EP0656049A1 - Pourable fluid aqueous cleaning agent concentrates - Google Patents

Pourable fluid aqueous cleaning agent concentrates

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Publication number
EP0656049A1
EP0656049A1 EP94908187A EP94908187A EP0656049A1 EP 0656049 A1 EP0656049 A1 EP 0656049A1 EP 94908187 A EP94908187 A EP 94908187A EP 94908187 A EP94908187 A EP 94908187A EP 0656049 A1 EP0656049 A1 EP 0656049A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
weight
cleaning agent
contain
sulfates
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
EP94908187A
Other languages
German (de)
French (fr)
Other versions
EP0656049B1 (en
Inventor
Rainer Jeschke
Eva Kiewert
Karl-Heinz Disch
Katica Bocarac
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
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0656049A1 publication Critical patent/EP0656049A1/en
Application granted granted Critical
Publication of EP0656049B1 publication Critical patent/EP0656049B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating 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
    • 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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to pourable liquid aqueous cleaning agent concentrates which can be used both as scouring agents and in dilute form as general-purpose cleaning agents.
  • Such agents are known and are based on the use of water-soluble abrasive components which have the abrasive function in concentrated media and practically dissolve in dilute media and, after use, can easily be removed from the substrate simply by rinsing with water.
  • US Pat. No. 4,179,414 discloses stable pastes composed of approximately 50 to 65% by weight sodium bicarbonate, approximately 50 to 35% by weight water and approximately 5 to 20% by weight sodium chloride as well as approximately 10 to 30% by weight Ci2- Ci6 fatty acid diethanolamide, both based on the water content, are known to have an abrasive effect in concentrated form and to clean hard surfaces in diluted form. No information is given on the particle size of the sodium bicarbonate.
  • EP 0 193375 A2 discloses liquid compositions of this type which contain 1.5 to 30% by weight of surfactants and, inter alia, 6 to 45% by weight of sodium bicarbonate with an average diameter of 10 to 500 ⁇ m (no further details are given ge made) can contain. The rest is water.
  • aqueous agents which contain 1.5 to 40% by weight surfactants, 2.0 to 65% by weight predominantly undissolved potassium sulfate with the same particle size as above, preferably 20-300 ⁇ m, and optionally contain 0.5 to 10 wt .-% sodium chloride.
  • liquid abrasives with water-soluble abrasives which contain 1.5 to 30% by weight of surfactants, about 45 to about 75% by weight of sodium bicarbonate with a small average particle size of can expressly contain less than 80 ⁇ m and more than 10% by weight of water. While most of these known cleaning agents foam too much when used and / or their abrasive effect does not reach that of the commercial standard marble powder because of too small a particle size, agents have been developed according to the invention which do not have these disadvantages.
  • the viscosity of very finely divided dispersions is considerably higher than that of dispersions of coarser particles (see Examples 1 and 2). Even if the Stokes equation in the above form does not absolutely apply in systems with a high solids content, such as those according to the invention, the Stokes descent rate V is nevertheless included in the approximate equations for more concentrated systems. A higher particle radius has a destabilizing effect on the dispersion, both in terms of the radius and the lower viscosity, even in concentrated systems.
  • This combination of surfactants consists essentially of alkyl polyglycol ether, alkyl sulfate, optionally alkyl ether sulfate, and soap, the alkyl polyglycol ether being a thickening agent with a narrow distribution of the ethylene oxide addition products (A.
  • Behler et al, soap-oil-fat waxes, 116 , 60-68 (1990) and DE 38 17415) is used, and is also distinguished characterized by the fact that the surfactants are very readily biodegradable.
  • the foam is regulated by adding the soap.
  • Coconut fatty acid, isostearic acid and mixtures thereof provide particularly good values.
  • Today, the lowest possible foaming is essential for the acceptance of modern household cleaning agents.
  • the present invention therefore relates to pourable liquid aqueous cleaning agent concentrates containing surfactants and a water-soluble salt, which can be used in concentrated form as abrasives and diluted as general-purpose cleaning agents, which are characterized in that they a) as water-soluble salt is at least 50, preferably 50 to 65 wt .-% sodium bicarbonate microns with an average particle size of about 200 i and 100 b) from about 2 to 30, preferably about 3 to 15 wt .-% of a surfactant mixture of alkyl sulfates little FDumen ⁇ to and / or contain alkyl ether sulfates and alkyl polyglycol ethers with a narrow homolog distribution and soap.
  • the low-foaming surfactant mixture consists essentially of about 0 to 13, preferably about 4 to 10% by weight of alkyl sulfates with about 8 to 22, preferably about 9 to 16, carbon atoms in the alkyl radical, about 0 to 13, preferably about 4 to 10,% by weight.
  • Alkyl ether sulfates with about 8 to 18, preferably about 9 to 16 carbon atoms in the alkyl radical and about 1 to 5, preferably about 2 to 4 E0 in the molecule, about 1.5 to 8, preferably about 2 to 6 wt .-% alkyl polyglycol ethers with about 8 to 18, preferably about 9 to 16 carbon atoms in the alkyl radical and about 2 to 8, preferably about 2 to 5, ethylene oxide units (E0) in the molecule, and about 0.05 to 5, preferably about 0.5 to 3% by weight.
  • alkyl (ether) sulfates and alkyl polyglycol ethers can be derived from technical alcohol mixtures, such as are obtained, for example, by high pressure hydrogenation of methyl esters based on vegetable or animal rons or by hydrogenation of aldehydes from ROELEN. see oxosynthesis receives.
  • the weight ratio of alkyl (ether) sulfate to alkyl polyglycol ethers is advantageously about 10: 1 to 1:10, preferably 5: 1 to 1: 5 and in particular 3: 1 to 1: 4.
  • the flow properties of the claimed cleaning agents can be increased by adding about 0 to 5, preferably from about 0.3 to 3,% by weight of polyols of the formula HO-R-0H, where R is an alkyl radical which is optionally substituted by hydroxyl groups and has about 2 to 6, preferably 2 to 4 carbon atoms, positively influence.
  • the polyols include, for example, ethylene glycol, n- and iso-propylene glycols and glycerin.
  • Another possible additive consists of naturally occurring polymers such as xanthan gum, other polysaccharides and / or gelatin in amounts of about 0 to 2, preferably about 0.5 to 1.8% by weight. This remarkably increases the cleaning performance of the agents.
  • agents according to the invention can contain customary constituents such as inorganic or organic framework substances, for example in the form of low molecular weight dicarboxylic acids or sodium chloride, known solvents, such as hydrotropes and solvents, preservatives, other antimicrobially active substances, colorants and fragrances.
