WO2006092246A1 - Nitriles d'ammonium et leur utilisation en tant qu'activateurs de blanchiment - Google Patents

Nitriles d'ammonium et leur utilisation en tant qu'activateurs de blanchiment Download PDF

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WO2006092246A1
WO2006092246A1 PCT/EP2006/001734 EP2006001734W WO2006092246A1 WO 2006092246 A1 WO2006092246 A1 WO 2006092246A1 EP 2006001734 W EP2006001734 W EP 2006001734W WO 2006092246 A1 WO2006092246 A1 WO 2006092246A1
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alkyl
group
compounds
acid
hydrogen
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PCT/EP2006/001734
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German (de)
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Lars Cuypers
Gerd Reinhardt
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Clariant Produkte (Deutschland) Gmbh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
    • C07C255/25—Aminoacetonitriles
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • 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
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions

Definitions

  • This invention relates to aromatic ammonium nitriles and their use for enhancing the bleaching effect of peroxygen compounds in bleaching colored stains on textiles as well as on hard surfaces, as well as detergents and cleaners containing these nitriles as bleach activators.
  • Inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes.
  • the oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with hydrogen peroxide or perborate in alkaline bleaching liquors only at temperatures above about 80 0 C, a sufficiently fast bleaching of soiled textiles.
  • peroxidic bleaches such as perborates, percarbonates, persilicates and perphosphates, can be improved at low temperatures by adding precursors of bleaching peroxyacids, so-called bleach activators.
  • bleach activators are usually reactive organic compounds having an O-acyl or N-acyl group which in alkaline solution together with a source of hydrogen peroxide form the corresponding peroxyacids.
  • Representative examples of bleach activators are, for example, NNN'.N'-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulphonate (SBOBS), sodium trimethylhexanoyloxybenzenesulphonate (STHOBS), tetraacetylglycoluril (TAGU), Tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxime (ADMG), 1-phenyl-3-acetylhydantoin (PAH), Sodium nonanoyloxy-benzenesulfonate (NOBS) and sodium isononanoyloxybenz
  • the bleaching effect of aqueous peroxide solutions can be increased so much that even at temperatures between 40 and 60 0 C substantially the same effects as with the peroxide solution alone at 95 ° C occur.
  • a major drawback of said bleach activators is that they mostly leave large volume leaving groups (e.g., phenolsulfonates) after perhydrolysis, which are of no importance to the bleaching process.
  • bleach activators are of interest in which a highly reactive peracid but no leaving group is liberated in the perhydrolysis step. This is e.g. achieved by a cyano group. In perhydrolysis, this probably forms a peroxyimidic acid, which then acts as a bleaching agent.
  • cationic bleach activators are described, for example, in GB-A-1 382 594, US-A-4 751 015, EP-A-0 284 292, EP-A-0 331 229.
  • ammonium nitriles of the type described above which have at least two cyanomethylammonium groups bound to an aromatic radical, exhibit a better bleaching action on hydrophobic soiling than the nitriles according to the prior art.
  • the invention relates to compounds of the formula
  • Y is the radical R 5 and Z is the radical R 4 or Y and Z together form a ring of the formula
  • A is a quaternary group of the formula
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may be the same or different and is hydrogen, hydroxyl, Cr to C 24 -AlkVl, C 2 - to C 24 alkenyl, C 1 -C alkyl, phenyl, Ci to C 4 alkylphenyl, carboxyl, sulfonyl, cyanomethyl, cyano or a cationic group a, with the proviso that at least one of the groups R 1, R 2-4 -alkoxy-C 1 -C 4 R 3 , R 4 , R 5 , R 6 and R 7 is a cationic group A;
  • R 8 represents a straight- or branched-chain C 1 - to C 24 -alkylene, C 2 - to C 24 -alkenylene or C 1 -C 4 -alkoxy-C 1 -C 4 -alkylene group;
  • R 9 and R 10 may be the same or different and represent a C 1 to C 24 alkyl, C 2 to C 24 alkenyl, cyanomethyl or C 1 C 4 alkoxy C 1 -C 4 alkyl group;
  • R 11 and R 12 may be the same or different and are hydrogen, Cr to C 24 - alkyl, C 2 - to C 24 -alkenyl, -C 4 alkoxy-CrC 4 alkyl, phenyl, CrC mean 4 alkylphenyl;
  • n has a value of two to six; and X "is an anion.
