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
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
  • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups

Definitions

• liquid, manual dishwashing detergents which can usually be used at slightly elevated temperatures, contain as active ingredients essentially mixtures of synthetic anionic surfactants in amounts of about 4 to 60% by weight and, if appropriate, z. B. as foam stabilizers, small amounts of nonionic surfactants, preferably alkanolamides, or amphoteric surfactants such as betaines, and solvents, solubilizers, hydrotropic substances, fragrances and dyes, preservatives, agents for viscosity adjustment, pH adjustment and electrolytes.
• the pH is around 5.5 to 8.0.
• the agents can still contain small amounts of builders or complexing agents, such as hexametaphosphate or ethylenediaminetetraacetate, for use in areas with highly iron-containing water.
• builders or complexing agents such as hexametaphosphate or ethylenediaminetetraacetate
• Also common commercial all-purpose cleaning agents i.e. agents for cleaning various hard surfaces in the household and in commercial premises, preferably contain combinations of anionic and nonionic surfactants in a total amount of about 5 to 15% by weight as well as cleaning-enhancing framework substances in amounts of about 0.1 as active ingredients up to 5% by weight and to increase the cleaning performance as organic polymers polyethylene glycols of the general formula HO- (CH2-CH2-O) n -H, where n can vary between 4,800 and 64,600. These agents are also made up with dyes and fragrances, electrolytes and viscosity regulators.
• British patent application 2 104 091 recommends ampholytic copolymers of anionic and cationic vinyl monomers for increasing the performance in surfactant formulations.
• European patent application 124 367 teaches the use of water-soluble polymers, e.g. B. polysaccharides or xanthan rubber, which are both intended to increase the viscosity of the surfactant formulation and to improve their cleaning performance and foam behavior.
• German Offenlegungsschrift 2,616,404 which also relates to multigrade cleaning agents and is the closest to the invention, claims additions of polymers, namely water-soluble cationic cellulose ethers with a molecular weight of 25,000 to 10,000,000, to improve the flow of liquid from hard surfaces.
• ampholytic cellulose ethers are prepared in a manner known per se by mixed etherification of (alkali) cellulose with monochloroacetic acid sodium and 2-chloroethyldiethylamine with variation of the amounts of the carboxymethylating or aminating agent.
• the degree of substitution of cellulose is 0.4 to 2, preferably 0.6 to 1.2.
• the viscosity (Brookfield) of a 2% by weight aqueous solution of the polymers should be between 3,000 and 120,000 mPas, preferably between 9,000 and 80,000 mPas.
• the liquid compositions according to the invention for cleaning hard surfaces are particularly characterized in that they 1 to 40% by weight, preferably 5 to 25% by weight of anionic surfactants, 0 to 20% by weight, preferably 0.5 to 15% by weight, of nonionic surfactants or amphoteric surfactants 0 to 10% by weight, preferably 0.5 to 5% by weight of builder substances, 1 to 15% by weight, preferably 1.5 to 12% by weight, of solubilizer, 0.01 to 1.5% by weight, preferably 0.03 to 1% by weight, of the polymers according to the invention, and, if appropriate, other customary auxiliaries, in particular fragrances and dyes, preservatives and agents for adjusting the pH, and the remainder up to 100% by weight of water.
• Formulations free of anionic surfactants can contain 0-5% by weight, preferably 0.1-3% by weight, of cationic surfactants, also in mixtures with nonionic surfactants. The rest of the wording above applies.
• Suitable synthetic anionic surfactants are those of the sulfonate, sulfate and synthetic carboxylate type.
• Suitable surfactants of the sulfonate type are C9 ⁇ 15 alkylbenzenesulfonates, mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonating group.
• suitable Alkanesulfonates which are obtainable from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins.
• esters of alpha sulfo fatty acids e.g. B. the alpha-sulfonic acids from hydrogenated methyl or ethyl esters of coconut, palm kernel or tallow fatty acid.
• Suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols (for example from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol) and those secondary alcohols. Sulfated fatty acid alkanolamides, fatty acid monoglycerides or reaction products of 1-4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols are also suitable.
• Suitable anionic surfactants are the fatty acid esters or amides of hydroxy or amino carboxylic acids or sulfonic acids, such as. B. the fatty acid sarcosides, glycolates, lactates, taurides or isethionates, alpha-sulfosuccinic acid esters and fatty acid cyanamides.
• the carbon chain length range of the hydrophobic residues of the surfactants is generally between 6 and 18, preferably between 8 and 16.
• 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 the mono-, di- or triethanolamine.
• the sodium salts are mostly preferred for cost reasons.
