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
  • C11D3/0094—High foaming compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/662—Carbohydrates or derivatives

Definitions

• the invention relates to an environmentally compatible, liquid cleaning agent.
• Liquid, foaming cleaning agents aim at the manual cleaning of hard surfaces, especially in the household, such as. B. ceramics, porcelain, glass, metal and plastic.
• the most important area of application are manual dishwashing detergents for cleaning dishes.
• Modern products consist of neutral aqueous formulations based on foaming surfactants.
• the main components are sulfonates, such as. B. alkylbenzenesulfonates or sec-alkanesulfonates, both combined with fatty alcohol ether sulfates or fatty alcohol sulfates (EP-A-0 112 047). Small amounts of fatty acid alkanolamides and, more rarely, oxyethylates are added. Other common ingredients are solubilizers, colors and fragrances, preservatives etc.
• the rinsing process usually takes place at a slightly elevated temperature (30 to 50 ° C) in dilute solutions. Of particular importance, because of the long skin contact of the user, the skin compatibility of the detergent.
• the foaming power of the solution plays a significant role, for example in the sense that the longer the cleaning solution foams during the rinsing process, the greater its cleaning power.
• Generally accepted test methods are a) the plate test, the end point of which is determined by the foam disintegration, and b) the fat titration, as a measure of the cleaning power, both of which lead to very similar results (see G. Jakobi in H. Stache, Tensid Taschenbuch , 2nd edition, Kunststoff 1981, pp. 252 ff.).
• Another disadvantage of the known detergents is their low skin-friendliness, since their essential components - namely the anionic surfactants of the sulfonate or sulfate type - are highly irritating to the skin.
• the object of the invention was therefore to provide a very skin-compatible cleaning agent with excellent cleaning action and moderate foaming power, the cleaning surfactant of which is largely biodegradable.
• liquid cleaning agent which, as cleaning surfactants, contains exclusively a mixture of alkyl polyglycosides of different alkyl chain lengths.
• alkyl polyglycosides in detergents and cleaning agents is known in combination with other surfactants.
• AT-PS 135 333 already describes the effect of lauryl glycoside combined with the sodium salt of ricin oil sulfuric acid ester as a wool detergent.
• alkyl polyglycosides in combination with builder substances, such as nitrilotriacetic acid or sodium tripolyphosphate are described as detergents.
• EP-A-0 105 556 claims the combination of alkyl polyglycosides with fatty alcohol oxyethylates as a liquid detergent.
• Alkyl polyglycosides used according to the invention satisfy the general formula in which R represents a linear or branched, saturated or unsaturated aliphatic alkyl radical and Z n represents a polyglycosyl radical.
• the alkyl polyglycosides used according to the invention can be produced by known processes based on renewable raw materials. For example, dextrose is reacted with n-butanol to give butylpolyglycoside mixtures in the presence of an acidic catalyst, which are transglycosidated with long-chain alcohols in the presence of an acidic catalyst to give the desired alkylpolyglycoside mixtures.
• the structure of the products can be varied within certain limits.
• the alkyl radical R is determined by the choice of the long-chain alcohol.
• the commercially available surfactant alcohols in particular native fatty alcohols from the hydrogenation of fatty acids or fatty acid derivatives, are favorable for economic reasons. Ziegler alcohols or oxo alcohols can also be used.
• the polyglycosyl radical Z n is determined, on the one hand, by the selection of the carbohydrate and, on the other hand, by setting the average degree of polymerization n. B. according to DE-OS 19 43 689.
• polysaccharides e.g. B. starch, maltodextrins, dextrose, galactose, mannose, xylose, etc.
• the commercially available carbohydrates starch, maltodextrins and especially dextrose are preferred.
• alkyl polyglycosides are always mixtures of oligomers, which in turn represent mixtures of different isomeric forms. They are side by side with ⁇ - and ß-glycosidic Bonds in pyranose and furanose form. The junctions between two Saccachrid residues are also different.
• Alkyl polyglycosides used according to the invention can also be prepared by mixing alkyl polyglycosides with alkyl monoglycosides.
• the latter can e.g. B. according to EP-A 0 092 355 using polar solvents, such as acetone, from alkyl polyglycosides.
• polar solvents such as acetone
• the degree of glycosidation is expediently determined by 1 H NMR certainly.
• the cleaning agents according to the invention usually contain 3 to 50 percent by weight, preferably 5 to 30 percent by weight, of total alkyl polyglycoside in aqueous solution.
• the total polyglycoside consists of at least two components, a hydrophilic component I and a hydrophobic component II.