  • R 1 to R 12 preferably have the following meanings: R 1, R 2, R 3, R 4, R 5, R 6 and R 7: d- to C 18 alkyl, C 2 - to C 18 alkenyl, C 1 -alkyl-C 1 -C 4 -alkyl, phenyl, C 1 -C 4 -alkylphenyl or a cationic group A, with the proviso that at least one of the groups R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 is a cationic group A;
  • R 8 is a C 1 - to C 18 - alkylene, C 2 - to C 18 -alkenylene or C 1 -alkoxy-C 1 -C 4 -alkylene;
  • R 9 and R 10 are C 1 - to C 18 -alkyl, C 2 - to C 18 -alkenyl or C 1 -alkoxy-C 1 -C 4 -alkyl;
  • anion X is, for example, chloride, bromide, iodide, fluoride, sulfate, hydrogen sulfate, carbonate, bicarbonate, phosphate, mono- and dihydrogen phosphate, pyrophosphate, metaphosphate, nitrate, methosulfate, dodecyl sulfate, dodecylbenzenesulfonate, phosphonate, methyl phosphonate, methanedisulfonate, methyl sulfonate, ethanesulfonate, Tolu ⁇ lsulfonat, benzenesulfonate or cumene sulfonate in question.
  • the variable n preferably has a value of two to four.
  • R 6 and R 7 are hydrogen, Ci- to C ⁇ -alkyl or a cationic group A, with the
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 is a cationic group A;
  • R 8 is a C 1 to C 4 alkylene group;
  • Each of R 9 and R 10 is a C 1 to C 6 alkyl or cyanomethyl group;
  • R 11 and R 12 are hydrogen and
  • Examples of these particularly preferred cationic nitriles are ⁇ , ⁇ 1 -Bis (cyanomethyl-dimethyl-ammonium) -ortho-xylene-dichloride, ⁇ , ⁇ '-bis (cyanomethyl-dimethyl-ammonium) -meta-xylene-dichloride and ⁇ , ⁇ '-bis (cyanomethyl-dimethyl-ammonium) -p-xylene dichloride.
  • the secondary amine of the formula NHR 9 R 10 is presented together with a base, preferably alkali metal carbonate or alkali metal hydroxide, in a solvent, preferably in absolute ethanol or in a toluene / water mixture.
  • a base preferably alkali metal carbonate or alkali metal hydroxide
  • a solvent preferably in absolute ethanol or in a toluene / water mixture.
  • chloroacetonitrile is added dropwise.
  • the organic phase is separated and the aqueous phase with an organic Solvent extracted. From the combined organic phases, the solvent is removed.
  • the crude product obtained can be further purified by fractional distillation.
  • the resulting dialkylaminoacetonitrile is taken up in an organic solvent and mixed with a compound of the type
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each individually hydrogen, hydroxyl, C 1 - to C 24 - alkyl, C 2 - to C 24 -alkenyl, Ci-C 4 alkoxy -C-C 4 alkyl, phenyl, C 1 - to C 4 - alkyl phenyl, carboxyl, sulfonyl, cyanomethyl, cyano or a group corresponding to R 8 -X, with the proviso that at least one of the groups R 1, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 corresponds to a group R 8 -X, R 9 and R 10 individually a C 1 - to C 24 alkyl, C 2 - to C 24 alkenyl , cyanomethyl, or C 1- C 4 alkoxy-C 1 -C 4 alkyl group;
  • R 8 is a straight-chain or branched-chain C 1 -C 24 -alkylene, C 2 -C 24 -alkenylene,
  • X represents an electron withdrawing leaving group such as sulfate or a halogen; reacted at temperatures between 20 and 150 0 C to the corresponding N-cyanomethyl-ammonium salt.
  • the salt can be recovered by conventional methods of workup such as extraction, crystallization, suction filtration, washing of the crystal slurry on the filter and drying.
