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
  • C11D3/395—Bleaching agents
• • 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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/391—Oxygen-containing compounds

Definitions

• peroxides such as sodium perborate are used as typical bleaching agents.
• the bleaching process requires temperatures of approx. 80 to 85 ° C. This requires a relatively large amount of energy and can lead to fiber damage and discoloration in the case of colored textiles. Since the peroxides react slowly at the desired lower temperatures, such as 40 to 60 ° C., bleach activators are added to the peroxide-containing detergents.
• the most widely used bleach activators include peracetylated compounds of polyamines such as tetracetylethylenediamine (TAED) or of polyols such as pentaacetylglucose (PAG).
• TAED tetracetylethylenediamine
• PAG pentaacetylglucose
• the TAED sets the standard.
• it has the disadvantage of being a nitrogen-containing compound, which should be avoided as much as possible because of the eutrophication of the waters by nitrogenous degradation products. Due to their reactivity, only two of the four acetyl groups in the molecule can serve as peroxide activators. In the nitrogen-free PAG, only two and a half of the five acetyl groups can be used for peroxide activation on average.
• the sodium salt of isononanoyloxibenzenesulfonic acid used, for example, as a bleach activator has the known disadvantage of phenol derivatives and, more
• the object of the invention is to provide new nitrogen-free bleach activators for detergents in which as far as possible all the acyl groups present have a peroxide-activating effect and which are technically easy to produce.
• the object is achieved according to the invention by using compounds of the formula in which the radicals R 1 are the same and a straight-chain or branched alkyl radical having 1 to 16 carbon atoms, which optionally contains one or more olefinic double bonds and / or by a carboxyl group, by an alkoxy group having 1 to 4 carbon atoms in the alkyl or by an optionally mono- or disubstituted by alkyl having 1 to 3 carbon atoms, alkoxy having 1 to 3 carbon atoms in the alkyl or by a carboxyl group substituted phenyl radical, the carboxyl groups present being in neutralized form, and R2 and R3 being the same or are different and are hydrogen atoms, a saturated straight-chain or branched alkyl radical having 1 to 16 carbon atoms, the sum of the carbon atoms of the two alkyl radicals R2 and R3 not exceeding 16 and the alkyl radicals R2 and R3 as substituents a carboxyl group, in the
• R1 are
• the radicals R2 and R3 are hydrogen or an alkyl radical having 1 to 16, preferably 1 to 4, carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, carboxyl, phenyl, dodecyl and hexadecyl.
• Compounds of the formula I in which one of the substituents R2 and R3 is hydrogen and the other is C1- to C1--alkyl are particularly preferably used.
• the compounds of formula I are known. They can advantageously be manufactured technically extremely simply by using a compound of the formula in which the radicals R2 and R3 have the meanings given for the radicals R2 and R3 in formula I and, moreover, one of the radicals R2 or R3 can be a hydroxymethyl radical, with an aqueous solution of glyoxal at temperatures from 20 to 80 ° C and in a pH range from 2 to 6 to an intermediate of the formula in which R2 and R3 have the meanings given for the formula II, the water and any solvent used are distilled off under reduced pressure at from 50 to 80 ° C. and the residue obtained in a conventional manner with acetic anhydride and Na acetate, pyridine, H2SO4 or an organic acid esterified as a catalyst.
• the compounds of formula II are preferably reacted in an equimolar amount with glyoxal. However, they can also be used in excess amounts of up to 50 mol%.
• the glyoxal is used in the form of its customary aqueous 20 to 50% by weight solutions, preferably in the form of the technical approx. 40% by weight aqueous solution.
• the preferred temperatures for the reaction of the compounds of formula II with glyoxal are 30 to 70 ° C.
• the reaction is preferably carried out in a pH range from 3 to 5. To maintain an appropriate or preferred pH range, the reaction to the intermediate of formula III can be carried out in the presence of an acid such as sulfuric acid, phosphoric acid or para-toluenesulfonic acid as a catalyst.
• the reaction can optionally be carried out in the presence of a solvent such as toluene.
• estersification of the compounds of formula III with the compounds of formula IV is carried out, for example, in the presence of sulfuric acid as a catalyst or in the system acyl anhydride / sodium acetate or acyl anhydride / pyridine.
• the esterification can of course also be carried out by reacting the compounds of the formula III with acid halides, preferably carboxylic acid chlorides.
• the bleach activators of the formula I mentioned above are particularly suitable for powdered or anhydrous liquid detergents. They are expediently used in amounts of 2 to 12% by weight, preferably 4 to 8% by weight, based on the detergent.
• the detergent formulations are obtained by mixing the individual components or by mixing prefabricated formulations.
• the connections of the Formula I can be used to prepare the detergents in the form of an aqueous solution or as a powder or granules.
• the invention therefore also relates to detergents which contain a compound of the formula I as a bleach activator for peroxides.
