US3925234A - Coated bleach activator - Google Patents

Coated bleach activator Download PDF

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Publication number
US3925234A
US3925234A US382595A US38259573A US3925234A US 3925234 A US3925234 A US 3925234A US 382595 A US382595 A US 382595A US 38259573 A US38259573 A US 38259573A US 3925234 A US3925234 A US 3925234A
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percent
weight
carbon atoms
acids
washing
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Klaus Hachmann
Herbert Saran
Gerhard Sperling
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected

Definitions

  • a stabilized bleaching assistant suitable for use in pulverulent washing and bleaching compositions comprising drop-shaped to globular-shaped particles at least 70 percent of which have a diameter within the range of 0.1 mm to 1 mm consisting of 10 percent to 70 percent by weight of at least one activator for active oxygen derived from compounds yielding H 0 in aqueous solution, substantially surrounded by from 30 percent to 90 percent by weightof a mixture of (a) from 2 to 10 parts of substantially saturated fatty acids having 12 to 24 carbon atoms and (b) 1 part of aliphatic alcohols having 10 to 20 carbon atoms or their lower alkoxylated products having 1 to 5 alkoxy units.
  • the particles are obtained by spraying a fluid mixture of the components through a nozzle or by a spray disc, and cooling.
  • the stabilized bleaching assistant can be incorporated with percompounds and other washing composition components.
  • Washing compositions which contain, in addition to the usual detergent substances with a cleaning action, builder substances and the so-called bleaching activators causing percompounds to have a bleaching action.
  • These activators are carboxylic acid derivatives which react with the percompounds with formation of peracids and, therefore, increase the bleaching action of the mixtures or make possible bleaching at relatively low washing temperatures.
  • the storage of such washing compositions causes considerable problems, since under the influence of relatively high air humidity, the percompounds and bleaching activators may react with one another even at room temperature, which leads to a loss of active oxygen. If substances susceptible to oxidation are added to the washing compositions, for example, optical brighteners, these may be oxidatively decomposed.
  • An object of the present invention is to develop a composition which is protected against decomposition during storage and has a sufficient solubility in cold water.
  • a further object of the present invention is to develop a stabilized bleaching assistant suitable for use in pulverulent washing and bleaching compositions
  • a stabilized bleaching assistant suitable for use in pulverulent washing and bleaching compositions
  • a yet further object of the present invention is the development of a process for the production of the above stabilized bleaching assistant which consists of dispersing solid particles of said activator for active oxygen in a melt of said mixture of acids and alcohols, forming droplets of said dispersion at least percent of which have a diameter within the range of 0.1 mm to 1 mm by means selected from the group condisting of (1) pressure spraying through a nozzle having an opening having a diameter of from 0.3 mm to 2.5 mm at a pressure of from 10 to 30 kg/cm and (2) spraying from a spray disc rotating at a peripheral speed of from 5 to m/sec, and cooling said droplets without contact below their solidifying temperature.
  • Another object of the invention is the development of pulverulent washing and bleaching compositions containing said stabilized bleaching assistant.
  • a bleaching assistant suitable for use in pulverulent washing and bleaching compositions which comprises drop-shaped to globe-shaped particles of which at least 70 percent have an average diameter of 0.1 to 1 mm, and not more than 30 percent have a diameter of not less than 0.01 and not more than 2.5 mm, and are constituted as follows: 10 percent to 70 percent by weight of at least one compound from the class of N-acyl and O-acyl compounds as well as carbonic acid esters and pyrocarbonic acid esters which act as an activator for percompounds, the activation value of which for the percompounds amounts to more than 3 in the Per-Acid Formation Test and 30 percent to 90 percent by weight of a mixture of substantially saturated fatty acids having 12 to 24 carbon atoms and aliphatic alcohols having 10 to 20 carbon atoms or their lower alkoxylated products in the proportion by weight of 10:1 to 2:1.
  • the alcohols may possibly have up to glycolether groups.
  • the invention comprises a stabilized bleaching assistant suitable for use in pulverulent washing and bleaching compositions comprising dropshaped to globular-shaped particles at least 70 percent of which have a diameter within the range of 0.1 mm to 1 mm consisting essentially of percent to 70 percent by weight of at least one activator for active oxygen derived from compounds yielding H 0 in aqueous solutions having an activating action at least 3 in the Per- Acid Formation Test selected from the group consisting of N-acyl compounds having 2 to 9 carbon atoms in the acyl, O-acyl compounds having 2 to 9 carbon atoms in the acyl, carbonic acid esters and pyrocarbonic acid esters, substantially surrounded by from 30 percent to 90 percent by weight of a mixture of (a) from 2 to 10 parts by weight of said mixture of acids having substantially from 12 to 24- carbon atoms selected from the group consisting of substantially saturated fatty acids, saturated hydroxy fatty acids, and mixtures thereof and (b) 1 part by weight of said mixture of alcohols selected from the group consisting of
  • the bleaching assistants are preferably present in the mixture together with further pulverulent bleaching agent components, especially granular to pelverulent pea-compounds which liberate hydrogen peroxide in aqueous solution. in these mixtures the proportion by weight of the bleaching assistant to the percompound should amount to 1:5 to 5:1 and be chosen so that 0.05 to 2 mols of activator are present per gram atom of active oxygen.
  • compositions useful in the preparation of aqueous coldbleaching baths, especially cold-bleaching washing liquors for textile consist essentially of (I) from 5 percent to 95 percent by weight of the above stabilized bleaching assistant, and (ll) from 5 percent to 95 percent by weight of at least one compound selected from the group consisting of (a) alkali metal builder salts, (b) percompounds giving H 0 in aqueous solutions and stabilizers for percompounds, (c) tensides selected from the group consisting of anionic surface-active compounds, non-ionic surface-active compounds and amphoteric surface-active compounds, (d) optical brighteners, (3) water-soluble organic builder salts, (f) antimicrobial agents, (g) soil suspension agents, (h) enzymes, (i) foam inhibitors, (k) textile softeners, and (l) corrosion inhibitors.
  • the activators for percompounds utilizable according to the invention are certain compounds of the N- acyl and O-acyl type as well as carbonic acid esters of pyrocarbonic acid esters, indicated below under (a) to (0), which have an activation value in the Per-Acid Formation Test of at least 3, preferably at least 4.5.
  • the activation value titre) for the activators is determined in the following way:
  • Solutions which contain 0.615 gin/liter of NaBO H O GH O (4 mlVlol/liter) and 2.5 grn/liter of Na P- 0 -10 R 0, are heated to C, and then are mixed with 4 mMol/liter of activator and maintained at the said temperature for 5 minutes with stirring. Then 100 ml of this liquid is added to a mixture of 250 mg of ice and 15 ml of glacial acetic acid and titrated immediately after addition of 0.35 gm of potassium iodide with 0.1 N sodium thiosulfate solution, using starch as indicator.
