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
  • C11D3/18—Hydrocarbons
• • 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
• • 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
  • C11D3/43—Solvents

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, as well as solvents, solubilizers, hydrotropic substances, fragrances and dyes, preservatives, agents for viscosity adjustment, for pH adjustment and electrolytes.
• the pH is around 5.5 to 8.0.
• Also common commercial all-purpose cleaning agents ie 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 as active ingredients Amounts from about 0.5 to 5% by weight.
• Solvents including terpene compounds, are usually used as further cleaning-enhancing constituents, and polyethylene glycols of the general formula HO- (CH 2 -CH 2 -O) n -H are used to increase the cleaning performance as organic polymers, where n can vary between 4,800 and 64,600 ' , added.
• These agents are also made up with dyes and fragrances, electrolytes and viscosity regulators.
• a highly polymeric water-soluble polyethylene glycol of the formula HO (-CH 2 -CH 2 -O) n H with n 4,800 to 64,600, b) 0.5 to 5, preferably 1 to 2% by weight of one or more terpene compounds, c ) 0.1
• nonionic and / or amphoteric surfactants and other auxiliaries customary in liquid cleaning agents in particular fragrances and colorants, solubilizers, hydrotropes, electrolytes and preservatives, can also be added to these agents.
• the claimed agents are preferably prepared by presenting the calculated amount of water, running in the surfactant mixture or the individual surfactants in separate form without stirring at room temperature, then gently stirring without foaming until the streaks formed disappear, sprinkling the builders onto the liquid surface and also gently stirring , Stirring in a 2 to 5 percent by weight aqueous solution of the polyethylene glycol, stirring in the terpene compound and optionally sprinkling in or stirring in other customary auxiliaries and adjusting the pH to 6.5 to 8 by adding acid or alkali.
• the claimed process results in improved dishwashing of greasy soiling and manual cleaning of heavily soiled hard surfaces as well as when using all-purpose cleaning agents with an otherwise common pH value of 8.5 to 11.
• Suitable synthetic anionic surfactants are in particular those of the sulfonate and sulfate type.
• the surfactants of the sulfonate type are primarily the alkylbenzenesulfonates with C 9-15 -alkyl groups and the surfactants of the sulfonate type, such as preferably the alkanesulfonates, which are obtained from C 12 -C 18 -alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or Neutralization or bisulfite addition to olefins, and the olefin sulfonates, which are mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline and acidic hydrolysis of the sulfonation products .
• Other useful surfactants are the esters of alpha sulfo fatty acids, e.g. B. alpha-sulfonated
• Particularly suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols of natural and synthetic origin, ie of fatty alcohols, such as, for. B. coconut fatty alcohols, Tallow fatty alcohols, oleyl alcohol, or the C 10 -C 20 oxo alcohols, and those of secondary alcohols of these chain lengths.
• the sulfuric acid monoesters of the aliphatic primary alcohols ethoxylated with 1 to 6 moles of ethylene oxide or ethoxylated secondary alcohols or alkylphenols are suitable.
• Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
• anionic surfactants are preferably used in the form of the salts, in particular in the form of the sodium salts, but also as potassium or ammonium salts or as soluble salts of organic bases, such as mono-, di- or triethanolamine.
• Their amounts in the agents used in the process are 10 to 40, preferably 15 to 25 percent by weight.
• Suitable nonionic surfactants which can optionally be added are addition products of 1 to 40, preferably 2 to 20, moles of ethylene oxide with 1 mole of an aliphatic compound having essentially 18 to 20, preferably 10 to 16, carbon atoms in the alkyl radical from the group of the alcohols, alkylphenols, carboxylic acids, Carboxamides and carboxylic acid mono-, di- and -polyalkanolamides.
