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
  • C11D3/39—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
  • C11D3/3917—Nitrogen-containing compounds
  • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames

Definitions

• This invention relates to the use of cyanopyridinium compounds as bleach activators and detergent compositions containing these quaternary bleach activators.
• peroxidic bleaching agents such as perborates, percarbonates, persilicates and perphosphates
• bleaching power of peroxidic bleaching agents can be improved so that the bleaching action begins at lower temperatures, for example at or below 60 ° C., by adding the precursors of bleaching peroxyacids which often referred to as bleach activators.
• bleach activators are usually reactive organic compounds with an O-acyl or N-acyl group which form the corresponding peroxy acids in alkaline solution together with a source of hydrogen peroxide.
• bleach activators are, for example, N, N, N ', N'-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyoxybenzenesulfonate (SBOBS), sodium trimethylhexanoyloxybenzenesulfonate (TetraHolUlSulfonate (TetraHolUtol) sulfonate (STetraHolOlol) tolurolSulfonuc (TetraHolOlol) tolurol) Tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxin (ADMG) and 1-phenyl-3-acetylhydantoin (PAH). See, for example, GB-A-836 988, GB-A-907 356, EP-A-0 098 129 and EP-A-0 120
• cationic peroxyacid precursors which contain, for example, a quaternary ammonium group in addition to O-acyl or N-acyl groups, have become more important because they are highly effective bleach activators.
• Such cationic peroxyacid precursors are described, for example, in US Pat. No. 5,460,747, US Pat. No. 5,047,577, US Pat. No. 4,933,103, US Pat. No. 4,751,015, US Pat. No. 4,397,757, GB-1,382,594, WO-95 21150, EP-A-403 152, EP-A-427 224, EP-A-402 971, EP-371 809, EP-A-284 292 and EP-A-284 292.
• Corresponding free, stable quaternary peracids are described, for example, in EP-340 754 and WO-94 01399.
• Ammonium nitriles of the formula form a special class of cationic bleach activators.
• Compounds of this type and their use as bleach activators in bleaching agents are described in EP-A-303 520, EP-A-464 880, EP-A-458 396 and US-A-4 883 917.
• the quaternary charge appears on the one hand to have an increased solubility on the other hand to cause a preferred fiber affinity.
• EP-303 520 in particular describes the use of 3-cyano-N-methylpyridinium iodide as a bleach activator.
• Unsubstituted C 1 to C 10 alkyl groups, C 2 to C 4 alkenyl groups or phenyl groups are preferably used for R 1 .
• the alkyl and alkenyl groups as defined by R 1 , R 2 , R 3 and R 4 can be substituted or unsubstituted.
• R 2 , R 3 and R 4 unsubstituted C 1 to C 4 alkyl groups, unsubstituted C 2 to C 4 alkenyl groups, phenyl groups or hydrogen are preferably used independently of one another.
• the anion X used is preferably chloride, bromide, iodide, fluoride, sulfate, hydrogen sulfate, carbonate, hydrogen carbonate, phosphate, mono- and di-hydrogen phosphate, pyrophosphate, metaphosphate, nitrate, methosulfate, dodecyl sulfate, dodecylbenzenesulfonate, phosphonate, methyl sulfonate, methane sulfonate, methane sulfonate Ethanesulfonate used.
• N-Alkyl-4-cyanopyridinium salts which carry hydrogen on the ring and alkyl substituents on the nitrogen atom, such as N-methyl-4-cyanopyridinium chloride, N-ethyl-4-cyanopyridinium chloride and N-hexyl-4-cyanopyridinium chloride, are particularly preferred.
• Isonicotinonitrile is known from the literature and is obtained by direct oxidation of 4-methylpyridine or by ammonium oxidation of 4-methylpyridine.
• alkylation of the isonicotinonitrile z. B. with methylating agents such as Methyl chloride or dimethyl sulfate at temperatures between 20 and 100 ° C, preferably between 70 and 80 ° C the corresponding N-alkyl-4-cyanopyridinium salts are obtained.
• the other cyanopyridinium salts can be prepared in an analogous manner.
• the invention also relates to the use of these cyanopyridinium compounds in bleaching detergents and cleaning agents.
• these washing and cleaning agents usually also contain surface-active compounds and other known ingredients.
• Suitable peroxy compounds are alkali peroxides, organic peroxides such as urea peroxide, and inorganic persalts, such as the alkali perborates, percarbonates, perphosphates, persilicates and persulfates. Mixtures of two or more of these compounds are also suitable.
• Sodium perborate tetrahydrate and in particular sodium perborate monohydrate are particularly preferred.
• Sodium perborate monohydrate is preferred because of its good storage stability and its good solubility in water.