  • Activators of the N-acyl or O-acyl compounds type contain an acyl residue R-CO-, in which R represents optionally substituted hydrocarbon residues with 1 to 8 carbon atoms. If the residues R are aliphatic, they preferably have 1 to 3 carbon atoms, and if they are aromatic, they may contain up to 8 carbon atoms. Consequently, the residue R is preferably one of the following: lower alkyl, such as methyl, ethyl, n-propyl or isopropyl; phenyl; alkylphenyl such as toluyl or xylyl residues.
  • Suitable substituents for both aliphatic and aromatic residues are C alkoxy groups, halogen atoms, nitro or nitrile groups; when R is an aromatic residue, it may be chloro and/or nitro-substituted, especially mchloro or in or p-nitro-substituted.
  • Such substituted R residues are, for example, chloroalkyi having 1 to 3 carbon atoms, m-chlorophenyl, p-nitrophenyl, and pmethoxyphenyi.
  • the activators described below compounds with a melting point of at least C, preferably at least C and especially at least 150C, are specially suitable.
  • the equivalent weight of these compounds should be not more than 170, preferably not more than 130 and especially not more than (the equivalent weight is here the quotient of the molecular weight and the number of R-CO- residues present in the molecuie where the compound is N-acylated or O- acylated).
  • N-diacylated amines of the formula I in which X represents a residue R or one of the residues la, lb or Ic.
  • diacetylaniline and N,N-diacetyl-p-toluidine are named as examples.
  • N-acylhydantoins of formula II in which at least one of the residues X and X represent an RCO- residue, while the other may also represent a residue R or a carboxymethyl or a lower alkoxycarbonylmethyl residue; Y and Y represent hydrogen or alkyl residues with l to 2 carbon atoms.
  • Suitable compounds are, for example, l,3-diacetyl-5,5-
  • R preferably signifies a C alkyl residue
  • Activators of this type are, for example, N-methyl-N- mesylacetamide (melting point 73 to 79C), N-methyl- N-mesylbenzamide (m.p. 116 to 118.5C), N-methyl- N-mesyl-p-nitrobenzamide (m.p. 159 to 160C) and N-methyl-N-mesyl-p-methoxybenzamide (m.p. 117 to d.
  • Cyclic N-acylhydrazides of formula IV in which the two nitrogen atoms are part of a 5- or 6-membered hetero ring from the group of maleic acid hydrazide, phthalic acid hydrazide, triazole or urazole.
  • a suitable compound for example, is mono-acetylmaleic acid hydrazide.
  • R represents a residue R, preferably a methyl or ethyl residue, an optionally substituted aryl residue or the group Va
  • X and X represent one of the residues RCO-, R-SO or one of the above-described aromatic residue, or each can be linked with the corresponding residue R or R to give a succinyl or phthalyl residue and n signifies a whole number from to 2.
  • Activators of this type are, for example, O-benzoyl- N,N-succinyl-hydroxylamine (m.p. 137 to 139C), 0- acetyl-N,N-succinyl-hydroxylamine (m.p. 132 to 134C), O-p-methoxybenzoyl-N,N-succinyl-hydroxylamine (m.p. 142 to 145C), O-p-nitrobenzoyl-N,N-suc- 6 cinyl-hydroxylamine (m.p. 212 to 215C) and O,N,N- triacetyl-hydroxylamine. f.
  • N,N-diacyl-sulfurylamides of formula VI in which R6 and R6 preferably represent C alkyl residues or aryl residues such as phenyl, while R and R preferably represent C alkyl residues, especially C alkyl residues.
  • Triacyl-cyanurates of formula VII oc R l H-O-CO-R x,, cH (V111) 0c R To these belong 1,3-diformyl-4,5-diacetoxy-imida2olidine (m.p. 160 to 165.5C), 1,3-diacetyl-4,5- diacetoxy-imidazolidine (m.p. 139 to 140.5C), 1,3- diacety1-4,5-dipropionyloxy-imidazolidine (m.p. 85 to 87C).
  • tetraacylated glycolurils and especially tetraacetylglycoluril are preferably used.
  • tetraacetylglycoluril m.p. 233 to 240C
  • the following acylated glycolurils are suitable:
  • acylated glycolurils are not only of special practical importance on account of their excellent properties as activators, but to their high melting point, they are very suitable for the preparation of pulverulent products which are stable on storage.
  • carboxylic acids as, for example, acetic acid, propionic acid and benzoic acid
  • an activation is already to be noted when amounts of 0.05 mol of activator per gram atom of active oxygen are used. It is preferred to work with 0.1 to 1 mol of activator, but the amount may also be increased to 2 mols of activator per gram atom of active oxygen.
  • Suitable fatty acids which are present in the activator-containing powder particles, as saturated fatty acids and saturated hydroxy-fatty acids having 12 to 24 carbon atoms, as well as their mixtures, such as lauric, myristic, palmitic, stearic, arachidic, behenic and lignoceric acid and also hydroxystearic and dihydroxystearic acids.
  • fatty acids When mixtures of naturally occurring or hydrogenated fatty acids are used, these may also contain some saturated fatty acids with 8 to 10 carbon atoms or some unsaturated fatty acids with 8 to 24 carbon atoms, for example, oleic acid, but the fraction of the low molecular weight acids or unsaturated acids or both should be less than 20 percent by weight and especially less than 10 percent by weight of the total fatty acids persent.
  • the composition of the fatty acid mixtures should preferably be such that the softening point or melting point is above 40C.
  • the substantially saturated aliphatic monohydric alcohols having from 10 to 20 carbon atoms, possibly alkoxylated, present in admixture with the bleaching activator and the fatty acids may be of natural or synthetic origin, such as decyl, lauryl, myristyl, cetyl and arachly (anachidyl) alcohols, and their mixtures, for example, coconut or tallow alcohols, and also 0x0- alcohols or alcohols from paraffin oxidation. Small portions, up to 10 percent, of unsaturated alcohols may be present.
  • the alcohols are preferably saturated.
  • alkoxylated that is, ethoxylated and/or propoxylated
  • the number of alkylene oxide groups, especially ethylene oxide groups should be chosen so that no water-soluble compounds are present, i.e., they shoud not amount to more than 5, preferably not more than 3.
  • Mixtures of non-alkoxylated and alkoxylated alcohols are also useful.
  • saturated fatty alcohols having 12 to 18 carbon atoms and their mixtures are utilized.
  • the proportion by weight of fatty acid to alcohol or ethoxylated alcohol should amount to 10:1 to 2:1, preferably 5:1 to 3:1.
  • the activator-containing particles of the stabilized bleaching assistant of the invention should be present approximately in drop to globular shape and at least percent by weight shoudl have a diameter with the range of 0.1 mm to 1 mm, preferably more than percent by weight, should have an average diameter of 0.1 mm to 1.6 mm.
  • Their composition should be largely homogeneous, and the surface should be smooth.
  • Powder particles which fulfill these requirements are obtainable by homogenizing the bleaching activator, the fatty acid and the possible alkoxylated alcohol at a temperature which lies above the melting points of the fatty acid and the alcohol and preferably below the melting point of the bleaching activator and spraying, for example, by means of a nozzle under high pressure or by a spray disc into a fall space, in which the temperature lies below that of the solidifying point of the mixture of fatty acid and alcohol.
  • the stabilized bleaching assistant is produced by a process which consists of dispersing solid particles of said activator for active oxygen in a melt of said mixture of acids and alcohols, forming droplets of said dispersion at least 70 percent of which have a diameter within the range of 0.1 mm to 1 mm, by means selected from the group consisting of (l) by pressure spraying through a nozzle having an opening having a diameter of from 0.3 mm to 2.5 mm at a pressure of from 10 to 30 kg/cm and (2) spraying from a spray disc rotating at a peripheral speed of from 5 to 150 m/sec., and cooling said droplets without contact below their solidifying temperature.
  • the aperature of the spray nozzle should have a diameter of 0.3 mm to 2.5 mm, preferably 0.6 mm to 1.8 mm.
  • the pressure with which the dispersed melt is fed to the nozzle should amount to to 30, preferably to 25, kg/cm