  • customary constituents such as inorganic or organic framework substances, for example in the form of low molecular weight dicarboxylic acids or sodium chloride, known solvents, such as hydrotropes and solvents, preservatives, other antimicrobially active substances, colorants and fragrances.
  • Sodium bicarbonate forms a buffer at pH 8.7, i.e. the pH can only be lowered when the buffer is exhausted; an increase in pH has a negative effect on the viscosity.
  • solubilizers individually or as a mixture with one another, can be incorporated, for which purpose, in addition to the water-soluble organic solvents such as, in particular, low molecular weight aliphatic alcohols with 1-4 carbon atoms, also the so-called hydrotropes Substances of the lower alkyl aryl sulfonate type, for example toluene, xylene or cumene sulfonates or short chain alkyl sulfates such as octyl sulfate. They can also be in the form of their sodium and / or potassium and / or alkylamino salts.
  • Water-soluble organic solvents can also be used as solubilizers, in particular those with boiling points above 75 ° C., such as, for example, the ethers from the same or different polyhydric alcohols or the partial ethers from polyhydric alcohols. These include, for example, di- or triethylene glycol polyglycerols and the partial ethers of ethylene glycol, propylene glycol, butylene glycol or glycerol with aliphatic alcohols containing 1 to 6 carbon atoms in the molecule.
  • ketones such as acetone, methyl ethyl ketone and aliphatic, cycloaliphatic and aromatic hydrocarbons, and also the terpene alcohols.
  • the cleaning agents according to the invention were prepared by mixing the constituents with stirring using a commercially available paddle stirrer in the following order: approx. 6% of the total amount of bicarbonate was dissolved in water at about 40 ° C, then the fatty acid was added in a molten form. After a homogeneous mixture was present, the mixture was cooled to 25 ° C. and the remaining constituents were then added.
  • the cleaning agent to be tested was placed on an artificially soiled plastic surface.
  • a mixture of carbon black, machine oil, triglyceride, saturated fatty acids and low-boiling aliphatic hydrocarbon was used as artificial soiling for the dilute use of the cleaning agent.
  • the test area of 26 x 28 cm was evenly coated with 2 g of the artificial soiling with the aid of a surface coater.
  • a plastic sponge was impregnated with 10 ml of the detergent solution to be tested and moved mechanically on the test surface, which was also coated with 10 ml of the detergent solution to be tested. After ten wiping movements with a plastic sponge, the cleaned test area was kept under running water and the loose dirt was removed.
  • the cleaning effect ie the whiteness of the so cleaned Plastic surface was made with a Microcolor color difference measuring device from Dr. Measured for a long time.
  • the clean white plastic surface served as the white standard. Since the measurement of the clean surface was set to 100% and the soiled area was displayed with 0, the read values for the cleaned plastic areas are to be equated with the percentage cleaning power (% RV).
  • test product was placed in a large beaker. Then, from a height of 30 cm, the amount of tap water was allowed to flow in freely, which, with the amount of product presented, gives the recommended application solution of the product.
  • the foam height in the beaker was read immediately after the addition of water and again after 3 minutes.
  • the foam height after 3 minutes was set in relation to the initial foam and the foam decay was calculated as follows:
  • An agent with a foam breakdown of more than 50% was defined as a low-foam cleaner.
  • Examples 1 and 2 should show the relationship between particle size and abrasiveness.
  • a commercially available liquid scouring agent with a content of 50% by weight of marble powder was chosen as the standard of comparison, and its abrasiveness was set to 100%.
  • the example represented a low-foam cleaner.
  • the foam breakdown when used diluted (3 ml / 1) was 73%.
  • a commercial product with 50% sodium bicarbonate and with 12% total surfactant was tested, which had a foam breakdown of less than 43% at an application concentration of 3 ml / 1.
  • Example 6 demonstrates the increase in the cleaning effect by adding gelatin.

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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)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

PCT No. PCT/EP93/02159 Sec. 371 Date Feb. 22, 1995 Sec. 102(e) Date Feb. 22, 1995 PCT Filed Aug. 13, 1993 PCT Pub. No. WO94/04648 PCT Pub. Date Mar. 3, 1994A pourable, aqueous cleaning composition containing: (a) at least 50% by weight of sodium bicarbonate having a mean particle size of about 200+/-100 mu m; (b) from about 2 to 30% by weight of a surfactant mixture selected from alkyl sulfates, alkyl ether sulfates, narrow-range alkyl polyglycol ethers and soap; and (c) the remainder, water.

Description

"GießfShioe flüssige wäßrige Reiniqunσsmittelkonzentrate" "Pouring liquid aqueous cleaning agent concentrates"
Die Erfindung betrifft gießfähige flüssige wäßrige Reinigungsmittelkon¬ zentrate, die sowohl als Scheuermittel als auch in verdünnter Form als Allzweckreinigungsmittel verwendet werden können. Derartige Mittel sind bekannt und basieren auf der Mitverwendung wasserlöslicher Abrasivkompo- nenten, die in konzentrierten Medien die scheuernde Funktion ausüben und sich in verdünnten Medien praktisch auflösen und nach der Anwendung je¬ denfalls leicht durch bloßes Abspülen mit Wasser vom Substrat entfernen lassen.The invention relates to pourable liquid aqueous cleaning agent concentrates which can be used both as scouring agents and in dilute form as general-purpose cleaning agents. Such agents are known and are based on the use of water-soluble abrasive components which have the abrasive function in concentrated media and practically dissolve in dilute media and, after use, can easily be removed from the substrate simply by rinsing with water.
