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

• Inorganic per-compounds especially hydrogen peroxide and solid per-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 disinfection and bleaching purposes.
• the oxidizing effect of these substances in dilute solutions depends strongly on the temperature; For example, with H2O2 or perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 80 ° C. At lower temperatures, the oxidation effect of the inorganic per compounds can be improved by adding so-called activators, for which numerous proposals have become known in the literature.
• carboxylic anhydrides have been proposed for this purpose (DE 893 049) and used in bleaching agents (DE 19 12 579). By adding these substances, the bleaching effect of aqueous peroxide liquors can be increased to such an extent that already at 60 ° C almost the same effects occur as with the peroxide liquor alone at 95 ° C.
• the present invention also aims to improve the oxidation and bleaching effect of inorganic per-compound at low temperatures below 80 ° C., in particular in the temperature range from approximately 15 to 45 ° C.
• isatoic anhydride and its derivatives can be used as activators wherever a particular increase in the oxidation activity of inorganic per-compounds is important at low temperatures, for. B. in the bleaching of textiles, hair or hard surfaces, in the oxidation of organic or inorganic intermediates and in disinfection. Most of these activators far outperform the best carbonic anhydride activators known to date.
• the use according to the invention is to create conditions under which hydrogen peroxide and isatoic anhydride or its derivatives can react with one another with the aim of obtaining secondary products which have a stronger oxidizing action.
• Such conditions exist in particular when the two reactants meet in an aqueous alkaline solution.
• the conditions can be varied widely depending on the intended use.
• mixtures of water and suitable organic solvents e.g. B. for the use in disinfection or in the oxidation of intermediates as a reaction medium in question.
• the pH of the reaction medium can be selected within wide limits, from the weakly acidic range (pH 4) to the strongly alkaline range (pH 13), depending on the application.
• the alkaline range from pH 8 to pH 11 is preferred since it is particularly advantageous for the activation reaction and the stability of the per compound formed.
• the activator according to the invention is also preferably used together with a sodium perborate or with sodium carbonate perhydrate, which already have pH values of this range in their solutions.
• Examples of other suitable per compounds are phosphate perhydrates and urea peroxide. Occasionally, it can also be expedient to shift the pH of the medium again after the activation reaction has taken place by means of suitable additives, especially in the acidic range.
• the amounts of per compounds are generally chosen so that the solutions contain between 10 ppm and 10% active oxygen, preferably between 50 and 5000 ppm active oxygen.
• the amount of activator used also depends on the application. Depending on the desired degree of activation, 0.03-1 mol, preferably 0.1-0.5 mol, of activator per mol of inorganic per-compound are used, but in special cases these limits can also be exceeded or fallen short of.
• the isatoic anhydride according to the invention or its derivatives can be used for activation in pure form or, if this is expedient, for example to increase the storage stability, in special forms of supply, such as tablets, granules or in finely divided coated form (so-called prills). Of particular importance are those granular shapes that are produced by agglomeration granulation. For the Machine dosing is suitable for solutions in organic solvents or liquid dispersions that contain the activator.
• pre-assembled agents in a mixture with the per compounds to be activated and, if appropriate, further components required for the desired bleaching or oxidation process, such as pH regulating agents and stabilizers for per compounds.
• further components required for the desired bleaching or oxidation process such as pH regulating agents and stabilizers for per compounds.
• activators can also be present. Mixing with selected amounts of per-compounds and other additives makes the application easier and the user achieves the desired result more reliably, since the optimal conditions are obtained when the agents are dissolved without further action. Such agents are therefore a further subject of the present invention.
