Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds

Definitions

• 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.
• 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.
• surfactants e.g. alkyl benzene sulfonates, alkane sulfonates or fatty alcohol ether sulfates
• Mg 2+ ions 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.
• 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.
• 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.
• 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.
• 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.
• glycerol monoalkyl ethers mentioned are compounds of the general formula
• 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.
• 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.
• a catalyst for example Na methylate
• 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.
• 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
• carboxylic acids 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.
• 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.
• alkaline builders If the content of alkaline builders is not sufficient to regulate the pH, organic or inorganic compounds such as z.
• organic or inorganic compounds such as z.
• 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.
• 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.
• ethers from the same or different polyhydric alcohols or the partial ethers from polyhydric alcohols 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.
• 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.
• the claimed agents may contain additives to colorants and fragrances, preservatives and nonionic surfactants known for this purpose as other usual constituents. Tries
• the cleaning agent to be tested was placed on an artificially soiled plastic surface.
• the above-mentioned soiling 2 was used as artificial soiling.
• 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.
• the read values for the cleaned plastic areas are to be equated with the percentage cleaning capacity (% RV).
• % RV percentage cleaning capacity
• 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.
• 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.
• the pH of the formulations was adjusted to 7.0 with 50% sodium hydroxide solution.
• Di-isooctylsulfosuccinate, Na salt was used as the dialkyl sulfosuccinate.
• NTA nitrilotriacetic acid
• EDTA ethylenediaminetetraacetic acid
• the cleaning services RL rel. (%) with concentrated application, d. H. with 10% surfactant content are listed in the first line.
• 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.

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• Chemical & Material Sciences (AREA)
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• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)
• Motor Or Generator Current Collectors (AREA)

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• 1989
  • 1989-12-27 DE DE19893943070 patent/DE3943070A1/de not_active Withdrawn
• 1990
  • 1990-12-17 JP JP3501238A patent/JPH05502687A/ja active Pending
  • 1990-12-17 EP EP19910900779 patent/EP0507791A1/de not_active Withdrawn
  • 1990-12-17 WO PCT/EP1990/002214 patent/WO1991009926A1/de not_active Application Discontinuation

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