US3833506A - Bleaching assistants and the preparation thereof - Google Patents

Bleaching assistants and the preparation thereof Download PDF

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Publication number
US3833506A
US3833506A US00276727A US27672772A US3833506A US 3833506 A US3833506 A US 3833506A US 00276727 A US00276727 A US 00276727A US 27672772 A US27672772 A US 27672772A US 3833506 A US3833506 A US 3833506A
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acid
weight
bleaching
mixture
activator
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W Fries
K Hachmann
D Walter
D Jung
P Neuhausen
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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
    • 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 bleaching assistant suitable for use in pulverulent washing and bleaching compositions comprising particulate matter consisting essentially of (A) 10% to 70% by weight of an activator for active oxygen and (B) from 30% to 90% by weight of a mixture of (1) fatty acids and (2) polyethylene glycol.
  • the process of forming this bleaching assistant comprises spraying a homogeneous liquid mixture of the activator, fatty acid and polyethylene glycol into a solidification zone to form particles thereof of which at least 70% have an average diameter of 0.1 to 1 mm.
  • washing compositions which contain so-called bleaching activators in addition to the usual detergent substances having a cleaning action, builder salts and bleaching percompounds are known.
  • These activators comprise carboxylic acid derivatives which react with the percompounds with the formation of peracids and therefore increase the bleaching action of the mixtures or make it possible to elfect bleaching at relatively low washing temperatures.
  • the storage of such washing compositions poses considerable problems, since under the influence of relatively high humidity, the percompounds and bleaching activators can react together even at room temperature, thereby leading to a loss of active oxygen. When substances sensitive to oxygen are present, for example optical brighteners, these may be decomposed by oxidation.
  • washing compositions in which the percompounds are provided with protective coatings or are stored separately from the other washing composition components, in order to exclude a reaction with the other constituents, no difiiculty occurs.
  • the bleaching activators represent very reactive acylation agents, they can react with sensitive washing composition components, for example perfumes or optical brighteners, and impair the properties of these.
  • the powder particles of the bleaching activator should be provided with a coating, in order to suppress a reaction between the activator and percompounds.
  • Suggested coating materials are inorganic, crystalline salts, for example sodium sulfate, high molecular substances such as polyethylene glycol, polyvinyl alcohol and cellulose ethers or fatty substances such as fatty acids, fatty alcohols or fatty acid alkylolamides. In such a case the coating material in solution should be sprayed or granulated on the activator.
  • An object of the invention is to develop a bleaching assistant which is protected against decomposition during storage and has sufiicient solubility to be employed in cold water bleaching baths.
  • the present invention is directed to a bleaching assistant suitable for use in pulverulent washing and bleaching compositions, which comprises particles of which at least 70% have an average diameter of 0.1 to 1 mm. and not more than 30% have a diameter of not less than 0.01 and not more than 2.5 mm., and which particles consist essentially of an intimate mixture containing (A) 10% to 70% by weight of at least one compound acting as an activator for active oxygen 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, said activator having an activating action of at least 3 in the Peracid Formation Test, and (B) 30% to 90% by weight of a mixture consisting essentially of (1) fatty acids consisting of from 80% to 100% by weight of saturated fatty acids having 12 to 24 carbon atoms and saturated hydroxy fatty acids having from 12 to 24 carbon atoms and from
  • the present invention also provides a solid, pulverulent to granular composition useful in the preparation of aqueous cold-bleaching baths, especially cold-bleaching washing liquors for textiles consisting essentially of (I) from 5% to 95% by weight based upon the total weight of the aforesaid bleaching assistant and ('II) from 5% to 95% by weight based upon the total weight of at least one compound selected from the group consisting of (a) alkali metal builder salts, (b) precompounds giving H 0 in aqueous solutions and stabilizers for percompounds, (c) tensides selected from the group consisting of anionic surface-active compounds, nonionic surface-active compounds and amphoteric surface-active compounds, (d) optical brighteners, and (e) Water-soluble organic builder salts.
  • a solid, pulverulent to granular composition useful in the preparation of aqueous cold-bleaching baths, especially cold-bleaching washing liquors for textiles consisting essentially
  • the present invention also provides a process for the preparation of the said bleaching assistant comprising the steps of spraying a homogeneous mixture of said activator, said fatty acid and said polyethylene glycol at a temperature above the melting point of at least one of said ingredients into a zone space at a temperature of at least C. below the solidification point of the mixture, under atomizing conditions whereby particles are formed of which at least 70% have an average diameter of 0.1 to 1 mm. and not more than have a diameter of not less than 0.01 and not more than 2.5 mm.; and collecting said particles.