• the activators according to the invention can be combined with almost all the usual components of detergents and bleaches. In this way it is possible to build up means which are particularly suitable for textile treatment at low temperatures and also means which are suitable in several temperature ranges up to the traditional area of cooked laundry.
• the main components of such detergents and bleaches are, besides per-compounds and activators, builders and surfactants.
• other customary auxiliaries and accompanying substances such as graying inhibitors, peroxide stabilizers, electrolytes, optical brighteners, enzymes, perfume oils, foam regulators and conditioning agents, can be present in these agents if this is expedient.
• customary builder substances are condensed phosphates, alkali silicates, alkali carbonates, salts of amino carboxylic acids, such as nitrilotriacetic acid, salts of polyphosphonic acids, such as hydroxyethane diphosphonic acid, salts of polycarboxylic acids, such as citric acid or polyacrylic acid, and insoluble sodium aluminum silicates and NaX type NaA zeolite NaA.
• Particularly suitable surfactants are those of the type of the nonionic and synthetic anionic surfactants.
• nonionic surfactants are the polyethylene glycol monoalkyl and polyethylene glycol monophenyl ethers prepared from long-chain alcohols or alkylphenols and ethylene oxide, and the long-chain alkylglycosides.
• the anionic surfactants are primarily sulfates and sulfonates of long-chain compounds, for example alkylbenzenesulfonates, fatty acid ester sulfonates, alkanesulfonates, olefin sulfonates, fatty alcohol sulfates and sulfates of polyethylene glycol monoethers. Soaps and salts of long-chain acylcyanamides can also be used.
• Typical detergents and bleaches according to the invention have approximately the following composition: 0.5 to 20% by weight, preferably 5 to 15% by weight of anionic and / or nonionic surfactants, 0.5 to 60% by weight, preferably 5 to 40% by weight, of builders from the group of condensed phosphates, alkali silicates, alkali carbonates, sodium aluminum silicates and mixtures thereof, 0 to 20% by weight, preferably 0.5 to 8% by weight, of builder substances from the group consisting of salts of aminocarboxylic acid ren, salts of polyphosphonic acids, salts of polycarboxylic acids and mixtures thereof, 2 to 35% by weight, preferably 5 to 30% by weight, of inorganic per-compounds, 0.3 to 20% by weight, preferably 1 to 10% by weight, of isatoic anhydride and / or its derivatives, ad 100% usual auxiliary and accompanying substances and water
• agents which are used as additives to peroxide-containing or peroxide-free detergents are also suitable as the form of preparation of the activators according to the invention for textile washing. They essentially contain activator or a mixture of activator and per compound and, if appropriate, further auxiliaries and additives, in particular stabilizers, pH-regulating agents, thickeners and surfactants.
• Typical bleach additives according to the invention have approximately the following composition: 5 to 50% by weight, preferably 15 to 35% by weight, of inorganic per-compound, 2 to 30% by weight, preferably 5 to 25% by weight, of isatoic anhydride and / or its derivatives, 0 to 5% by weight, preferably 0.1 to 3% by weight, of peroxide stabilizers, 0 to 40% by weight, preferably 5 to 30% by weight of pH-regulating agents, ad 100% by weight of other customary auxiliaries and additives.
• agents intended for cleaning hard surfaces contain, in particular, surfactants and framework substance zen and, in the case of polishing and abrasive agents, abrasive components. Since these agents are often used at room temperature, the use of the activators according to the invention has a particularly advantageous effect on the bleaching and germicidal action.
• Disinfectants based on the activators according to the invention generally contain, in addition to this and inorganic per-compounds, further auxiliaries and additives, such as pH-regulating substances, stabilizers and surfactants. In special cases, they can additionally contain special microbicides which increase the very broad killing effect of the activated per-compound against certain germs.
• Typical disinfectants according to the invention have approximately the following composition: 5 to 40% by weight, preferably 10 to 20% by weight, of inorganic per-compounds, 2 to 40% by weight, preferably 5 to 20% by weight, of isatoic anhydride and / or its derivatives, 0 to 5% by weight, preferably 0.1 to 3% by weight, of peroxide stabilizers, 0.1 to 20% by weight, preferably 0.2 to 5% by weight of surfactants, ad 100% by weight of other auxiliaries and additives.
• the use of the activators according to the invention is in no way limited to the use in the ready-made form of these described or other types.