Aus der US 4,179,414 sind stabile Pasten aus etwa 50 bis 65 Gew.-% Na- triumbicarbonat, etwa 50 bis 35 Gew.-% Wasser und etwa 5 bis 20 Gew.-% Natriumchlorid sowie etwa 10 bis 30 Gew.-% Ci2-Ci6-Fettsäurediethanolamid, beide bezogen auf den Wasseranteil, bekannt, die in konzentrierter Form scheuernd wirken und in verdünnter Form harte Oberflächen reinigen. Über die Teilchengröße des Natriumbicarbonats werden keine Angaben gemacht. Aus der EP 0 193375 A2 sind flüssige derartige Mittel bekannt, die 1,5 bis 30 Gew.-% Tenside und u.a. 6 bis 45 Gew.-% Natriu bicarbonat mit einem mitt¬ leren Durchmesser von 10 bis 500 μm (genauere Angaben werden nicht ge¬ macht) enthalten können. Der Rest besteht aus Wasser. Aus der EP 0334566 A2 wiederum sind solche wäßrigen Mittel bekannt, die 1,5 bis 40 Gew.- Tenside, 2,0 bis 65 Gew.-% überwiegend ungelösten Kaliumsulfats mit glei¬ cher Teilchengröße wie vorstehend, vorzugsweise 20 - 300 μm, sowie gege¬ benenfalls 0,5 bis 10 Gew.-% Natriumchlorid enthalten. Aus der interna¬ tionalen Patentanmeldung WO 91/08282 sind flüssige Scheuermittel mit was¬ serlöslichen Abrasivstoffen bekannt, die 1,5 bis 30 Gew.-% Tenside, etwa 45 bis etwa 75 Gew.-% Natriumbicarbonat mit einer geringen mittleren Teil¬ chengröße von ausdrücklich kleiner als 80 μm und mehr als 10 Gew.-% Wasser enthalten können. Während die meisten dieser bekannten Reinigungsmittel bei der Anwendung zu stark schäumen und/oder ihre Abrasivwirkung wegen zu geringer Teilchen¬ größe nicht die des handelsüblichen Standards Marmormehl erreicht, wurden erfindungsgemäß solche Mittel entwickelt, die diese Nachteile nicht auf¬ weisen.US Pat. No. 4,179,414 discloses stable pastes composed of approximately 50 to 65% by weight sodium bicarbonate, approximately 50 to 35% by weight water and approximately 5 to 20% by weight sodium chloride as well as approximately 10 to 30% by weight Ci2- Ci6 fatty acid diethanolamide, both based on the water content, are known to have an abrasive effect in concentrated form and to clean hard surfaces in diluted form. No information is given on the particle size of the sodium bicarbonate. EP 0 193375 A2 discloses liquid compositions of this type which contain 1.5 to 30% by weight of surfactants and, inter alia, 6 to 45% by weight of sodium bicarbonate with an average diameter of 10 to 500 μm (no further details are given ge made) can contain. The rest is water. From EP 0334566 A2 such aqueous agents are known which contain 1.5 to 40% by weight surfactants, 2.0 to 65% by weight predominantly undissolved potassium sulfate with the same particle size as above, preferably 20-300 μm, and optionally contain 0.5 to 10 wt .-% sodium chloride. From the international patent application WO 91/08282, liquid abrasives with water-soluble abrasives are known which contain 1.5 to 30% by weight of surfactants, about 45 to about 75% by weight of sodium bicarbonate with a small average particle size of can expressly contain less than 80 μm and more than 10% by weight of water. While most of these known cleaning agents foam too much when used and / or their abrasive effect does not reach that of the commercial standard marble powder because of too small a particle size, agents have been developed according to the invention which do not have these disadvantages.
Es ist wesentlich schwieriger, größere Teilchen stabil zu dispergieren als feinere, denn nach dem Stokesschen Gesetz zur Sedimentation von disper- gierten Partikeln (s. Gleichung 1) hängt die Sinkgeschwindigkeit V von dem Quadrat des Radius r der Teilchen und der Viskosität n des Mediums ab. Dabei erhöht sie sich mit steigendem Radius, was einer Destabilisierung gleichkommt und sie sinkt mit steigender Viskosität, was einer Stabilisie¬ rung gleichkommt.It is much more difficult to stably disperse larger particles than finer ones, because according to Stokes law for the sedimentation of dispersed particles (see equation 1) the rate of descent V depends on the square of the radius r of the particles and the viscosity n of the medium . It increases with increasing radius, which equates to destabilization, and decreases with increasing viscosity, which equates to stabilization.
2*r2*( . Q)*g Gleichung 1: V = 2 * r 2 * (. Q ) * g Equation 1: V =
*g*G
Die Viskosität von feinstteiligen Dispersionen ist bei gleicher Menge we¬ sentlich höher als die von Dispersionen gröberer Teilchen (s. Beispiele 1 und 2). Auch wenn in festkörperreichen Systemen, wie den erfindungsgemä¬ ßen, die Stokessche Gleichung in der obigen Form nicht absolut gilt, so geht die Stokessche Sinkgeschwindigkeit V dennoch in die Näherungsglei¬ chungen für konzentriertere Systeme ein. Ein höherer Teilchenradius wirkt also auch bei konzentrierten Systemen sowohl über den Radius als auch über die niedrigere Viskosität destabilisierend auf die Dispersion.With the same amount, the viscosity of very finely divided dispersions is considerably higher than that of dispersions of coarser particles (see Examples 1 and 2). Even if the Stokes equation in the above form does not absolutely apply in systems with a high solids content, such as those according to the invention, the Stokes descent rate V is nevertheless included in the approximate equations for more concentrated systems. A higher particle radius has a destabilizing effect on the dispersion, both in terms of the radius and the lower viscosity, even in concentrated systems.
überraschenderweise konnte eine wenig schäumende Tensidkombination gefun¬ den werden, die nicht nur die zu erwartende Reinigungswirkung entfaltet, sondern die es erlaubt, im Vergleich zur Lehre gemäß WO 91/8282 wesentlich gröberes Natriumbicarbonat stabil zu dispergieren. Diese Tensidkombination besteht im wesentlichen aus Alkylpolyglykolether, Alkylsulfat, gegebenen¬ falls Alkylethersulfat, und Seife, wobei als Alkylpolyglykolether ein ver¬ dickend wirkendes mit einer eingeengten Verteilung der Ethylenoxidanla- gerungsprodukte (A. Behler et al, Seifen-Öle-Fette-Wachse, 116, 60 - 68 (1990) und DE 38 17415) eingesetzt wird, und zeichnet sich darüber hinaus noch dadurch aus, daß die Tenside biologisch sehr gut abbaubar sind. Die Schaumregulierung erfolgt durch den Zusatz der Seife. Besonders gute Werte liefern Kokosfettsäure, Isostearinsäure und Gemische daraus. Wesentlich für die Akzeptanz von modernen Haushaltsreinigungsmitteln ist heute eine möglichst geringe Schaumentwicklung.Surprisingly, it was possible to find a low-foaming surfactant combination which not only has the cleaning action to be expected, but which, in comparison with the teaching according to WO 91/8282, makes it possible to stably disperse substantially coarser sodium bicarbonate. This combination of surfactants consists essentially of alkyl polyglycol ether, alkyl sulfate, optionally alkyl ether sulfate, and soap, the alkyl polyglycol ether being a thickening agent with a narrow distribution of the ethylene oxide addition products (A. Behler et al, soap-oil-fat waxes, 116 , 60-68 (1990) and DE 38 17415) is used, and is also distinguished characterized by the fact that the surfactants are very readily biodegradable. The foam is regulated by adding the soap. Coconut fatty acid, isostearic acid and mixtures thereof provide particularly good values. Today, the lowest possible foaming is essential for the acceptance of modern household cleaning agents.