  • a rotating spray disc which may be provided with round or slot-like orifices, may also be used.
  • the peripheral speed of such a disc which has usually a diameter of 150 to 300 mm, and rotates at 800 to 10,000 revolutions per minute, should be 5 to 150 m/sec., preferably 10 to 100 m/sec.
  • the fall space in which the sprayed particles solidify, suitably consists of a cylindrical chamber, which is fitted with supply lines for cooling air and a discharge divice for the powder, arranged at the conical base of the chamber.
  • the cooling air the temperature of which lies at least 10C below the solidifying temperature of the mixture of fatty acid and alcohol and, for example, ranges from -10 to +40C, may be led in the same direction or countercurrent.
  • the sprayed particles may be naturally cooled.
  • the natural color may be masked or altered.
  • the stabilized bleaching assistants may be present alone, admixture with percompounds or in admixture with pulverulent to granular washing compositions with or without bleaching agents.
  • These washing compositions consist of at least one compound from the class of anionic, amphoteric and non-ionic surface-active compounds, at least one compound from the class of polymeric phosphates, sequestering agents and washing alkalis and at least one compound from the class of optical brighteners.
  • the most suitable percompounds which liberate hydrogen peroxide in aqueous solution are the perhydrates, for example, anhydrous or crystalline sodium perborate, also alkali metal percarbonates, perpyrophosphates and persilicates and urea perhydrate.
  • Sodium perborate tetrahydrate is preferably used.
  • the average particle size of the percompounds and the possibly additionally used powder components should amount to 0.1 to 2 mm.
  • the granular size of the percompounds as well as of possible further powder components is not in itself critical, but should be chosen so that at least 50 percent and preferably more than 80 percent of the particles have a diameter of at least 0.05 and not more than 2.5 mm, in order to prevent a dust formation, on the one hand, and on the other hand, to keep the powder mixture easy to trans port and pourable.
  • Relatively large variations in the grain size of the individual powder components should be avoided in order to prevent an undesired setting of fines and specifically heavier particles to the bottom of the packing container during transport.
  • Preparations which comprise substantially the stabilized bleaching assistant are suitabale for use in the textile industry or in industrial laundries, where they are used together with hydrogen peroxide or solid per compounds and possibly the usual additions for the preparation of the bleaching baths and bleaching washing baths.
  • compositions of the invention contain other constituents usually present in bleaching baths, the composition of such preparation lies approximately in the range of the following formulation:
  • bleaching or bleaching washing compositions 95 percent to 5 percent, preferably 93 percent to 50 percent, by weight of neutral and/or preferably alkaline-reacting builder salts and possibly other constituents usual in bleaching or bleaching washing compositions, such as, for example, surface-active compounds, soil suspension agents, foam stabilizers, dyestuffs and perfumes and so forth.
  • the preparations according to the invention represent specially interesting bleaching compositions for practical purposes, which on dissolving in water give coldbleaching washing liquors, in which the active oxygen is already effective at temperatures from 20 to C, especially 30 to 60C.
  • the ratio of the activator in the stabilized bleaching assistant of the invention to the percompound is always such that from 0.05 to 2 mols, preferably 0. l to 1 mol, of activator is present per gram-atom of active oxygen of the percompound.
  • bleaching compositions contain more than 40 percent by weight of activator and percompound, this quantity relating to the pure activator and the pure percompound without the other constituents of the stabilized bleaching assistant, these preparations are preferably used as bleaching agent concentrates in the textile industry or in industrial laundries.
  • the bleaching compositions of the invention contain up to 40 percent by weight of pure activator and percompound in the above-defined ratios, they are useful as bleaching washing compositions and washing assistants, which are of special practical interest and, therefor, represent a preferred field of application of the present invention.
  • the proportions of activator and percompound constitute together mostly from 5 percent to 40 percent, especially from 10 percent to 35 percent, by weight of the composition.
  • the composition of such bleaching agents generally lies within the range of the following formulation, the constituents of the granulate of the above-defined activator component being distributed according to the formulation in the various categories listed below:
  • a surface-active component containing at least one surface-active compound of the type of the sulfonates, sulfates, soaps, non-ionics and, optionally, one or more of the following substances:
  • non-surface-active foam inhibitors 0 to 10 percent, preferably 0.5 percent to 8 percent, by weight of non-surface-active foam inhibitors
  • bleaching and washing compositions constituents such as, for example, soil suspension agents, textile softeners, enzymes, optical brighteners, dyestuffs and perfumes, water,
  • the activator in the above-defined stabilized bleaching assistant is present in an amount corresponding to 0.05 to 2 mols, preferably 0.1 to 1 mol per gram-atom of active oxygen of the percompound.
  • bleaching fine washing compositions to be used at temperatures up to 70C, the surface-active compound content of which is generally in the range from 8 percent to 40 percent, preferably 12 percent to 40 percent, by weight.
  • these fine washing compositions are not intended for use in washing machines, especially in drum washing machines, they need not also contain foam inhibitors.
  • Bleaching softening or after-rinsing compositions have usually a surface-active compound content of less than 5 percent by weight, and they also need not contain foam inhibitors.
  • the bleaching washing compositions intended for use in washing machines, preferably in drum Washing machines, are of particular practical importance in which the surface-active compound component constitutes usually 7 percent to percent by weight. These mostly contain at least one of the following two types of surface-active compound in the amounts there indicated:
  • the foaming power, however, of the surface-active component being reduced either by simultaneous presence of different surface-active compounds reducing the foaming power and/or foam-inhibiting soap and/or non-surface-active foam inhibitors.
  • the said bleaching washing compositions are generally prepared by mixing the stabilized bleaching assistant according to the invention with granular percompounds and washing compositions which have been obtained by admixing a washing composition powder prepared by hot spray drying. Such cold-bleaching washing compositions are marked by a good stability on storage.
  • compositions according to the invention are described below in more detail according to the class of substance.
  • Suitabale detergent substances which may be used in the washing agent-containing powder components are those anionic surface-active compounds of the sulfonate or sulfate type, for example, alkylbenzenesulfonates, especially n-dodecylbenzenesulfonate, and also olefinsulfonates, such as are obtained, for example, by sulfonation of primary or secondary aliphatic monoolefins with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis, as well as alkylsulfonates, such as are obtainable from nalkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization, or by addition of bisulfite to olefins.
  • Suitable anionic surface-active compounds are alkali metal soaps from fatty acids of natural or synthetic origin, for example, the sodium soaps of coconut, palm kernel or tallow fatty acids.
