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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
• • 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
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
• • 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
• • 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
  • C11D3/3942—Inorganic per-compounds

Definitions

• Bleaching agents that release active oxygen are important components of detergents and cleaning agents.
• Preferred areas of application are heavy-duty detergents, stain salts, machine dishwashing detergents, cleaning agents for hard surfaces and denture cleaners.
• Your main task is the oxidative destruction of tea, coffee or fruit stains.
• they prevent the transfer of detached dye particles, kill bacteria and germs and ensure an improved smell of the laundry by decomposing adhering odor substances.
• the bleaching system used consists of a mixture of an inorganic persalt with a bleach activator, which is usually in the form of a reactive ester or an amide-containing compound. If this mixture is introduced into water at pH 7-12, the hydrogen peroxide released from the persalt reacts with the dissolved activator to release an inorganic peroxycarboxylic acid which has a higher oxidation potential than hydrogen peroxide itself and is consequently more reactive.
• Activated systems are usually used for washing temperatures of 20 - 60 ° C, since hydrogen peroxide alone is not very effective in this area.
• enzymes eg proteases, which in particular remove protein-containing impurities from fibers or surfaces.
• lipases, amylases and cellulases are being used more and more recently. Their chemical structure makes enzymes susceptible to oxidants. If bleach and enzymes react with each other, this leads both to the destruction of the enzymatic activity, as well as a loss of bleaching active oxygen.
• enzymes and bleaching agents in coated form are normally used in washing powders.
• a number of coating agents and processes have been described to improve the storage stability of bleaching systems and enzymes.
• a common coating material for enzymes are e.g. Silicones.
• nonionic surfactants, carboxymethyl cellulose, bentonite or polyacrylates are used as granulation aids.
• the invention relates to bleaching agents containing a coated persalt and an enzyme, the persalt being coated with a C 8 -C 18 fatty acid, a wax or a silicone oil, and optionally a bleach activator or a bleach catalyst.
• the persalts coated with these substances have the property that less than 25% of the existing amount of persalt dissolves in water or releases the theoretically present amount of hydrogen peroxide within 3 minutes at 20 ° C. This effectively prevents an early interaction of the persalt or hydrogen peroxide with the enzyme.
• the persalt in its coated form is preferably 1-99% by weight, in particular 70-90% by weight
• the enzyme is preferably 0.05-10% by weight, in particular 0.2-5% by weight .-%, contain.
• a bleach activator it is used in concentrations of preferably 0.1-40% by weight, in particular 1-25% by weight.
• concentrations of preferably 0.001-10% by weight, in particular 0.005-5% by weight are customary.
• persalts examples include inorganic persalts such as alkali metal perborates, percarbonates, perphosphates or persulfates or hydrogen peroxide adducts with inorganic salts or organic molecules (eg urea adducts).
• Sodium perborate, mono- or tetrahydrate, sodium percarbonate or caroate are particularly preferred.
• the persalts are used in the bleaching agent according to the invention in coated form. The most important thing here is that the coating is uniform and complete, so that the dissolution of the products in water is considerably delayed.
• Fatty acids, waxes or silicone oils are used as coating substances for the persalts.
• the fatty acids can be saturated or unsaturated; Examples include lauric acid, stearic acid, myristic acid.
• waxes for example, montan waxes, paraffin waxes, ester waxes or polyolefin waxes.
• the persalt can be used in powder form or, in accordance with the prior art, in granular form.
• the amount and degree of distribution of the coating substance have a decisive influence on the dissolving behavior.
• a coating substance content of 5-30% by weight in the coated persalt has proven to be optimal.
• the coating substance can be applied by a large number of techniques described in the literature. It is thus possible to carry out the coating in a mixing unit by spraying on the coating substance.
• Mixers with a spraying device and fluidized bed apparatus can be used to apply the coating substances.
• a mixer e.g. Ploughshare mixers (continuous and batch-wise)
• ring layer mixers or Schugi mixers are conceivable.
• post-drying or tempering may be necessary, e.g. Fluid bed dryers and fluidized bed apparatus can be used.
• the coating stage is carried out in a fluidized bed spray granulator using a two-component nozzle.