• coconut or tallow fatty alcohols on oleyl alcohol, on oxo alcohols of the corresponding chain lengths, or on corresponding secondary alcohols, and on mono- or dialkylphenols with 6 to 14 carbon atoms in the alkyl radicals.
• water-soluble nonionics non-fully or not completely water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether radicals in the molecule are also of interest, since they coexist with water-soluble anionic surfactants are used. Because of their good biodegradability, the ethoxylation products of primary aliphatic alkanols and alkenols are of particular practical interest.
• EO ethylene oxide
• tallow fatty alcohol 5-E0 oleyl / cetyl alcohol 5-EO (iodine number 30 to 50)
• Tallow fatty alcohol 7-E0 synthetic C 12 -C 16 fatty alcohol 6-E0, C 11 -C 15 oxo alcohol 3-E0, C
• Exemplary representatives of the nonionic surfactants with an average degree of ethoxylation of 8 to 20, in particular 9 to 15, are the compounds coconut fatty alcohol-12-E0, synthetic C12 / C14 fatty alcohol-9-EO, oleyl / cetyl alcohol-10-E0 , Tallow fatty alcohol-14-E0, C 11 -C 15 -oxoalcohol-13-E0, C15-C18-oxoalcohol-15 E0, iC 15 -C 17 -alkanediol-9-E0, C 14 / C 15 -oxoalcohol-11- E0, sec-C 11 -C 15 alcohol-9-E0.
• non-ionic surfactants which can be used are the water-soluble adducts of ethylene oxide with 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol, alkylenediamine-poly-propylene glycol and with alkylpolypropylene glycols having 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic radical .
• Nonionic surfactants of the amine oxide or sulfoxide type can also be used, for example the compounds N-coco-alkyl-N, N-dimethylamine oxide, N-hexadecyl-N, N-bis (2,3- jihydroxypropylaminoxid), N-tallow alkyl-N, N-dihydroxy-ethylamine oxide.
• nonionic surfactants used are 0 to 5 percent by weight. However, preference is given to working without the addition of nonionic surfactants.
• 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.
• 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.
• C 12 -C 18 -Acylamido-propyldimethylammonium betaines are preferably
• the framework substances in their entirety are alkaline inorganic or organic Compounds, in particular inorganic or organic complexing agents, which are preferably present 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, 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: methylene diphosphonic 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-dihydroxydiphosphonic acid, phosphonosuccinic acid, 1-aminoethane-1,1-diphosphonic acid, aminotri- (methylenephosphonic acid ), Methyl-amino- or ethylamino-di- (methylenephosphonic acid) and ethylenediamine-tetra- (methylenephosphonic acid).
• N- or P-free polycarboxylic acids have recently been proposed as builder substances in the literature, although in many cases, if not exclusively, they are carboxyl groups containing polymers.
• a large number of these polycarboxylic acids have a complexing ability for calcium. These include e.g. As citric acid, tartaric acid, benzothexacarboxylic acid, tetrahydrofuran tetracarboxylic acid, etc.
• the terpene compounds include commercially available compounds on terpineols such as pine oil and terpene hydrocarbons such as limonene, preferably those with a lemon-like fragrance.
• the water-soluble polyethylene glycols to be used according to the invention have a molecular weight of between approximately 200,000 and 4,000,000, preferably between approximately 500,000 and 1,000,000. They are produced in a known manner by subjecting ethylene glycols to a polycondensation process. They can also be seen as condensation polymers of ethylene oxide with ethylene glycol or water. They have the general formula HO (-CH 2 -CH 2 -O) n H, where n can vary between 4,800 and 64,600 in the case of the polyethylene glycols used according to the invention. Such polymers are also commercially available and z. B. from Union Carbide Corporation (UCC) under the name "POLYOX (R) ".
• solubilizers can be incorporated, such as the water-soluble organic solvents, in particular low-molecular aliphatic alcohols having 1 to 4 carbon atoms, and also those with boiling points above 75 ° C., such as 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, P-ropylene glycol, butylene glycol or glycerol with aliphatic monohydric alcohols containing 1 to 4 carbon atoms in the molecule but also the so-called hydrotropic substances of the lower alkyl aryl sulfonate type, which include, for example, toluene, xylene or cumene sulfonates. They can be in the form of their sodium and / or potassium and / or alkylamino salts.