  • Suitable amphoteric surface-active compounds are alkylbetaines and especially alkylsulfobetaines, for example, 3-(N,N-dimethyl-N-alkylammonium)-propane-l-sulfonate and 3- (N,N-dimethyl-N-alkylammonium)-2-hydroxypropanel -sulfonate.
  • the anionic surface-active compounds may be present as the alkali metal salts such as the sodium and potassium salts and ammonium salts as well as salts of organic bases, for example, lower alkanolamines, such as mono, dior triethanolamines. If the said anionic and amphoteric compounds contain an aliphatic hydrocarbon residue, this should preferably have a straight chain and contain 8 to 22 carbon atoms. in the compounds with an araliphatic hydrocarbon residue, the preferably unbranched alkyl chains contain and average of 6 to 16 carbon atoms.
  • the most important non-ionic surface-active compounds are the polyglycolether derivatives of alcohols, fatty acids and alkylphenols, which contain 3 to 30 ethoxy units, and 8 to 20 carbon atoms in the hydrocarbon residue.
  • Polyglycolether derivatives are particularly suitable in which the number of ethoxy units amounts to 5 to 15 and the hydrocarbon residues of which are derived from straight-chain primary alkanols having 12 to 18 carbon atoms or from alkylphenols having a straight alkyl chain having 6 to 14 carbon atoms.
  • non-ionic surface-active compounds are the water-soluble polyethyleneoxide adducts to polypropyleneglycol, ethylenediaminepolypropyleneglycol and alkylenepolypropyleneglycol with l to 10 carbon atoms in the alkylene chain, which adducts contain 20 to 250 ethoxy units and 10 to propoxy units.
  • the said compounds usually contain 1 to 5 ethoxy units per propoxy unit.
  • Non-ionic compounds of the aminoxide and sulfoxide type which may possibly also be ethoxylated, are also utilizable.
  • alkali metal polymeric phosphates may be contained in the powder component containing washing agents, especially pentasodium tripolyphosphate.
  • the tripolyphosphates may also be present in admixture with higher condensed phosphates, such as tetrapolyphosphates, or their hydrolysis products, such as acid or neutral pyrophosphates.
  • the condensed phosphates may also be replaced wholly or partly by sequestering agents, for example, aminopolycarboxylic acids and their alkali metal salts. These include especially alkali metal salts of nitrilotriacetic acid and ethylenediaminetetraacetic acid. Further, the salts of diethylenetriamine-pentaacetic acid and the higher homologs of the said aminopolycarboxylic acids are suitable.
  • homologs may be prepared, for example, by polymerization of an ester, amide or nitrile of N-acetic acid-aziridine and subsequent saponification to give carboxylic acid or salts or by reaction of polyamines such as polyethyleneimine with a molecular weight of 500 to 10,000 with salts of chloroacetic acids or bromoacetic acids in alkaline me- 2 dium.
  • polyamines such as polyethyleneimine with a molecular weight of 500 to 10,000 with salts of chloroacetic acids or bromoacetic acids in alkaline me- 2 dium.
  • Further suitable aminopolycarboxylic acids are poIy-(N-succinic acid)-ethyleneimine and poIy-(N-tricarballylic acid)-ethyleneimine of average molecular weight 500 to 500,000, which are obtainable similarly to the N-acetic acid derivatives.
  • nitrogen-free compounds may be used as sequestering agents, for example, the water-soluble alkali metal salts, such as potassium and especially sodium salts of polyvalent hydrocarboxylic acids or ethercar-. boxylic acids, such as citric acid, gluconic acid, glucuronic acid and hydroxydiacetic acid, as well as of higher molecular weight polycarboxylic acids, for example, of polymerizates of ethylenic mono-, diand tricarboxylic acids, such as acrylic acid, maleic acid, fumaric acid, itaconic acid, citric acid, aconitic acid, mesaconic acid and methylenemalonic acid.
  • boxylic acids such as citric acid, gluconic acid, glucuronic acid and hydroxydiacetic acid
  • higher molecular weight polycarboxylic acids for example, of polymerizates of ethylenic mono-, diand tricarboxylic acids, such as acrylic acid, maleic acid, fuma
  • Copolymerizates of these carboxylic acids with one another or with other copolymerizable substances as, for example, ethylenically unsaturated hydrocarbons, such as ethylene, propylene, isobutylene and styrene, with ethylenic monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid and 3-butenecarboxylic acid or with other ethylenically unsaturated alcohols, ethers, esters, amides and nitriles, such as vinyl alcohol, allyl alcohol, vinylmethylether, acrolein, vinyl acetate, acrylamide and acrylonitrile, can also be used.
  • ethylenically unsaturated hydrocarbons such as ethylene, propylene, isobutylene and styrene
  • ethylenic monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and 3-butenecarboxylic
  • Copolymerizates from ethylenic mono-, diand tricarboxylic acids and several ethylenically unsaturated compounds of different structure are also suitable.
  • the polymerizates and copolymerizates have an average degree of polymerization of 3 to 6,000 and should contain 1 to 9, preferably 2 to 9, carboxyl groups capable of forming salts, for every 3 monomer units.
  • washing alkalis may be mentioned as further builder salts, such as the alkali metal silicates, especially sodium silicate, in which the ratio of Na O to SiO amounts to 1:35 to 1:1, and also carbonates, bicarbonates and borates of alkali metals such as sodium or potassium.
  • the amount of alkaline-reacting substances including the washing alkalis and phosphates should be such that the pH value of a usable alkali Iiquor amounts to 9 to l l and during the washing process does not fall below values under 8 on account of consumption of alkali through the hydrolysis of the bleaching activator.
  • Increased effects may in many cases be obtained by suitable combination of different surface-active washing substances or builder salts with one another, for example, an improved washing power or a reduced foaming capacity.
  • Such improvements are possible, for example, by combination of anionic with non-ionic and- /or amphoteric surface-active compounds with one anotheror by mixing washing substances of the same type, which differ with respect to their structure in the number of carbon atoms, the number and position of the double bonds or chain branchings in the hydrocarbon residue.
  • Mixtures of inorganic and organic builder salts with a synergistic action may be used or may be combined with the abovementioned mixtures.
  • the washing compositions may also contain optical brighteners, especially derivatives of diaminostilben'edisulfonic acid or their alkali metal salts of the formula wherein R, and R may represent halogen atoms, lower alkoxy groups, the amino group or radicals of aliphatic, aromatic or heterocyclic primary or secondary amines as well as radicals of aminosulfonic acids where the aliphatic radicals, present in the above groups, contain preferably 1 to 4, and particularly 2 to 4 carbon atoms, while the heterocyclic ring systems are primarily rings with 5 or 6 members.
  • aromatic amine radicals preferably aniline, anthranilic acid or anilinesulfonic acid are of interest.
  • Brighteners derived from the diaminestilbene sulfonic acids are mostly used as brighteners for cotton.
  • salts of 4,4'-bis-(2"-anilino-4"-morpholino-l ,3 ,S-triazinyl- 6 '-amino)-stilibene-2,2 -disulfonic acid, or similarly constructed compounds, which instead of the morpholino group contain' 'fa diethanolamine group, a methylamino group or a B-methoxylethylamine group are suitable.
  • suitable brighteners for polyamide fibers are those of the diarylpyrazoline type, for example, l-(p-sulfonamidophenyl)-3-(p-chlorophenyl)-A pyrazoline, as well as similarly constructed compounds which, instead of the sulfonamindo group, contain a carboxymethyl or acetylamino group.
  • substituted aminocoumarins for example, 4-methyl-7-dimethylamino-coumarin or 4-methyl- 7-diethylamino-courmarin