  • the bleaching assistants are preferably present in admixture with further pulverulent bleaching agent components, especially granular to pulverulent percompounds, which in aqueous solution liberate hydrogen peroxide.
  • the proportion by weight of the bleaching assistant to the percompound should be from 1:5 to 5 :1 and should be chosen so that 0.05 to 2 mol of activator are present per gram atom of active oxygen.
  • the :Peracid Formation Test activation value is determined in the following manner.
  • the equivalent weight of these compounds should be at most 170, preferably at most and especially at most 110.
  • the activators usable according to the invention, include:
  • N-diacylated and N,N'-tetraacylated amines described in the German Pats. 1,162,967 and 1,291,317, such as N,N,N,N'-tetraacetyl-methylenediamine, N,N,N', N'-tetraacetyl-ethylenediamine, N,N-diacetylaniline and N,N-diacetyl-p-toluidine or 1,3-diacylated hydantoins, such as the compounds 1,3-diacetyl-5,5-dimethylhydantoin and 1,3-dipropionyl-hydantoin;
  • N-alkyl-N-sulfonyl-carbonamides described in the British Pat. 1,003,310; for example, the compounds N-methyl-N-mesyl-acetamide, N-methyl-N-mesylbenzamide, -N-methyl-N-mesyl-p-nitrobenzamide and N- methyl-N-mesyl-p-methoxybenzamide;
  • N,N'-diacyl-sulfurylamides described in the German Published Application -DOS 1,801,713, such as N,N-dimethyl-N,N-diacetyl-sulfurylamide and N,N'-diethyl-N,N'-dipropionyl-sulfurylamide;
  • carboxylic acids such as acetic acid, propionic acid, benzoic acid
  • an activation is visible already in using amounts of 0.05 mols of activator per gm.-atm of active oxygen.
  • Preferably 0.1 to 1 mol of activator are used.
  • the amount may, however, be raised up to 2 mols of activator per gm.-atom of active oxygen if desired.
  • Suitable fatty acids which are present in the activatorcontaining powder particles are saturated fatty acids and saturated hydroxy-fatty acids with 12 to 24 carbon atoms, as well as mixtures thereof, such as lauric, myristic, palmitic, stearic, arachidic, behenic and lignoceric acids and the hydroxystearic and dihydroxystearic acids. If mixturesof naturally occurring or hydrogenated fatty acids are used, these may also contain saturated fatty acids with 8 to 10 carbon atoms and unsaturated fatty acids, for example oleic acid, but the fraction of the low-molecular weight and unsaturated acids should be less than 20% by weight and especially less than 10% by weight of the total fatty acids present.
  • the composition of the fatty acid mixtures is preferably such that the softening point or melting point lies above 50 C.
  • the polyethyleneglycols present in admixture with the bleaching activator and the fatty acids should melt at a temperature above 35 C.
  • the proportion by weight of fatty acid to polyethyleneglycol should amount to :1 to 1:4, preferably 3:1 to 1:25.
  • the activator-containing particles should be present approximately in drop form to globular form and have at least 70% by weight, preferably more than 90% by weight with an average diameter of 0.1 to 1 mm. Its composition should be largely homogeneous and the surface should be smooth. Particles of powder which fulfil these conditions, are obtainable by homogenizing the bleaching activator, the fatty acid and the polyglycol at a temperature which lies above the melting point of at least one of the ingredients, and preferably above the melting point of the fatty acid and the polyglycol so as to form a suspension of the bleaching activator. This suspension is then sprayed through a nozzle under high pressure under atomizing conditions into a space zone, the temperature of which lies below the solidification point of the mixture.
  • the aperture of the spray nozzle should have a diameter of 0.3 to 2.5 mm., and preferably from 0.6 to 1.8 mm.
  • the pressure at which the molten material is fed to the nozzle should be to 30 kg./cm. and preferably to kg./ cm.
  • a rotating spray disc may also be used which may be provided with round or slot-like apertures so as to apply an angular velocity to this molten material.