Die vorliegende Erfindung betrifft daher gießfähige flüssige wäßrige Rei¬ nigungsmittelkonzentrate mit einem Gehalt an Tensiden und einem wasser¬ löslichen Salz, die in konzentrierter Form als Scheuermittel und verdünnt als Allzweckreinigungsmittel verwendet werden können, die dadurch gekenn¬ zeichnet sind, daß sie a) als wasserlösliches Salz mindestens 50, vorzugsweise 50 bis 65 Gew.-% Natriumbicarbonat mit einer mittleren Korngröße von etwa 200 i 100 μm und b) etwa 2 bis 30, vorzugsweise etwa 3 bis 15 Gew.-% eines wenig schäumen¬ den Tensidgemisches aus Alkylsulfaten und/oder Alkylethersulfaten und Alkylpolyglykolethern mit enger Homologenverteilung und Seife enthal¬ ten.The present invention therefore relates to pourable liquid aqueous cleaning agent concentrates containing surfactants and a water-soluble salt, which can be used in concentrated form as abrasives and diluted as general-purpose cleaning agents, which are characterized in that they a) as water-soluble salt is at least 50, preferably 50 to 65 wt .-% sodium bicarbonate microns with an average particle size of about 200 i and 100 b) from about 2 to 30, preferably about 3 to 15 wt .-% of a surfactant mixture of alkyl sulfates little schäumen¬ to and / or contain alkyl ether sulfates and alkyl polyglycol ethers with a narrow homolog distribution and soap.
Außer den unter b) genannten Tensiden können auch noch übliche Alkylpoly¬ glykolether mit normaler Verteilung der Ethylenoxideinheiten enthalten sein.In addition to the surfactants mentioned under b), conventional alkyl polyglycol ethers with normal distribution of the ethylene oxide units can also be present.
Das wenig schäumende Tensidgemisch besteht im wesentlichen aus etwa 0 bis 13, vorzugsweise etwa 4 bis 10 Gew.-% Alkylsulfaten mit etwa 8 bis 22, vorzugsweise etwa 9 bis 16 Kohlenstoffatomen im Alkylrest, etwa 0 bis 13, vorzugsweise etwa 4 bis 10 Gew.-% Alkylethersulfaten mit etwa 8 bis 18, vorzugsweise etwa 9 bis 16 Kohlenstoffatomen im Alkylrest und etwa 1 bis 5, vorzugsweise etwa 2 bis 4 E0 im Molekül, etwa 1,5 bis 8, vorzugsweise etwa 2 bis 6 Gew.-% Alkylpolyglykolethern mit etwa 8 bis 18, vorzugsweise etwa 9 bis 16 Kohlenstoffatomen im Alkylrest und etwύ 2 bis 8, vorzugs¬ weise etwa 2 bis 5 Ethylenoxideinheiten (E0) im Molekül, und etwa 0,05 bis 5, vorzugsweise etwa 0,5 bis 3 Gew.-% einer gerad- oder verzweigtket- tigen, gesättigten oder ungesättigten Carbonsäure mit etwa 7 bis 22, vor¬ zugsweise etwa 10 bis 22 Kohlenstoffatomen im Alkylrest und/oder ihren Alkali-, Ammonium-und/oder Alkylam oniumsalzen. Die einzelnen Tensidklas- sen können durch eine oder mehrere ihrer Verbindungen vertreten sein. Wie in der Tensidchemie üblich, können sich die Alkyl(ether)sulfate und Al¬ kylpolyglykolether von technischen Alkoholgemischen ableiten, wie man sie beispielsweise durch Hochdr.'.khydrierung von Methylestern auf Basis pflanzlicher oder tierischer Ronstoffe oder durch Hydrierung von Aldehyden aus der ROELEN'sehen Oxosynthese erhält. Das Gewichtsverhältnis von Al¬ kyl(ether)sulfat zu Alkylpolyglykolethern beträgt zweckmäßig etwa 10 : 1 bis 1 : 10, vorzugsweise 5 : 1 bis 1 : 5 und insbesondere 3 : 1 bis 1 : 4.The low-foaming surfactant mixture consists essentially of about 0 to 13, preferably about 4 to 10% by weight of alkyl sulfates with about 8 to 22, preferably about 9 to 16, carbon atoms in the alkyl radical, about 0 to 13, preferably about 4 to 10,% by weight. -% Alkyl ether sulfates with about 8 to 18, preferably about 9 to 16 carbon atoms in the alkyl radical and about 1 to 5, preferably about 2 to 4 E0 in the molecule, about 1.5 to 8, preferably about 2 to 6 wt .-% alkyl polyglycol ethers with about 8 to 18, preferably about 9 to 16 carbon atoms in the alkyl radical and about 2 to 8, preferably about 2 to 5, ethylene oxide units (E0) in the molecule, and about 0.05 to 5, preferably about 0.5 to 3% by weight. % of a straight-chain or branched-chain, saturated or unsaturated carboxylic acid with about 7 to 22, preferably about 10 to 22, carbon atoms in the alkyl radical and / or their alkali metal, ammonium and / or alkyl ammonium salts. The individual surfactant class sen can be represented by one or more of their connections. As is customary in surfactant chemistry, the alkyl (ether) sulfates and alkyl polyglycol ethers can be derived from technical alcohol mixtures, such as are obtained, for example, by high pressure hydrogenation of methyl esters based on vegetable or animal rons or by hydrogenation of aldehydes from ROELEN. see oxosynthesis receives. The weight ratio of alkyl (ether) sulfate to alkyl polyglycol ethers is advantageously about 10: 1 to 1:10, preferably 5: 1 to 1: 5 and in particular 3: 1 to 1: 4.
Die Fließeigenschaften der beanspruchten Reinigungsmittel lassen sich durch Zusatz von etwa 0 bis 5, vorzugsweise von etwa 0,3 bis 3 Gew.-% Polyolen der Formel H0-R-0H, wobei R einen gegebenenfalls durch Hydroxyl¬ gruppen substituierten Alkylrest mit etwa 2 bis 6, vorzugsweise 2 bis 4 Kohlenstoffatomen bedeutet, positiv beeinflussen. Dadurch lassen sich die Mittel besonders gut und leicht dosieren. Zu den Polyolen gehören zum Beispiel Ethylenglykol, n- und iso-Propylenglykole und Glycerin.The flow properties of the claimed cleaning agents can be increased by adding about 0 to 5, preferably from about 0.3 to 3,% by weight of polyols of the formula HO-R-0H, where R is an alkyl radical which is optionally substituted by hydroxyl groups and has about 2 to 6, preferably 2 to 4 carbon atoms, positively influence. As a result, the agents can be dosed particularly well and easily. The polyols include, for example, ethylene glycol, n- and iso-propylene glycols and glycerin.