• Powdery or anhydrous liquid detergent formulations are preferred. Because of the sensitivity to hydrolysis of the compounds of formula (I), the detergents should contain as little free water as possible in the interest of the best possible shelf life. With liquid detergents, this means practically complete freedom from water within the limits of what is technically possible, i.e. Water content of at most about 0.5%. In the case of powder detergents, the tolerance limit for unbound water is significantly higher, namely a maximum of about 10%; any water of crystallization present in the powder detergents is bound so tightly that it is harmless to the compounds of the formula (I).
• Phosphate-containing and phosphate-free formulations come into consideration as framework regulations for suitable detergent formulations with the bleach activators to be used according to the invention.
• the detergents and cleaning agents each contain 6 to 25% by weight, based on the total weight, of surfactants and further customary constituents, such as 5 to 50% by weight builders and optionally co-builders, 5 to 35% by weight.
• Bleaching agents and optionally 3 to 30% by weight of auxiliaries such as enzymes, foam regulators, corrosion inhibitors, optical brighteners, fragrances, dyes or formulation auxiliaries, such as sodium sulfate.
• auxiliaries such as enzymes, foam regulators, corrosion inhibitors, optical brighteners, fragrances, dyes or formulation auxiliaries, such as sodium sulfate.
• the components of detergents usually used for the production of detergent formulations are mentioned as examples:
• Suitable surfactants are those which contain at least one hydrophobic organic radical and one water-solubilizing anionic, zwitterionic or nonionic group in the molecule.
• the hydrophobic radical is usually an aliphatic hydrocarbon radical with 8 to 26, preferably 10 to 22 and in particular 12 to 18 carbon atoms, or an alkyl aromatic radical with 6 to 18, preferably 8 to 16, aliphatic carbon atoms.
• Suitable synthetic anionic surfactants are in particular those of the sulfonate, sulfate or synthetic carboxylate type.
• the surfactants of the sulfonate type are alkylbenzenesulfonates with 4 to 15 carbon atoms in alkyl, 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 sulfonation products receives.
• alkanesulfonates which can be obtained from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins.
• esters of ⁇ -sulfo fatty acids e.g. the ⁇ -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, e.g. from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol, and those from secondary alcohols. Sulfated fatty acid alkanolamines, fatty acid monoglycerides or reaction products of 1 to 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 aminocarboxylic acids or sulfonic acids, e.g. the fatty acid sarcosides, glycolates, lactates, taurides or isothionates.
• the anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
• the usual soaps, i.e. Salts of natural fatty acids should not go unmentioned.
• Nonionic surfactants e.g. Addition products of 3 to 40, preferably 4 to 20, moles of ethylene oxide and 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide can be used.
• the addition products of 5 to 16 moles of ethylene oxide with coconut oil or tallow fatty alcohols, with oleyl alcohol or with synthetic alcohols with 8 to 18, preferably 12 to 18 carbon atoms, and with mono- or dialkylphenols with 6 to 14 carbon atoms in are particularly important the alkyl residues.
• water-soluble polyglycol ethers with 1 to 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 are the water-soluble adducts of ethylene oxide with polypropylene glycol containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups ether, alkylenediaminopolypropylene glycol and alkylpolypropylene glycols with up to 10 carbon atoms in the alkyl chain can be used, in which the polypropylene glycol ether chain acts as a hydrophobic radical.
• Nonionic surfactants of the amine oxide or sulfoxide type can also be used.
• the foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants. A reduction can also be achieved by adding non-surfactant-like organic substances.
• Suitable builder substances are, for example: washing alkalis, such as sodium carbonate and sodium silicate, or complexing agents, such as phosphates, or ion exchangers, such as zeolites, and mixtures thereof.
• These builders and builders have the task of eliminating the hardness ions, which come partly from water, partly from dirt or the textile material, and to support the surfactant effect.
• co-builders can also be contained in the builder, so-called co-builders.
• the co-builders have the task of adopting some properties of the phosphates, e.g. Sequestering effect, dirt-carrying capacity, primary and secondary washing effect.
• water-insoluble silicates as described for example in DE-PS 24 12 837, and / or phosphates.
• Pyrophosphate, triphosphate, higher polyphosphates and metaphosphates can be used from the group of phosphates.
• Organic complexing agents containing phosphorus, such as alkane polyphosphonic acids, amino and hydroxyalkane polyphosphonic acids and phosphonocarboxylic acids, are also suitable as further detergent ingredients. Examples of such detergent additives are e.g.
• methane diphosphonic acid propane-l, 2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 1-amino-1-phenyl1,1- diphosphonic acid, aminotrismethylene-triphosphonic acid, methylamino- or ethylaminobismethylene-diphosphonic acid, ethylenediaminotetramethylene-tetraphosphonic acid, diethylene-triaminopentamethylene-pentaphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, phosphonoacetic and phosphonopropionic acid, mixed polymers or partially or acrylate-derived from vinylphosphonate and / or maleated acid from vinylphosphonate and theirs or methane-derived maleinates from vinylphosphonate and partially or maleated from vinylphosphonic acid and vinyl or phosphonic acid from vinylphosphonate and / or maleated
• organic compounds which act as complexing agents for calcium ions and can be present in detergent formulations are polycarboxylic acids, hydroxycarboxylic acids and aminocarboxylic acids, which are mostly used in the form of their water-soluble salts.
