WO1991009926A1

WO1991009926A1 - Liquid cleaning material for hard surfaces

Info

Publication number: WO1991009926A1
Application number: PCT/EP1990/002214
Authority: WO
Inventors: Birgit Middelhauve; Frantisek Jost; Fritz Lange; Eva Kiewert; Peter Jeschke
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1989-12-27
Filing date: 1990-12-17
Publication date: 1991-07-11
Also published as: JPH05502687A; DE3943070A1; EP0507791A1

Abstract

A liquid cleaning material for hard surfaces is based on aqueous solutions of anionic and nonionic tensides, possibly organic and/or inorganic skeleton substances, water-soluble solvents or solubilizers and other usual constituents of such cleaning materials. The content of anionic or nonionic tensides, which consist of a mixture of dialkyl sulphosuccinates and glyceryne monoalkyl ethers in a weight ratio of 1:10 to 10:1, is 0.02 to 40 wt.%.

Description

Liquid detergent for hard surfaces

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 swarm, with which the hard surfaces made of metal, lacquered wood, plastic, ceramic products, such as porcelain, tiles, tiles and the like, are wiped off and thereby dust, greasy dirt and Stains are removed. It is desired that this surface treatment in turn does not leave any detergent stains and strips behind and does not require any aftertreatment, for example with a cloth soaked in clear water, that is to say moist.

Dialkyl sulfosuccinates have long been commercially available as surface-active substances. Numerous cleaning agents for various purposes, which contain dialkyl sulfosuccinates, are therefore known from the literature. For example, DE 23 17 076 (Unilever) describes dishwashing detergents made from dialkyl sulfosuccinate and alkyl sulfate or alkyl ether sulfate, which are suitable for manual washing. EP 71 411 (Unilever) describes liquid detergent compositions which consist of a mixture of dialkyl sulfosuccinates and various anionic and / or nonionic surfactants. These mixtures are also said to be distinguished by good cleaning performance and good foaming properties and are therefore also predominantly usable for manual dishwashing.

EP 112 044 (Unilever) 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. They are described as high-foaming and can therefore preferably be used as manually applicable dishwashing detergents.

EP 112 045 (Unilever) describes liquid, high-foaming 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 ⁺ ions leads to performance advantages and improves the packaging. They are primarily recommended as manually applicable dishwashing detergents.

EP 112 047 (Unilever) describes liquid detergent compositions comprising dialkysulfosuccinates, alkylbenzenesulfonates, alkanesulfonates and fatty alcohol ether sulfates. The ternary combinations should be characterized by improved performance and packaging properties. The products are high-foaming and therefore particularly suitable for manual dishwashing. In JP 183781 (Kao) compositions are described which can consist, among other things, of dialkyl sulfosuccinates and glycerol dialkyl ethers. These compositions are said in the

Medicine can be used as carriers for pharmaceuticals.

No indications of cleaning agents containing dialkyl sulfosuccinates and glycerin ethers could be found, although glycerin ethers themselves are often used as surfactants or in combinations of surfactants. DE 2657518 (Procter & Gamble) describes the production of polyethoxylated glycerol ethers. Combinations with anionic surfactants and builders are used to remove oil and grease stains from textiles.

DE 2139447 and 2139448T (Ugine-Kuhlmann) claims the production of ethoxylated glycerol dialkyl ethers. These substances are said to have good surfactant properties and to be readily biodegradable.

JP 179967 (Kao) describes the use of branched glycerol monoalkyl ethers for hair treatment.

DE 3414042 (L'Oreal) describes products for hair and skin cleaning which, for. B. consist of a glycerol mono (hydroxyalkyl) ether in combination with a polymer described.

JP 109699 (Nippon Surfactant KK) describes the use of polyethoxylated glycerol ethers for cosmetics. DE 2252637 (Chemisch-Pharm. Fabrik Adolf Klinge & Co.) describes the production of short-chain glycerol-1,3-dialkyl ethers which have a bile-forming effect and can therefore be used pharmaceutically.

In US 4,288,334 and US 4,372,444 (Texaco) the use of combinations of glycerol ethers with e.g. B. alkylarylsulfonates for tertiary oil production - by surfactant flooding - described.

Various glycerin ethers have already been used many times, but no use in cleaning agents for hard surfaces has been determined.

Glycerol monoalkyl ethers, prepared as described in DE 3726911 (Henkel), also show unexpectedly, together with anionic surfactants generally used in all-purpose cleaners, no cleaning performance at any mixing ratio as would be expected for good products.