  • substituted aminocoumarins for example, 4-methyl-7-dimethylamino-coumarin or 4-methyl- 7-diethylamino-courmarin
  • the compounds l-(2-benzimidazolyl)-2-( l-hydroxyethyl-2- benzimidazolyl)-ethylene and l-ethyl-3-phenyl-7-diethylamino-carbostyril are useful as polyamide brighten- 15 ers.
  • the compounds 2,5-di-(2-benzoxazolyl)-thiophene, 2-(2 benzoxazolyl)-naphtho-[2,3-b]-thiophene and l,2-di-(5-methyl-2-benzoxazolyl)-ethylene are suitable as brighteners for polyester and polyamide fibers. Brighteners of the substituted diphenylstyril type may also be present. Mixtures of the above-mentioned brighteners may also be used.
  • optical brighteners are present in the products of the invention, particularly in the washing agents, according to the invention, generally in amounts of from 0.05 percent to 1.5 percent, preferably from 0.07 percent to 1 percent by weight.
  • compositions may also contain enzymes from the class of proteases, lipases and amylases or their mixtures.
  • Enzymic substances obtained from strains of bacteria or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are specially suitable.
  • Further constituents which may be contained in the powder components containing washing agents are neutral salts, especially sodium sulfate, antimicrobial substances, such as halogenated phenolethers and thioethers, halogenated carbanilides and salicylanilides, as well as halogenated diphenylmethanes, also stabilizing agents for percompounds, such as magnesium silicate.
  • the washing compositions may contain known foam-inhibiting means, such as saturated fatty acids or their alkali metal soaps with 20 to 24 carbon atoms, higher molecular weight fatty acid esters or triglycerides, trialkylmelamines or dialkyl and tetraalkyl ureas.
  • foam-inhibiting means such as saturated fatty acids or their alkali metal soaps with 20 to 24 carbon atoms, higher molecular weight fatty acid esters or triglycerides, trialkylmelamines or dialkyl and tetraalkyl ureas.
  • the constituents contained in the powder component containing washing agent may be contained in homogeneously composed powder particles. Such powder particles are obtainable, for example, by spray drying or granulation from aqueous concentrates or granulating the remaining constituents on previously formed powders in a known way.
  • the powder component containing washing agent may also consist of granular mixtures, in which the powder particles have a variable composition.
  • a specified fraction of the powder particles may contain the detergent substances and a part of the builder salts and have been obtained by hot spray drying, while a further part of the particles prepared, for example, by granulation, contains the residue of the builder salts and those active substances which decompose, volatilize or lose activity under the conditions of the hot spray drying as, for example, perfumes, biocides and certain foam inhibitors.
  • the proportion by weight of the powder component containing washing agent to the sum of the stabilized bleaching assistant, according to the invention, and percompound should amount to 1:2 to l:l. preferably 111 to :1.
  • the bleaching assistants according to the invention as well as their mixtures with percompounds and/or washing agents are marked by a very high stability on storage, i.e., the decline of the bleaching activity occurs considerably more slowly than with known mixtures.
  • the formation of undersired odorous substances by decomposition of components sensitive to oxidation is thereby avoided.
  • the mixtures show excellent solubility properties, i.e., they are dissolved without residue within a short time on use. This was all the more surprising since neither the fatty acid nor the alcohol are sufficiently quickly soluble in cold alkali solutions. lf, therefore, fatty acid or higher melting fatty alcohols are used alone as coating substances for the bleaching activators, under the same conditions, no solution or only very slow solution takes place.
  • water-soluble ethoxylated alcohols are suitable as coating substances, since they do not improve the stability on storage of the bleaching activators.
  • the preparation of the powder particles is particularly simple in comparison with the known process, in which the bleaching activators are grandulated or coated with coating substances, since the use of solvents for the powders and a recovery of the solvents, always combined with losses, is omitted.
  • EXAMPLE 1 20 parts by weight of stearic acid, 20 parts by weight of palmitic acid and 10 parts by weight of a tallow fatty alcohol, consisting of percent by weight of stearyl alcohol, 35 percent by weight of cetyl alcohol and 5 percent by weight of myristyl alcohol, were melted at 80C and, after addition of 50 parts by weight of tetraacetylglycoluril, the suspension was homogenized.
  • the homogenized melt was sprayed by means of a nozzle with an aperture of 1 mm diameter at a pressure of 20 atmospheres into a spraying chamber.
  • the temperature of the cooling air entering the chamber in countercurrent was 18C, and that of the issuing air 20C.
  • the easily pourable non-adhering sprayed powder had mostly a globular structure and gave the following grain distribution on a screen analysis:
  • the fractional amount of the still active perborate was determined by titration at weekly intervals and from this the half value time t /2 in which the perborate had half decomposed was determined.
  • the stability factor F gives the quotients from the half value time found and the half value time for washing composition according to Experiment A, in which, as described, the bleaching activator was incorporated by addition to the washing composition slurry of the powder component (c).
  • a factor above 1 denotes a better, and one of less than 1 denotes a worse, perborate stabilization.
  • the comparative experiments show that the stability on storage of the compositions according to the invention is greater than that of the comparative samples A and B belonging to the state of the art.
  • the comparative sample E which likewise is not within the state of the art, merely has similarly favorable storage properties.
  • Cotton brighteners, polyamide brighteners, polyester brighteners and their combinations may be used as optical brighteners, depending upon the purpose for which the washing composition according to the invention is to be used.
  • preparations containing enzymes are to be made, 7 percent to 15 percent by weight of commercial products are used which, where solid enzyme concentrates are concerned, are adjusted by the manufacturer to the following activities by addition of inorganic salts, mostly sodium sulfate or sodium tripolyphosphate:
  • a stabilized bleaching assistant suitable for use in pulverulent washing and bleaching compositions comprising drop-shaped to globular-shaped particules at least 70 percent of which have an average diameter within the range of 0.1 mm to 1 mm consisting essentially of percent to 70 percent by weight of at least one activator for active oxygen derived from compounds yielding H O in aqueous solutions having an activating action of at least 3 in the Per-Acid Formation Test selected from the group consisting of N-acyl compounds having 2 to 9 carbon atoms in the acyl, O- acyl compounds having 2 to 9 carbon atoms in the acyl, carbonic acid esters and pyrocarbonic acid esters, substantially surrounded by from 30 percent to 90 percent by weight of a mixture of (a) from 2 to 10 parts by weight of said mixture of acids having substantially from 12 to 24 carbon atoms selected from the group consisting of substantially saturated fatty acids, saturated hydroxy-fatty acids, and mixtures thereof, and (b) 1 part by weight of said mixture of alcohols selected from the group
  • the stabilized bleaching assistant of claim 1 wherein said alcohol is an ethylene oxide adduct of a saturated primary aliphatic alkanol having 12 to 18 carbon atoms adducted with l to 3 ethoxy units.
  • the stabilized bleaching assistant of claim 1 wherein at least percent by weight of said particles have a diameter within the range of 0.1 mm to 1.6 mm.