• Sodium percarbonate may be preferred for environmental reasons.
• Alkyl hydroperoxides are another suitable group of peroxy compounds. Examples of these substances are cumene hydroperoxide and t-butyl hydroperoxide.
• the cyanopyridinium bleach activator according to the invention can be present in a weight fraction of approximately 0.1% to 20%, preferably 0.5% to 10%, in particular 1% to 7.5%, together with a peroxy compound .
• the weight fraction of these peroxy compounds is usually from 2% to 40%, preferably from 4% to 30%, in particular from 10% to 25%, the molar ratio of peroxide anion to bleach activator being from 1500: 1 to 1: 2.
• TAED cyanopyridinium bleach activators
• the surfactant can be derived from natural products, such as soap, or is a synthetic compound from the group of anionic, nonionic, amphoteric, zwitterionic or cationic surfactants, or mixtures thereof.
• natural products such as soap
• suitable substances are commercially available and are described in the literature, for example in "Surface active agents and detergents", Vol. 1 and 2, by Schwartz, Perry and Berch.
• the total proportion of the surface-active compounds can be up to 50% by weight, preferably 1% by weight to 40% by weight, in particular 4% by weight to 25% by weight.
• Synthetic anionic surfactants are typically water-soluble alkali metal salts of organic sulfates and sulfonates with alkyl groups of about 8 to 22 carbon atoms, the term "alkyl” including the alkyl substituents of higher aryl groups.
• Suitable anionic detergents are sodium and ammonium alkyl sulfates, especially the sulfates obtained by sulfating higher (C 8 to C 18 ) alcohols; Sodium and ammonium alkylbenzenesulfonates with an alkyl radical from C 9 to C 20 , in particular linear secondary sodium alkylbenzenesulfonates with an alkyl radical from C 10 to C 15 ; Sodium alkyl glycerol ether sulfates, especially the esters of higher alcohols derived from tallow and coconut oil; the sodium sulfates and sulfonates of the coconut fatty acid monoglycerides; Sodium and ammonium salts of the sulfuric acid esters of higher (C 9 to C 18 ) alkoxylated, in particular the fatty alcohols alkoxylated with ethylene oxide; the reaction products of the esterification of fatty acids with isethionic acid and subsequent neutralization with sodium hydroxide; Sodium and ammonium salts
• nonionic surface-active compounds which are preferably used together with anionic surface-active compounds, are in particular the reaction products of alkylene oxides (usually ethylene oxide) with alkylphenols (alkyl radicals from C 5 to C 22 ), the reaction products generally 5 to 25 ethylene oxide units (EO) contained in the molecule; the reaction products of aliphatic (C 8 to C 18 ) primary or secondary, linear or branched alcohols with ethylene oxide, with generally 6 to 30 EO, and the addition products of ethylene oxide with reaction products of propylene oxide and ethylenediamine.
• Other nonionic surfactants are alkyl polyglycosides, long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulfoxides.
• Amphoteric or zwitterionic surface-active compounds can also be used in the compositions according to the invention, but this is mostly undesirable because of their high cost. If amphoteric or zwitterionic compounds are used, this is usually done in small amounts in compositions which mainly contain anionic and nonionic surfactants.
• Soaps can also be used in the compositions according to the invention, preferably in a proportion of less than 25% by weight. They are particularly suitable in small amounts in binary (soap / anionic surfactant) or in ternary mixtures together with nonionic or mixed synthetic anionic and nonionic surfactants.
• the soaps used are preferably the sodium salts, and less preferably the potassium salts are more saturated or unsaturated C 10 to C 24 fatty acids, or mixtures thereof.
• the proportions of such soaps can be from 0.5% by weight to 25% by weight, smaller amounts from 0.5% by weight to 5% by weight are generally sufficient for foam control. Soap contents between about 2% and about 20%, especially between about 5% and about 10%, have a positive effect. This is particularly the case in hard water, where the soap serves as an additional builder.
• the detergents and cleaning agents generally also contain a builder.
• Possible builders are: calcium-binding substances, precipitants, calcium-specific ion exchangers and their mixtures.
• calcium binding agents include alkali metal polyphosphates such as sodium tripolyphosphate; Nitrilotriacetic acid and its water-soluble salts; the alkali metal salts of carboxymethyloxysuccinic acid, ethylenediaminetetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid; and polyacetal carboxylates as disclosed in U.S. 4,144,226 and U.S. 4,146,495.