Surprisingly, it has been found that an unpredictable excellent cleaning performance of liquid cleaning agents for hard surfaces is achieved if a mixture of glycerol monoalkyl ethers and dialkyl sulfosuccinates is used as the surfactant.

The cleaning performance of these agents reaches the level of known, good alkylbenzenesulfonate-containing recipes with a cleaning-enhancing polymer component, as z. B. fall under the scope of protection of DE 2840463. The present invention thus relates to a liquid cleaning agent for hard surfaces based on aqueous solutions of anionic and nonionic surfactants, optionally together with organic and / or inorganic builders, water-soluble solvents or solubilizers, and other usual constituents of such cleaning agents, which is characterized in that it is 0 , 02 to 40, preferably 0.05 to 15 wt .-% of a mixture of dialkyl sulfosuccinates and glycerol monoalkyl ethers.

The weight ratio of dialkyl sulfosuccinates to glycerol monoalkyl ethers is preferably 1:10 to 10: 1 and in particular 4: 1 to 1: 4.

The glycerol monoalkyl ethers mentioned are compounds of the general formula

CH ₂ -O- (CH ₂ CH ₂ O) _n -R

CH -O- (CH ₂ CH ₂ O) _x -H

CH ₂ -O- (CH ₂ CH ₂ O) _y -H,

in which R stands for an alkyl radical with 1-22, preferably 8-18 C atoms, n for a number in the range 0-20, preferably 0-10 and x + y for a number in the range 0-60, preferably 0-30 stand, as well as mixtures of several such compounds.

These glycerol monoalkyl ethers can advantageously be prepared by combining excess glycerol in a reaction kettle with sodium hydroxide solution and heating under a nitrogen atmosphere, with water being distilled off. The batch is stirred for several hours. Then you set this reaction product with fatty alcohol sulfate, Na salt, or fatty alcohol polyethyleneglycol ether sulfate, Na salt, and further heats the reaction mixture for a few hours. The raw product is washed several times with water. Residual water in the organic phase is removed under reduced pressure. The glycerol monoalkyl ethers (GE) obtained in this way can then, if appropriate in the presence of a catalyst (for example Na methylate), be reacted with ethylene oxide in a pressure vessel under a nitrogen atmosphere at elevated temperature.

The dialkyl sulfosuccinates are alkali metal, ammonium or substituted ammonium salts and can be derived from a C ₇ , C ₈ or C ₉ 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 customary methods, e.g. B. 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 also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The sodium salts are mostly preferred for reasons of cost.

For the liquid cleaning agents according to the invention, inorganic or organic compounds, as well as inorganic or organic complexing agents, which are preferably in the form of their alkali or amine salts, in particular the sodium and potassium salts, can be used as framework substances in their entirety. The alkali hydroxides also belong to the framework substances here. Further usable inorganic substances which can optionally be added to the agents according to the invention are, for example, bicarbonates, carbonates, borates, silicates or polyphosphates such as pentasodium triphosphate, pyrophates or orthophosphates.

The organic complexing agents of the aminopolycarboxylic acid type include, among others, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid and polyphosphonic acids: methylenediphosphonic acids, 1-hydroxyethane-1,1-diphosphonic acid, propane-1,1,3-triphosphonic acid, Butane-1,2,3,4-tetraphonic acid, polyvinylphosphonic acid, copolymers of vinylphosphonic acid and acrylic acid, ethane-1,2, dirarboxy-1,2-diphosphonic acid, ethane-1,2-dicarboxy-1,2-dihydroxydiphosphonic acid, phosphonosuccinic acid, 1-aminoethane-1,2-diphosphonic acid, aminotri- (methylenephosphonic acid), methylamino- or ethylamino-di- (methylenephosphonic acid) and ethylenediaminetetra- (methylenephosphonic acid).

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

Since household cleaning agents are generally neutral to weakly alkaline, that is to say their aqueous use solutions at application concentrations of usual 2-20, preferably 5-15 g / l of water or aqueous solution have a pH in the range of 7.0-10.5, preferably 7.0-9.5, can be added to regulate the pH acidic and / or alkaline components, also as buffers, may be required.

Suitable acidic substances are customary inorganic or organic acids or acidic salts, such as, for example, hydrochloric acid, sulfuric acid or else the 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 carboxamides, Part amides of phosphoric acids or anhydrous phosphoric acid, lactic acid, polycarboxylic acids, wi; e.g. 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 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 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. As a mediator Furthermore, water-soluble organic solvents can be used, 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 monohydric alcohols containing 1 to 6 carbon atoms in the molecule.