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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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US382595A 1972-07-31 1973-07-25 Coated bleach activator Expired - Lifetime US3925234A (en)

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AT659472A AT326611B (de) 1972-07-31 1972-07-31 Als bestandteil von pulverförmigen wasch- und bleichmitteln geeignetes bleichhilfsmittel

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Cited By (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4003841A (en) * 1974-08-14 1977-01-18 Henkel & Cie G.M.B.H. Coated stabilized bleach activators, process and washing compositions
US4124734A (en) * 1976-04-30 1978-11-07 Lever Brothers Company Encapsulated particles
US4145183A (en) * 1975-12-19 1979-03-20 E. I. Du Pont De Nemours And Company Method for the oxidative treatment of textiles with activated peroxygen compounds
US4179390A (en) * 1976-10-06 1979-12-18 The Procter & Gamble Company Laundry additive product
US4283301A (en) * 1980-07-02 1981-08-11 The Procter & Gamble Company Bleaching process and compositions
US4367156A (en) * 1980-07-02 1983-01-04 The Procter & Gamble Company Bleaching process and compositions
US4372868A (en) * 1980-03-28 1983-02-08 Henkel Kommanditgesellschaft Auf Aktien Process for the preparation of a stable, readily soluble granulate with a content of bleach activators
US4417994A (en) * 1981-01-24 1983-11-29 The Procter & Gamble Company Particulate detergent additive compositions
US4444674A (en) * 1980-11-06 1984-04-24 The Procter & Gamble Company Granular bleach activator compositions and detergent compositions containing them
US4457858A (en) * 1981-07-17 1984-07-03 Henkel Kommanditgesellschaft Auf Aktien Method of making coated granular bleach activators by spray drying
US4486327A (en) * 1983-12-22 1984-12-04 The Procter & Gamble Company Bodies containing stabilized bleach activators
US4657784A (en) * 1986-03-10 1987-04-14 Ecolab Inc. Process for encapsulating particles with at least two coating layers having different melting points
US4681695A (en) * 1984-09-01 1987-07-21 The Procter & Gamble Company Bleach compositions
US4818425A (en) * 1986-05-28 1989-04-04 Akzo N.V. Process for the preparation of diperoxydodecanedioic acid-containing agglomerates and compositions in which these agglomerates are used as bleaching component
US4988451A (en) * 1989-06-14 1991-01-29 Lever Brothers Company, Division Of Conopco, Inc. Stabilization of particles containing quaternary ammonium bleach precursors
US5055217A (en) * 1990-11-20 1991-10-08 Lever Brothers Company, Division Of Conopco, Inc. Polymer protected bleach precursors
US5124480A (en) * 1989-10-10 1992-06-23 Monsanto Company Peroxygen bleach activators and bleaching compositions
US5130045A (en) * 1987-10-30 1992-07-14 The Clorox Company Delayed onset active oxygen bleach composition
US5183584A (en) * 1989-10-10 1993-02-02 Monsanto Company Peroxygen bleach activators and bleaching compositions
WO1993011869A1 (en) * 1991-12-13 1993-06-24 The Procter & Gamble Company Encapsulation of liquids in microorganisms
US5234616A (en) * 1987-10-30 1993-08-10 The Clorox Company Method of laundering clothes using a delayed onset active oxygen bleach composition
US5496728A (en) * 1991-12-13 1996-03-05 The Procter & Gamble Company Encapsulation of liquids in micro-organisms
US5505740A (en) * 1989-05-04 1996-04-09 The Clorox Company Method and product for enhanced bleaching with in situ peracid formation
US5705091A (en) * 1995-09-11 1998-01-06 The Clorox Company Alkoxylated peracid activators
US5981463A (en) * 1998-06-08 1999-11-09 Noramtech Corporation Anhydrous detergent/bleach composition and method of preparing same
WO2000077160A1 (fr) * 1999-06-16 2000-12-21 Kao Corporation Detergent particulaire
AU2007338863B2 (en) * 2006-08-15 2011-03-24 American Sterilizer Company A one part, solids containing decontamination blend composition
US8729296B2 (en) 2010-12-29 2014-05-20 Ecolab Usa Inc. Generation of peroxycarboxylic acids at alkaline pH, and their use as textile bleaching and antimicrobial agents
US8846107B2 (en) 2010-12-29 2014-09-30 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
US8889900B2 (en) 2010-12-29 2014-11-18 Ecolab Usa Inc. Sugar ester peracid on site generator and formulator
US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9518013B2 (en) 2014-12-18 2016-12-13 Ecolab Usa Inc. Generation of peroxyformic acid through polyhydric alcohol formate
US9845290B2 (en) 2014-12-18 2017-12-19 Ecolab Usa Inc. Methods for forming peroxyformic acid and uses thereof
US9926214B2 (en) 2012-03-30 2018-03-27 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10031081B2 (en) 2013-03-05 2018-07-24 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US10472265B2 (en) 2015-03-26 2019-11-12 Clean Chemistry, Inc. Systems and methods of reducing a bacteria population in high hydrogen sulfide water
US10501346B2 (en) 2012-09-07 2019-12-10 Clean Chemistry, Inc. System and method for generation of point of use reactive oxygen species
US10577698B2 (en) 2011-05-31 2020-03-03 Clean Chemistry, Inc. Electrochemical reactor and process
US10611656B2 (en) 2015-12-07 2020-04-07 Clean Chemistry, Inc. Methods of microbial control
US10875798B2 (en) 2014-09-04 2020-12-29 Clean Chemistry, Inc. Systems and method for oxidative treatment utilizing reactive oxygen species and applications thereof
US10883224B2 (en) 2015-12-07 2021-01-05 Clean Chemistry, Inc. Methods of pulp fiber treatment
US10893674B2 (en) 2013-03-05 2021-01-19 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US11001864B1 (en) 2017-09-07 2021-05-11 Clean Chemistry, Inc. Bacterial control in fermentation systems
US11040902B2 (en) 2014-12-18 2021-06-22 Ecolab Usa Inc. Use of percarboxylic acids for scale prevention in treatment systems
US11260040B2 (en) 2018-06-15 2022-03-01 Ecolab Usa Inc. On site generated performic acid compositions for teat treatment
US11311012B1 (en) 2017-09-07 2022-04-26 Clean Chemistry, Inc. Bacterial control in fermentation systems
US12058999B2 (en) 2018-08-22 2024-08-13 Ecolab Usa Inc. Hydrogen peroxide and peracid stabilization with molecules based on a pyridine carboxylic acid
US12096768B2 (en) 2019-08-07 2024-09-24 Ecolab Usa Inc. Polymeric and solid-supported chelators for stabilization of peracid-containing compositions

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1561333A (en) * 1975-11-03 1980-02-20 Unilever Ltd Bleaching assistants
US4269722A (en) * 1976-09-29 1981-05-26 Colgate-Palmolive Company Bottled particulate detergent
DE2963842D1 (en) 1978-06-26 1982-11-18 Procter & Gamble Particulate detergent additive product
FI67092C (fi) 1980-12-09 1985-01-10 Unilever Nv Blekningsaktivator-korn avsedda foer tvaett- och/eller blekningsblandningar
JPS6096801U (ja) * 1983-12-09 1985-07-02 東京コスモス電機株式会社 スライド形可変抵抗器
US4678594A (en) * 1985-07-19 1987-07-07 Colgate-Palmolive Company Method of encapsulating a bleach and activator therefor in a binder
GB8907100D0 (en) * 1989-03-29 1989-05-10 Unilever Plc Particulate detergent additive product,preparation and use thereof in detergent compositions
GB8925621D0 (en) * 1989-11-13 1990-01-04 Unilever Plc Process for preparing particulate detergent additive bodies and use thereof in detergent compositions
US5480575A (en) * 1992-12-03 1996-01-02 Lever Brothers, Division Of Conopco, Inc. Adjuncts dissolved in molecular solid solutions
US5905067A (en) * 1997-02-10 1999-05-18 Procter & Gamble Company System for delivering hydrophobic liquid bleach activators

