stability than equal amounts of a mixture of ethanol and 1,2-propanediol with the same, given weight ratio ethanol: 1,2-propanediol. In addition, glycerin is obtained from native and not from petrochemical raw materials. The use of glycerin in the liquid detergent according to the invention therefore also appears to be particularly advantageous from an ecological point of view. The proportion of water is chosen so that non-gelling solutions are formed which are stable against segregation, for which 45-55% by weight of water are generally sufficient. A greater dilution of the agents with water has no advantages because of the greater packaging requirement.
Bevorzugte Enzyme sind Proteasen, insbesondere Gemische aus Protease und Amylase, wobei das Gewichtsverhältnis Protease : Amylase vorteilhafter¬ weise zwischen 15 : 1 und 5 : 1 liegt. Der Anteil der Enzyme insgesamt beträgt vorzugsweise 0,2 bis 1 Gew.-% und insbesondere 0,2 bis 0,8 Gew.-%.Preferred enzymes are proteases, in particular mixtures of protease and amylase, the weight ratio protease: amylase advantageously being between 15: 1 and 5: 1. The total proportion of the enzymes is preferably 0.2 to 1% by weight and in particular 0.2 to 0.8% by weight.
Die erfindungsgemäßen Flüssigwaschmittel können als weitere Bestandteile nichtionische Tenside enthalten. Besonders bevorzugte Ausführungsformen enthalten 1 bis 10 Gew.-% Alkylglucoside der allgemeinen Formel R0(G)x, wobei R einen Fettalkylrest, G eine Glucoseeinheit und x eine Zahl zwi¬ schen 1 und 10 darstellt. Als Fettalkylglucoside eignen sich Glucoside mit einem Cg- bis C22-Alkylrest. Die höheren Fettalkohole werden vorzugsweise durch Reduktion natürlicher Fette gewonnen, so daß im Rahmen dieser Offen¬ barung der Begriff Alkyl in Alkylglucosid gesättigte und ethylenisch unge¬ sättigte Reste und deren Gemische einschließlich solcher mit verschiedenen Kettenlängen im Gemisch umfaßt. Ein bevorzugter Alkylrest ist ein im wesentlichen aus (42 bis Cjg bestehender Alkylrest, der sich von Lauryl-, Myristyl-, Cetyl- und Stearylalkohol sowie von technischen Fraktionen, die vorzugsweise gesättigte Alkohole enthalten, ableitet. Besonders bevorzugt ist der Einsatz von Alkylglucosiden, deren Alkylrest zu 50 - 70 Gew.-% (42 und 18 - 30 Gew.-% (44 enthält. Die Indexzahl x ist eine beliebige Zahl zwischen 1 und 10; sie gibt den Oligo erisierungsgrad, d. h. die Vertei¬ lung von Monoglucosiden und Oligoglucosiden an. Während x in einer gegebe¬ nen Verbindung immer eine ganze Zahl sein muß und hier vor allem die Werte x = 1 - 6 annehmen kann, ist der Wert x für ein spezielles Produkt eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise hat der mittlere Oligomerisierungsgrad x einen Wert von 1,1 - 3,0 und insbesondere .von deutlich kleiner als 1,5. Besonders bevorzugt ist ein Oligomerisierungsgrad zwischen 1,1 und 1,4.The liquid detergents according to the invention can contain nonionic surfactants as further constituents. Particularly preferred embodiments contain 1 to 10% by weight of alkyl glucosides of the general formula R0 (G) x , where R is a fatty alkyl radical, G is a glucose unit and x is a number between 1 and 10. Suitable fatty alkyl glucosides are glucosides with a Cg to C22 alkyl radical. The higher fatty alcohols are preferably obtained by reducing natural fats, so that within the scope of this disclosure the term alkyl in alkyl glucoside includes saturated and ethylenically unsaturated residues and their mixtures, including those with different chain lengths in the mixture. A preferred alkyl radical is an im essentially from (42 to Cjg existing alkyl radical, which is derived from lauryl, myristyl, cetyl and stearyl alcohol and from technical fractions, which preferably contain saturated alcohols. Particularly preferred is the use of alkyl glucosides, the alkyl radical of 50-70 wt % (42 and 18-30% by weight (44. The index number x is any number between 1 and 10; it indicates the degree of oligo erization, ie the distribution of monoglucosides and oligoglucosides. While x in one Given the compound must always be an integer and here can assume the values x = 1 - 6, the value x for a special product is an analytically determined arithmetic parameter, which usually represents a fractional number. The average degree of oligomerization is preferred x has a value of 1.1-3.0 and in particular of significantly less than 1.5. A degree of oligomerization between 1.1 and 1.4 is particularly preferred.