Other suitable 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.

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 advisable to add sodium chloride and / or urea to regulate the viscosity.

In addition, the claimed agents may contain additives to colorants and fragrances, preservatives and nonionic surfactants known for this purpose as other usual constituents. 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 according to 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 above-mentioned soiling 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 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 a surfactant content of 0.1% by weight and the test area was also soaked or coated with 10 ml of the cleaning agent solution to be tested and mechanically moved on the test area. At 10 wt .-% surfactant solution only the test area is 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 determined using 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 capacity (% RV). In the experiments below, the values RL rel. (%) the values determined according to 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 triplicate determinations.

Examples 1. Preparation of glycerol monoethers

1.1 Glycerol mono-C _12/14 alkyl ether

45 kg (488.7 mol) of glycerol were combined in a reaction kettle with 7.2 kg (90 mol) of sodium hydroxide solution (50% by weight in water) and heated to 150 ° C. under a nitrogen atmosphere, water distilling off. The mixture was stirred for a further 4 hours. Then 26.1 kg (90 mol) of C ₁₂ -

_{/ 14} -fatty alcohol sulfate, Na salt (needles), added and the reaction mixture heated to 175 ° C. After 8 hours of reaction with constant stirring, the mixture was cooled to 90 ° C. and washed twice with 20 kg of water. After the organic phase had been separated off, it was freed from residual water at 90 ° C. under reduced pressure. The product obtained was a colorless, solid mass with a hydroxyl number (according to DGF unit method CV-17a) of 366.3.

1.2 Glycerol mono (C ₁₂ ) alkyl ether

A polyol monoether was prepared from glycerol and a lauryl sulfate, Na salt by the process according to Example 1.1. The product had a hydroxyl number of 421.3.

1.3 glycerol mono- (C _16/18 ) alkyl ether

A polyol monoether was prepared from glycerol and a (C _16/18 ) fatty alcohol sulfate, Na salt, by the process according to Example 1.1. The product had a hydroxyl number of 282.1.

1.4 (C _12/14 ) alkyl diethylene glycol ether glycerol monoalkyl ether According to the procedure in Example 1.1, glycerol and a (C _12/14 ) fatty alcohol diethylene glycol ether sulfate, NA

Salt, a polyol monoether made. The product had a hydroxyl number of 407.6.

1.5 glycerol mono (C _12/14 ) ether + 8 moles of ethylene oxide

428.5 g of the reaction product according to 1.1 were treated with 4.6 g of sodium methylate solution (30% by weight in methanol) in a pressure vessel under a nitrogen atmosphere after removal of the methanol at a temperature of 150 ° C. with 493.5 g of ethylene oxide ( Molar ratio 1: 8) implemented, the pressure rising to 5 bar. After the reaction had ended (drop in pressure), the mixture was kept at 70 ° C. under a reduced pressure of 0.05 bar for a further 45 minutes. A yellow liquid with a hydroxyl number of 169.0 was obtained.

1.6 Glycerol mono- (C ₁₂ ) alkyl ether + 10 moles of ethylene oxide

An adduct of 10 moles of ethylene oxide was prepared by the same method as in 1.5.

1.7 Glycerol mono- (C _15/18 ) alkyl ether + 8 moles of ethylene oxide

An adduct of 8 moles of ethylene oxide was prepared by process 1.5.

1.8 glycerol mono- (C _16/18 ) alkyl ether + 20 mol ethylene oxide

According to the procedure as under 1.5, an adduct of 20 moles of ethylene oxide was prepared. The product had a hydroxyl number of 31.3. 1.9 (C _12/14 ) alkyl diethylene glycol ether glycerol monoalkyl ether + 8 moles of ethylene oxide

According to the procedure as under 1.5, an adduct of 8 moles of ethylene oxide was prepared. The product had a hydroxyl number of 179.7.

1.10 (C _12/14 ) alkyl diethylene glycol ether glycerol monoalkyl ether + 10 moles of ethylene oxide

According to the procedure as under 1.5, an adduct of 10 moles of ethylene oxide was prepared. The product had a hydroxyl number of 153.8.

1.11 (C _12/14 ) alkyl diethylene glycol ether glycerol monoalkyl ether + 20 moles of ethylene oxide

According to the procedure as under 1.5, an adduct of 20 moles of ethylene oxide was prepared. The product had a hydroxyl number of 97.9.