Ein weiterer möglicher Zusatz besteht aus in der Natur vorkommenden Poly¬ meren wie etwa Xanthangum, weiteren Polysacchariden und/oder Gelatine in Mengen von etwa 0 bis 2, vorzugsweise etwa 0,5 bis 1,8 Gew.-%. Dadurch wird die Reinigungsleistung der Mittel bemerkenswert gesteigert.Another possible additive consists of naturally occurring polymers such as xanthan gum, other polysaccharides and / or gelatin in amounts of about 0 to 2, preferably about 0.5 to 1.8% by weight. This remarkably increases the cleaning performance of the agents.
Darüber hinaus können die erfindungsgemäßen Mittel übliche Bestandteile wie anorganische oder organische Gerüstsubstanzen etwa in Form von nie¬ dermolekularen Dicarbonsäuren oder Natriumchlorid, bekannte Lösungsver¬ mittler wie Hydrotrope und Lösungsmittel, Konservierungsmittel, andere an- timikrobiell wirksame Substanzen, Färb- und Duftstoffe enthalten.In addition, the agents according to the invention can contain customary constituents such as inorganic or organic framework substances, for example in the form of low molecular weight dicarboxylic acids or sodium chloride, known solvents, such as hydrotropes and solvents, preservatives, other antimicrobially active substances, colorants and fragrances.
Natriumbicarbonat bildet einen Puffer bei pH 8,7, d.h. erst bei Er¬ schöpfung des Puffers läßt sich der pH-Wert erniedrigen; eine pH-Wert- Erhöhung wirkt sich negativ auf die Viskosität aus.Sodium bicarbonate forms a buffer at pH 8.7, i.e. the pH can only be lowered when the buffer is exhausted; an increase in pH has a negative effect on the viscosity.
Außerdem kann man an sich bekannte Lösungsvermittler, einzeln oder als Gemisch untereinander, einarbeiten, wozu außer den wasserlöslichen orga¬ nischen Lösungsmitteln wie insbesondere niedermolekularen aliphatischen Alkoholen mit 1 - 4 Kohlenstoffatomen auch die sogenannten hydrotropen Stoffe vom Typ der niederen Alkylarylsulfonate, beispielsweise Toluol-, Xylol- oder Cumolsulfonate oder kurzkettige Alkylsulfate wie Octylsulfat gehören. Sie können auch in Form ihrer Natrium- und/oder Kalium- und/oder Alkylaminosalze vorliegen. Als Lösungsvermittler sind weiterhin wasser¬ lösliche organische Lösungsmittel verwendbar, insbesondere solche mit Siedepunkten oberhalb von 75 °C wie beispielsweise die Ether aus gleich- oder verschiedenartigen mehrwertigen Alkoholen oder die Teilether aus mehrwertigen Alkoholen. Hierzu gehören beispielsweise Di- oder Triethylen- glykolpolyglycerine sowie die Teilether aus Ethylenglykol, Propylenglykol, Butylenglykol oder Glycerin mit aliphatischen, 1 - 6 Kohlenstoffatome im Molekül enthaltenen einwertigen Alkoholen.In addition, known solubilizers, individually or as a mixture with one another, can be incorporated, for which purpose, in addition to the water-soluble organic solvents such as, in particular, low molecular weight aliphatic alcohols with 1-4 carbon atoms, also the so-called hydrotropes Substances of the lower alkyl aryl sulfonate type, for example toluene, xylene or cumene sulfonates or short chain alkyl sulfates such as octyl sulfate. They can also be in the form of their sodium and / or potassium and / or alkylamino salts. Water-soluble organic solvents can also be used as solubilizers, in particular those with boiling points above 75 ° C., such as, for example, the ethers from the same or different polyhydric alcohols or the partial ethers from polyhydric alcohols. These include, for example, di- or triethylene glycol polyglycerols and the partial ethers of ethylene glycol, propylene glycol, butylene glycol or glycerol with aliphatic alcohols containing 1 to 6 carbon atoms in the molecule.
Als wasserlösliche oder mit Wasser emulgierbare organische Lösungsmittel kommen auch Ketone, wie Aceton, Methylethylketon sowie aliphatische, cycloaliphatische und aromatische Kohlenwasserstoffe, ferner die Terpen- alkohole in Betracht.Also suitable as water-soluble or water-emulsifiable organic solvents are ketones, such as acetone, methyl ethyl ketone and aliphatic, cycloaliphatic and aromatic hydrocarbons, and also the terpene alcohols.
Die Herstellung der erfindungsgemäßen Reinigungsmittel erfolgte durch Mi¬ schen der Bestandteile unter Rühren mit einem handelsüblichen Flügelrührer in folgender Reihenfolge: Ca. 6 % der Gesamtmenge an Bicarbonat wurden in Wasser von ca. 40°C aufgelöst, dann wurde die Fettsäure in geschmolzener Form zugesetzt. Nachdem eine homogene Mischung vorlag, wurde der Ansatz auf 25°C gekühlt und danach die restlichen Bestandteile zugefügt. The cleaning agents according to the invention were prepared by mixing the constituents with stirring using a commercially available paddle stirrer in the following order: approx. 6% of the total amount of bicarbonate was dissolved in water at about 40 ° C, then the fatty acid was added in a molten form. After a homogeneous mixture was present, the mixture was cooled to 25 ° C. and the remaining constituents were then added.
B e s p e l eB e s p e l e
Zum Nachweis der Vorteile der erfindungsgemäßen Reinigungsmittel wurden Versuche nach folgenden Methoden durchgeführt:To demonstrate the advantages of the cleaning agents according to the invention, tests were carried out using the following methods:
Zur Messung der Abrasivität wurde 6 g unverdünnter Reiniger unter krei¬ sender Bewegung mit einem Schwämmchen bei definierten Druck von 2,5 kg zwanzigmal auf einer bei 200 °C eingebrannten Anschmutzung von Kondens¬ milch, Puderzucker und Quarkpulver (50 : 8 : 10) hin und her bewegt. Nach Abspülen und Trocknen der angeschmutzten Bleche wurde die abgetragene Schmutzmenge berechnet und in Bezug gesetzt zu einem marktüblichen flüs¬ sigen Scheuermittel auf Basis Marmormehl.To measure the abrasiveness, 6 g of undiluted cleaner was rotated twenty times with a sponge at a defined pressure of 2.5 kg on a soiling of condensed milk, powdered sugar and curd powder (50: 8: 10) baked at 200 ° C and moved here. After rinsing and drying the soiled sheets, the amount of dirt removed was calculated and related to a commercially available liquid abrasive based on marble powder.