Die klarflüssigen Mittel können zusätzlich zu Alkylglucosid weitere nicht¬ ionische Tenside vom Typ der Anlagerungsprodukte von 1 - 10 Mol Ethylen- oxid an primäre (42- bis Cig-Fettalkohole und deren Gemische wie Kokos-, Taigfett- oder Oleylalkohole enthalten. Oxoalkohole (nach der Methode der Oxosynthese bzw. Hydroformylierung hergestellte Alkohole) sind gleichfalls geeignet, jedoch aufgrund ihrer Herkunft aus fossilen Rohstoffen weniger bevorzugt. Der Anteil der Fettal oholethoxylate in den Mitteln kann 0 - 17 Gew.-%, vorzugsweise bis zu 14 Gew.-%, betragen.In addition to alkyl glucoside, the clear liquid agents can contain further non-ionic surfactants of the type of the adducts of 1-10 mol ethylene oxide with primary (42 to cig fatty alcohols and their mixtures such as coconut, tallow or oleyl alcohols. Oxo alcohols (according to The alcohols produced by the oxosynthesis or hydroformylation method are likewise suitable, but are less preferred on account of their origin from fossil raw materials, and the proportion of the fatty alcohol ethoxylates in the compositions can be 0-17% by weight, preferably up to 14% by weight .
Der pH-Wert der erfindungsgemäßen Mittel beträgt im allgemeinen 7 bis 10,5, vorzugsweise 7 bis 9,5. Dabei können die Mittel geringe Mengen an freier Natronlauge enthalten, die zur Einstellung höherer pH-Werte zwischen 8,5 und 10,5 erforderlich sind.The pH of the agents according to the invention is generally 7 to 10.5, preferably 7 to 9.5. The agents can contain small amounts of free sodium hydroxide solution, which are required to set higher pH values between 8.5 and 10.5.
Außer den genannten Inhaltsstoffen können die Mittel bekannte, in Wasch¬ mitteln üblicherweise eingesetzte Zusatzstoffe, beispielsweise Salze der Citronensäure in Mengen von 0,1 - 2, vorzugsweise 0,3 - 1 Gew.-% (berech¬ net als freie Säure), Salze von Polyphosphonsäuren, optische Aufheller, weitere Enzymstab lisatoren, Füllsalze sowie Färb- und Duftstoffe enthal¬ ten. Als Salze von gegebenenfalls vorhandenen Polyphosphonsäuren werden vor¬ zugsweise die neutral reagierenden Natriumsalze von beispielsweise 1-Hy- droxyethan-1,1-diphosphonat und Diethylentriamin-pentamethylenphosphonat in Mengen von 0,1 - 1,5 Gew.-% verwendet. Vorzugsweise beträgt der Phos¬ phor-Gesamtanteil in den Mitteln weniger als 0,5 %.In addition to the ingredients mentioned, the detergents can contain known additives commonly used in detergents, for example salts of citric acid in amounts of 0.1-2, preferably 0.3-1% by weight (calculated as free acid), salts of polyphosphonic acids, optical brighteners, further enzyme stabilizers, filler salts and colorants and fragrances. The salts of optionally present polyphosphonic acids are preferably the neutral reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and diethylenetriamine pentamethylene phosphonate in amounts of 0.1-1.5% by weight. The total phosphorus content in the compositions is preferably less than 0.5%.
Zusätzlich zu den mono- und polyfunktionellen Alkoholen können die Mittel weitere Enzymstabilisatoren enthalten. Beispielsweise können 0,5 bis 1 Gew.-% Natriumformiat eingesetzt werden. Möglich ist auch der Einsatz von Proteasen, die mit löslichen Calciumsalzen und einem Calciumgehalt von vorzugsweise 1,2 Gew.-%, bezogen auf das Enzym, stabilisiert sind. Beson¬ ders vorteilhaft ist jedoch der Einsatz von Borverbindungen, beispielswei¬ se von Borsäure, Boroxid, Borax und anderen Alkalimetallboraten wie den Salzen der Orthoborsäure (H3BO3), der Metaborsäure (HBO2) und der Pyro- borsäure (Tetraborsäure H2B4O7).In addition to the mono- and polyfunctional alcohols, the agents can contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous.