• I has no or very little cleaning action and serves to increase the solubility in water or to lower the clear point.
• the hydrophobic component II is the actual cleaning agent. What is completely surprising with the mixture is that the cleaning action of component II is largely retained, although I itself has practically no cleaning action.
• the measure for adjusting the hydrophilicity is primarily the hydrophobic remainder of the alkyl polyglycoside.
• hydrophobic alkyl radical is in the range ⁇ C10.
• the adjustment of the hydrophobic component is a little more subtle.
• the alkyl radical should be> C10, at the same time the degree of glycosidation must be reduced to such an extent that the cleaning effect is optimal.
• the quantitative ratio of the two components I / II should be between 1: 1 and 1:10, preferably between 1: 2 and 1: 5.
• the alkyl polyglycosides are considered to be extremely environmentally compatible.
• the degree of biodegradation for the alkyl polyglycosides according to the invention determined by means of a sewage treatment plant simulation model / DOC analysis, is 96 ⁇ 3%. This number can be seen against the background that with this test method (total degradation) a degree of degradation> 70% already indicates that the substance is readily degradable.
• the acute oral toxicity LD 50 (rat) as well as the aquatic toxicity LC SO (gold orfe) and EG 50 (daphnia) and values of> 10,000 mg / kg, 12 or 30 mg / l are 3 to 5 times cheaper than the corresponding values of today's most important surfactants. The same applies to the skin and mucous membrane compatibility, which is particularly important for detergents.
• the alkyl polyglycosides according to the invention fall as synthesis-related about 50% aqueous amber solution.
• solvents such as low-molecular, mono- and polyhydric alcohols and glycol ethers
• the solubility can be increased significantly, especially at low temperatures.
• Particularly suitable solvents are ethanol, isopropanol, propylene glycol-1.2, etc.
• the ratio of alkyl polyglycoside / solvent can be 1: 1 to 4: 1.
• the solubility can be increased considerably, especially at low temperatures.
• Alkali and alkaline earth metal halides have proven to be suitable electrolytes.
• the solvent / electrolyte ratio can be 1: 1 to 4: 1.
• constituents of the cleaning agents according to the invention in small amounts are conventional dyes and perfume oils, and also alkanolamines or hydrotropes, such as non-surfactant alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical - usually as sodium salts - and urea.
• Water-soluble polymers such as carboxymethyl cellulose, hydroxyethyl cellulose, xanthans, polyethylene oxide, polyacrylate, etc., can optionally be added to adjust the viscosity.
• Citric acid, EDTA, NTA and other complexing agents have proven to be further suitable additives.
• the mini dish test (cf. RM Anstett and EJ Schuck JAOCS 43, 576 (1966) was carried out to test the detergent action.
• Watch glasses loaded with grease are manually cleaned at elevated temperature with a brush in the surfactant solution.
• the test conditions (preparations, geometries, amounts and concentrations of substances, temperatures, temperature gradients, times) are precisely defined. The test is carried out by several people and provides reproducible results. Disappearing foam shows the number of cleaned plates (watch glasses). Pork lard served as soiling, which was applied to the glasses at 50.0 ° C, which are then subject to a defined cooling process to 23 ° C (room temperature). The initial rinse temperature is also 50 ° C.
• Table 1 compares the cleaning effect of individual surfactants, which increases sharply with increasing molecular hydrophobicity in the case of alkyl polyglycosides.
• Table 2 demonstrates that even a strong increase in the surfactant concentration only gives unsatisfactory cleaning effects if the alkyl polyglycoside is too hydrophilic, as in the case of Triton CG 110.
• Table 3a compares the cleaning action of the alkyl polyglycosides according to the invention with those of optimized branded products depending on the detergent concentration for a medium water hardness; Table 3b the analogous conditions for soft water.
• Table 4 summarizes the physical data of some of the preparations according to the invention. Their solubility behavior (clear point) on the one hand and their cleaning values (mini plate test) on the other hand demonstrate the high effectiveness of the new cleaning systems.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Molecular Biology (AREA)
• Detergent Compositions (AREA)

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• 1990
  • 1990-02-26 DE DE19904005958 patent/DE4005958A1/de not_active Withdrawn
  • 1990-12-11 DK DK90123844T patent/DK0444262T3/da active
  • 1990-12-11 DE DE59010166T patent/DE59010166D1/de not_active Expired - Fee Related
  • 1990-12-11 EP EP90123844A patent/EP0444262B2/fr not_active Expired - Lifetime

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