Zur Messung der Viskosität in m-Pas wurde ein Brookfield-Viskosimeter, RVT, Spindel 4, 20 Umdrehungen pro Minute, verwendet. Die Messungen wurden bei 20°C durchgeführt.A Brookfield viscometer, RVT, spindle 4, 20 revolutions per minute was used to measure the viscosity in m-Pas. The measurements were carried out at 20 ° C.
Zur Prüfung des Reinigungsvermögens diente die unten beschriebene Test¬ methode, die sehr gut reproduzierbare Ergebnisse liefert. Die Schmutzab¬ lösung von harten Oberflächen wurde nach dem Reinigungsvermögen-Test, be¬ schrieben in Seifen-Öle-Fette-Wachse 112, 371 (1986), beurteilt.The test method described below was used to test the cleaning ability and provides very reproducible results. The detachment of dirt from hard surfaces was assessed according to the cleaning ability test described in soap-oil-fat waxes 112, 371 (1986).
Das zu prüfende Reinigungsmittel wurde auf eine künstlich angeschmutzte KunststoffOberfläche gegeben. Als künstliche Anschmutzung für die ver¬ dünnte Anwendung des Reinigungsmittels wurde ein Gemisch aus Ruß, Maschi¬ nenöl, Triglycerid gesättigter Fettsäuren und niedersiedendem aliphati- schen Kohlenwasserstoff verwendet. Die Testfläche von 26 x 28 cm wurde mit Hilfe eines Flächenstreichers gleichmäßig mit 2 g der künstlichen An¬ schmutzung beschichtet.The cleaning agent to be tested was placed on an artificially soiled plastic surface. A mixture of carbon black, machine oil, triglyceride, saturated fatty acids and low-boiling aliphatic hydrocarbon was used as artificial soiling for the dilute use of the cleaning agent. The test area of 26 x 28 cm was evenly coated with 2 g of the artificial soiling with the aid of a surface coater.
Ein Kunststoffschwamm wurde jeweils mit 10 ml der zu prüfenden Reini¬ gungsmittellösung getränkt und mechanisch auf der ebenfalls mit 10 ml der zu prüfenden Reinigungsmittellösung beschichteten Testfläche bewegt. Nach zehn Wischbewegungen mit einem Kunststoffschwamm wurde die gereinigte Testfläche unter fließendes Wasser gehalten und der lose sitzende Schmutz entfernt. Die Reinigungswirkung, d. h. der Weißgrad der so gereinigten Kunststoffoberfläche wurde mit einem Farb-Differenz-Meßgerät Microcolor der Firma Dr. Lange gemessen. Als Weiß-Standard diente die saubere weiße KunststoffOberfläche. Da bei der Messung der sauberen Oberfläche auf 100 % eingestellt und die angeschmutzte Fläche mit 0 angezeigt wurde, sind die abgelesenen Werte bei den gereinigten Kunststoff-Flächen mit dem Prozent¬ gehalt Reinigungsvermögen (% RV) gleichzusetzen. Bei den nachstehenden Versuchen sind die angegebenen Werte RL rel. (%) die nach dieser Methode ermittelten Werte für das Reinigungsvermögen der untersuchten Reinigungs¬ mittel, bezogen auf die Reinigungsleistung des als Standard verwendeten Reinigungsmittels (RL = 100 %). Sie stellen jeweils Mittelwerte aus Drei¬ fachbestimmungen dar.A plastic sponge was impregnated with 10 ml of the detergent solution to be tested and moved mechanically on the test surface, which was also coated with 10 ml of the detergent solution to be tested. After ten wiping movements with a plastic sponge, the cleaned test area was kept under running water and the loose dirt was removed. The cleaning effect, ie the whiteness of the so cleaned Plastic surface was made with a Microcolor color difference measuring device from Dr. Measured for a long time. The clean white plastic surface served as the white standard. Since the measurement of the clean surface was set to 100% and the soiled area was displayed with 0, the read values for the cleaned plastic areas are to be equated with the percentage cleaning power (% RV). In the experiments below, the values RL rel. (%) the values determined by this method for the cleaning ability of the investigated cleaning agents, based on the cleaning performance of the cleaning agent used as standard (RL = 100%). They each represent mean values from triple determinations.
Das Schaumverhalten der erfindungsgemäßen Mittel wurde folgendermaßen ge¬ prüft:The foam behavior of the agents according to the invention was tested as follows:
Das Prüfprodukt wurde in einem weitlu igen Becherglas vorgelegt. Sodann wurde darauf aus 30 cm Höhe im freien Fall die Menge an Leitungswasser zufließen gelassen, die mit der Menge an vorgelegtem Produkt die empfoh¬ lene Anwendungslösung des Produkts ergibt.The test product was placed in a large beaker. Then, from a height of 30 cm, the amount of tap water was allowed to flow in freely, which, with the amount of product presented, gives the recommended application solution of the product.
Die Schaumhöhe im Becherglas wurde sofort nach Beendigung der Wasserzugabe und abermals nach 3 Minuten abgelesen. Die Schaumhöhe nach 3 Minuten wurde in Relation zum Anfangsschaum gesetzt und der Schaumzerfall folgendermaßen berechnet:The foam height in the beaker was read immediately after the addition of water and again after 3 minutes. The foam height after 3 minutes was set in relation to the initial foam and the foam decay was calculated as follows:
Schaumhöhe Anfang-Schaumhöhe nach 3 Min.Foam height start-foam height after 3 min.
Schaumzerfall (%) = • 100Foam breakdown (%) = • 100
Schaumhöhe AnfangFoam height beginning
Als schaumarmer Reiniger wurde ein Mittel mit einem Schaumzerfall von mehr als 50 % definiert.An agent with a foam breakdown of more than 50% was defined as a low-foam cleaner.
Die in den Beispielen angegebenen Mengen beziehen sich auf Gewichtspro¬ zent. Beispiel 1 und 2The amounts given in the examples relate to percent by weight. Examples 1 and 2
Die Beispiele 1 und 2 sollten den Zusammenhang von Teilchengröße und Abra¬ sivität aufzeigen.Examples 1 and 2 should show the relationship between particle size and abrasiveness.