Beim Einsatz in maschinellen Waschverfahren kann es von Vorteil sein, den Mitteln übliche Schauminhibitoren zuzusetzen. Geeignete nichttensidartige Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemi¬ sche mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Pa¬ raffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure. Mit Vorteil können auch Gemische verschiedener Schauminhibi¬ toren verwendet werden, z. B. solche aus Silikonen, Paraffinen oder Wachsen.When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of different foam inhibitors can also advantageously be used, eg. B. from silicone, paraffins or waxes.
In einer bevorzugten Ausführungsform enthalten die Mittel 5 bis 15 Gew.-% Fettalkylsulfat, 10 bis 20 Gew.-% Seifen, bestehend aus dem Salz der 01- säure und dem Salz gesättiger C42- bis (45-Fettsäuren oder deren Gemischen im Gewichtsverhältnis Oleat zu gesättigter Seife wie 2 : 1 bis 1 :2, 1 bis 5 Gew.-% Fettalkylglucosid, 12 bis 17 Gew.-% Ethanol und Glycerin, 0,5 bis 1 Gew.-% Protease sowie 0,2 bis 1 Gew.-% Salz der Citronensäure (bezogen auf freie Säure).In a preferred embodiment, the compositions contain 5 to 15% by weight of fatty alkyl sulfate, 10 to 20% by weight of soaps, consisting of the salt of 01-acid and the salt of saturated C42- bis (45-fatty acids or mixtures thereof in the weight ratio of oleate to saturated soap such as 2: 1 to 1: 2, 1 to 5% by weight of fatty alkyl glucoside, 12 to 17% by weight of ethanol and glycerol, 0.5 to 1% by weight of protease and 0.2 to 1% by weight. -% salt of citric acid (based on free acid).
Besonders vorteilhaft sind Flüssigwaschmittel, die 3 bis 8 Gew.-% Fett¬ alkylsulfat, 12 bis 20 Gew.-% Seifen, bestehend aus Natriumoleat und dem Natriumsalz von gesättigten (42- bis (46-Fettsäuren oder deren Gemischen im Gewichtsverhältnis Oleat zu gesättigter Seife wie 2 : 1 bis 1 : 2, 0 bis 3 Gew.-% Fettalkylglucosid, 8 bis 14 Gew.-% Fettalkohol mit 1 bis 10 Mol Ethylenoxid pro Mol Fettalkohol, 8 bis 12 Gew.-% Ethanol und Glycerin im Gewichtsverhältnis 2 : 1 bis 1 : 1,5, 0,5 bis 1 Gew.-% Protease oder einer Mischung aus Protease und Amylase sowie 0 bis 1 Gew.-% Salz der Ci- tronensäure (bezogen auf freie Säure) enthalten.Liquid detergents which contain 3 to 8% by weight of fatty alkyl sulfate, 12 to 20% by weight of soaps and consist of sodium oleate and the sodium salt of saturated (42- to (46-fatty acids or mixtures thereof) are particularly advantageous in the weight ratio of oleate to saturated soap such as 2: 1 to 1: 2, 0 to 3 wt .-% fatty alkyl glucoside, 8 to 14 wt .-% fatty alcohol with 1 to 10 moles of ethylene oxide per mole of fatty alcohol, 8 to 12 wt .-% ethanol and glycerol in a weight ratio of 2: 1 to 1: 1.5, 0.5 to 1% by weight of protease or a mixture of protease and amylase and 0 to 1% by weight of salt of citric acid (based on free acid) contain.
Ebenso bevorzugt ist die Verwendung von Mitteln, enthaltend 5 bis 12 Gew.-% Fettalkylsulfat, 10 bis 18 Gew-% Seifen, bestehend aus Natriumoleat und dem Natriumsalz von gesättigten (42- bis Cjö-Fettsäuren oder deren Gemischen im Gewichtsverhältnis Oleat zu gesättigter Seife wie 2 : 1 bis 1 : 1, 1 bis 4 Gew.-% Fettalkylglucosid, 2 bis 5 Gew.-% Fettalkohole mit 1 bis 10 Mol Ethylenoxid pro Mol Fettalkohol, 10 - 17 Gew.-% Ethanol und Glycerin, 0,3 - 1 Gew.-% Salz der Citronensäure (berechnet als freie Säure), 0,3 bis 1 Gew.-% Enzym sowie 0,5 bis 1,5 Gew.-% Borsäure.Likewise preferred is the use of agents containing 5 to 12% by weight of fatty alkyl sulfate, 10 to 18% by weight of soaps consisting of sodium oleate and the sodium salt of saturated (42 to Cjo fatty acids or their mixtures in the weight ratio of oleate to saturated soap such as 2: 1 to 1: 1, 1 to 4% by weight of fatty alkyl glucoside, 2 to 5% by weight of fatty alcohols with 1 to 10 moles of ethylene oxide per mole of fatty alcohol, 10 to 17% by weight of ethanol and glycerin, 0.3 - 1% by weight of citric acid salt (calculated as free acid), 0.3 to 1% by weight of enzyme and 0.5 to 1.5% by weight of boric acid.
