EP0373349A2 - Liquid detergent for hard surfaces - Google Patents

Abstract

A liquid cleansing agent with improved detergency for hard surfaces contains 0.02 to 40 wt.% of a mixture of anionic tensides consisting of (a) sulphated hydroxyalkylpolyethylene glycol ethers or hydroxyalkylpolypropylene glycol ethers of general formula R<1>-CH(SO3M)-CH(R<3>)-(OCHR<4>-CH2)n-OR<2> where R<1> = H or C1-16 alkyl; R<2> = C1-22 alkyl; R<3> = C1-16 alkyl or preferably H; R<4> = -CH3 or preferably H; M = H, ammonium, alkylammonium, alkanolammonium (C1-4) or a univalent metal atom; n = 0-20, and (b) dioctylsulphosuccinates in a mixing ratio of 1:10 to 10:1, as well as organic or inorganic skeleton substances. Preferably, the aqueous solutions of the detergent contain solubilizers such as toluol, xylol or cumol sulphonate, low molecular alcohols or short-chain fatty alcohols and in particular ethers of identical or different polyhydric alcohols (C1-6), in a weight ratio of tenside to solubilizer of 1:0 to 1:2, as well as other usual constituents such as colorants and aromas, preservatives and non-ionic tensides.

Description

Liquid all-purpose detergents for household and commercial use have taken their place in the past decade because they are easy and straightforward to use. The agents are usually marketed as preferably aqueous concentrates. They can be applied diluted or undiluted to a damp, absorbent cloth of any nature or a sponge, with which the hard surfaces made of metal, lacquered wood, plastic, ceramic products such as porcelain, tiles, tiles and the like can be wiped off and thereby dust, greasy dirt and stains are removed. It is desired that this surface treatment does not leave any detergent stains and strips and does not require any aftertreatment, for example with a damp cloth soaked in clear water.

Numerous cleaning agents of this type are known from the market and from the literature. DE 23 17 076 describes dishwashing detergents made from dialkyl sulfosuccinate and alkyl sulfate or alkyl ether sulfate, which have good foam resistance.

EP 71 411 describes liquid detergent compositions which consist of a mixture of dialkyl sulfosuccinates with anionic and / or nonionic surfactants. These mixtures are said to have good cleaning performance and good foaming properties.

EP 112 044 describes liquid detergent compositions comprising dialkyl sulfosuccinates in combination with alkyl ether sulfates which have a special carbon chain distribution. The formulations are characterized by improved performance and assembly.

EP 112 045 describes liquid detergent compositions composed of dialkyl sulfosuccinates in combination with other surfactants (e.g. alkyl benzene sulfonates, alkane sulfonates or fatty alcohol ether sulfates) and small amounts of Mg 2+ ions. The addition of Mg²⁺ leads to performance advantages and improves the packaging.

EP 112 047 describes liquid detergent compositions comprising dialkyl sulfosuccinates with alkyl benzene sulfonates, alkane sulfonates and fatty alcohol ether sulfates. The ternary combinations should be characterized by improved performance and packaging properties.

mit 0 < x < 15 und
0 < y < 15 und
13 < x + y < 15 mit Alkylbenzolsulfonaten insbesondere zur Verwendung zum manuel­len Spülen beschrieben. Für y = 0 folgt, daß die C-Kettenlänge 13 < x < 15 beträgt. Die in dieser Schrift bevorzugt beanspruchten Tenside weisen eine C-Kettenlänge von maximal 12 auf.No. 3,639,291 describes the synergistic surfactant combination of vicinal alkyl ether sulfates of the formula

with 0 <x <15 and
0 <y <15 and
13 <x + y <15 with alkylbenzenesulfonates, in particular for use in manual rinsing. For y = 0 it follows that the C chain length is 13 <x <15. The surfactants preferably claimed in this document have a maximum C chain length of 12.