Beispiel 1 Beispiel 2Example 1 Example 2
(Vergleich)(Comparison)
Relative Abrasivität 90 % 70 %Relative abrasiveness 90% 70%
Viskosität ( Pas) 5000 6600Viscosity (Pas) 5000 6600
Als Vergleichsstandard wurde ein derzeit handelsübliches flüssiges Scheu¬ ermittel mit einem Gehalt an 50 Gew.-% Marmormehl gewählt und dessen Ab¬ rasivität gleich 100 % gesetzt.A commercially available liquid scouring agent with a content of 50% by weight of marble powder was chosen as the standard of comparison, and its abrasiveness was set to 100%.
Die Beispiele zeigen, daß mit Natriumbicarbonat der erfindungsgemäßen Korngröße nahezu die Abrasivität von Marmormehl erreichbar ist, während nach Beispiel 2 eine Bicarbonat-Korngröße entsprechend WO 91/8282 deutlich schwächer wirksam war.The examples show that with sodium bicarbonate of the grain size according to the invention almost the abrasiveness of marble powder can be achieved, while according to example 2 a bicarbonate grain size according to WO 91/8282 was significantly less effective.
Beispiel 3 9 % Ci2/Ci4-Fettalkoholethersulfat, Na-Salz 5,5 % C12/C14-FA + 2,5 E0, (eingeengte Homologenverteilung) 1 % Isostearinsäure 1,5 % Propylenglykol-1,2Example 3 9% Ci2 / Ci4 fatty alcohol ether sulfate, Na salt 5.5% C12 / C14-FA + 2.5 E0, (narrow homolog distribution) 1% isostearic acid 1.5% propylene glycol 1,2
55 % Natriumbicarbonat, mittlerer Korndurchmesser 200 μm ad 100 % Wasser, vollentsalzt55% sodium bicarbonate, average grain diameter 200 μm ad 100% water, fully desalinated
Das Beispiel stellte trotz des relativ hohen Gesamttensidgehalts von 15,5 % einen schaumarmen Reiniger dar. Der Schaumzerfall betrug bei verdünnter Anwendung (3 ml/1) : 73 %. Zum Vergleich wurde ein Handelsprodukt mit 50 % Natriumbicarbonat und mit 12 % Gesamttensid geprüft, welches bei einer Anwendungskonzentration von 3 ml/1 einen Schaumzerfall von weniger als 43 % aufwies.Despite the relatively high total surfactant content of 15.5%, the example represented a low-foam cleaner. The foam breakdown when used diluted (3 ml / 1) was 73%. For comparison, a commercial product with 50% sodium bicarbonate and with 12% total surfactant was tested, which had a foam breakdown of less than 43% at an application concentration of 3 ml / 1.
Beispiel 4Example 4
2 % Ci2/Ci4-Fettalkoholethersulfat, Na-Salz2% Ci2 / Ci4 fatty alcohol ether sulfate, Na salt
4 % C12/C14 - FA + 2,5 E0, (eingeengte HomologenVerteilung)4% C12 / C14 - FA + 2.5 E0, (narrow homolog distribution)
1,3 % C12/C14 - FA + 4 E0, (normale Homologenverteilung)1.3% C12 / C14 - FA + 4 E0, (normal homolog distribution)
0,8 % Kokosfettsäure0.8% coconut fatty acid
0,5 % Glycerin0.5% glycerin
0,3 % Parfümöl0.3% perfume oil
55 % Natriumbicarbonat, mittlerer Korndurchmesser 200 μm ad 100 % Wasser, vollentsalzt55% sodium bicarbonate, average grain diameter 200 μm ad 100% water, fully desalinated
Es handelte sich um ein wirksames Reinigungsmittel, das bei unverdünnter Anwendung eine hohe Abrasivität aufwies und bei verdünnter Anwendung (3 ml/1) einen Schaumzerfall von 93 % zeigte.It was an effective cleaning agent that showed high abrasiveness when used undiluted and showed a foam breakdown of 93% when used diluted (3 ml / 1).
Beispiel 5 und 6Examples 5 and 6
C12/C14 - Alkylsulfat, Na-Salz 5 % 5 % C12/C14 - FA + 2,5 E0, (einge¬ engte HomologenVerteilung) 3,5 % 3,5 % C12/C14 - FA + 4 E0, (normale Homologenverteilung) Kokosfettsäure Glycerin C12 / C14 - alkyl sulfate, Na salt 5% 5% C12 / C14 - FA + 2.5 E0, (narrow homolog distribution) 3.5% 3.5% C12 / C14 - FA + 4 E0, (normal homolog distribution ) Coconut fatty acid glycerin
Natriumbicarbonat, mittlerer Korndurchmesser 200 μm 50 % 50 Gelatine - 0,5 %Sodium bicarbonate, average grain diameter 200 μm 50% 50 Gelatin - 0.5%
Wasser, vollentsalzt ad 100 ad 100Water, fully desalinated ad 100 ad 100
Relatives Reinigungsvermögen bei 3 ml/1 = 100 % 115 % gesetztRelative cleaning power set at 3 ml / 1 = 100% 115%
Das Beispiel 6 belegt die Steigerung der Reinigungswirkung durch Zusatz von Gelatine. Example 6 demonstrates the increase in the cleaning effect by adding gelatin.

Claims

Patentansprüche Claims
1. Gießfähige flüssige wäßrige Reinigungsmittelkonzentrate mit einem Ge¬ halt an Tensiden und einem wasserlöslichen Salz, dadurch gekennzeich¬ net, daß sie a) als wasserlösliches Salz mindestens 50, vorzugsweise 50 bis 65 Gew.-% Natriumbicarbonat mit einer mittleren Korngröße von etwa 200 i 100 μm und b) etwa 2 - 30 Gew.-%, vorzugsweise etwa 3 - 15 Gew.-% eines wenig schäumenden Tensidgemisches aus Alkylsulfaten und/oder Alkylether¬ sulfaten und Alkylpolyglykolethern mit eingeengter Homologenver¬ teilung und Seife enthalten.1. Pourable liquid aqueous detergent concentrates containing Ge surfactants and a water-soluble salt, characterized in that they a) as water-soluble salt at least 50, preferably 50 to 65% by weight sodium bicarbonate with an average grain size of about 200 i 100 μm and b) contain about 2 to 30% by weight, preferably about 3 to 15% by weight, of a low-foaming surfactant mixture of alkyl sulfates and / or alkyl ether sulfates and alkyl polyglycol ethers with a narrow homolog distribution and soap.
