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
  • C11D3/3932—Inorganic compounds or complexes

Definitions

• Bleaches that release active oxygen are an essential part of modern washing and cleaning agents. Its main task is to remove stubborn stains such as tea, coffee, red wine or fruit juices from textile fibers or solid surfaces. This is done by oxidative destruction of the chromophoric system; At the same time, adhering microorganisms are killed and odorants neutralized.
• Hydrogen peroxide, organic or inorganic peracid are mostly used as bleaching agents.
• a persalt is usually used as a source of active oxygen in powdery products.
• Typical examples are sodium perborates or percarbonates or urea adducts.
• bleach activators are often added.
• Examples include tetraacetylethylenediamine (TAED), diacetyldioxohexahydrotriazine (DADHT), pentaacetylglycose (PAG), benzoyloxibenzenesulfonate (BOBS) and nonanoyloxibenzenesulfonate (NOBS).
• TAED tetraacetylethylenediamine
• DADHT diacetyldioxohexahydrotriazine
• PAG pentaacetylglycose
• BOBS benzoyloxibenzenesulfonate
• NOBS nonanoyloxibenzenesulfonate
• transition metals in free or complex form catalyze the decomposition of hydrogen peroxides.
• the effectiveness of the compounds described so far is unsatisfactory in most cases.
• the addition of metal salts leads to catalytic decomposition of the hydrogen peroxide, but no bleaching effect is observed. This is usually associated with damage to the textile fabric. The occurrence of free transition metals during the washing and cleaning process is therefore undesirable.
• the metal salt is used in complexed form, the corresponding complex must be stable to hydrolysis and oxidation during storage and under conditions of use in order to suppress these side effects.
• EP A 458 397 and 458 398 describes the use of macrocyclic polyamines as complex ligands in multinuclear, oxygen-bridged manganese complexes. In combination with oxidizing agents, especially on tea stains, these complexes show good bleaching properties.
• the difficult to access complex ligand of the triazacyclononane type has a disadvantage. It is only accessible in a multi-stage, by-product-rich manufacturing process. Similar complexes are described in EP 544 519, again the synthesis of the complex ligand is very complex and difficult to implement on an industrial scale.
• L is preferably a ligand of the formula II.
• R is preferably C 1 -C 4 -alkyl, in particular methyl.
• anion A are Cl - , Br - , J - , NO 3 - , ClO 4 - , NCS - , PF 6 - , RSO 3 - , RSO 4 - , SO 4 2- , BPh 4 - , OAc - .
• Preferred anions are PF 6 - , ClO 4 - , tosylate.
• the ligands of the formula III contained in these manganese complex salts are prepared by reacting 2- (chloromethyl) pyridinium chloride with an alkylenediamine in the presence of a phase transfer catalyst (see Synthesis, June 1992, p. 539-540) or in an analogous manner for the substituted other ligands of formula III.
• the ligands of the formula II are prepared in the same way by reacting 2- (chloromethyl) pyridinium chloride or analogous pyridinium compounds with an amine R-NH 2 .
• the manganese complex salts of the formula I are prepared in accordance with the information in Inorg. Chem.
• the metal complexes can either be added to the washing and cleaning agent in prefabricated form or generated in situ from the ligand and transition metal during the washing process.
• the bleaching catalysts are used in combination with an oxidizing agent.
• oxidizing agents that can be used are hydrogen peroxide, alkali metal perborates, percarbonates, perphosphates or persulfates. If the catalysts are used in powdery products, sodium perborate mono- or tetrahydrate, caroate in the form of the triple salt and sodium percarbonate, the latter in particular in coated form, are particularly preferred. These compounds can be used either with the catalysts alone or, in accordance with a preferred embodiment, additionally together with a bleach activator. This extends the range of applications and strengthens the germicidal properties of the formulation.
• Bleach activators are known from numerous patent applications. Examples of these are reactive esters and amides such as in GB 836,988, 864,798, 907,356, 1,003,310 and 1,519,351; EP 284,292, 331,229, 303,520, 185,522, 174,132, 120,591 and US 1,246,339, 3,332,882, 4,128,494, 4,412,934, 4,675,393, 4,751,015 and 4,397,757.
• organic peroxycarboxylic acids can also be used directly as oxidizing agents.
• Typical representatives are peroxibenzoic acid and substituted derivatives, aliphatic mono- and dicarboxylic acids such as pernonanoic acid, perlauric acid, 1,9-diperoxiazeldic acid and 1,12-dodecanediperic acid.
• N, N'-phthaloylaminoperoxycarboxylic acids such as N, N'-phthaloylaminoperoxihexanoic acid (PAP), 6-octylamino-6-oxoperoxihexanoic acid, monoperoxiphthalic acid and its salts, 2-alkylperoxi-1,4-butanedioic acids or 4,4'-sulphonylbisperoxiboesoes.
• composition of the bleaching agent system according to the invention can vary within wide limits and is generally between 0.0005 to 2% by weight, preferably 0.001 to 0.5% by weight of the bleaching catalyst described and 1 to 99.9995%, preferably 5 to 99.999 % of an oxidizing agent from the group of inorganic or organic peracids or persalt, and optionally 0 to 70%, preferably 10 to 60% of a bleach activator.