• Hexane hexacarboxylic acid cyclic di- or polycarboxylic acids, such as cyclopentane tetracarboxylic acid, cyclohexane hexacarboxylic acid, tetrahydrofuran tetracarboxylic acid, phthalic acid, terephthalic acid, benzene tri-, tetra- or pentacarboxylic acid and mellitic acid.
• hydroxymono- or polycarboxylic acids examples include glycolic acid, lactic acid, malic acid, tartronic acid, methyltartronic acid, gluconic acid, glyceric acid, citric acid, tartaric acid, salicylic acid.
• aminocarboxylic acids are glycine, glyclglycine, alanine, asparagine, glutamic acid, aminobenzoic acid, iminodi- or triacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminotetraacetic acid, hydroxyethyl-ethylenediamine-triacetic acid, diethylenetriamine-pentaacetic acid and polymerisation of a, e.g. of acetic acid, succinic acid, tricarballylic acid, and subsequent saponification, or by condensation of polyamines with a molecular weight of 500 to 10,000 with chloroacetic or bromoacetic salts.
• Polymeric carboxylic acids are preferably used as co-builders. These polymeric carboxylic acids include the carboxymethyl ethers of sugar, starch and cellulose.
• the polymeric carboxylic acids e.g. the polymers of acrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid, methylene malonic acid, citraconic acid and the like
• the copolymers of the above-mentioned carboxylic acids with one another e.g. Copolymers of acrylic acid and maleic acid (especially those in a ratio of 70:30 and a molecular weight of 70,000), or the 1: 1 copolymers of maleic anhydride and methyl vinyl ether of a molecular weight of 70,000 or the copolymers of maleic anhydride and ethylene or propylene play a special role.
• the co-builders can also contain dirt carriers which keep the dirt detached from the fibers suspended in the liquor and thus inhibit graying.
• Water-soluble colloids mostly of an organic nature, are suitable for this, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic acids Sulfuric acid esters of cellulose or starch.
• Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, such as degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
• Bleaching agents are especially hydrogen peroxide and derivatives or active chlorine-providing compounds.
• Sodium perborate hydrates such as NaBO2 ⁇ H2O2 ⁇ 3H2O and NaBO2 ⁇ H2O2
• these compounds can be partially or completely replaced by other active oxygen carriers, in particular by peroxyhydrates, such as peroxycarbonates, peroxyphosphonates, citrate perhydrates, urea-H2O2- or melamine-H2O2-compounds as well as by H2O2-delivering peracid salts, e.g. Persulfates, perbenzoates or peroxyphthalates can be replaced.
• the suitability of the bleach activators produced is determined by washing and bleaching tests on artificially soiled cotton fabrics. Artificial, bleachable stains suitable for test purposes have been found to be cotton fabrics treated with tea or red wine. The results are described in Table 1. The bleaching tests were carried out at 20 ° C, 38 ° C and 60 ° C.
• Test conditions were as follows: Washing machine: Launder-O-meter Water hardness: 16.8 ° d (approx: Mg 4: 1) Amount of fabric: 20 g Fleet quantity: 250 ml Detergent concentration: 8 g / l Washing time: 30 min Detergent composition (powder): 6.25% C12 alkylbenzenesulfonate 4.7% Tallow fatty alcohol reacted with 11 moles of ethylene oxide 2.8% Soap 15% Na perborate tetrahydrate 7.2% Nasilicate 3.6% Mg sulfate ⁇ 7 H2O 1.0% Carboxymethyl cellulose 0.2% Ethylenediaminetetraacetic acid, sodium salt 20.0% Zeolite A 10.0% Na carbonate 17.5% Na sulfate 4% Bleach activator rest Water to 100%
• the bleaching effect was determined by measuring the degree of whiteness with an Elrepho photometer. A detergent in which sodium sulfate was used instead of the bleach activator was used as a control test.

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• Engineering & Computer Science (AREA)
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• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
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• Detergent Compositions (AREA)
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• 1988
  • 1988-09-06 DE DE3830213A patent/DE3830213A1/de not_active Withdrawn
• 1989
  • 1989-08-24 US US07/397,890 patent/US4952332A/en not_active Expired - Fee Related
  • 1989-08-31 EP EP19890116077 patent/EP0358109A3/fr not_active Withdrawn
  • 1989-09-06 KR KR1019890012946A patent/KR900004925A/ko not_active Application Discontinuation
  • 1989-09-06 JP JP1229468A patent/JPH0292999A/ja active Pending

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