1.12 (C _12/14 ) -aikyidiethylene glycol ether-glycerol monoalkyl ether +

30 moles of ethylene oxide.

According to the procedure as under 1.5, an adduct of 30 moles of ethylene oxide was prepared. The product had a hydroxyl number of 72.3.

Example 2:

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 2840463:

8% by weight alkylbenzenesulfonate, Na salt

2% by weight adduct of 10 moles of ethylene oxide with 1 mole of a mixture of oleyl and cetyl alcohol (C ₁₀ - C ₁₃ ) 2% by weight Na gluconate

0.1% polyethylene glycol with a molecular weight of approx. 600,000

(Commercial product Polyox WSR 205 (R) from UCC), the rest 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 glycerol monoalkyl ethers (GE) tested here is:

CH ₂ -O (CH ₂ CH ₂ O) _n R

CH -O (CH ₂ CH ₂ O) _x H

CH ₂ -O (CH ₂ CH ₂ O) _y H

The parameters R, n, x and y thus clearly characterize the GE.

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

The experiments show that powerful formulations can be prepared by synergistic combinations of glycerol monoalkyl ethers with dialkyl sulfosuccinates. The parameters R, n, x and y can vary over a wide range. Example 3:

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 2 was tested, which was diluted 1: 100 with water.

Recipes:

Example 4:

The following experiments are intended to show that, in particular, combinations with a glycerol monoalkyl ether, characterized by the parameters R = C12 / 14, n = 0 and x + y = 8, over a wide concentration range with different builder components, solvents and solubilizers or their mixtures too much good cleaning performance. 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 adjusted to 7 in each case with sodium hydroxide solution or citric acid.

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 services RL rel. (%) with concentrated application, d. H. with 10% surfactant content are listed in the first line. The cleaning services RL rel. (%) at application concentration, d. H. 0.1% by weight of surfactant.

Example 5:

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 even very low Have cleaning level. The pH of the 10% solutions was 7 in each case.

Examples are combinations with the glycerol monoalkyl ether, characterized by R = C12 / 14, n = 0 and x + y = 8, and the following cosurfactants:

ABS: C _10-13 alkyl benzene sulfonate, sodium salt FAS: C _12-14 alkyl sulfate, sodium salt SAS: C _13-17 alkane sulfonate, sodium salt

FES: C _12-14 alkyl ether sulfate, Na salt listed with approx. 2 EO.

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. (%) at application concentration, ie 0.1% by weight of surfactant. These results are summarized in the second line.

Claims

Patent claims

1. Liquid cleaning agent for hard surfaces based on aqueous solutions of anionic and nonionic surfactants, optionally together with organic and / or inorganic builders, water-soluble solvents or solubilizers and other usual components of such cleaning agents, characterized in that it is 0.02 to 40, preferably Contains 0.05 to 15 wt .-% of a mixture of dialkyl sulfosuccinates and glycerol monoalkyl ethers.

2. Composition according to claim 1, characterized in that the weight ratio of dialkyl sulfosuccinates to glycerol monoalkyl ethers is 1:10 to 10: 1, preferably 4: 1 to 1: 4.

3. Composition according to claim 1 and 2, characterized in that it contains alkali metal, ammonium or substituted ammonium salts of such dialkyl sulfosuccinates as dialkyl sulfosuccinates, which are derived from a linear or branched chain C ₇ -, C ₈ - or C ₉ alcohol, or any mixture thereof.

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 3, characterized in that it is a glycerol monoalkyl ether compounds of the general formula CH ₂ -O (CH ₂ CH ₂ O) _n R

CH- O (CH ₂ CH ₂ O) _x H

CH ₂ -O (CH ₂ CH ₂ O) _y H,

in which R is a linear alkyl radical having 1 to 22, preferably 8 to 18, carbon atoms, n is a number in the range from 0 to 20, preferably 0 to 10, x + y is a number in the range from 0 to 60, preferably 0 to 30, and contains mixtures of several such compounds.

6. Composition according to one of claims 1 to 5, 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.

7. Agent according to one of claims 1 to 6, characterized in that it contains as a solubilizer ether from the same or different types of polyhydric alcohols with 1-6 carbon atoms.

8. Composition according to one of claims 1 to 7, 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.

9. Agent according to one of claims 1 to 8, characterized in that it further contains dyes and fragrances and preservatives as other usual ingredients.