  • the peripheral speed of such a disc which usually has 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 space, in which the sprayed particles solidify preferably comprises a cylindrical chamber which is fitted with supply lines for cooling air and a discharge device for the powder at the conical base of the chamber.
  • the cooling air which has a temperature of at least 10 C. below the solidifying temperature of the mixture and may be for example 10 to C., may be fed in cocurrent or countercurrent.
  • the sprayed particles may have a natural color. This may be 6 masked or altered by addition of dyestuffs or color pigments before the spraying or by dusting the grains obtained with pigments, for example titanium dioxide.
  • the bleaching assistants may be present alone in admixture with percompounds or mixed with pulverulent to granular washing compositions with or without bleaching agents.
  • These washing compositions consist of at least one compound selected from anionic, amphoteric and nonionic detergent substances, at least one compound selected from polymeric phosphates, sequestering agents and washing alkalis, and at least one optical brightener.
  • washing composition compounds it is possible to utilize antimicrobial agents, soil suspension agents, enzymes, foam stabilizers, non-surface-active foam inhibitors, textile softeners, corrosion inhibitors, and water as components in the washing compositions.
  • alkali metal perborates such as sodium perborate containing water of crystallization or anhydrous sodium perborate
  • alkali metal percarbonates, perpyrophosphates and persilicates as well as urea perhydrate.
  • Sodium perborate tetrahydrate is preferably used.
  • the average grain size of the percompounds and the optionally additionally used powder components should be from 0.1 to 2 mm.
  • the grain size of the percompounds as well as optionally further powder components is not critical in itself, but should be so chosen that at least 50% and preferably more than of the grains have a diameter of at least 0.05 and not more than 2.5 mm., so as to prevent dust on the one hand, and on the other hand to keep the powder mixture easily transportable and pourable. Relatively large deviations in the grain size of the single powder components should be avoided in order to avoid the unwanted settling of fine and specifically heavy grains at the bottom of the packing containcr during transportation.
  • Uniting of the different powder components into a homogeneous powder mixture or the addition of further powder constituents is effected in known way with the usual mixing devices, while the shape and size of the individual constituents should be preserved as far as possible.
  • Detergent compositions are usually comprised by a mixture containing from 5% to by weight based on the total detergent composition weight of the above described bleaching assistant and from 5% to 95% by weight based upon the total detergent composition weight of suitable detergent substances. Suitable detergent ingredient substances may be further contained in the washing composition containing the bleaching assistant powder component.
  • the anionic, amphoteric or non-ionic tensides contain in the molecule at least one hydrophobic residue mostly containing 8 to 26, preferably 10 to 22 and especially 10 to 18, carbon atoms and at least one anionic, non-ionic or amphoteric water-solubilizing group.
  • the preferably saturated hydrophobic residue is mostly aliphatic, but possibly also alicyclic in nature. It may be combined directly with the water-solubilizing group or through intermediate members.
  • Suitable intermediate members are, for example, benzene rings, carboxylic acid ester or carboxylic acid amide groups, residues of polyhydric alcohols linked in ether or ester-like form, such as, for example, those of ethylene glycol, propylene glycol, glycerine or corresponding polyether residues.
  • the hydrophobic residue is preferably an aliphatic hydrocarbon residue with 10 to 18, preferably 12 to 18, carbon atoms but deviations from the preferred range of carbon atoms are possible, depending on the nature of the surface-active compound in question.
  • the anionic tenside may be present in the form of their alkali metal salts, such as sodium and potassium, ammonium salts and salts of organic bases such as mono-, diand triethanolamines.
  • Soaps from natural or synthetic fatty acids, possibly also from resin or naphthenic acids, are utilizable as anionic detergent substances, especially when these acids have iodine values of not more than 30, and preferably of less than 10, for example the sodium soaps f coconut, palm kernel or tallow fatty acids.
  • the sulfonates and sulfates possess special practical importance.
  • the sulfonates include, for example, the alkylaryl sulfonates, especially alkylbenzene sulfonates, which are obtained from preferably straight-chain aliphatic hydrocarbons having 9 to 15, especially to 14 carbon atoms, by chlorinating and alkylating benzene or from corresponding terminal or non-terminal olefins by alkylation of ben- Zene and sulfonation of the alkylbenzenes obtained.