Die Mittel zeichnen sich durch eine gute Konfektionierbarkeit, Lagersta¬ bilität insbesondere auch bei tiefen Temperaturen zwischen +5°C und -5°C und leichte Vermischbarkeit mit Wasser aus. Bei der Verwendung in maschi¬ nellen Waschverfahren zeigen sie zudem ein gutes Einspülverhalten.The agents are notable for easy assembly, storage stability, especially at low temperatures between + 5 ° C. and -5 ° C., and easy miscibility with water. When used in mechanical washing processes, they also show good washing-in behavior.
Die Flüssigwaschmittel können in an sich bekannter Weise hergestellt wer¬ den. Vorzugsweise werden die Ölsäure und die C42- bis (46-Fettsäure bzw. das Ci2-Ci6-Fettsäuregemisch und ggf. Citronensäure zunächst in einer auf 50 - 80 °C vorgewärmten Mischung, die Wasser, Natriumhydroxid und Glycerin enthält, unter Rühren gelöst und in ihre Salze überführt. Die übrigen Be¬ standteile des Flüssigwaschmittels können in beliebiger Reihenfolge zuge¬ geben werden. Vorteilhafterweise erfolgt die Zugabe von Alkylsulfat vor der Zugabe von Alkylglucosid und Fettalkoholethoxylat. Das Enzym bzw. das Eπzymgemisch wird als letzte Komponente, vorzugsweise bei Raumtemperatur in das Flüssigwaschmittel eingerührt. B e i s p i e l eThe liquid detergents can be produced in a manner known per se. Preferably, the oleic acid and the C42 bis (46 fatty acid or the Ci2-Ci6 fatty acid mixture and optionally citric acid are first dissolved in a preheated mixture to 50-80 ° C., which contains water, sodium hydroxide and glycerol, and stirred in The remaining constituents of the liquid detergent can be added in any order. Advantageously, alkyl sulfate is added before the addition of alkyl glucoside and fatty alcohol ethoxylate. The enzyme or the enzyme mixture is added as the last component, preferably at room temperature Liquid detergent stirred in. Examples
Erfindungsgemäße Flüssigwaschmittel können aus den in Tabelle 1 aufgeführ¬ ten Komponenten zusammengesetzt sein, wobei im einzelnen bedeutet:Liquid detergents according to the invention can be composed of the components listed in Table 1, where in particular means:
<<
(A) Natriumfettalkylsulfat mit einer C-Kettenverteilung von 1 Gew.- CIQ , 62 Gew.-% C12, 23 Gew.-% Ci4, 11 Gew.-% Ci6, 3 Gew.-% Cis; der Gehalt an freiem Fettalkohol im Fettalkoholsulfat betrug weniger als 1 Gew.-%.(A) sodium fatty alkyl sulfate with a carbon chain distribution of 1% by weight CIQ, 62% by weight C12, 23% by weight Ci4, 11% by weight Ci6, 3% by weight cis; the content of free fatty alcohol in the fatty alcohol sulfate was less than 1% by weight.
(Bl) Ölsäure, technisch(Bl) oleic acid, technically
(B2) Kokosfettsäure (C12-C18)(B2) coconut fatty acid (C12-C18)
Das Fettsäuregemisch (Bl + B2) enthielt insgesamt 10 Gew.-% Stearinsäure, bezogen auf das Fettsäuregemisch; technische Ölsäure bestand zu 12 Gew.-% aus Palmitinsäure.The fatty acid mixture (B1 + B2) contained a total of 10% by weight of stearic acid, based on the fatty acid mixture; Industrial oleic acid consisted of 12% by weight of palmitic acid.