• Addition products of 4-40, preferably 4-20 moles of ethylene oxide or ethylene oxide and propylene oxide with 1 mole of fatty alcohol, alkanediol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide can be used as nonionic surfactants.
• non-fully or not fully water-soluble polyglycol ethers with 1-4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.
• non-ionic surfactants that can be used are the water-soluble adducts of ethylene oxide with polypropylene oxide, alkylene diamine poly-propylene glycol and alkyl polypropylene glycols with 1-10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain functions as a hydrophobic residue, containing polypropylene oxide, alkylene diamine poly-propylene glycol and 10-100 propylene glycol ether groups.
• Nonionic surfactants of the amine oxide type can also be used. Typical representatives are, for example, the compounds N-dodecyl-N, N-dimethylamine oxide, N-tetradecyl-N, N-dihydroxyethylamine oxide, N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) amine oxide.
• Alkyl glucosides with 12 to 18, preferably 12 to 14 carbon atoms in the straight-chain or branched alkyl radical and 1 to 4, preferably 1 to 2, glucose units in the molecule are also suitable.
• Suitable addable amphoteric surfactants are those which contain both acidic groups, such as, for. B. carboxyl, sulfonic acid, sulfuric acid half-ester, phosphonic acid and phosphoric acid partial ester groups, as well as basic groups, such as. B. contain primary, secondary, tertiary and quaternary ammonium groups.
• Amphoteric compounds with quaternary ammonium groups belong to the type of betaines or zwitterionic surfactants. These are in particular derivatives of aliphatic quaternary ammonium compounds in which one of the aliphatic radicals consists of a C8-C18 alkyl radical and another contains an anionic, water-solubilizing carboxy, sulfo or sulfato group.
• Typical representatives of such surface-active betaines are, for example, the compounds 3- (N-hexadecyl-N, N-dimethylammonio) propanesulfonate, 3- (N-tallow alkyl-N, N-dimethylammonio) -2-hydroxypropanesulfonate, 3- (N-hexadecyl- N, N-bis (2-hydroxyethyl) -ammonio) -2-hydroxypropyl sulfate, 3- (N-cocoalkyl-N, N-bis (2,3-dihydroxypropyl) -ammonio) propane sulfonate, N-tetradecyl-N, N -dimethyl-ammonioacetate, N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonium acetate.
• C12-C18-Acylamido-propyldimethylammonium betaines are preferably used.
• the cationic surfactants which may be added contain at least one hydrophobic and at least one basic group which, if appropriate, is present as a salt and makes water-soluble.
• the hydrophobic group is an aliphatic or cycloaliphatic hydrocarbon group with preferably 10-22 carbon atoms or an alkyl or cycloalkylaromatic group with preferably 8-16 aliphatic carbon atoms.
• basic nitrogen atoms primarily basic nitrogen atoms come into question, which can also be present several times in a surfactant molecule; it is preferably quaternary ammonium compounds such as N-dodecyl-N, N, N-trimethylammonium methosulfate, N-hexadecyl or N-octadecyl-N, N, N-trimethylammonium chloride, N, N-dicocosalkyl-N, N-dimethylammonium chloride , N-dodecyl-N, N-dimethyl-N-benzylammonioumbromid, the reaction product of 1 mol tallow alkylamine with 10 mol ethylene oxide, N-dodecyl-N, N ', N'-trimethyl-1,3-diaminopropane, N-hexadecylpyridinium chloride.
• the nitrogen compounds mentioned can be replaced by corresponding compounds with a quaternary phosphorus atom or with a tertiary sulfur atom.
• Cleaning agents containing cationic surfactants are mostly used for disinfectant purposes.
• alkaline inorganic or organic compounds in particular inorganic or organic complexing agents, are used as builders, which are preferably in the form of their alkali or amine salts, in particular the potassium salts.
• the framework substances here also include the alkali metal hydroxides, of which the potassium hydroxide is preferably used.
• the alkaline polyphosphates in particular the tripolyphosphates and the pyrophosphates, are particularly suitable as inorganic complex-forming framework substances. 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, ethylenediaminetetraacetic acid, N-hydroxyethylethylene diamine triacetic acid and polyalkylene polyamine N-polycarboxylic acids.
• di- and polyphosphonic acids examples include: methylene diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic 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, phosphono succinic acid, 1-aminoethane-1,1-diphosphonic acid, aminotri- (methylenephosphonic acid), methylamino- or ethylamino-di- (methylenephosphonic acid) and ethylenediamine-tetra- (methylenephosphonic acid).
• N- or P-free polycarboxylic acids have also been proposed as builders, many, if not exclusively, of polymers containing carboxyl groups.
• 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.