  • alkylaryl sulfonates especially alkylbenzene sulfonates, which are obtained from preferably straight-chain aliphatic hydrocarbons having 9 to 15, especially to 14 carbon atoms, by chlorinating and alkylating benzene or from corresponding terminal or non-terminal olefins by alkylation of ben- Zene and sulfonation of the alkylbenzenes obtained.
  • aliphatic sulfonates are of interest, such as are obtainable, for example, from preferably saturated hydrocarbons containing 8 to 18 and preferably 12 to 18 carbon atoms in the molecule by sulfochlorination with sulfur dioxide and chlorine or sulfoxidation with sulfur dioxide and oxygen, and conversion of the products thereby obtained into the sulfonates.
  • aliphatic sulfonates mixtures containing alkene sulfonates, hydroxyalkane sulfonates and disulfonates are useful, which are obtained from terminal or non-terminal C and preferably C olefins by sulfonation with sulfur trioxide and acid or alkaline hydrolysis or the sulfonation products.
  • the sulfonate group is frequently found attached to a secondary carbon atom; however, sulfonates with a terminal sulfonate group obtained by reaction of terminal olefins with bisulfite can also be used.
  • salts preferably dialkali metal salts of a-sulfo-fatty acids, and salts of esters of these acids with monoor poly-hydric alcohols containing 1 to 4, and preferably l to 2 carbon atoms belong to the sulfonates to be used according to the invention.
  • sulfonates are salts of fatty acid esters of hydroxyethanesulfonic acid or dihydroxypropane sulfonic acid, the salts of the fatty alcohol esters of lower aliphatic or aromatic sulfomonoor di-carboxylic acids containing 1 to 8 carbon atoms, alkylglycerylether sulfonates and the salts of the amide-like condensation products of fatty acids or sulfonic acids with aminoethanesulfonic acid.
  • fatty alcohol sulfates especially those prepared from coconut fat alcohols, tallow fat alcohols or oleyl alcohol.
  • Useful sulfonation products of the sulfate type are also obtainable from terminal or non-terminal C olefins.
  • Sulfated fatty acid alkylolamides or fatty acid monoglycerides and sulfated alkoxylation products of alkylphenols (C alkyl), fatty alcohols, fatty acid amides or fatty acid alkylolamides, which may contain in the molecule 0.5 to 20, preferably 1 to 8 and especially 2 to 4 ethylene and/or propylene glycol residues, also belong to this group of surface-active compounds.
  • Suitable anionic surface-active compounds of the carboxylate type are the fatty acid esters or fatty alcohol ethers of hydroxycarboxylic acids, and the amide-like condensation products of fatty acids or sulfonic acids with aminocarboxylic acids, for example, with glycocoll, sarcosin or protein hydrolysates.
  • non-ionic surface-active compounds here called non-ionics, for the sake of simplicity, include products which owe their solubility in water to the presence of polyether chains, amineoxide, sulfoxide or phosphineoxide groups, alkylolamide groups and very generally, to an accumulation of hydroxyl groups.
  • fatty amines, fatty acid and sulfonic acid amides are of special practical interest. These non-ionics may contain per molecule 4 to 100, preferably 6 to 40 and especially 8 to 20 ether residues, particularly ethylene glycol ether residues. Moreover, propylene or butylene glycol ether residues or polyether chains may be present in or at the ends of these polyether residues.
  • products known by the trade name of Pluronics of Tetronics belong to the non-ionics. They are obtained from water-insoluble polypropylene glycols or from water-insoluble propoxylated lower aliphatic alcohols containing 1 to 8, preferably 3 to '6 carbon atoms and/or from water-insoluble propoxylated alkylenediamines. These water-insoluble (i.e. hydrophobic) propylene oxide derivatives are converted into the said non-ionics by ethoxylation until they become soluble in water. Finally, the reaction products of the above-mentioned aliphatic alcohols with propylene oxide known as Ucon- Fluid some of which are still water-soluble, are useful as non-ionics.
  • Ucon- Fluid some of which are still water-soluble
  • the non-ionics also include fatty acid or sulfonic acid alkylolamides which are derived, for example, from monoor di-ethanolamine, dihydroxypropylamine or other polyhydroxyalkylamines, for example the glycamines. They can be replaced by amides from higher primary or secondary alkylamines and polyhydroxycarboxylic acids.