2. Reinigungsmittelkonzentrate nach Anspruch 1, dadurch gekennzeichnet, daß sie als Alkylsulfate etwa 0 - 13 %, vorzugsweise etwa 4 - 10 Gew.-% C8-C22-. vorzugsweise Cio-Ciö-Alkylsulfate enthalten.2. Detergent concentrates according to Claim 1, characterized in that they are about 0 - 13%, preferably about 4 - 10% by weight C8-C22- as alkyl sulfates . preferably contain Cio-Ciö-alkyl sulfates.
3. Reinigungsmittel nach Anspruch 1 und 2, dadurch gekennzeichnet, daß sie als Alkylethersulfate etwa 0 - 13, vorzugsweise etwa 4 - 10 Gew.-% Alkylethersulfate mit einem Cß-Cig-, vorzugsweise Cιo-Ci6-Alkylrest und etwa 1 - 5, vorzugsweise etwa 2 - 4 Mol, Ethylenoxid im Molekül enthalten.3. Cleaning agent according to claim 1 and 2, characterized in that it contains about 0 - 13, preferably about 4 - 10 wt .-% alkyl ether sulfates with a Cß-Cig, preferably Cιo-Ci6-alkyl radical and about 1-5 as alkyl ether sulfates, preferably contain about 2-4 moles of ethylene oxide in the molecule.
4. Reinigunsmittelkonzentrate nach Anspruch 1 bis 3, dadurch gekennzeich¬ net, daß sie etwa 1,5 - 8, vorzugsweise etwa 2 - 6 Gew.-% eines oder mehrerer Alkylpolyglykolether mit einem Cs-Cis-Alkylrest und etwa 2 - 8 Mol Ethylenoxid im Molekül und eingeengter Verteilung der Ethylen- oxidho ologen enthalten.4. cleaning agent concentrates according to claims 1 to 3, characterized gekennzeich¬ net that they about 1.5 - 8, preferably about 2 - 6 wt .-% of one or more alkyl polyglycol ethers with a Cs-Cis-alkyl radical and about 2 - 8 mol ethylene oxide contained in the molecule and narrow distribution of the ethylene oxide ho ologists.
5. Reinigungsmittel nach Anspruch 1 - 4, dadurch gekennzeichnet, daß sie als Seife etwa 0,05 - 5, vorzugsweise etwa 0,5 - 3 Gew.-% einer oder mehrerer Carbonsäuren mit einem C7-C22-» vorzugsweise Ci6-C22~Al yl- rest, wobei dieser geradkettig oder verzweigt, gesättigt oder ungesät¬ tigt sein kann und die teilweise oder vollständig in Salzform, vor¬ zugsweise als Alkali-, Ammonium- oder Alkylammoniumslaze vorliegen können, enthalten. 5. Cleaning agent according to claim 1-4, characterized in that it is about 0.05 - 5, preferably about 0.5 - 3 wt .-% of one or more carboxylic acids with a C7-C22- » preferably Ci6-C22 ~ as soap Al yl radical, which may be straight-chain or branched, saturated or unsaturated, and which may be partially or completely in salt form, preferably in the form of an alkali metal, ammonium or alkylammonium salt.
6. Reinigungsmittel nach Anspruch 1 - 5, dadurch gekennzeichnet, daß sie zusätzlich bis zu etwa 5 Gew.-% Polyole enthalten.6. Cleaning agents according to claims 1-5, characterized in that they additionally contain up to about 5 wt .-% polyols.
7. Reinigungsmittel nach Anspruch 1 - 6, dadurch gekennzeichnet, daß sie zusätzlich etwa 0 - 2, vorzugsweise etwa 0,1 - 1,8 Gew.-% Polymere enthalten.7. Cleaning agent according to claims 1-6, characterized in that they additionally contain about 0 - 2, preferably about 0.1 - 1.8 wt .-% polymers.
8. Reinigungsmittel nach Anspruch 1 - 7, dadurch gekennzeichnet, daß sie weiterhin in Reinigungsmitteln übliche Bestandteile wie Parfümöle, organische oder anorganische Gerüstsubstanzen, Lösungsvermittler, Kon¬ servierungsmittel und/oder andere antimikrobiell wirksame Verbindungen sowie Farbstoffe enthalten. 8. Detergents according to claims 1-7, characterized in that they further contain constituents customary in detergents such as perfume oils, organic or inorganic builders, solubilizers, preservatives and / or other antimicrobial compounds and dyes.
EP94908187A 1992-08-22 1993-08-13 Pourable fluid aqueous cleaning agent concentrates Expired - Lifetime EP0656049B1 (en)

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DE4227863 1992-08-22
PCT/EP1993/002159 WO1994004648A2 (en) 1992-08-22 1993-08-13 Pourable fluid aqueous cleaning agent concentrates

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DE19646520A1 (en) * 1996-11-12 1998-05-14 Henkel Kgaa Dishwashing detergent with increased cleaning effect
AU1373999A (en) * 1997-11-25 1999-06-15 Cognis Corporation Use of narrow range ethoxylates of fatty alcohols in agricultural pesticide and adjuvant formulations
US6758411B2 (en) 2002-08-09 2004-07-06 S. C. Johnson & Son, Inc. Dual bottle for even dispensing of two flowable compositions
US6583103B1 (en) 2002-08-09 2003-06-24 S.C. Johnson & Son, Inc. Two part cleaning formula resulting in an effervescent liquid
US20050282722A1 (en) * 2004-06-16 2005-12-22 Mcreynolds Kent B Two part cleaning composition
US7846888B2 (en) * 2006-02-07 2010-12-07 Battelle Energy Alliance, Llc Long lasting decontamination foam
PL2041255T3 (en) * 2006-07-14 2011-02-28 Ecolab Inc Alkaline floor cleaning composition and method of cleaning a floor
US9499772B2 (en) 2013-03-13 2016-11-22 Battelle Energy Alliance, Llc Methods of decontaminating surfaces and related compositions

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WO1994004648A2 (en) 1994-03-03
ATE160375T1 (en) 1997-12-15
DE4227863A1 (en) 1994-02-24
EP0656049B1 (en) 1997-11-19
CA2143002A1 (en) 1994-03-03
US5562856A (en) 1996-10-08
WO1994004648A3 (en) 1994-03-31
DE59307714D1 (en) 1998-01-02
DK0656049T3 (en) 1998-07-27
ES2110734T3 (en) 1998-02-16
JPH08500377A (en) 1996-01-16
GR3025870T3 (en) 1998-04-30

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