(C) Ci2-Ci4-Alkylglucosid (native Basis); Oligomerisierungsgrad x = 1,4(C) Ci2-Ci4-alkyl glucoside (native basis); Degree of oligomerization x = 1.4
(D) Natriumhydroxid(D) sodium hydroxide
(E) Ci2-Cιg-Fettalkohol mit 7 Ethylenoxidgruppen (EO) (Fl) Ethanol(E) Ci2-Cιg fatty alcohol with 7 ethylene oxide groups (EO) (Fl) ethanol
(F2) Glycerin(F2) glycerin
(G) Citronensäure (berechnet als freie Säure)(G) citric acid (calculated as free acid)
(H) Protease(H) protease
Die Mittel wurden in der Weise hergestellt, daß zunächst eine Mischung aus Wasser, Natriumhydroxid (D) und Glycerin (F2) auf 70 °C erwärmt wurde. In die warme Lösung wurden die Fettsäuren (Bl) und (B2) und ggf. Citronen¬ säure (G) eingerührt. Die Zugabe von Fettalkylsulfat (A), Alkylglucosid (C) und Fettalkoholethoxylat (E) erfolgte in der angegebenenen Reihenfolge unter ständigem Rühren. Nach Abkühlung auf 35 °C wurde der klaren Lösung Ethanol (Fl) zugefügt. Nach dem Abkühlen auf Raumtemperatur erfolgte die Zugabe von Enzym sowie von Färb- und Duftstoffen, die zu den restlichen Bestandteilen gehören. 9The agents were prepared by first heating a mixture of water, sodium hydroxide (D) and glycerol (F2) to 70 ° C. The fatty acids (B1) and (B2) and optionally citric acid (G) were stirred into the warm solution. Fatty alkyl sulfate (A), alkyl glucoside (C) and fatty alcohol ethoxylate (E) were added in the order given with constant stirring. After cooling to 35 ° C., ethanol (Fl) was added to the clear solution. After cooling to room temperature, the enzyme and colorants and fragrances, which belong to the remaining constituents, were added. 9
Weitere erfindungsgemäße Mittel werden erhalten, wenn das Fettalkylsulfat in der obigen Zusammensetzung teilweise oder ganz durch Lauryl-, Myristyl- oder Cetylsulfat, durch das Sulfatierungsprodukt von Oleylalkohol oder durch die Sulfatierungsprodukte von aus Palm- und Pal kernöl und Talg ge¬ wonnenen Fettalkoholgemischen sowie durch Mischungen von diesen ersetzt wird.Further agents according to the invention are obtained if the fatty alkyl sulfate in the above composition is partly or wholly by lauryl, myristyl or cetyl sulfate, by the sulfation product of oleyl alcohol or by the sulfation products of fatty alcohol mixtures obtained from palm and palm kernel oil and tallow, and by mixtures is replaced by these.
Weitere erfindungsgemäße Mittel werden auch erhalten, wenn die in der obi¬ gen Zusammensetzung angegebenen seifenbildenden gesättigten Fettsäuren (B2) teilweise oder ganz durch Laurin-, Myristin- oder Palmitinsäure oder durch natürliche Fettsäuregemische wie hydriertem Talg sowie durch Mi¬ schungen von diesen ersetzt werden.Further agents according to the invention are also obtained if the soap-forming saturated fatty acids (B2) specified in the above composition are partially or completely replaced by lauric, myristic or palmitic acid or by natural fatty acid mixtures such as hydrogenated tallow and by mixtures of these.
Ebenso werden weitere erfindungsgemäße Mittel dadurch erhalten, daß das in den obigen Mitteln eingesetzte Fettalkoholethoxylat ganz oder teilweise durch reinen Cχ2-ι C14-, Ci6-, gesättigten und ungesättigten Cχg-Fettal- kohol mit 1 - 10 Ethylenoxidgruppen (E0) oder anderen nativen Fettalkohol- 3 mischungen, die beispielsweise aus Palm-, Palmkernöl oder Taigfett gewon¬ nen werden, durch Ci2-Ci4-Fettalkohol mit 3 EO, Ci2-Ci4-Fettalkohol mit 4 EO, Ci2-Ci8-Fettalkohol mit 3 EO, Ci2-Ci8-Fettalkohol mit 5 EO, durch ein Gemisch von Ci2-Cχ8-Fettalkohol mit 5 EO und Ci2-Ci4-Fettalkohol mit 3 EO, durch Cetyloleylalkohol (Jodzahl 50 - 55) mit 2 EO, Cetyloleylalkohol (Jodzahl 50 - 55) mit 7 EO, Cetyloleylalkohol (Jodzahl 50 - 55) mit 50 % E0, durch ein Gemisch von Cetyloleylalkohol mit 5 E0 und Cetyloleylalkohol mit 10 E0 oder durch Mischungen von diesen ersetzt wird.Likewise, further agents according to the invention are obtained in that the fatty alcohol ethoxylate used in the above agents is wholly or partly by pure Cχ2 ι C14, Ci6, saturated and unsaturated Cχg fatty alcohol with 1-10 ethylene oxide groups (E0) or other native fatty alcohol - 3 mixtures, which are obtained, for example, from palm oil, palm kernel oil or dough fat, by means of Ci2-Ci4 fatty alcohol with 3 EO, Ci2-Ci4 fatty alcohol with 4 EO, Ci2-Ci8 fatty alcohol with 3 EO, Ci2-Ci8 fatty alcohol with 5 EO, by a mixture of Ci2-Cχ8 fatty alcohol with 5 EO and Ci2-Ci4-fatty alcohol with 3 EO, by cetyloleyl alcohol (iodine number 50 - 55) with 2 EO, cetyloleyl alcohol (iodine number 50 - 55) with 7 EO, cetyloleyl alcohol (Iodine number 50-55) with 50% E0, by a mixture of cetyloleyl alcohol with 5 E0 and cetyloleyl alcohol with 10 E0 or by mixtures of these.