DE 26 51 925 claims 1-methoxy sulfates, their preparation and their use in detergents and cleaning agents. They should be characterized by a high cleaning ability. Additional surfactants include anionic surfactants, as well as other active substances usually contained in detergents, dishwashing detergents and cleaning agents, but without proving their effectiveness in liquid cleaning agents on hard surfaces.

In the as yet unpublished patent application DE 37 23 548.8 describes a process for the preparation of new sulfated hydroxy mixed ethers and their use as wetting agents and detergent raw materials.

In addition, it is also known from the patent literature to add different polymers to cleaning agents to increase their cleaning power.

Liquid cleaning agents are known from US Pat. No. 3,406,208, which can contain water-soluble high-molecular substances as dirt carriers. Water-soluble salts of polyacrylic acid and also water-soluble derivatives of cellulose such as carboxymethyl cellulose are mentioned as examples.

From US 35 91 509 liquid general-purpose cleaners are known which, in addition to water-soluble synthetic surface-active substances, organic solvents and optionally water-soluble builders, contain a small amount of a special water-soluble carboxymethyl cellulose and water.

US Pat. No. 3,970,594 discloses liquid, builders-containing cleaning agents for hard surfaces with small amounts of surfactants in combination with small amounts of a mixture of polyvinyl alcohol and / or polyvinylpyrrolidone and polysaccharide salt, which are also said to have improved dirt removal properties.

DE 27 09 690 discloses liquid cleaning agents for hard surfaces, which can also contain cleaning-enhancing additives in water-soluble high-molecular substances, such as polyvinyl alcohol, polyvinyl pyrrolidone and carboxymethyl cellulose.

Finally, from DE 28 40 463 liquid cleaning agents for hard surfaces are known which contain water-soluble polyethylene glycols as cleaning-enhancing additives.

Not all of the above-mentioned polymeric cleaning enhancers meet the strictest ecological criteria (complete mineralization of the raw materials used) fully meet the requirements that consumers now place on a liquid cleaning agent for hard surfaces. Some of the known polymers also have disadvantages such. B. insufficient solubility, excessive thickening or residue, d. H. Streaks or film formation when using the agents, if they contain these polymers in the amounts that are necessary for a significant cleaning enhancement.

The alkylbenzenesulfonate and polymer-containing formulations now have an excellent performance profile, that of polymer Free formulations based on surfactants alone have not yet been achieved.

Hydroxy mixed ether sulfates, produced as described in DE 37 23 354.8, unexpectedly show, together with anionic surfactants which are customary in all-purpose cleaners, no cleaning performance at any mixing ratio as one would expect for good products.

Surprisingly, it has been found that an unpredictable increase in the cleaning performance of liquid cleaning agents for hard surfaces is achieved if a mixture of hydroxy mixed ether sulfates and sulfosuccinates is used. With optimal mixing ratios, the cleaning performance of these mixtures reaches the level of good alkylbenzenesulfonate-containing recipes with a polymer content even in the absence of polymers.

The present invention therefore relates to a liquid cleaning agent for hard surfaces based on dilute, preferably aqueous solutions containing anionic surfactants, organic and / or inorganic builders, optionally water-soluble solvents or solubilizers, and other conventional components of such cleaning agents, which is characterized in that it contains, as anionic surfactants, 0.02 to 40, preferably 0.05 to 15% by weight of a mixture of hydroxy mixed ether sulfates and dialkyl sulfosuccinates in a weight ratio of 1:10 to 10: 1, preferably 4: 1 to 1: 4.