  • R 1, R 2, R 3, R 4, R 5, R 6 and R 7 are each individually hydrogen, hydroxyl, C 1 - to C 24 - alkyl, C 2 - to C 24 -alkenyl, -C 4 -alkoxy-C -AIk ⁇ 1 -C 4, phenyl, C 1 - alkylphenyl, carboxyl, sulfonyl, cyanomethyl, cyano or a group corresponding to NR 8 R 9 R 10, with the proviso that at least one of the groups R 1, - to C 4 R 2 , R 3 , R 4 , R 5 , R 6 and R 7 corresponds to a group NR 8 R 9 R 10 ;
  • R 8 represents a straight or branched chain C 1 to C 24 alkylene, C 2 to C 24 alkenylene, C 1 to C 4 alkoxy C 1 to C 4 alkylene group;
  • R 9 and R 10 each individually represents a C 1 - to C 24 -alkyl, C 2 - to C 24 alkenyl, cyanomethyl, or Ci -C 4 -alkoxy-C 1 -C 4 alkyl group.
  • the precipitated N-cyanomethyl-ammonium chloride is filtered off, washed with an organic solvent and dried.
  • R 1, R 2, R 3, R 4, R 5, R 6 and R 7 are each individually hydrogen, hydroxyl, Cr to C 24 - alkyl, C 2 - to C 24 -alkenyl, Ci-C 4 -alkoxy-CrC 4 alkyl, phenyl, d- to C 4 - alkyl phenyl, carboxyl, sulfonyl, cyanomethyl, cyano or a group corresponding to R 8 -NHR 9 group, with the proviso that at least one of the groups R 1, R 2, R 3, R 4 , R 5 , R 6 and R 7 corresponds to a group R 8 -NHR 9 ;
  • R 8 represents a straight or branched chain Cr to C 24 alkylene, C 2 to C 24 alkenylene, CrC 4 alkoxy-CrC 4 alkylene group;
  • R 9 is a C 1 - to C 24 -alkyl, C 2 - to C 24 -alkenyl, cyano-methyl-, or -C 4 alkoxy CrC 4 alkyl group; is combined with sodium cyanide and an aldehyde or a ketone, preferably formaldehyde in the form of a 36% formalin solution, in a solvent, preferably an ethanol / water mixture or water.
  • aqueous hydrochloric acid is added to the approach.
  • the aqueous phase is extracted with a suitable organic solvent, for example methylene chloride or diethyl ether. From the combined organic phases, the solvent is stripped off after drying over magnesium sulfate.
  • the crude product obtained can be further purified by fractional distillation.
  • the resulting Arylalkylaminoacetonitril is taken up in an organic solvent and with a
  • Alkylating agent such as methyl chloride, dimethyl sulfate or Arylsulfonklarealkylester reacted at temperatures between 20 and 100 ° C to the corresponding N-cyanomethyl ammonium salt.
  • the salt can be recovered by conventional methods of workup such as extraction, crystallization, suction filtration, washing of the crystal slurry on the filter and drying.
  • the invention also provides the use of these ammonium nitriles as bleach activators in bleaching detergents, cleaners and disinfectants.
  • bleaching is understood here to mean both bleaching with the aid of peroxide bleaches of dirt present on the textile surface and bleaching of dirt located in the wash liquor and detached from the textile surface. The same applies mutatis mutandis to the bleaching of stains on hard surfaces. Further potential applications are in the personal care field, for example in the bleaching of hair and to improve the effectiveness of denture cleaners.
  • the complexes according to the invention find use in commercial laundries, in wood and paper bleaching, bleaching of cotton and in disinfectants.
  • the invention relates to a process for the purification of textiles as well as hard surfaces, in particular dishes, using said cationic nitriles in aqueous, optionally further detergent or cleaning agent components, in particular oxidizing agents
  • Peroxygen-based solution and detergents and hard surface cleaners, especially dishwashing detergents, those preferred for use in machine processes containing such cationic nitriles.
  • the use according to the invention consists essentially in creating conditions under which a peroxidic oxidizing agent and the cationic nitrile can react with one another in the presence of a hard surface contaminated with colored stains or a correspondingly soiled textile, with the aim of having a stronger oxidizing effect
  • Such conditions are especially present when the reactants meet in aqueous solution.
  • This can be done by separately adding the peroxygen compound and the cationic nitrile to an optionally washing or cleaning agent-containing solution.