  • the surface-active amineoxides include, for example, the products derived from higher tertiary amines having a hydrophobic alkyl residue and two shorter alkyl and/ or alkylol residues containing up to 4 carbon atoms each.
  • Suitable as non-ionic dispersing agents are possibly nonsurface-active water-soluble compounds or compounds emulsifiable or dispersible in water, such as, for example, fatty acid part glycerides and also compounds which do not contain hydrophobic residues within the meaning of the above-described surface-active compounds, as for example, solid or liquid polyethylene glycols, ethylene 0X- ide adducts of glycerine and other polyalcohols.
  • the preferred non-ionic surface-active detergent substances are polyglycolether derivatives of alcohols, fatty acids and alkylphenols which contain 3 to 30 glycolether groups and 8 to 20 carbon atoms in the hydrocarbon residue.
  • Polyglycolether derivatives in which the number of ethyleneglycolether groups is from 5 to 15 and the hydrocarbon residues of which are derived from straight-chain primary alcohols with 12 to 18 carbon atoms or from alkylphenols with a straight alkyl chain containing 6 to 14 carbon atoms, are specially suitable. Washing agents which are marked by a particularly low foaming power may be obtained by the addition of 3 to 15 mol of propylene oxide to the last-mentioned polyethyleneglycolether or by conversion into the acetals.
  • non-ionic washing substances are the water-soluble polyethylene oxide adducts of polypropyl ene glycol, ethylenediaminopolypropyleneglycol and alkylpolypropyleneglycol, with l to 10 carbon atoms in the alkyl chain, containing 20 to 250 ethyleneglycolether groups and 10 to propyleneglycolether groups.
  • the said compounds usually contain 1 to 5- ethylene-glycol units per propyleneglycol unit.
  • Non-ionic compounds of the amine oxide and sulfoxide type which if desired may also be ethoxylated, are also useful.
  • Amphoteric surface-active compounds contain the molecule both acid and basic hydrophilic groups. Carboxyl, sulfonic acid, sulfuric acid half ester, phosphonic acid and phosphoric acid partial ester groups are the acid groups. Basic groups include primary, secondary, tertiary and quaternary ammonium groups, Amphoteric compounds -with quaternary ammonium groups belong to the betaine type.
  • Carboxy, sulfate and sulfonate betaines have particular practical interest on account of their good compatibility with other surface-active compounds.
  • Suitable sulfobetaines are obtained, for example, by reacting tertiary amines containing at least one hydrophobic alkyl residue with sultones, for example, propaneor butane-sultone.
  • Corresponding carboxybetaines are obtained by reacting the said tertiary amines with chloroacetic acid, or its salts or with chloroacetic acid esters and splitting the ester linkage.
  • polymeric phosphates especially pentasodium triphosphate
  • the triphosphates may also be present in admixture with higher condensed phosphates such as tetraphosphates, or their hydrolysis products such as acid or neutral pyrophosphates.
  • the condensed phosphates may also be Wholly or partly replaced by sequestering agents, for example aminopolycarboxylic acids.
  • aminopolycarboxylic acids include alkali metal salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid.
  • the salts of diethylenetriaminopentaacetic acid and the higher homologues of the said aminopolycarboxylic acids are suitable.
  • These homologues may be prepared, for example by polymerization of an ester, amide or nitrile of N-acetic acid aziridine followed by subsequent saponification to form carboxylic acid salts or by reaction of polyamines having a molecular weight of 500 to 10,000 with salts of chloracetic acids or bromacetic acids in an alkaline medium.
  • aminopolycarboxylic acids are poly-(N-succinic acid)-ethyleneimines and poly-(N-tricarballylic acid)-ethyleneimines of average molecular weight 500 to 500,000, which are obtainable in an analogous way to the N-acetic acid derivatives.
  • nitrogen-free compounds can be used as sequestering agents, for example the water-soluble potassium and especially sodium salts of polyvalent hydroxycarboxylic acids or ethercarboxylic acids, such as citric acid, gluconic acid, glucuronic acid and hydroxydiacetic acid, and also of higher molecular weight polycarboxylic acids, for example polymerizates of ethylenically unsaturated mono-, di and tri-carboxylic acids such as acrylic acid, maleic acid, fumaric acid, itaconic acid, citric acid, aconitic acid, mesaconic acid and methylenemalonic acid.