in der
R¹ für Wasserstoff oder einen linearen Alkylrest mit 1 bis 16, vorzugsweise 8 bis 12 C-Atomen,
R² für einen linearen oder verzweigten, gesättigten Alkylrest mit 1 bis 22, vorzugsweise 1 bis 16 C-Atomen,
R³ für vorzugsweise Wasserstoff, aber auch einen linearen Alkyl­rest mit 1 bis 16 C-Atomen,
R⁴ für vorzugsweise Wasserstoff, aber auch eine Methylgruppe,
M für Wasserstoff, Ammonium, Alkylammonium, Alkanolammonium, worin die Alkyl- und Alkanolreste je 1 bis 4 C-Atome haben, oder ein einwertiges Metallatom und
n für eine Zahl im Bereich von 0 bis 20, vorzugsweise 0 bis 15 stehen sowie von Mischungen mehrerer derartiger Verbindungen. Sie wurden dadurch hergestellt, daß man Epoxide der all­gemeinen Formel

in der R¹ und R³ die oben angegebenen Bedeutungen haben, mit Alko­holalkoxylaten der allgemeinen Formel

in der R², R⁴ und n die oben angegebenen Bedeutungen haben, bei erhöhter Temperatur in Gegenwart eines Katalysators zu Hydroxy­alkylpolyethylen- und/oder Hydroxyalkylpolypropylenglykolethern der allgemeinen Formel

in der R¹, R², R³, R⁴ und n die oben angegebenen Bedeutungen haben, oder deren Mischungen umsetzte, die so erhaltenen Ver­bindungen (IV) oder deren Mischungen bei erhöhter Temperatur mit einem Sulfatierungsreagenz zur Umsetzung brachte, das rohe Sul­fierungsprodukt in eine wäßrige basische Lösung eintrug und das Gemisch bei erhöhter Temperatur hielt, das Gemisch auf einen pH-Wert im neutralen bzw. schwach alkalischen Bereich brachte und die so erhaltenen Produkte (I) oder deren Mischungen gewünschten­falls in an sich bekannter Weise aus dem Reaktionsgemisch iso­lierte.The hydroxy mixed ether sulfates mentioned are sulfated hydroxyalkyl polyethylene and / or hydroxyalkyl polypropylene glycol ethers of the general formula

in the
R¹ is hydrogen or a linear alkyl radical having 1 to 16, preferably 8 to 12, carbon atoms,
R² is a linear or branched, saturated alkyl radical having 1 to 22, preferably 1 to 16, carbon atoms,
R³ is preferably hydrogen, but also a linear alkyl radical having 1 to 16 carbon atoms,
R⁴ is preferably hydrogen, but also a methyl group,
M for hydrogen, ammonium, alkylammonium, alkanolammonium, in which the alkyl and alkanol radicals each have 1 to 4 carbon atoms, or a monovalent metal atom and
n stands for a number in the range from 0 to 20, preferably 0 to 15, and of mixtures of several such compounds. They were prepared by using epoxides of the general formula

in which R¹ and R³ have the meanings given above, with alcohol alkoxylates of the general formula

in which R², R⁴ and n have the meanings given above, at elevated temperature in the presence of a catalyst to give hydroxyalkyl polyethylene and / or hydroxyalkyl polypropylene glycol ethers of the general formula

in which R¹, R², R³, R⁴ and n have the meanings given above, or reacting their mixtures, reacting the compounds (IV) thus obtained or their mixtures at elevated temperature with a sulfating reagent, the crude sulfonation product into an aqueous basic solution entered and the mixture was kept at elevated temperature, the mixture was brought to a pH in the neutral or weakly alkaline range and, if desired, the products (I) or their mixtures thus obtained were isolated from the reaction mixture in a manner known per se.

The dialkyl sulfosuccinates are alkali metal, ammonium or substituted ammonium salts and can be derived from a C₇, C₈ or C₉ alcohol, which can be linear or branched, or from any mixture thereof. The preferred material is the straight chain and branched di-octylsulfosuccinate. The dialkyl sulfosuccinates were prepared by conventional methods, e.g. by esterification of maleic acid and subsequent sulfonation with bisulfite.

The anionic surfactants can be present in the form of their alkali, alkaline earth and ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The sodium salts are mostly preferred for cost reasons.

For the liquid cleaning agents according to the invention, alkaline organic or inorganic compounds, in particular inorganic or organic complexing agents, are used as framework substances in their entirety, which are preferably present in the form of their alkali or amine salts, in particular the sodium and potassium salts. The alkali hydroxides also belong to the framework substances here.