• the bleaching systems according to the invention are used in heavy-duty detergents, multi-component detergents (modular systems), stain salts, stain pretreatment agents, machine dishwashing detergents, cleaning agents for hard surfaces, disinfectants and denture cleaners.
• the catalysts also act as dye transfer inhibitors.
• the catalysts are normally added to the washing and cleaning agent in granular form.
• Inorganic salts such as sodium sulfate, chloride, phosphate or silicates can be used as granulation aids. In a preferred application form, they are incorporated into the activator granulate.
• inorganic or organic auxiliaries can be used for granulation, film-forming materials such as surfactants, fatty acids, celulose derivatives or polymers are preferred.
• the granules can additionally be provided with a coating, which on the one hand increases their storage stability and interactions with other detergent ingredients can be prevented during storage, but on the other hand their release kinetics can also be influenced.
• the bleach system according to the invention can be added to the washing and cleaning agents in the form of a powder or as granules.
• washing and cleaning agents normally also contain surface-active compounds such as anionic, nonionic, zwitterionic, amphoteric or cationic surfactants, builders, enzymes and additives.
• Surfactants can be of natural or synthetic origin and are e.g. in "Surface Active Agents and Detergents" Volumes I and II by Schwartz, Perry and Berch. Examples are alkyl sulfates, alkyl sulfonates, alkylarylsulfonates, alpha-sulfofatty acid methyl esters, soaps and alkyl ether sulfonates. Nonionic surfactants such as alkyl polyglycol ethers, alkyl polyglucosides, glucamides, sugar esters and amine oxides can also be used.
• Important builder and cobuilder substances which can be used in combination with the bleaching system according to the invention are phosphates such as sodium tripolyphosphate, zeolites of the types A, X and P, alkali metal carbonates and bicarbonates, amorphous and crystalline silicates, in particular layered silicates such as SKS-6, 7, 9 or 10 from Hoechst AG or disilicates such as those sold by Akzo under the trade name Britesil ® .
• Organic carboxylic acids such as citric acid or amino acids can be used as co-builders, but also polymers of the polyacrylic acid type or copolymers of acrylic acid and maleic acid or their derivatives. Phosphonate or other complexing agents can also be added.
• Amylase, proteases, lipases, cellulases and peroxidases can be used as enzymes, cellulose ethers, silicones, bentonites, optical brighteners and perfume as further additives.
• N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine were dissolved in 30 ml of a mixture of ethanol and water (5: 1) and then Mn (acetate) 3 ⁇ 2H 2 O (0.96 g; 3.6 mmol) was added. Then was 2.2 g (20 mmol) sodium butyrate were added and then 2 ml HClO 4 (70%). A pH of 7.5 was established. Then 3 g (24.48 mmol) NaClO 4 were added and this mixture was stirred for 4 hours at room temperature.
• TAED tetraacetylethylene diamine
• Example 3 Washing tests in a Linitest device
• Example 3 The tests were carried out as described in Example 3. Instead of the test soil tea (BC-1), beetroot and curry on cotton (manufacturer laundry research Krefeld) were used. catalyst Beetroot ⁇ RE Curry ⁇ RE without 0 0 K1 + 2.0 + 0.6 K4 + 1.1 + 0.1 K2 + 4.0 + 0.9
• the bleaching results on the test soils beetroot and curry can also be significantly increased.
• the washing tests were carried out in the Linitest réelle at 40 ° C; Washing time 30 min. 1.5 g / l WMP were pre-dissolved in 200 ml water (15 ° dH) and 0.5 g / l sodium perborate monohydrate was added. Before the start of the washing tests, 0; 1.5; 3; 6; 12; 25 mg / l of the catalysts added. The washing tests were carried out analogously to Example 3. The table shows the reflectance differences ⁇ RE of the washes with and without a catalyst.
• Example 7 Influence of various oxidizing agents on the bleaching result

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• Chemical & Material Sciences (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
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• Detergent Compositions (AREA)
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Citations (30)

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• 1996
  • 1996-01-04 DE DE19600159A patent/DE19600159A1/de not_active Withdrawn
  • 1996-12-23 DE DE59610733T patent/DE59610733D1/de not_active Expired - Lifetime
  • 1996-12-23 ES ES96120743T patent/ES2207663T3/es not_active Expired - Lifetime
  • 1996-12-23 AT AT96120743T patent/ATE250660T1/de not_active IP Right Cessation
  • 1996-12-23 EP EP96120743A patent/EP0783035B1/fr not_active Expired - Lifetime
  • 1996-12-27 JP JP8350981A patent/JPH09194886A/ja not_active Withdrawn
• 1997
  • 1997-01-03 CA CA002194342A patent/CA2194342A1/fr not_active Abandoned
  • 1997-01-03 US US08/775,354 patent/US5942152A/en not_active Expired - Lifetime

Patent Citations (31)

Non-Patent Citations (3)

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