  • the process according to the invention is particularly advantageously carried out using a detergent or hard surface cleaning agent according to the invention which contains the cationic nitriles and optionally a peroxygen-containing oxidizing agent.
  • the peroxygen compound may also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, when a non-oxygen detergent or cleaner is used.
  • the washing and cleaning agents according to the invention may contain, in principle, all known ingredients customary in such agents, as well as the said bleach-enhancing active substance.
  • the compositions according to the invention may contain, in particular, builder substances, surface-active surfactants, peroxygen compounds, additional peroxygen activators or organic peracids, water-miscible organic solvents, sequestering agents, thickeners, preservatives, pearlescing agents, emulsifiers and enzymes, as well as special additives with color or fiber-sparing action.
  • Other auxiliaries such as electrolytes, pH regulators, silver corrosion inhibitors, foam regulators as well as dyes and fragrances are possible.
  • a hard surface cleaning agent according to the invention may contain abrasive constituents, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and glass microspheres and mixtures thereof.
  • Abrasive substances are preferably not more than 20% by weight, in particular from 5% by weight to 15% by weight, in the cleaning agents according to the invention.
  • Suitable peroxidic bleaches are hydrogen peroxide and under the washing and cleaning conditions hydrogen peroxide donating compounds such as alkali metal peroxides, organic peroxides such as urea-hydrogen peroxide adducts and inorganic persalts such as alkali metal perborates, percarbonates, perphosphates, persilicates, persulfates and peroxynitrite. Mixtures of two or more of these compounds are also suitable. Particularly preferred are sodium perborate tetrahydrate and in particular sodium perborate monohydrate and sodium percarbonate. Sodium perborate monohydrate is preferred for its good storage stability and good solubility in water. Sodium percarbonate may be preferred for environmental reasons.
  • Alkali hydroperoxides are another suitable group of peroxide compounds. Examples of these substances are cumene hydroperoxide and t-butyl hydroperoxide.
  • Aliphatic or aromatic mono- or dipercarboxylic acids and the corresponding salts are suitable as peroxy compounds.
  • Examples thereof are peroxynaphthoic acid, peroxylauric acid, peroxystearic acid, N, N-phthaloylaminoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxyisophthalic acid, 2-decyldiperoxybutane-1,4-diacid and 4,4'-sulfonyl-bisperoxybenzoic acid.
  • the cationic, nitrile bleach activator according to the invention may be present in a proportion by weight of about 0.1 to 20%, preferably of 0.5 to 10%, in particular of 0.5 to 5.0%, together with a peroxy compound.
  • the proportion by weight of this peroxy compound is usually from 2 to 40%, preferably from 4 to 30%, especially from 10 to 25%.
  • bleach activators in addition to the cationic, nitrile bleach activators according to the invention, other suitable bleach activators may be present in the detergents and cleaners in the usual amounts (about 1 to 10% by weight).
  • Suitable bleach activators are organic compounds having an O-acyl or N-acyl group, in particular from the group of the activated carboxylic acid esters, in particular sodium nonanoyloxybenzenesulfonate, sodium isononanoyloxybenzenesulfonate, sodium 4-benzoyloxybenzenesulfonate, sodium trimethylhexanoyloxy-benzenesulfonate, carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, lactones, acylals, carboxamides, acyl lactams, acylated ureas and oxamides, N-acylated hydantoins, for example 1 Phenyl-3-acetylhydantoin, hydrazides, triazoles, hydrotriazines,
  • N-benzoyl-caprolactam but also quaternary nitrile compounds, for example quaternary Trialkylammoniumnitrilsalze as described in EP-A-303 520, EP-A-458 396 and EP-A-464 880, in particular the Cyanomethyltrimethylammoniumsalz, but also heterocyclic substituted quaternary nitrile compounds, such as in EP-A-790,244.
  • sulfonimines open chain or cyclic quaternary iminium compounds such as dihydroisoquinolinium betaines, and / or other bleach-enhancing transition metal salts, or mono- or polynuclear transition metal complexes having acyclic or macrocyclic ligands can also be included.