  • polyvalent hydroxycarboxylic acids or ethercarboxylic acids such as citric acid, gluconic acid, glucuronic acid and hydroxydiacetic acid
  • polymerizates of ethylenically unsaturated mono-, di and tri-carboxylic acids such as acrylic acid, maleic acid, fumaric acid, itaconic acid, cit
  • copolymerizates of these carboxylic acids with one another or with other copolymerizable substances for example olefinic hydrocarbons such as ethylene, propylene, isobutylene and styrene, with olefinic monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and B-butene-carboxylic acid, or with other olefinic alcohols, ethers, esters, amides and nitriles such as vinyl alcohol, allyl alcohol, vinylmethylether, acrolein, vinyl acetate, acrylamide and acrylonitrile.
  • olefinic hydrocarbons such as ethylene, propylene, isobutylene and styrene
  • monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and B-butene-carboxylic acid
  • other olefinic alcohols, ethers, esters, amides and nitriles
  • Copolymerizates from olefinic mono-, diand tricarboxylic acids and polyolefinic compounds of various structure are also suitable.
  • the polymerizates and copolymerizates have an average degree of polymerization of 3 to 6000 and should contain 1 to 9, preferably 2 to 9 (referred to 3 monomer units) carboxyl groups capable of forming .salts.
  • Builder salts which may be used are the so-called washing alkalis such as alkali metal silicates, especially sodium silicates, in which the proportion of Na O to SiO is from 1:35 to 1:1, and also carbon-ates, 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 utilizable liquor is from 9 to 11 and during the washing process does not fall below 8 owing to consumption of alkali by the hydrolysis of the bleaching activator.
  • Increased activity for example an improved washing power or a reduced foaming power, may be obtained in many cases by suitable combination of dilferent surfaceactive washing substances or builder salts with one another.
  • Such improvements are possible, for example by a combination of anionic with non-ionic and/or amphoteric compounds with one another or by mixtures of washing substances of the same type, which in regard to their structure differ in the number of carbon atoms, the number and position of double bonds or chain branchings in the hydrocarbon residue.
  • mixtures of inorganic and organic builder salts having a synergistic action may be used or may be combined with the aforementioned mixtures.
  • the washing compositions may contain known foam-inhibiting substances such as saturated fatty acids or their alkali metal soaps having 20 to 24 carbon atoms, higher molecular weight fatty acid esters or triglycerides, trialkylmelamines or dialkylor tetraalkylnreas.
  • optical brighteners are the diaminostilbene sulfonic acid derivatives of the general formula in which A represents hydrogen, sodium, potassium, ammonium or an ammonium group derived from an organic base, for example, mono-, diand tri-ethanolamine or morpholine, and in which 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 diaminostilbene sulfonic acids are mostly used as brighteners for cotton.
  • the following products, derived from formula I, are commercially available, where R and R may be the same or different and represent Some of the brighteners are, in regard to their fiber affinity, to be considered as transitional types to the polyamide brighteners, such as when the brightener has R equal to NHC H
  • To the cotton brighteners of the diaminostilbene sulfonic acid type also belongs the compound 4,4-bis-(4-phcnyl-vicinal-triazolyl-2) stilbene disulfonic acid-2,2.
  • R is an anilino and R is a methylamino, diethanolamino, methoxyethylamino or morpholino group
  • Mixtures of the aforementioned brighteners are also suitable, for example combinations of a compound in which R represents an anilino group and R a morpholino group with a second compound in which R represents an anilino group and R a methylamino, methoxyethylamino or methoxypropylamino group.
  • the optical brighteners are preferably present as their sodium salts.
  • optical brighteners are those of the carbostyril, N-dialkylaminocoumarin, thiophen-bis-benzoxazole and ethylene-bis-benzoxazole type. Mixtures of such brighteners with the above mentioned brighteners of the triazinylstilbenedisulfonic acid type are also suitable.
  • 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% to 1.5%, preferably from 0.07% to 1% by weight.
  • neutral salts especially sodium sulfate
  • bacteriostatic substances such as halogenated phenolethers and thioethers, halogenated carbanilides and salycylanides and halogenated diphenylmethanes, and also stabilizers for percompounds such as magnesium silicate.
  • Known greying inhibitors especially sodium cellulose glycollate (carboxymethylcellulose) may be added to increase the dirt-carrying power.
  • the powder component of the washing compositions are preferably in the form of homogeneous particles.
