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
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3707—Polyethers, e.g. polyalkyleneoxides

Definitions

• DE-AS 10 51 440 discloses liquid cleaning agents which are used for all purposes, but especially for washing textiles, and to increase the dirt-carrying capacity, inter alia, water-soluble cellulose or starch derivatives or else water-soluble or colloidally soluble polymers, such as polyvinylpyrrolidone. can contain.
• AT-PS 2 78 216 discloses liquid cleaning agents which can also 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.
• liquid all-purpose cleaners which, in addition to water-soluble synthetic surface-active substances, organic solvents and optionally water-soluble builders, a small amount of a special water-soluble carboxymethyl cellulose, namely one with a degree of substitution of about 1 to about 2 and a degree of polymerization of contain about 1000 to about 3000 as well as water.
• a special water-soluble carboxymethyl cellulose namely one with a degree of substitution of about 1 to about 2 and a degree of polymerization of contain about 1000 to about 3000 as well as water.
• liquid builder-containing cleaning agents for hard surfaces with small amounts of surfactants in combination with small amounts of a mixture of polyvinyl alcohol and / or polyvinyl pyrrolidone and polysaccharide salt are known, which should also have an improved dirt removal capacity.
• liquid cleaning agents for hard surfaces which can also contain cleaning-enhancing additives to water-soluble high-molecular substances, such as polyvinyl alcohol, polyvinyl pyrrolidone and carboxymethyl cellulose.
• the present invention therefore relates to a liquid detergent for hard surfaces in the form of dilute, preferably aqueous solutions containing anionic, nonionic or cationic surfactants or suitable mixtures thereof, organic and / or inorganic builders, optionally water-soluble solvents or solubilizers and other customary components of such Detergent and organic polymers, which is characterized in that 0.05 to 0.5, preferably 0.08 to 0.4% by weight of water-soluble polyethylene glycols with a molecular weight between 300,000 and 4,000,000, preferably between 500,000, are used as organic polymers and deploys 1,000,000. With these amounts of use, which bring about an unexpected cleaning enhancement, none of the above-mentioned disadvantages of the known polymers can be observed.
• the polyethylene glycols mentioned are prepared in a known manner by subjecting ethylene glycols to a polycondensation process in a known manner. They can also be considered as condensation polymers of ethylene oxide with ethylene glycol or water. They have the general formula FO (-CH 2 -CH 2 -O) n H, where n can vary between 4800 and 64,600 in the case of the polyethylene glycols used according to the invention.
• Such polymers are also commercially available and are sold by Union Carbon Carbide Corporation (UCC) under the name "POLYOX.
• surfactants and mixtures of surfactants which contain at least one hydrophobic organic residue and one water-solubilizing anionic, nonionic or cationic residue in the molecule.
• the hydrophobic residue is usually an aliphatic hydrocarbon residue with 8-26, preferably 10-22 and in particular 12-18 C atoms or an alkyl aromatic radical having 6 to 18, preferably 8 to 16 aliphatic C atoms.
• the surfactant mixtures the known incompatibility of most anionic and cationic surfactants would have to be taken into account.
• surfactants from the group of synthetic anionic surfactants, soaps and nonionic surfactants and mixtures thereof are used.
• surfactant combinations of anionic surfactants from the group of the sulfonate and sulfate surfactants and the nonionic surfactants of the ethoxylated alkanols, alkenols and alkylphenols type are particularly preferred.
• a soap can be included as a further component.
• the weight ratio of the total amount of surfactant to the polymer is at least 10: 1, in particular at least 20: 1.
• anionic surfactants such as Soaps from natural or synthetic, preferably saturated fatty acids, optionally also from resin or naphthenic acids.
• Suitable synthetic anionic surfactants are those of the sulfonate, sulfate and synthetic carboxylate type.
• Suitable surfactants of the sulfonate type are alkylbenzenesulfonates (C 9-15 -alkyl), mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonating group , into consideration.
• alkanesulfonates which can be obtained from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins.
• esters of d-sulfo fatty acids e.g. B. the d-sulfonic acids from hydrogenated methyl or ethyl esters of coconut, palm kernel or tallow fatty acid.
• Suitable sulfate-type surfactants are the sulfuric acid monoesters of primary alcohols (for example from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol) and those of 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.
• 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.
• 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.
• 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 which can be used are the water-soluble adducts of ethylene oxide with polypropylene oxide, alkylene diamine polypropylene glycol and alkyl polypropylene glycols with 1-10 C atoms in the alkyl chain, in which the polypropylene glycol chain functions as a hydrophobic residue, containing polypropylene oxide, alkylene diamine polypropylene 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.
• the cationic surfactants contain at least one hydrophobic and at least one basic group, which may be in the form of a salt and which 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-ti, N -dimethylammonium, - chloride, N-dodecyl-N, N-dimethyl-N-benzylammonium bromide, the reaction product of 1 mol of tallow alkylamine with 10 mol of ethylene oxide, N-dodecyl-N, N ', N'-trimethyl-1,3-diaminopropane , N-hexadecylpyridinium chloride.
• quaternary ammonium compounds such as N
• the nitrogen compounds mentioned can be replaced by corresponding compounds with a quaternary phosphorus atom or with a tertiary sulfur atom.