  • the detergents and cleaners may comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
  • surfactants are present in detergent compositions according to the invention in proportions of preferably from 1 to 50% by weight, in particular from 3 to 30% by weight, whereas in hard-surface cleaners normally lower proportions, that is to say amounts of up to 20% by weight. , in particular up to 10 wt .-% and preferably in the range of 0.5 to 5 wt .-% are included.
  • Dishwashing detergents typically use low-foam compounds.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups.
  • Suitable surfactants of the sulfonate type are preferably C 9 -C 3 -alkylbenzenesulfonates, olefinsulfonates, that is to say mixtures From alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from monoolefins having terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration.
  • alkanesulfonates the 2 -C 8 alkanes, for example, obtained by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization from Ci.
  • esters of alpha-sulfo fatty acids for example the alpha-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by sulfonating the methyl esters of fatty acids of vegetable and / or animal origin having 8 to 20 carbon atoms be prepared in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts.
  • alk (en) ylsulfate are the alkali metal and in particular the sodium salts of sulfuric acid half esters of Ci2-Ci ⁇ - fatty alcohols, for example, from coconut fatty alcohol, tallow, lauryl, myristyl, cetyl or stearyl alcohol or C 8 -C 2 o-oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) ylsulfates of said chain length which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis.
  • 2,3-alkyl sulfates are also suitable anionic surfactants.
  • sulfuric acid monoesters of straight-chain or branched alcohols which are ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 1 -C 4 -n alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 -C 18 -fatty alcohols having 1 to 4 EO.
  • the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 -C 15 fatty alcohol residues or mixtures of these.
  • anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosinate) into consideration.
  • anionic surfactants are in particular soaps, for example in amounts of 0.2 to 5 wt .-%, into consideration.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants including soaps, may be in the form of their
  • anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Anionic surfactants are preferably present in detergents according to the invention in amounts of from 0.5 to 10% by weight and in particular in amounts of from 5 to 25% by weight.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position , or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 4 -alcohols with 3 EO or 4 EO, C 9- Cn alcohols with 7 EO, C 13 -C 5 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci 2 -Ci 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci 2 -Ci 4 -AlkOhOl with 3 EO and C 12 -Ci 8 -AlkOhOl with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • NRE narrow range ethoxylates
  • riichtionischen surfactants and fatty alcohols can be used with more than 12 EO. Examples of these are (TaIg) fatty alcohols with 14 EO, 16 EO 1 20 EO, 25 EO, 30 EO or 40 EO.
  • the nonionic surfactants also include alkyl glycosides. of the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and 6 for a glycoside unit having 5 or 6 C Atoms, preferably for glucose, stands.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1, 2 to 1, 4.
  • polyhydroxy fatty acid amides of the formula (I) in which R 1 is CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen; is an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) R 3 for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 for a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 5 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, preference being given to C 1 -C 4 -alkyl or phenyl radicals, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain has at least two hydroxyl groups is substituted, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group.
  • [Z] will also here preferably obtained by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-allyloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, in particular
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl N, N-dimethylamine oxide and N-tallow alkyl N, N-dihydroxyethyl amine oxide and the fatty acid alkanolamides may also be suitable.
  • surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called “spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides. Other surfactant types may have dendrimeric structures.
  • Suitable organic and inorganic builders are neutral or in particular alkaline salts which precipitate or complex calcium ions.
  • Suitable and especially ecologically harmless builders are crystalline, layered silicates of the general formula NaMSi ( X ) O ( 2 ⁇ + i), where M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1, 9 to 4 and y is a number from 0 to 33, for example Na -SKS-5 ((X-Na 2 Si 2 O 5 ), Na-SKS-7 ( ⁇ -Na 2 Si 2 O 5l natrosilite), Na-SKS-9 (NaHSi 2 (VH 2 O) 1 Na-SKS -10 (NaHSi 2 O 3 * 3H 2 O, kanemite), Na-SKS-11 (T-Na 2 Si 2 O 5) and Na-SKS-13 (NaHSi 2 O 5), but in particular Na-SKS-6 (5-Na 2 Si 2 O 5 ) and finely crystalline, synthetic hydrous ze
  • non-neutralized or partially neutralized (co) polymeric polycarboxylic acids are suitable. These include the homopolymers of acrylic acid or methacrylic acid or their copolymers with other ethylenically unsaturated monomers such as acrolein, dimethylacrylic acid, ethylacrylic acid, vinylacetic acid, allylacetic acid, maleic acid, fumaric acid, itaconic acid, meth (allylsulfonic acid), vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid and phosphorous groups Monomers such as vinylphosphoric acid, allylphosphoric acid and acrylamidomethylpropanephosphoric acid and their salts, and hydroxyethyl (meth) acrylate sulfate, allyl alcohol sulfate and allyl alcohol phosphates.