  • Such particles for example, are obtainable by spray drying or granulation from aqueous concentrates or preformed powders and granulation of the other constituents thereof in known manner.
  • the powder component may also consist of granular mixtures, in which the powder particles have a variable composition.
  • a certain fraction of the powder particles may contain the detergent substances and a part of the builder salts and may have been obtained by hot spray drying, while a further part of the particles, for example prepared 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 components to the sum of bleaching assistants and percompound according to the invention may be from 1:2 to 10:1, preferably from 1:1 to 5:1.
  • the bleaching assistant according to the invention as Well as their mixtures with percompounds and/or washing compositions are marked by a very high stability on storage, i.e. the decrease of the bleaching activity takes place considerably more slowly than with known mixtures. The formation of undesired odors by decomposition of components sensitive to oxidation is thereby avoided.
  • the mixtures show good solubility properties, i.e. when used in fully automatic washing machines during the rinsing process, they dissolve in a short time without leaving a residue.
  • the preparation of the powder particles is readily accomplished, as compared with the known process in which the bleaching activators are granulated or coated with coating substances, since it is not necessary in the present invention to use solvents for the powder or to recover the solvents, which are always combined into the resulting prior art losses.
  • Another advantage of the present invention over the known processes is that the melt of fatty acid, polyglycol and bleaching activator specifically utilized for the spraying has little or no tendency to separate into the components of the mixture. After the mixing, therefore, it can be stored and transported or conveyed in pipe lines over a relatively long time, i.e. more than an hour, without any problems occurring through the settling or deposition of the constituents.
  • fatty acids are used exclusively as the carrier for the bleaching activator instead of the mixture consisting of fatty acid and polyglycol, a substantial separation of the melt into its substituents occurs within a few minutes resulting in the deposition of the bleaching activator.
  • Molten mixtures of polyglycol and bleaching activator also separate within a short time. Such mixtures have the disadvantage, moreover, that the sprayed particles stick together and therefore the sprayed material is not sufiiciently flowable.
  • the powder particles of the present invention are sutficiently soluble as well as quickly soluble in cold or moderately warm washing liquors; and this solubility is of special importance for their use in wash- 12 ing machines with programmed working cycles.
  • the bleaching activators enclosed in the particles are protected against decomposition, especially by oxidizing agents or moisture, and do not undergo any loss of effectiveness even after prolonged periods of storage.
  • EXAMPLE 1 46 parts by weight of a fatty acid mixture consisting of 94% by weight of stearic acid and 6% by weight of palmitic acid and 17 parts by weight of a polyethyleneglycol of molecular weight 10,000 (melting point 63 C.) were melted at C. and were homogenized after the addition of 37 parts by weight of tetraacetylglycoluril. The melt, which had a viscosity of 340 cp. at 80 C. and which at this temperature showed no tendency to separate into its components over a period of 30 minutes, was sprayed through a nozzle with an aperture diameter of 1 mm. at a pressure of 20 atm. into a spraying chamber.
  • the tem perature of the cooling air passing in counter current was 19 C. on entry and that of the issuing air 21 C.
  • the easily pourable nonadhering sprayed powder had mostly a spherical structure and on a screen analysis gave the following grain size distribution:
  • the average grain size was 0.6 mm.
  • EXAMPLE 3 27 parts by weight of the sprayed product (a) prepared according to Example 1 were mixed with 10 parts by weight of sodium perborate tetrahydrate (b) with a weight per liter of 1000 g. and an average grain size of 0.3 mm. and with 63 parts by Weight of a washing composition mixture (c) obtained by hot spray drying, the weight per liter of which was 420 g. and the average grain size was 0.65 mm.
  • the finished powdered mixture had the following composition (quantities in weight percent):
  • the results Water 7.5 are shown in the following Table.
  • the mixture was filled into folding boxes, 650 g. per box and stored at and 70% relative humidity. During the observation period of 10 weeks no decline in the available active oxygen took place.
  • COMPARATIVE EXAMPLES 3(A) to 3 (E) For comparative purposes the packages were stored in a conditioning cabinet at C. and 80% relative humidity. In a first comparative experiment 3(A) a washing composition of the same composition was used, in which, however, the tetraacetylglycoluril was not melted with the powder particles consisting of fatty acid and polyglycol, but was added to the mixture (c) before the spraying of the liquid concentrate (slurry).