The alkaline polyphosphates, in particular the tripolyphosphates and the pyrophosphates, are particularly suitable as inorganic complex-forming framework substances. For reasons of water entrophication, they can be replaced in whole or in part by organic complexing agents. Further inorganic builder substances which can be used according to the invention are, for example, bicarbonates, carbonates, borates, silicates or orthophosphates of the alkalis.

The organic complexing agents of the aminopolycarboxylic acid type include, among others, nitrilotriacetic acid, ethylene diamine tetraacetic acid, N-hydroxyethyl ethylene diamine triacetic acid and polyalkylene polyamine N-polycarboxylic acids. Examples of di- and polyphosphonic acids are: methylenediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphonic acid, polyvinylphosphonic acid, copolymers of vinylphosphonic acid and Acrylic acid, ethane-1,2, dicarboxy-1,2-diphosphonic acid, ethane-1,2-dicarboxy-1,2-dihydroxydiphosphonic acid, phosphonosuccinic acid, 1-aminoethane-1,2-diphosphonic acid, aminotri- (methylenephosphonic acid), methyl amino- or ethylamino-di- (methylenephosphonic acid) and ethylenediamine-tetra- (methylenephosphonic acid).

Compounds containing carboxyl groups are often, though not exclusively, suggested as examples of N- or P-free polycarboxylic acids or their salts as builder substances. A large number of these polycarboxylic acids have a complexing ability for calcium. These include e.g. B. citric acid, tartaric acid, benzene hexacarboxylic acid, tetrahydrofuran tetracarboxylic acid, glutaric acid, succinic acid, adipic acid or mixtures thereof.

Since household cleaning agents are generally neutral to slightly alkaline, ie their aqueous use solutions have a pH in the range from 7.0 to 10.5 at application concentrations of 2 to 20, preferably 5 to 15 g / l of water or aqueous solution , preferably 7.0 - 9.5, an acidic and / or alkaline component, also as a buffer, may be required to regulate the pH.

Suitable acidic substances are customary inorganic or organic acids or acidic salts, such as, for example, hydrochloric acid, sulfuric acid, bisulfates of alkalis, aminosulfonic acid, phosphoric acid or other acids of phosphorus, in particular the anhydrous acids of phosphorus or their acidic salts or their acid-reacting solid compounds with urea or other lower carboxylic acid amides, partial amides of phosphoric acids or anhydrous phosphoric acid, lactic acid, polycarboxylic acids, such as. B. citric acid, tartaric acid, glutaric acid, succinic acid, adipic acid or mixtures thereof and the like.

If the content of alkaline builders is not sufficient to regulate the pH, organic or inorganic compounds such as z. B. sodium hydroxide, alkanolamines, namely mono-, di- or triethanolamine or ammonia.

In addition, known solubilizers, individually or as mixtures with one another, can be incorporated, for which purpose, in addition to the water-soluble organic solvents such as, in particular, low-molecular aliphatic alcohols having 1-4 carbon atoms, also the so-called hydrotropic substances of the lower alkylarylsulfonate 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 of identical or different polyhydric alcohols or Partial ether 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 monohydric alcohols containing 1 to 6 carbon atoms in the molecule.

Other suitable water-soluble or water-emulsifiable organic solvents are ketones, such as acetones, methyl ethyl ketone and aliphatic, cycloaliphatic, aromatic and chlorinated hydrocarbons, and also the terpene alcohols.

The weight ratio of surfactant to solvent or solubilizer can be 1: 0 to 1: 2, preferably 1: 0.05 to 1: 1.

To regulate the viscosity, it may be advisable to add higher polyglycol ethers with molecular weights up to about 600 or polyglycerol. It is also recommended to add sodium chloride and / or urea to regulate the viscosity.