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3042621A (en) * 1957-11-01 1962-07-03 Colgate Palmolive Co Detergent composition
US3163606A (en) * 1959-06-19 1964-12-29 Konink Ind Mij Vorheen Noury & Textile bleaching composition
US3441507A (en) * 1965-07-03 1969-04-29 Henkel & Cie Gmbh Bleaching detergents and washing adjuvants
US3459665A (en) * 1965-03-27 1969-08-05 Henkel & Cie Gmbh Bleaching detergents and washing adjuvants
US3519570A (en) * 1966-04-25 1970-07-07 Procter & Gamble Enzyme - containing detergent compositions and a process for conglutination of enzymes and detergent compositions
US3789002A (en) * 1970-10-01 1974-01-29 Henkel & Cie Gmbh Solid, pulverulent to granular compositions containing bleaching activators
US3833506A (en) * 1971-08-02 1974-09-03 Henkel & Cie Gmbh Bleaching assistants and the preparation thereof
US3847830A (en) * 1971-01-27 1974-11-12 Laporte Industries Ltd Stabilizing peroxygen compounds by enveloping in a water-dispersible layer

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3637339A (en) * 1968-03-07 1972-01-25 Frederick William Gray Stain removal

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3042621A (en) * 1957-11-01 1962-07-03 Colgate Palmolive Co Detergent composition
US3163606A (en) * 1959-06-19 1964-12-29 Konink Ind Mij Vorheen Noury & Textile bleaching composition
US3459665A (en) * 1965-03-27 1969-08-05 Henkel & Cie Gmbh Bleaching detergents and washing adjuvants
US3441507A (en) * 1965-07-03 1969-04-29 Henkel & Cie Gmbh Bleaching detergents and washing adjuvants
US3519570A (en) * 1966-04-25 1970-07-07 Procter & Gamble Enzyme - containing detergent compositions and a process for conglutination of enzymes and detergent compositions
US3789002A (en) * 1970-10-01 1974-01-29 Henkel & Cie Gmbh Solid, pulverulent to granular compositions containing bleaching activators
US3847830A (en) * 1971-01-27 1974-11-12 Laporte Industries Ltd Stabilizing peroxygen compounds by enveloping in a water-dispersible layer
US3833506A (en) * 1971-08-02 1974-09-03 Henkel & Cie Gmbh Bleaching assistants and the preparation thereof