• the individual dosing of reagents in the foreground since it is often the cheaper method.
• AS Acrylic acid
• CMC Carboxymethyl cellulose
• EDTA Tetrasodium salt of ethylenediaminetetraacetic acid
• EDTMP Hexasodium salt of ethylenediaminetetramethylenephosphonic acid (peroxide stabilizer)
• EO Ethylene oxide
• HEC Hydroxyethyl cellulose
• MA Maleic anhydride
• composition in percent by weight: Soap (C12-C18) 1.5 Na dodecylbenzenesulfonate 9.0 Fatty alcohol ethoxylate (C12-C18 + 10 EO) 3.5 Sodium triphosphate 20.0 Sodium silicate (3.2) 5.0 Zeolite NaA 15.0 EDTMP 0.3 MA-AS copolymer (60:40) 1.5 Sodium perborate monohydrate 18.0 Isatoic anhydride 3.0 Brightener, perfume, enzyme ad 100 Carboxymethyl cellulose, Na2SO4 and water
• the test was carried out in a launderometer, type Atlas Standard, using a phosphate-free detergent under the following conditions: Fleet volume 250 ml Fabric: 6.3 g fill fabric (white cotton) 2.1 g test fabric Water hardness: 17 ° d. H. Temperatures: 30 or 40 ° C Washing time: 30 minutes including heating up time (3 ° C / min) Rinse: 3 x 30 sec.
• Detergent composition (% by weight): Alkylbenzenesulfonate Na salt 7 Tallow alcohol + 5 EO 5.5 Na2CO3 12 Sodium silicate (3.2) 3.3 Zeolite NaA 28 EDTA 0.3 Sodium perborate tetrahydrate 28 CMC + HEC 1.5 Na2SO4 and water ad 100 Dosage: detergent 7.16 g / l Activator 143 mg / l or 1.26 mmol / l
• Table 3 contains the test results on various test soils in comparison to activators customary today (mean values from 4 tests): Table 3 Try at 24 ° C Activator Currant on cotton Red wine on refined cotton Tea on finished cotton Red wine on polyester / cotton Without perborate and activator 40.5 36.9 27.1 47.7 Isatoic anhydride 45.7 39.6 33.0 50.3 Tetraacetylethylenediamine 42.7 38.0 31.1 48.7 Sulfophenyl isononate Na salt 41.8 38.5 30.3 48.9
• the storage was carried out in a mixture with a powdered phosphate-free detergent, this mixture containing 3% by weight of activator either in pure form or in the form of agglomeration granules.
• the detergent had the following composition (in% by weight): Soap 1.5 Na dodecylbenzenesulfonate 8.0 Fatty alcohol ethoxylate 4.0 Na2CO3 8th Sodium silicate (3.2) 3.5 Zeolite NaA 25th Hydroxyethane diphosphonate (Na salt) 0.3 MA-AS copolymer (60:40) 5 Sodium perborate tetrahydrate 26 Brightener, perfume, enzyme, carboxymethyl cellulose Na2SO4 and water ad 100
• the activator granules had been prepared from the pure, powdery activators and carboxymethyl cellulose as binders according to DE 30 11 998 and contained 94% by weight of active substance.
• the mixtures containing the activators in granular form were stored in laminated cardboard boxes in a climatic cell at 30 ° C. and 80% relative humidity. The other mixtures were stored in unlaminated boxes in the laboratory. In all cases, the peracid, which formed when the mixtures were dissolved in water, was determined iodometrically at the beginning and after 4 and 8 weeks of storage under standard conditions. Table 3 contains the results in relative numbers, based on 100% peracid formation at the start of storage. The superior stability of the isatoic anhydride is evident under both storage conditions.
• composition (percent by weight) Sodium perborate monohydrate 12.0 Isatoic anhydride 12.0 Na2CO3 15.0 Na4P2O7 25.0 EDTMP 1.2 Nonylphenol ethoxylate (9 EO) 1.3 Na2SO4 and water ad 100
• the powdery agent After being dissolved in water at room temperature, the powdery agent was used in the form of a bath for instrument disinfection. When using about 4 g per liter, the necessary disinfection times were less than 60 minutes.
• Test solution detergent according to Example 2 in water at 17 ° dH, adjusted to pH 10, Dosage: Detergent: 10 g / l Activator: 150, 300 or 600 mg / l Temperature: 37 ° C Culture medium: casein peptone soybean meal peptone agar

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• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (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)
• Detergent Compositions (AREA)

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Citations (2)

• 1988
  • 1988-03-10 DE DE3807921A patent/DE3807921A1/de not_active Withdrawn
• 1989
  • 1989-03-02 WO PCT/EP1989/000210 patent/WO1989008696A1/fr not_active Application Discontinuation
  • 1989-03-02 EP EP89902941A patent/EP0409846A1/fr active Pending
  • 1989-03-02 KR KR1019890702113A patent/KR900070586A/ko not_active Application Discontinuation
  • 1989-03-02 JP JP1502726A patent/JPH03503292A/ja active Pending
  • 1989-03-02 EP EP89103637A patent/EP0332050A1/fr not_active Ceased
• 1990
  • 1990-08-07 DK DK188290A patent/DK188290A/da unknown

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