• Suitable water-soluble or water-emulsifiable organic solvents are also ketones, such as acetone, methyl ethyl ketone and aliphatic, cycloaliphatic, aromatic and chlorinated hydrocarbons.
• the cleaning agents can contain additives of colors and fragrances, preservatives and, if desired, antimicrobial agents of any kind.
• formaldehyde-amino alcohol condensation products can be used as antimicrobial agents.
• the products are obtained by reacting an aqueous solution of formaldehyde with amino alcohols, e.g. B. 2-aminoethanol, 1-aminoethanol, 1-amino-2-propanol, 2-aminoiso-butanol, 2 (2'-aminoethyl) aminoethanol.
• Suitable pH-regulating agents are customary inorganic or organic acids or acidic salts, such as hydrochloric acid, sulfuric acid, bisulfates of alkalis, aminosulfonic acid, phosphoric acid or other acids of phosphorus, especially the anhydrous acids of phosphorus or their salts or their acidic acids solid compounds reacting with urea or other lower carboxamides, partial amides of phosphoric acids or anhydrous phosphoric acid, citric acid, tartaric acid, lactic acid and the like.
• Organic or inorganic compounds such as alkanolamines, namely mono-, di- or triethanolamine or ammonia, can also be added as basic substances.
• alkaline builder substances and washing alkalis such as. B. sodium tripolyphosphate, sodium carbonate and sodium bicarbonate, potassium carbonate and bicarbonate, sodium silicate and the sodium aiumosilicate.
• 14 cm diameter plates were alternatively soiled with 2 g beef tallow (melting point 40 to 42 ° C, acid number 9 to 10) or with a mixed soiling of protein, fat and carbohydrates, for 15 hours at + 0 to + 5 ° C stored and rinsed at 45 ° C with tap water hardness 16 ° d.
• the test products were used with a dosage of 0.5 g / l water.
• the number of plates that are rinsed clean with 5 liters of wash liquor number of plates serves as a measure of the cleaning effect.
• a plastic sponge was soaked in each case with 12 ml of the cleaning agent solution to be tested and moved mechanically on the test surface. After 6 wiping movements, the cleaned test area was kept under running water and the loose dirt was removed. The cleaning effect, d. H. the whiteness of the plastic surface cleaned in this way was measured using a LF 90 photoelectric colorimeter (Dr. B. Lange). 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 ability (% RV). The% -RV values given are averages from quadruple determinations.
• composition of the cleaning agents according to the invention is given in Table 1 (formulations 8 to 14).
• formulations 8 to 14 there are comparative tests with commercially available, manual dishwashing detergents (recipes 1 to 5) and commercially available all-purpose cleaning agents (recipes 6 to 7). If necessary, the recipes were adjusted to the specified pH values with citric acid or sodium hydroxide solution.
• the formulations 8a, 8b and 14a and b show that the combination of builders, terpene compounds and polyethylene glycols is important and that if one of these components is left out, the desired success is not achieved.
• recipe example 14 b shows that the fat-emulsifying power of dishwashing detergents is already significantly increased by the addition of polymer alone.
• Table 2 shows that the cleaning ability of the The agent according to the invention already corresponds to the alkaline, commercially available all-purpose cleaning agent at a neutral pH, which also brings the advantage of improved skin compatibility for the user.

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• Oil, Petroleum & Natural Gas (AREA)
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• Detergent Compositions (AREA)

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Citations (2)

• 1985
  • 1985-04-06 DE DE19853512535 patent/DE3512535A1/de not_active Withdrawn
• 1986
  • 1986-03-29 EP EP86104371A patent/EP0197480A3/fr not_active Withdrawn
  • 1986-04-04 JP JP7681386A patent/JPS61233098A/ja active Pending

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