Cited By (94)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4003841A (en) * 1974-08-14 1977-01-18 Henkel & Cie G.M.B.H. Coated stabilized bleach activators, process and washing compositions
US4145183A (en) * 1975-12-19 1979-03-20 E. I. Du Pont De Nemours And Company Method for the oxidative treatment of textiles with activated peroxygen compounds
US4124734A (en) * 1976-04-30 1978-11-07 Lever Brothers Company Encapsulated particles
US4179390A (en) * 1976-10-06 1979-12-18 The Procter & Gamble Company Laundry additive product
US4248928A (en) * 1976-10-06 1981-02-03 The Procter & Gamble Company Laundry additive product
US4372868A (en) * 1980-03-28 1983-02-08 Henkel Kommanditgesellschaft Auf Aktien Process for the preparation of a stable, readily soluble granulate with a content of bleach activators
US4367156A (en) * 1980-07-02 1983-01-04 The Procter & Gamble Company Bleaching process and compositions
US4283301A (en) * 1980-07-02 1981-08-11 The Procter & Gamble Company Bleaching process and compositions
US4444674A (en) * 1980-11-06 1984-04-24 The Procter & Gamble Company Granular bleach activator compositions and detergent compositions containing them
US4417994A (en) * 1981-01-24 1983-11-29 The Procter & Gamble Company Particulate detergent additive compositions
US4457858A (en) * 1981-07-17 1984-07-03 Henkel Kommanditgesellschaft Auf Aktien Method of making coated granular bleach activators by spray drying
US4486327A (en) * 1983-12-22 1984-12-04 The Procter & Gamble Company Bodies containing stabilized bleach activators
US4681695A (en) * 1984-09-01 1987-07-21 The Procter & Gamble Company Bleach compositions
US4657784A (en) * 1986-03-10 1987-04-14 Ecolab Inc. Process for encapsulating particles with at least two coating layers having different melting points
US4818425A (en) * 1986-05-28 1989-04-04 Akzo N.V. Process for the preparation of diperoxydodecanedioic acid-containing agglomerates and compositions in which these agglomerates are used as bleaching component
US4919836A (en) * 1986-05-28 1990-04-24 Akzo N.V. Process for the preparation of diperoxydodecanedioic acid-containing agglomerates and compositions in which these agglomerates are used as bleaching component
US5130045A (en) * 1987-10-30 1992-07-14 The Clorox Company Delayed onset active oxygen bleach composition
US5234616A (en) * 1987-10-30 1993-08-10 The Clorox Company Method of laundering clothes using a delayed onset active oxygen bleach composition
US5505740A (en) * 1989-05-04 1996-04-09 The Clorox Company Method and product for enhanced bleaching with in situ peracid formation
US4988451A (en) * 1989-06-14 1991-01-29 Lever Brothers Company, Division Of Conopco, Inc. Stabilization of particles containing quaternary ammonium bleach precursors
US5124480A (en) * 1989-10-10 1992-06-23 Monsanto Company Peroxygen bleach activators and bleaching compositions
US5183584A (en) * 1989-10-10 1993-02-02 Monsanto Company Peroxygen bleach activators and bleaching compositions
US5055217A (en) * 1990-11-20 1991-10-08 Lever Brothers Company, Division Of Conopco, Inc. Polymer protected bleach precursors
WO1993011869A1 (en) * 1991-12-13 1993-06-24 The Procter & Gamble Company Encapsulation of liquids in microorganisms
US5496728A (en) * 1991-12-13 1996-03-05 The Procter & Gamble Company Encapsulation of liquids in micro-organisms
US5705091A (en) * 1995-09-11 1998-01-06 The Clorox Company Alkoxylated peracid activators
US5981463A (en) * 1998-06-08 1999-11-09 Noramtech Corporation Anhydrous detergent/bleach composition and method of preparing same
WO2000077160A1 (fr) * 1999-06-16 2000-12-21 Kao Corporation Detergent particulaire
AU2007338863B2 (en) * 2006-08-15 2011-03-24 American Sterilizer Company A one part, solids containing decontamination blend composition
US12274263B2 (en) 2010-12-29 2025-04-15 Ecolab Usa Inc. Continuous on-line adjustable disinfectant/sanitizer/bleach generator
US11330818B2 (en) 2010-12-29 2022-05-17 Ecolab Usa Inc. Water temperature as a means of controlling kinetics of onsite generated peracids
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US8889900B2 (en) 2010-12-29 2014-11-18 Ecolab Usa Inc. Sugar ester peracid on site generator and formulator
US8933263B2 (en) 2010-12-29 2015-01-13 Ecolab Usa Inc. Water temperature as a means of controlling kinetics of onsite generated peracids
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US9505715B2 (en) 2010-12-29 2016-11-29 Ecolab Usa Inc. Sugar ester peracid on site generator and formulator
US8729296B2 (en) 2010-12-29 2014-05-20 Ecolab Usa Inc. Generation of peroxycarboxylic acids at alkaline pH, and their use as textile bleaching and antimicrobial agents
US9763442B2 (en) 2010-12-29 2017-09-19 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
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US10827751B2 (en) 2010-12-29 2020-11-10 Ecolab Usa Inc. Water temperature as a means of controlling kinetics of onsite generated peracids
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US10477862B2 (en) 2010-12-29 2019-11-19 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
US10010075B2 (en) 2010-12-29 2018-07-03 Ecolab Usa Inc. Water temperature as a means of controlling kinetics of onsite generated peracids
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US9883672B2 (en) 2010-12-29 2018-02-06 Ecolab Usa Inc. Sugar ester peracid on site generator and formulator
US11311011B2 (en) 2010-12-29 2022-04-26 Ecolab Usa Inc. Continuous on-line adjustable disinfectant/sanitizer/bleach generator
US9861101B2 (en) 2010-12-29 2018-01-09 Ecolab Usa Inc. Continuous on-line adjustable disinfectant/sanitizer/bleach generator
US10577698B2 (en) 2011-05-31 2020-03-03 Clean Chemistry, Inc. Electrochemical reactor and process
US9902627B2 (en) 2011-12-20 2018-02-27 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9926214B2 (en) 2012-03-30 2018-03-27 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10017403B2 (en) 2012-03-30 2018-07-10 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing enzymes for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10023484B2 (en) 2012-03-30 2018-07-17 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10501346B2 (en) 2012-09-07 2019-12-10 Clean Chemistry, Inc. System and method for generation of point of use reactive oxygen species
US10875799B2 (en) 2012-09-07 2020-12-29 Clean Chemistry, Inc. System and method for generation of point of use reactive oxygen species
US11939241B2 (en) 2012-10-05 2024-03-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US11180385B2 (en) 2012-10-05 2021-11-23 Ecolab USA, Inc. Stable percarboxylic acid compositions and uses thereof
US10893674B2 (en) 2013-03-05 2021-01-19 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US10031081B2 (en) 2013-03-05 2018-07-24 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US11206826B2 (en) 2013-03-05 2021-12-28 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US11026421B2 (en) 2013-03-05 2021-06-08 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US10875798B2 (en) 2014-09-04 2020-12-29 Clean Chemistry, Inc. Systems and method for oxidative treatment utilizing reactive oxygen species and applications thereof
US11827543B2 (en) 2014-09-04 2023-11-28 Clean Chemistry, Inc. Method for continuous supply of superoxide-containing peracetate oxidant solution
US9845290B2 (en) 2014-12-18 2017-12-19 Ecolab Usa Inc. Methods for forming peroxyformic acid and uses thereof
US10709131B2 (en) 2014-12-18 2020-07-14 Ecolab Usa Inc. Generation of peroxyformic acid through polyhydric alcohol formate
US9518013B2 (en) 2014-12-18 2016-12-13 Ecolab Usa Inc. Generation of peroxyformic acid through polyhydric alcohol formate
US10233149B2 (en) 2014-12-18 2019-03-19 Ecolab Usa Inc. Methods for forming peroxyformic acid and uses thereof
US11040902B2 (en) 2014-12-18 2021-06-22 Ecolab Usa Inc. Use of percarboxylic acids for scale prevention in treatment systems
US10542751B2 (en) 2014-12-18 2020-01-28 Ecolab Usa Inc. Generation of peroxyformic acid through polyhydric alcohol formate
US10834924B2 (en) 2014-12-18 2020-11-17 Ecolab Usa Inc. Generation of peroxyformic acid through polyhydric alcohol formate
US11325887B2 (en) 2014-12-18 2022-05-10 Ecolab Usa Inc. Methods for forming peroxyformic acid and uses thereof
US10433547B2 (en) 2014-12-18 2019-10-08 Ecolab Usa Inc. Generation of peroxyformic acid through polyhydric alcohol formate
US10899707B2 (en) 2014-12-18 2021-01-26 Ecolab Usa Inc. Methods for forming peroxyformic acid and uses thereof
US11772998B2 (en) 2014-12-18 2023-10-03 Ecolab Usa Inc. Use of percarboxylic acids for scale prevention in treatment systems
US11684067B2 (en) 2014-12-18 2023-06-27 Ecolab Usa Inc. Generation of peroxyformic acid through polyhydric alcohol formate
US10941063B2 (en) 2015-03-26 2021-03-09 Clean Chemistry, Inc. Method for down-hole treatment of a production well for sulfur based contaminants
US10472265B2 (en) 2015-03-26 2019-11-12 Clean Chemistry, Inc. Systems and methods of reducing a bacteria population in high hydrogen sulfide water
US11111629B2 (en) 2015-12-07 2021-09-07 Clean Chemistry, Inc. Methods of pulp fiber treatment
US10611656B2 (en) 2015-12-07 2020-04-07 Clean Chemistry, Inc. Methods of microbial control
US11795615B2 (en) 2015-12-07 2023-10-24 Clean Chemistry, Inc. Methods of pulp fiber treatment
US11225755B2 (en) 2015-12-07 2022-01-18 Clean Chemistry, Inc. Methods of paper mill processing using recycled white water with microbial control
US10883224B2 (en) 2015-12-07 2021-01-05 Clean Chemistry, Inc. Methods of pulp fiber treatment
US12215460B2 (en) 2015-12-07 2025-02-04 Clean Chemistry, Inc. Methods of microbial control
US11311012B1 (en) 2017-09-07 2022-04-26 Clean Chemistry, Inc. Bacterial control in fermentation systems
US11001864B1 (en) 2017-09-07 2021-05-11 Clean Chemistry, Inc. Bacterial control in fermentation systems
US11771673B2 (en) 2018-06-15 2023-10-03 Ecolab Usa Inc. On site generated performic acid compositions for teat treatment
US11260040B2 (en) 2018-06-15 2022-03-01 Ecolab Usa Inc. On site generated performic acid compositions for teat treatment
US12058999B2 (en) 2018-08-22 2024-08-13 Ecolab Usa Inc. Hydrogen peroxide and peracid stabilization with molecules based on a pyridine carboxylic acid
US12096768B2 (en) 2019-08-07 2024-09-24 Ecolab Usa Inc. Polymeric and solid-supported chelators for stabilization of peracid-containing compositions

Also Published As

Publication number Publication date
IT991421B (it) 1975-07-30
GB1441416A (en) 1976-06-30
BE802940A (fr) 1974-01-30
ES417385A1 (es) 1976-03-01
FR2194772A1 (enrdf_load_stackoverflow) 1974-03-01
JPS4945107A (enrdf_load_stackoverflow) 1974-04-30
BR7305716D0 (pt) 1974-09-05
AT326611B (de) 1975-12-29
ATA659472A (de) 1975-03-15
ZA735211B (en) 1974-08-28
NL7309263A (enrdf_load_stackoverflow) 1974-02-04
DE2338412C2 (de) 1982-07-08
CA1003160A (en) 1977-01-11
DE2338412A1 (de) 1974-02-14
FR2194772B1 (enrdf_load_stackoverflow) 1978-10-27
CH581691A5 (enrdf_load_stackoverflow) 1976-11-15

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