• Suitable acidic substances are customary inorganic or organic acids or acidic salts, such as, for example, hydrochloric acid, sulfuric acid, bisulfates or 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, citric acid, tartaric acid, lactic acid and the like.
• organic or inorganic compounds such as alkanol can also have an alkaline effect amines, namely mono-, di- or triethanolamine or ammonia can be added.
• solubilizers can be incorporated, which in addition to the water-soluble organic solvents such as, in particular, low-molecular aliphatic alcohols with 1-4 carbon atoms, also include the so-called hydrotropic substances of the lower alkylarylsulfonate type, for example toluene, xylene or cumene sulfonate. 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., 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 4 carbon atoms in the molecule.
• ketones such as acetone, methyl ethyl ketone and aliphatic, cycloaliphatic, aromatic and chlorinated hydrocarbons, and also the terpene alcohols.
• the latter generally have an odor-forming effect at the same time.
• the claimed agents can contain additives of colorants and fragrances, preservatives and, if desired, antimicrobial agents of any kind.
• Suitable antimicrobial agents to be used are, for example, those compounds which are stable and effective in the liquid compositions according to the invention, for example of the quaternary ammonium compound type, for example a benzylalkyldimethylammonium chloride.
• Plates of 14 cm in diameter were soiled with 2 g of beef tallow (melting point 40 to 42 ° C, acid number 9 to 10), stored for 15 hours at + 0 to + 5 ° C and at 50 ° C with tap water of hardness 16 ° d rinsed.
• the test products were used with a dosage of 0.5 g / l water, based on total agent, or 0.15 g individual surfactant / l water.
• the number of plates that are rinsed clean with 5 liters of washing solution number of plates serves as a measure of the cleaning effect.
• 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.
• the test area of 26 x 28 cm was evenly coated with 2 g of the artificial soiling with the help of a surface coater and then cut into seven equally large areas of 26 x 4 cm.
• a plastic sponge was impregnated with 6 ml of the undiluted detergent solution to be tested and moved mechanically on the test surface. After 10 wiping movements, the cleaned test area was kept under running water and the loose dirt was removed. The cleaning effect, d. that is, the whiteness of the plastic surface thus cleaned was measured with an LF 90 photoelectric colorimeter (Dr. B. Lange). The clean white plastic surface served as the white standard.
• the read values for the cleaned plastic areas were to be equated with the percentage cleaning ability (% RV).
• % RV percentage cleaning ability
• the% -RV values given are the values determined by this method for the cleaning ability of the cleaning agents examined. They each represent mean values from 4-fold determinations (cf. quality standards of the Industry Association for Cleaning and Care Agents (IPP), Frankfurt / Main (1982 version) in "Soaps, Fats, Oils, Waxes", 108 , (1982) 527-528.
• the soiling used to determine the cleaning ability consisted of: Petrol 80/110 - White spirit K 30 44.8 Special black 4 4.8 Coray 34 - Myritol 318 4.8 Vaseline 5.6 Kaolin 20.0 Durcal 2 20.0 (Data% by weight)
• composition of the cleaning agents according to the invention is given in the tables.
• comparative tests according to DE 26 16 404 The difference to 100% by weight in any case consists of water.
• a cationic cellulose ether derivative namely the polymer JR 400 (R) from Union Carbide (cf. US 3,472,840) with an average molecular weight of 400,000 was used.
• ampholytic cellulose ethers according to the invention have a higher performance increase in the detergents than cationic cellulose ethers according to DE 26 16 404.
• Table 2 shows that the ampholytic cellulose ethers according to the invention, incorporated in small proportions in general-purpose or disinfectant cleaning agents, bring about distinct cleaning-enhancing effects.
• ampholytic cellulose ethers Another surprising advantage of the ampholytic cellulose ethers was the removal of fat on newly soiled plates that had already been cleaned in a polymer-containing washing liquor. The following experiment made this advantage clear:
• the plates cleaned in the polymeric washing liquor were - as already described - again soiled with 2 g beef tallow / plate and stored for 15 hours at temperatures of 0 - 5 ° C.
• a plate was then placed horizontally in 5 liters of rinse liquor at 50 ° C. and the time until the grease removal from the plate surface was completed without any additional manual action.
• the cleaning time was approximately 2.5 minutes;

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• 1987
  • 1987-08-13 DE DE19873726912 patent/DE3726912A1/de not_active Withdrawn
• 1988
  • 1988-06-08 TR TR414/88A patent/TR23342A/xx unknown
  • 1988-08-04 EP EP88112708A patent/EP0303188A3/fr not_active Withdrawn
  • 1988-08-10 DK DK446888A patent/DK446888A/da unknown
  • 1988-08-12 US US07/231,799 patent/US4976885A/en not_active Expired - Fee Related
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