• precipitants are sodium orthophosphate, sodium carbonate and soaps from long-chain fatty acids.
• ion exchangers which are specific for calcium are the various types of water-insoluble, crystalline or amorphous aluminum silicates, of which the zeolites are the best known representatives.
• These builder substances can be present from 5% by weight to 80% by weight, a proportion of 10% by weight to 60% by weight being preferred.
• the washing and cleaning agents can contain any of the conventional additives in amounts that are usually found in such agents.
• these additives include foaming agents such as alkanolamides, especially the monoethanolamides made from palm kernel oil fatty acids and coconut fatty acids; anti-foaming agents such as alkyl phosphates and silicones; Graying inhibitors and similar auxiliaries such as sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers; Stabilizers such as ethylenediaminetetraacetic acid; Softeners for textiles; inorganic salts such as sodium sulfate; and, usually in small amounts, fluorescent substances, perfumes, enzymes such as proteases, cellulases, lipases and amylases, disinfectants and dyes.
• the bleach activators of this invention can be used in a variety of products. These include textile detergents, textile bleaches, surface cleaners, toilet cleaners, dishwasher cleaners, and also denture cleaners.
• the detergents can be in
• the bleach activators in the form of granules which, in addition to the bleach activator, contain a binder.
• Various methods for producing such granules are described in the patent literature, for example in CA-1 102 966, GB-1 561 333, US-4 087 369, EP-A-0 240 057, EP-A-0 241 962, EP-A-0 101 634 and EP-A-0 062 523. Each of these methods can be used for the bleach activators according to the invention.
• the granules containing the bleach activators are generally added to the detergent composition along with the other dry ingredients such as enzymes, inorganic peroxide bleaches.
• the detergent composition to which the activator granules are added can be obtained in various ways, such as dry blending, extrusion, spray drying.
• the bleach activators according to the invention are particularly suitable for non-aqueous liquid detergents, together with a bleaching peroxy compound, for example sodium perborate, in order to give the detergent great cleaning properties for fabrics and textiles.
• a bleaching peroxy compound for example sodium perborate
• Such non-aqueous, liquid detergents which include pasty and gelatinous detergent compositions, are known in the art and are described, for example, in US 2,864,770, US 2,940,938, US-4,772,412, US-3,368,977, GB-A-1205,711 GB-A-1,370,377, GB-A-1,270,040, GB-A-1,292,352, GB-A-2,194,536, DE-A-2 233 771, EP-A-0 028 849.
• compositions in the form of a non-aqueous, liquid medium in which a solid phase can be dispersed can be a liquid, surface-active substance, preferably a non-ionic surface-active substance; a non-polar liquid medium such as liquid paraffin; a polar solvent, such as polyols, for example glycerol, sorbitol, ethylene glycol, possibly in combination with low molecular weight monohydric alcohols such as ethanol or isopropanol; or mixtures thereof.
• the solid phase can consist of builder substances, alkalis, abrasive substances, polymers and other solid ionic surface-active substances, bleaching agents, fluorescent substances and other common solid substances.
• a bleaching agent composition was obtained by combining 200 ml of an aqueous solution of 5 g / l reference detergent (WMP) obtained from WFK-Testgewebe GmbH, Krefeld, 150 mg sodium perborate monohydrate (PB * 1) and 50 mg of an activator.
• WMP 5 g / l reference detergent
• PB * 1 sodium perborate monohydrate
• the bleaching agent compositions given in Table 1 with the activators 1 and 2 and the comparison compound 3 were prepared. Their effectiveness was determined by comparing the remissions of the fabric before and after the bleaching process. The results are shown in Table 1.

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• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
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• Pyridine Compounds (AREA)

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• 1996
  • 1996-05-08 DE DE1996118408 patent/DE19618408A1/de not_active Withdrawn
• 1997
  • 1997-04-29 EP EP97107051A patent/EP0806473A3/fr not_active Withdrawn
  • 1997-05-07 JP JP11715297A patent/JPH1046194A/ja not_active Withdrawn

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