  • ethylenically unsaturated monomers such as acrolein, dimethylacrylic acid
  • Preferred (co) polymers have an average molar mass of from 1000 to 100 000 g / mol, preferably from 2000 to 75000 g / mol and in particular from 2000 to 35000 g / mol.
  • the degree of neutralization of the acid groups is advantageously from 0 to 90%, preferably from 10 to 80% and in particular from 30 to 70%
  • Particularly suitable polymers include homopolymers of acrylic acid and copolymers of (meth) acrylic acid with maleic acid or maleic anhydride.
  • copolymers are derived from terpolymers that are characterized by Polymerization of 10 to 70 wt .-% of monoethylenically unsaturated dicarboxylic acids having 4 to 8 carbon atoms, their salts, 20 to 85 wt .-% monoethylenically unsaturated monocarboxylic acids having 3 to 10 carbon atoms or their salts, 1 to 50 wt. % monounsaturated monomers which, after saponification, release hydroxyl groups on the polymer chain, and 0 to
  • graft polymers of monosaccharides, oligosaccharides, polysaccharides and modified polysaccharides and animal or vegetable proteins are also suitable.
  • Copolymers of sugar and other polyhydroxy compounds, and a monomer mixture of 45 to 96 wt .-% of monoethylenically unsaturated C3 to C-io-monocarboxylic acids or mixtures of C 3 are preferably - to C 0 monocarboxylic acids and / or their salts with monovalent cations, 4 to 55 wt .-% monoethylenically unsaturated
  • Monosulfonic acid-containing monomers monoethylenically unsaturated sulfuric acid esters, vinylphosphoric acid esters and / or the salts of these acids with monovalent cations and 0 to 30 wt .-% of water-soluble unsaturated compounds which are modified with 2 to 50 moles of alkylene oxide per mole of monoethylenically unsaturated compounds.
  • polyspartic acid or its derivatives in non-neutralized or only partially neutralized form.
  • graft polymers of acrylic acid, methacrylic acid, maleic acid and other ethylenically unsaturated monomers to salts of polyaspartic acid, as usually obtained in the hydrolysis of the polysuccinimide described above. This can be dispensed with the otherwise necessary addition of acid for the preparation of only partially neutralized form of polyaspartic acid.
  • the amount of polyaspartate is usually chosen so that the degree of neutralization of all incorporated in the polymer carboxyl groups does not exceed 80%, preferably 60%.
  • Further usable builders are, for example, preferably in the form of their Sodium salts of percarboxylic acids such as citric acid, especially trisodium citrate and trisodium citrate dihydrate, nitrilotriacetic acid and their water-soluble salts; the alkali metal salts of carboxymethyloxuccinic acid, ethylenediaminetetraacetic acid, mono-, dihydroxysuccinic acid, ⁇ -hydroxypropionic acid, gluconic acid, mellitic acid, benzopolycarboxylic acids, and those disclosed in U.S. Patent Nos. 4,144,226 and 4,146,495.
  • percarboxylic acids such as citric acid, especially trisodium citrate and trisodium citrate dihydrate, nitrilotriacetic acid and their water-soluble salts
  • Phosphate-containing builders for example alkali phosphates, which may be present in the form of their alkaline neutral or acidic sodium or potassium salts are also suitable. Examples of these are trisodium phosphate, tetrasodium diphosphate,
  • Disodium dihydrogen phosphate pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with Oligomerleitersmengen in the range of 5 to 1000, especially 5 to 50, and mixtures of sodium and potassium salts.
  • These builders may be contained from 5 to 80 wt .-%, preferably a proportion of 10 to 60 wt .-%.
  • the desired viscosity of the liquid agents can be adjusted by adding water and / or organic solvents or by adding a combination of organic solvents and thickeners.
  • Alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, straight-chain and branched butanol, glycerol and mixtures of the alcohols mentioned are preferably used.
  • More preferred alcohols are polyethylene glycols having a molecular weight less than 2,000. In particular, use of polyethylene glycol having a molecular weight of between 200 and 600 and up to 45% by weight and polyethylene glycol having a molecular weight of between 400 and 600 in amounts of 5 to 25 wt .-% preferred.
  • solvents consists of monomeric alcohol, for example ethanol and polyethylene glycol in a ratio of 0.5: 1 to 1, 2: 1.
  • suitable solvents include triacetin (glycerol triacetate) and 1-methoxy-2-propanol.
  • Preferred thickeners are hardened castor oil, salts of long-chain fatty acids, preferably in amounts of from 0 to 5% by weight and in particular in amounts of from 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium and titanium stearates or the sodium and / or potassium salts of behenic acid, and polysaccharides, in particular xanthan gum, guar-guar, agar-agar, alginates and tyloses, carboxymethylcellulose and hydroxyethylcellulose, furthermore higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, Polyvinyl alcohol and polyvinylpyrrolidone and electrolytes such as sodium chloride and ammonium chloride used.
  • Suitable thickeners are water-soluble polyacrylates which are, for example, cross-linked with about 1% of a polyallyl ether of sucrose and which have a relative molecular mass of more than one million. Examples include under the name Carbopol ® 940 and 941 polymers available.
  • the cross-linked polyacrylates are used in amounts not exceeding 1% by weight, preferably in amounts of from 0.2 to 0.7% by weight.
  • the enzymes optionally contained in the agents according to the invention include proteases, amylases, pullulanases, cellulases, cutinases and / or lipases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®, amylases such as Termamy®, amylase-LT, Maxamyl®, Duramyl®, Purafectel OxAm, cellulases such as Celluzyme®, Carezyme®, K-AC® and / or those disclosed in International Patent Applications WO 96/34108 and WO 96/34092 known cellulases and / or lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®.
  • proteases such as BLAP®, Optimase®, Opticlean®, Max
  • the enzymes used can be adsorbed on carriers and / or embedded in encapsulants, as described, for example, in International Patent Applications WO 92/111347 or WO 94/23005, in order to protect them against premature inactivation. They are in inventive detergents and cleaners preferably in amounts to to 10 wt .-%, in particular from 0.05 to 5 wt .-%, with particular preference against oxidative degradation stabilized enzymes are used.
  • Machine dishwashing detergents according to the invention preferably comprise the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates may be present in amounts of up to 40% by weight. in particular from 3 to 30% by weight, based on the total agent.
  • the alkali carrier system preferably used in cleaning agents according to the invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which may be present in an amount of up to 50% by weight, preferably 5 to 40% by weight.
  • a further subject of the invention is a machine for machine dishwashing containing 15 to 65 wt .-%, in particular 20 to 60 wt .-% of water-soluble builder component, 5 to 25 wt .-%, in particular 8 to 17 wt .-%.
  • Oxygen-based bleaching agents respectively; based on the total agent, and 0.1 to 5 wt .-% of one or more of the above defined cationic nitrile activators.
  • Such an agent is preferably low alkaline, that is its weight percent solution has a pH of 8 to 11, 5, in particular 9 to 11.
  • inventive means for the automatic cleaning of dishes are 20 to 60 wt .-% of water-soluble organic builder, in particular alkali citrate, 3 to 20 wt .-% alkali carbonate and 3 to 40 wt .-% Alkalidisilikat included.
  • silver corrosion inhibitors can be used in dishwashing detergents according to the invention.
  • Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, hafnium, molybdenum, vanadium or cerium salts and / or complexes.
  • the agents foam too much during use, they may still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-regulating compound, preferably from the group consisting of silicones, paraffins, paraffin-alcohol combinations , Hydrophobicized silicic acids, Bisfettklareamide and mixtures thereof and other other known commercially available foam inhibitors are added.
  • a foam-regulating compound preferably from the group consisting of silicones, paraffins, paraffin-alcohol combinations , Hydrophobicized silicic acids, Bisfettklareamide and mixtures thereof and other other known commercially available foam inhibitors are added.