Ebenfalls erfinduπgsgemäße Produkte werden erhalten, wenn das in der obi¬ gen Zusammensetzung angegebene Alkylglucosid ganz oder teilweise durch Ci2-Alkylglucosid mit x = 1,1 - 3, Ci4-Alkylglucosid mit x = 1,1 - 3, C - Alkylglucosid mit x = 1,1 - 3, Ci8-Alkylglucosid mit x = 1,1 - 3 sowie Alkylglucosiden mit x = 1,1 - 3, deren Fettalkylrest sich von anderen technischen Fraktionen ableitet, die im wesentlichen gesättigte Fettalko¬ hole enthalten, ableitet, ersetzt wird.Products according to the invention are also obtained if the alkyl glucoside specified in the above composition is wholly or partly by Ci2-alkyl glucoside with x = 1.1 - 3, Ci4-alkyl glucoside with x = 1.1 - 3, C - alkyl glucoside with x = 1,1-3, Ci8-alkyl glucoside with x = 1.1-3 and alkylglucosides with x = 1.1-3, whose fatty alkyl radical is derived from other technical fractions which essentially contain saturated fatty alcohols .
Die erfindungsgemäßen Mittel zeichnen sich durch eine hautfreundliche Ten- sidkombination aus, die sehr gut biologisch abbaubar ist.The agents according to the invention are distinguished by a skin-friendly surfactant combination which is very readily biodegradable.
Zur Ermittlung der enzymatischen Stabilität wurde die Proteaseaktivität der Mittel 1 bis 4, nach 1 Stunde bei 50 °C durch Extinktionsmessung (Cenco-Autoanalyzer) bei 420 nm relativ zu einem bekannten Standard be¬ stimmt. Die absolute Aktivität des Standards wurde nach einer zweiten Me¬ thode bestimmt ("Zur Bestimmung der proteolytischen Aktivität in Enzymkon¬ zentraten und enzy haltigen Wasch-, Spül- und Reinigungsmittel", H. G. van Raay, H. Saran, H. Verbeek, Tenside Detergents, 7. Jahrgang, Seiten 125 bis 132, 1*970). Die Proteaseaktivität der Mittel i bis 4_ lag nach 1 Stunde zwischen 79 und 83 %, jeweils bezogen auf den Anfangswert. Zum Vergleich wurde die Proteaseaktivität der Mittel VI bis V4 gemessen, die sich von I bis 1 nur darin unterschieden, daß sie (F2) 1,2-Propandiol statt Glycerin enthielten. Die Proteaseaktivität lag in den Mitteln VI bis V4 nach 1 Stunde zwischen 68 und 73 %, jeweils bezogen auf den Anfangswert. Die Enzymstabilität ist in den erfindungsgemäßen Mitteln i bis 1 somit signi¬ fikant höher als in den Vergleichsmitteln VI bis V4. To determine the enzymatic stability, the protease activity of agents 1 to 4 was determined after 1 hour at 50 ° C. by absorbance measurement (Cenco autoanalyzer) at 420 nm relative to a known standard. The absolute activity of the standard was determined by a second method ("For determining the proteolytic activity in enzyme concentrates and detergents, detergents and cleaning agents containing enzymes", HG van Raay, H. Saran, H. Verbeek, Tenside Detergents , 7th year, pages 125 to 132, 1 * 970). The protease activity of agents i to 4_ was between 79 and 83% after 1 hour, in each case based on the initial value. For comparison, the protease activity of agents VI to V4 was measured, which differed from I to 1 only in that they contained (F2) 1,2-propanediol instead of glycerol. The protease activity in means VI to V4 after 1 hour was between 68 and 73%, in each case based on the initial value. The enzyme stability in the agents i to 1 according to the invention is therefore significantly higher than in the comparison agents VI to V4.