• the shell material can also be applied in dissolved form (for example in water or an organic solvent), it has proven to be useful to spray the shell material in the form of a melt.
• the persalt is preferably kept at an elevated temperature (30-80 ° C).
• a heat treatment step has proven itself for complete coating, in which the persalt with sprayed-on coating material is held for a certain time at temperatures above the melting point of the coating material.
• Proteases, lipases, amylases, cellulases or peroxidases can be used as enzymes.
• the bleach activators used in the bleaching agents according to the invention 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, 303520, 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.
• tetraacetylethylenediamine nonanoyloxibenzenesulfonate, benzoyloxibenzenesulfonate, nonanoyl and benzoylcaprolactam
• isatoic maleic, succinic and citric acid anhydrides as well as acylated sugar or sugar derivatives, as well as alkyl, aryl or aminonitriles.
• the following compounds can be used as bleaching catalysts in the formulations according to the invention.
• US 3,532,634 teaches the use of picolinic acids, pyrrolidone carboxylic acids or phenanthroline.
• US 4,430,243 claims EDTA and EDTMP complexes of copper, iron and manganese as bleaching catalysts; US 4,478,733 successfully uses manganese salts in detergent formulations based on zeolite / orthophosphate.
• catalysts are metal-free organic molecules which form intermediates reactive with organic or inorganic peracids, such as e.g. Oxaziridines or dioxiranes that have a bleaching effect.
• organic or inorganic peracids such as e.g. Oxaziridines or dioxiranes that have a bleaching effect.
• imines or ketones as described in US 5437686.
• the persalts coated according to the invention can be used either with the activators or catalysts alone or, in a preferred embodiment, in combination with both. This broadens the range of applications and strengthens the germicidal properties of the formulation. But even without the addition of an activator and / or catalyst, better bleaching and enzyme results can be obtained when using the persalt coated according to the invention than with persalts that are not coated and therefore dissolve quickly.
• the bleaching agents according to the invention are used in detergents and cleaning agents of all kinds, such as, for example, 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. In addition to bleaching, they also act as dye transfer inhibitors.
• washing and cleaning agents according to the invention normally also contain other surface-active compounds, such as anionic, nonionic, zwitterionic, amphoteric or cationic surfactants, builders, enzymes and additives.
• 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 Detergens" 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 systems according to the invention are phosphates such as sodium tripolyphosphate, type A, X and P zeolites, 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 silicates as 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. Phosphonates or other complexing agents can also be added.
• Cellulose ethers, silicones, bentonites, optical brighteners and perfume can be used as further additives.
• Example 1 110 g of myristic acid (Edenor C14, 98-100%, from Henkel, DE) were sprayed onto 500 g of sodium perborate monohydrate (from Degussa, DE) at 48 ° C. at 14 g / min. After a cooling period of 2 minutes, the product was isolated.
• myristic acid Esdenor C14, 98-100%, from Henkel, DE
• sodium perborate monohydrate from Degussa, DE
• the tests were carried out in a Linitest device from Heraeus, Hanau, DE. 1 g of phosphate-free WMP detergent (incl. 0.5% protease) was dissolved in a beaker with 200 ml of water (15 ° dH). After adding 50 mg of TAED powder (tetraacetyl-ethylenediamine), 150 mg of percarbonate or granules according to Example 3 (calculated as 100% product) and the test soiling are added. Tea on cotton (WFK Krefeld, DE) and blood-milk-ink (BMT) on cotton (Empa 116, EMPA, CH) were used for this. To simulate the heating rate, the cups were first kept at 20 ° C.
• Example 6 The washing tests were carried out in accordance with Example 6. In addition, 2% by weight of Durazym (Novo Nordisk) based on WMP were added to the wash liquor. Coated sodium perborate monohydrate, prepared according to Example 2, was used as the persalt according to the invention. EMPA red wine and blood (EMPA, CH), grass (WFK-Krefeld, DE) was used as the test fabric. % Remission after washing Persalt red wine grass blood total Perborate, untreated 80.4 61.3 35.5 177.2 Perborate, according to Example 2 80.4 66.8 40.5 187.7

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)

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Citations (37)

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• 1996
  • 1996-02-21 DE DE19606343A patent/DE19606343A1/de not_active Withdrawn
• 1997
  • 1997-02-11 EP EP97102139A patent/EP0791647A3/fr not_active Withdrawn
  • 1997-02-20 JP JP9036409A patent/JPH09316496A/ja not_active Withdrawn

Patent Citations (38)

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