  • the foam inhibitors in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance.
  • mixtures of paraffins and bistearylethylenediamide are preferred.
  • Further optional ingredients in the compositions according to the invention are, for example, perfume oils.
  • organic solvents which can be used in the compositions according to the invention, especially if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compounds ethers.
  • Such water-miscible solvents are preferably present in the detergents according to the invention not more than 20% by weight, in particular from 1 to 15% by weight.
  • the compositions of the invention system and environmentally acceptable acids especially citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators are preferably not more than 10% by weight, in particular from 0.5 to 6% by weight, in the compositions according to the invention.
  • Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, pentanediol or sorbic acid.
  • Suitable pearlescing agents are, for example, glycol distearate esters, such as ethylene glycol distearate, but also fatty acid monoglycol esters.
  • Suitable salts or setting agents are, for example, sodium sulfate, sodium carbonate or sodium silicate (water glass).
  • Typical individual examples of further additives include sodium borate, starch, sucrose, polydextrose, RAED, stilbene compounds, methylcellulose, toluenesulfonate, cumene sulfonate, soaps and silicones.
  • compositions according to the invention are preferably in the form of pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roll compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and the bleach catalyst are to be expected, can be prepared.
  • Solutions according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
  • compositions according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range from 800 to 1000 g / l can also be achieved by using the builder components with at least a proportion of liquid mixture components in a first process stage increasing the bulk density this premix is mixed and subsequently - if desired, after an intermediate drying - the other constituents of the agent, including the cationic nitrile activator, combined with the thus obtained premix.
  • compositions according to the invention in tablet form, the procedure is preferably such that all components are mixed together in a mixer and the mixture is compressed by means of conventional tablet presses, for example Exzeriterpressen or rotary presses.
  • a tablet produced in this way has a weight of 1-5 g to 40 g, in particular from 20 g to 30 g; at a diameter of 3-5 mm to 40 mm.
  • Detergents contain any of the conventional additives in amounts commonly found in such compositions.
  • the reaction mixture was stirred at 60 ° C. for 5 hours.
  • the reaction mixture was cooled to room temperature and the precipitated solid was filtered off.

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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  • Detergent Compositions (AREA)

Abstract

L'invention concerne des nitriles d'ammonium et leur utilisation en tant qu'activateurs de blanchiment hydrophobes. L'invention concerne également des composés de formule (I), dans laquelle Y représente le résidu de R5 et Z représente le résidu de R4 ou Y et Z représentent un noyau de formule (II). Les symboles A, R1, R2, R3, R4, R5, R6, R7, n et X sont spécifiés dans la description. Lesdits composés sont utilisés en tant qu'activateurs de blanchiment dans des agents de lavage, de nettoyage et de désinfection, et lors du blanchiment de textiles et de papier.
PCT/EP2006/001734 2005-03-01 2006-02-24 Nitriles d'ammonium et leur utilisation en tant qu'activateurs de blanchiment WO2006092246A1 (fr)

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DE102005009135.0 2005-03-01

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0303520A2 (fr) * 1987-08-14 1989-02-15 Kao Corporation Composition de blanchiment
JPH02132196A (ja) * 1988-11-11 1990-05-21 Kao Corp 漂白剤及び漂白洗剤組成物
EP0790244A1 (fr) * 1996-02-15 1997-08-20 Hoechst Aktiengesellschaft Activateurs de blanchiment à de nitriles d'ammonium
EP1312665A1 (fr) * 2001-01-04 2003-05-21 Unilever Plc Compositions pour le nettoyage de surface dures

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0303520A2 (fr) * 1987-08-14 1989-02-15 Kao Corporation Composition de blanchiment
JPH02132196A (ja) * 1988-11-11 1990-05-21 Kao Corp 漂白剤及び漂白洗剤組成物
EP0790244A1 (fr) * 1996-02-15 1997-08-20 Hoechst Aktiengesellschaft Activateurs de blanchiment à de nitriles d'ammonium
EP1312665A1 (fr) * 2001-01-04 2003-05-21 Unilever Plc Compositions pour le nettoyage de surface dures

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 014, no. 363 (C - 0746) 7 August 1990 (1990-08-07) *

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