Claims

1 -P A T E N T A N S P R Ü C H E 1 -PATENT REQUESTS
1. Enzymatisches Flüssigwaschmittel, enthaltend anionische Tenside sowie als Lösungsmittel Wasser und eine Mischung aus mono- und polyfunkti- onellen Alkoholen, dadurch gekennzeichnet, daß es als Aniontenside Fettalkylsulfate in Form der Natriumsalze und Seifen, bestehend aus Salzen ethylenisch ungesättigter Cj2- bis Cig-Fettsäuren und gesät¬ tigter Cχ2- bis Ci8-Fettsäuren im GewichtsVerhältnis 3 : 1 bis 1 : 3, als organisches Lösungsmittel eine Mischung aus Ethanol und Glycerin und Enzyme aus der Gruppe der Proteasen, Amylasen, Lipasen und Ge¬ mische aus diesen enthält.1. Enzymatic liquid detergent containing anionic surfactants and water as a solvent and a mixture of mono- and polyfunctional alcohols, characterized in that it contains fatty alkyl sulfates as anionic surfactants in the form of the sodium salts and soaps, consisting of salts of ethylenically unsaturated Cj2 to Cig fatty acids and saturated Cχ2 to Ci8 fatty acids in a weight ratio of 3: 1 to 1: 3, as organic solvent contains a mixture of ethanol and glycerol and enzymes from the group of proteases, amylases, lipases and mixtures thereof.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß es 3 - 20 Gew.-% Fettalkylsulfate in Form der Natriumsalze, 10 bis 25 Gew.-% Seifen, bestehend aus Salzen ethylenisch ungesättigter Ci2-bis Cig-Fettsäuren und gesättigter C12- bis Cig-Fettsäuren im GewichtsVerhältnis von 3 : 1 bis 1 : 3, 5 bis 20 Gew.-% einer Mischung aus Ethanol und Glycerin im Gewichtsverhältnis 3 : 1 bis 1 : 3 und 0,2 bis 1 Gew.-% Enzyme aus der Gruppe der Proteasen, Amylasen, Lipasen und Gemische aus diesen enthält.2. Composition according to claim 1, characterized in that there are 3 - 20 wt .-% fatty alkyl sulfates in the form of the sodium salts, 10 to 25 wt .-% soaps, consisting of salts of ethylenically unsaturated Ci2 to cig fatty acids and saturated C12 to Cig fatty acids in a weight ratio of 3: 1 to 1: 3, 5 to 20% by weight of a mixture of ethanol and glycerol in a weight ratio of 3: 1 to 1: 3 and 0.2 to 1% by weight of enzymes from the group which contains proteases, amylases, lipases and mixtures thereof.
3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß es ein Fettalkylsulfat enthält, in dem die Anteile der Alkylreste wie folgt verteilt sind: 50 - 70 Gew.-% C12, 18 - 30 Gew.-% C14, 5 - 15 Gew.-% Ci6# unter 3 Gew.-% Cχo und unter 10 Gew.-% Cig.3. Composition according to claim 1 or 2, characterized in that it contains a fatty alkyl sulfate in which the proportions of the alkyl radicals are distributed as follows: 50-70% by weight C12, 18-30% by weight C14, 5-15 % By weight Ci6 # below 3% by weight Cχo and below 10% by weight Cig.
4. Mittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Seifengemisch aus Natriumoleat und dem Natriumsalz der Laurin- säure oder eines gesättigten Ci2-Ci6-Fettsäuregemisches besteht, wo¬ bei das Gewichtsverhältnis Oleat zu gesättigter Seife 2 : 1 bis 1 : 2 beträgt.4. Composition according to one of claims 1 to 3, characterized in that the soap mixture consists of sodium oleate and the sodium salt of lauric acid or a saturated Ci2-Ci6 fatty acid mixture, where the weight ratio of oleate to saturated soap is 2: 1 to 1 : 2 is.
5. Mittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es 1 bis 10 Gew.-% Alkylglucoside der allgemeinen Formel R0(G)x, wo- <l bei R einen Fettalkylrest mit 8 bis 22 C-Atomen, G eine Glucoseein- heit und x eine Zahl zwischen 1 und 10 darstellt, enthält.5. Composition according to one of claims 1 to 4, characterized in that it contains 1 to 10 wt .-% alkyl glucosides of the general formula R0 (G) x , where <1 for R is a fatty alkyl radical with 8 to 22 C atoms, G is a glucose unit and x is a number between 1 and 10.
6. Mittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß ^ es Anlagerungsprodukte von 1 bis 10 Mol Ethylenoxid an primäre C12- bis Cig-Fettalkohole und deren Gemische enthält.6. Agent according to one of claims 1 to 5, characterized in that ^ it contains addition products of 1 to 10 mol of ethylene oxide with primary C12 to Cig fatty alcohols and mixtures thereof.
7. Mittel nach Anspruch 6, dadurch gekennzeichnet, daß der Anteil der Fettalkoholethoxylate bis zu 17 Gew.-%, vorzugsweise bis zu 14 Gew.-% beträgt.7. Composition according to claim 6, characterized in that the proportion of fatty alcohol ethoxylates is up to 17 wt .-%, preferably up to 14 wt .-%.
8. Mittel nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß es 7 bis 17 Gew.-% organische Lösungsmittel, bestehend aus Ethanol und Glycerin in einem Gewichtsverhältnis von 2 : 1 bis 1 : 1,5, und als Enzym Protease oder ein Gemisch aus Protease und Amylase enthält. 8. Composition according to one of claims 1 to 7, characterized in that there are 7 to 17 wt .-% organic solvents consisting of ethanol and glycerol in a weight ratio of 2: 1 to 1: 1.5, and as an enzyme protease or contains a mixture of protease and amylase.
EP91918230A 1990-11-02 1991-10-25 Enzymatic liquid detergent Expired - Lifetime EP0555258B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4034840A DE4034840A1 (en) 1990-11-02 1990-11-02 ENZYMATIC LIQUID DETERGENT
DE4034840 1990-11-02
PCT/EP1991/002022 WO1992007930A1 (en) 1990-11-02 1991-10-25 Enzymatic liquid detergent

Publications (2)

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EP0555258A1 true EP0555258A1 (en) 1993-08-18
EP0555258B1 EP0555258B1 (en) 1996-04-24

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AT (1) ATE137261T1 (en)
DE (2) DE4034840A1 (en)
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WO (1) WO1992007930A1 (en)

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Publication number Priority date Publication date Assignee Title
DE102008061686A1 (en) 2008-12-11 2010-06-17 Bayer Materialscience Ag Process for the preparation of isocyanates in the gas phase

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Publication number Priority date Publication date Assignee Title
DE4315854A1 (en) * 1993-05-12 1994-11-17 Henkel Kgaa Detergents and cleaning agents containing lipase
EP0798371A1 (en) * 1996-03-29 1997-10-01 The Procter & Gamble Company Detergent compositions comprising specific amylase and alkyl poly glucoside surfactants
DE19626620A1 (en) * 1996-07-03 1998-01-08 Clariant Gmbh Enzyme-containing detergent formulation
EP2906674B1 (en) * 2012-10-12 2018-11-07 Henkel AG & Co. KGaA Liquid detergent compositions with soap, sulfo-estolide surfactant and cellulase

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IT1129814B (en) * 1980-07-02 1986-06-11 Unilever Nv LIQUID ENZYMATIC DETERGENT COMPOSITION
EP0162033B1 (en) * 1984-05-14 1989-12-13 The Procter & Gamble Company Liquid detergents containing boric acid to stabilize enzymes
EP0214278A1 (en) * 1985-03-07 1987-03-18 A.E. Staley Manufacturing Company Detergent composition containing an enzyme and a glycoside surfactant
DE3910974A1 (en) * 1989-04-05 1990-10-11 Henkel Kgaa Liquid detergent
DE3920480A1 (en) * 1989-06-22 1991-01-03 Henkel Kgaa FLUESSIGWASCHMITTEL
BR9006827A (en) * 1989-06-26 1991-08-06 Unilever Nv ENZYMATIC DETERGENT COMPOSITES

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008061686A1 (en) 2008-12-11 2010-06-17 Bayer Materialscience Ag Process for the preparation of isocyanates in the gas phase

Also Published As

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WO1992007930A1 (en) 1992-05-14
ES2085488T3 (en) 1996-06-01
JPH06502197A (en) 1994-03-10
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DE4034840A1 (en) 1992-05-07
EP0555258B1 (en) 1996-04-24
ATE137261T1 (en) 1996-05-15

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