In addition, the claimed agents can contain, as other conventional constituents, additives to colorants and fragrances, preservatives and nonionic surfactants known therefor.

tries

To demonstrate the advantages of the cleaning agents according to the invention over the known cleaning agents for hard surfaces, comparisons were made with regard to their cleaning ability.

Testing the cleaning effect

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 in the cleaning ability test, described in soap-oil-fat waxes 112 , 371 (1986).

The cleaning agent to be tested was placed on an artificially soiled plastic surface. For the diluted application (0.1% by weight of surfactant), the cited contamination 2 was used as artificial soiling. When using a detergent with 10% by weight of surfactant, a mixture of petroleum jelly ^(R) , fatty acid glycerol esters and pigments was used as the test soiling . 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 or coated with 10 ml of the surfactant content at 0.1% by weight and the test area was also impregnated or coated with 10 ml of the cleaning agent solution to be tested and moved mechanically on the test area. In the case of a 10% strength by weight surfactant solution, only that Test area coated with 10 ml of the detergent solution. After ten wiping movements, the cleaned test area was kept under running water and the loose dirt was removed. The cleaning effect, ie the degree of whiteness of the plastic surface cleaned in this way, was measured using an LF 90 photoelectric colorimeter (Dr. B. Lange). 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 ability (% 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 comparison recipe (RL = 100%). They represent mean values from triple determinations.

Examples Example 1:

The following all-purpose cleaner formulations were tested for their cleaning performance in concentrated use, as is customary for stubborn stains in the household.

A powerful, alkylbenzenesulfonate and polymer-containing formula of the following composition served as a comparison; as it falls under the scope of protection of DE 28 40 463:
8% C₁₀ - C₁₃ alkylbenzenesulfonate, sodium salt
2% adduct of 10 moles of ethylene oxide with 1 mole of a mixture of oleyl and cetyl alcohol
2% Na gluconate
0.1% polyethylene glycol with a molecular weight of approximately 600,000 (commercial product Polyox WSR 205 ^(R) from UCC).
Rest of water

The pH of the formulations was adjusted to 7.0 with 50% sodium hydroxide solution.

The cleaning performance (RL rel.) Of the formulations is given in [%], based on the cleaning performance of the comparison formulation as standard (RL = 100), in the following.

The general formula of the hydroxy mixed ether sulfates (HMS) tested here is:

The parameters m, x and n thus clearly characterize the HMS.

Di-isooctylsulfosuccinate, Na salt was used as the dialkyl sulfosuccinate.

The experiments show that powerful formulations can be prepared by synergistic combinations of hydroxy mixed ether sulfates with dialkyl sulfosuccinates. The parameters m, x and n can vary over a wide range.

Example 2:

The following all-purpose cleaner formulations were tested for their cleaning performance at normal household use concentrations (0.1% by weight of surfactant).

In comparison, the alkyl benzene sulfonate and polymer-containing formula described in Example 1 was tested, which was diluted 1: 100 with water.

The tests show that synergistic effects can also be observed at this application concentration, which lead to good to very good cleaning performance. Such compositions can also be packaged in the form of spray cleaners.

Example 3:

The following experiments are intended to demonstrate that combinations with a hydroxy mixed ether sulfate (HMS), characterized by the parameters n = 4, x = 10 and m = 12, over a wide concentration range with different builder components, solvents and solubilizers or their mixtures are very good Perform cleaning services. The products were optically transparent (clear) at room temperature. When using mixtures of solvents and solubilizers, e.g. B. from cumene sulfonate and octyl sulfate or ethanol and octyl sulfate, you needed smaller amounts of these components to achieve clear detergent solutions than when using the individual components. The pH of the 10% formulations was 7 in each case.

The names for the products listed in the table have the following meaning:
NTA: nitrilotriacetic acid
EDTA ethylenediaminetetraacetic acid
STP: sodium tripolyphosphate
Sokalan ^(R) DCS: Mixture of glutaric acid, succinic acid and adipic acid from BASF

The cleaning performance RL rel. [%] determined at the application concentration, ie 0.1% by weight of surfactant. The cleaning services RL rel. [%] with concentrated application, ie with 10% surfactant content, are summarized in the second line.