• alkaline organic or inorganic compounds are used as framework substances in their entirety, which are preferably present in the form of their alkali metal 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, dicarbonates, 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: 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-dihydroxy-diphosphonic acid, phosphonosuccinic acid, 1-aminoethane-1,1-diphosphonic acid, aminotri- (me - Thylenephosphonic acid), methylamino- or ethylamino-di- (methylenephosphonic acid) and ethylenediamine-tetra- (methylenephosphonic acid).
• N- or P-free polycarboxylic acids have recently been proposed as builders in the literature, 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. As citric acid, tartaric acid, benzene hexacarboxylic acid, tetrahydrofuran tetracarboxylic acid, etc.
• 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, citric acid, tartaric acid, lactic acid and the like.
• hydrochloric acid sulfuric acid, bisulfates of alkalis, aminosulfonic acid, phosphoric acid or other acids of phosphorus
• 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.
• alkaline builders If the content of alkaline builders is not sufficient to regulate the pH, organic or inorganic compounds such as alkanolamines, namely mono-, di- or triethanolamine or ammonia, can also be added.
• alkanolamines namely mono-, di- or triethanolamine or ammonia
• 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 types of 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.
• Suitable water-soluble or water-emulsifiable organic solvents are also ketones, such as acetone, methyl ethyl ketone and aliphatic, cycloaliphatic, aromatic and chlorinated hydrocarbons, and also the terpene alcohols.
• 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 those compounds which are stable and effective in the liquid agents according to the invention. These are phenolic compounds of the halogenated phenol type with 1-5 halogen substituents, in particular chlorinated phenols; Alkyl, cycloalkyl, aralkyl and phenylphenols with 1-12 carbon atoms in the alkyl radicals and with 1-4 halogen substituents, in particular chlorine and bromine in the molecule; Alkylene bisphenols, in particular derivatives substituted by 2-6 halogen atoms and optionally lower alkyl or trifluoromethyl groups, with an alkylene bridge member having 1-10 carbon atoms; Hydroxybenzoic acids or their esters and amido, in particular anilides, which can be substituted in the benzoic acid and / or A nilinrest, in particular also 2 or 3-halogen atoms and / or trifluoromethyl groups; Orthophenoxyphenols, which can be substituted by 1 7, preferably 2- 5
• Particularly preferred antimicrobial agents of the phenyl type are e.g. B. O-phenylphenol, 2-phenylphenol, 2-hydroxy-2 ', 4,4'-trichlorodiphenyl ether, 3,4', 5-tribromosalicylanilide and 3,3 ', 5,5', 6,6'-hexachloro- 2,2'-dihydroxy-diphenylmethane.
• Bis-diguanides such as, for. B. the 1,6-bis (p-chlorophenyldiguanido) hexane in the form of the hydrochloride, acetate or gluconate and also N, N'-disubstituted 2-thione-tetrahydro-1,3,5-thiadinazines such as. B, the 3,5-dimethyl-, 3,5-diallyl-, 3-benzl-5-methyl- and especially the 3-benzyl-5-carboxymethyl-tetrahydro-1,3,5-thiadiazine as additional anticrobial agents.
• Formaldehyde-amino alcohol condensation products can preferably be used.
• the products are obtained by reacting an aqueous solution of formaldehyde with amino alcohols, e.g. B. 2-aminoethanol, 1-amino-2-propanol 2- Aminoiso-butanol, 2 (2'-aminoethyl) aminoethanol.
• test method described below was used to test the cleaning ability and provides very reproducible results. Furthermore, the cleaning agents according to the invention and a comparison product each were handed over to housewives for several weeks for use testing. After the test period, these test persons were asked about their experiences with regard to cleaning effect and residue behavior.
• the cleaning agent to be tested is placed on an artificially soiled plastic surface.
• a mixture of carbon black, machine oil, triglyceride, saturated fatty acids and low-boiling aliphatic hydrocarbon is used as artificial soiling.
• the test area of 26 x 28 cm is evenly coated with 2 g of the artificial soiling with the help of a surface coater.
• a plastic sponge is soaked with 1 " 2 ml of the detergent solution to be tested and moved mechanically on the test surface. After 6 wiping movements, the cleaned test surface is kept under running water and the loose dirt is removed. The cleaning effect, ie, the whiteness of the plastic surface cleaned in this way is measured with a photoelectric color measuring device LF 90 (Dr. B. Lange) The clean white plastic surface serves as the white standard.
• the read values for the cleaned plastic surfaces are to be equated with the percentage cleaning capacity (% RV).
• % RV values given are the values determined by this method for the cleaning ability of the investigated cleaning agents. They represent mean values from fourfold determinations.
• the all-purpose cleaner shows an RV of 85% when used as a 1% aqueous solution.
• the comparative product without POLYOX an RV of 64%. If 0.3% by weight of polyvinyl alcohol was added to the comparison product, only a value of 63% RV was likewise obtained. If its proportion was increased to 0.5% by weight, there was still no increase in cleaning performance. In addition, the product became so highly viscous that a further increase in the proportion of polyvinyl alcohol no longer made sense for this reason alone.
• RV of the undiluted product 98% RV of the undiluted comparison product without polymer: 75%.
• RV of the 1% solution 84% RV of the 1% solution of the comparison sample without POLYOX: 60%.
• RV of the 2% solution 64% RV of the 2% solution of the comparative product without polymer: 42%.

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• Detergent Compositions (AREA)

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• 1978
  • 1978-09-16 DE DE2840463A patent/DE2840463C2/de not_active Expired
• 1979
  • 1979-09-10 AT AT79103371T patent/ATE400T1/de not_active IP Right Cessation
  • 1979-09-10 EP EP79103371A patent/EP0009193B1/fr not_active Expired

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