Example 4:

Attempting to incorporate the anionic surfactants commonly used in all-purpose cleaners, such as alkyl benzene sulfonate (ABS), alkyl sulfate (FAS), alkane sulfonate (SAS) or alkyl ether sulfate (FAES), into the formulations instead of the dialkyl sulfosuccinate led to products that were low to very low Have cleaning level. The pH of the 10% solutions was 7 in each case.

Examples here are combinations with the hydroxy mixed ether sulfate, characterized by m = 12, x = 10 and n = 4, and the following cosurfactants:
ABS: C₁₀₋₁₃ alkylbenzenesulfonate, Na salt
FAS: C₁₂₋₁₄ alkyl sulfate, Na salt
SAS: C₁₃₋₁₇ alkanesulfonate, sodium salt
FES: C₁₂₋₁₄ alkyl ether sulfate, Na salt with about 2 EO
listed.

The cleaning performance RL rel. [%] given a total surfactant concentration of 10 wt .-%. After dilution (1: 100) of the recipes with water, the cleaning performance RL rel. [%] determined at the application concentration, ie 0.1% by weight of surfactant. These results are summarized in the second line.

Claims (8)

1. Liquid cleaning agent for hard surfaces, based on dilute, preferably aqueous solutions containing anionic surfactants, organic and / or inorganic builders, optionally water-soluble solvents or solubilizers as well as other common components of such cleaning agents, characterized in that it is as anionic surfactants 0 , 02 to 40, preferably 0.05 to 15% by weight of a mixture of hydroxy mixed ether sulfates and dialkyl sulfosuccinates in a weight ratio of 1:10 to 10: 1, preferably 4: 1 to 1: 4. 2. Composition according to claim 1, characterized in that it is sulfated hydroxyalkyl polyethylene and / or hydroxyalkyl polypropylene glycol ethers of the general formula as hydroxy mixed ether sulfates

in the
R¹ is hydrogen or a linear alkyl radical having 1 to 16, preferably 8 to 12, carbon atoms,
R² is a linear or branched, saturated alkyl radical having 1 to 22, preferably 1 to 16, carbon atoms,
R³ is preferably hydrogen, but also a linear alkyl radical having 1 to 16 carbon atoms,
R⁴ is preferably hydrogen, but also a methyl group,
M for hydrogen, ammonium, alkylammonium, alkanolammonium, in which the alkyl and alkanol radicals each have 1 to 4 carbon atoms, or a monovalent metal atom and
n stands for a number in the range from 0 to 20, preferably 0 to 15, and of mixtures of several such compounds
contains. 3. Composition according to one of claims 1 or 2, characterized in that it contains as alkali metal, ammonium or substituted ammonium salts of dialkyl sulfosuccinates which are derived from a linear or branched chain C₇, C₈ or C₉ alcohol, or from one any mix of them. 4. Composition according to one of claims 1 to 3, characterized in that it contains straight-chain and / or branched-chain di-octylsulfosuccinates as dialkyl sulfosuccinates. 5. Composition according to one of claims 1 to 4, characterized in that it further contains solubilizers, preferably, toluene, xylene or cumene sulfonate, low molecular weight alcohols or short-chain fatty alcohol sulfates or mixtures thereof. 6. Composition according to one of claims 1 to 5, characterized in that it contains as a solubilizer ether from the same or different types of polyhydric alcohols with 1-6 carbon atoms. 7. Composition according to one of claims 1 to 6, characterized in that the weight ratio of surfactant to solvent or solubilizer is 1: 0 to 1: 2, preferably 1: 0.05 to 1: 1. 8. Composition according to one of claims 1 to 8, characterized in that it further contains dyes and fragrances, preservatives and nonionic surfactants as other usual ingredients.