  • a process for the preparation of bleaching assistants suitable for use in pulverulent washing and bleaching compositions having particles consisting essentially of an intimate mixture containing (A) 10% to 70% by weight of at least one compound acting as an activator for active oxygen 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, said activator having an activating action of at least 3 in the P'eracid Formation Test, and (B) 30% to 90% by weight of a mixture consisting essentially of (1) fatty acids consisting of from 80% to 100% by weight of saturated fatty acids having 12 to 24 carbon atoms and saturated hydroxy fatty acids having 12 to 24 carbon atoms and from to 20% by weight of a mixture of saturated fatty acids having from 8 to 10 carbon atoms and unsaturated fatty acids having 12 to 24 carbon atoms and (2) a polyethylene glycol with an average molecular weight of
  • a bleaching assistant suitable for use in pulverulent washing and bleaching compositions produced by the process of claim 1.
  • the bleaching assistant of claim 2 in which at least by weight of the powder particles have a diameter of 0.1 to 1.6 mm.
  • a solid, pulverulent to granular composition useful in the preparation of aqueous cold-bleaching baths, especially cold-bleaching washing liquors for textiles consisting essentially of (I) from 5% to by weight based upon the total weight of the bleaching assistant of claim 2 and (II) from 5% to 95 by weight based upon the total 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, nonionic surface-active compounds and amphoteric surface-active compounds, ((1) optical brighteners, and (e) water-soluble organic builder salts.
  • composition of claim 7, in which the weight ratio of the bleaching assistant to the percompound is from 1:5 to 5:1 and is chosen so that 0.05 to 2 mol of activator is present per gram atom of active oxygen.
  • composition of claim 8 in which 0.1 to 1 mol of activator is present per gram atom of active oxygen.
  • composition of claim 9 in which the percompound is selected from the group consisting of anhydrous sodium perborate and sodium perborate containing water of crystallization.
  • a process for the preparation of bleaching assistants suitable for use in pulverulent washing and bleaching compositions having particles consisting essentially of an intimate mixture containing (A) 10% to 70% by weight of at least one compound acting as an activator for active oxygen 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, said activator having an activating action of at least 3 in the Peracid Formation Test, and (B) 30% to 90% by weight of a mixture consisting essentially of (1) fatty acids consisting of from 80% to 100% by weight of saturated fatty acids having 12 to M carbon atoms and saturated hydroxy fatty acids having 12 to 24 carbon atoms and from 0% to 20% by weight of a mixture of saturated fatty acids having from 8 to 10 carbon atoms and unsaturated fatty acids having 12 to 24 carbon atoms and (2) a polyethylene glycol with an average molecular weight

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US00276727A 1971-08-02 1972-07-31 Bleaching assistants and the preparation thereof Expired - Lifetime US3833506A (en)

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DE2138584A DE2138584C3 (de) 1971-08-02 1971-08-02 Zur Verwendung in Waschmitteln geeignetes lagerbeständiges Bleichmittel und Verfahren zu dessen Herstellung
DE2207974A DE2207974A1 (de) 1971-08-02 1972-02-21 Zur verwendung in wasch- und bleichmitteln geeignetes bleichhilfsmittel und verfahren zu dessen herstellung

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CA (1) CA991363A (en:Method)
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DE (2) DE2138584C3 (en:Method)
FR (1) FR2148203B1 (en:Method)
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3925234A (en) * 1972-07-31 1975-12-09 Henkel & Cie Gmbh Coated bleach activator
US3975280A (en) * 1974-03-21 1976-08-17 Henkel & Cie G.M.B.H. Storage-stable, readily-soluble detergent additives, coating compositions and process
US4003841A (en) * 1974-08-14 1977-01-18 Henkel & Cie G.M.B.H. Coated stabilized bleach activators, process and washing compositions
US4078099A (en) * 1976-08-25 1978-03-07 Lever Brothers Company Encapsulated bleaches and methods for their preparation
US4290903A (en) * 1978-06-26 1981-09-22 The Procter & Gamble Company Packaged free flowing bleach activator product
US4457858A (en) * 1981-07-17 1984-07-03 Henkel Kommanditgesellschaft Auf Aktien Method of making coated granular bleach activators by spray drying
US4545784A (en) * 1983-04-14 1985-10-08 Interox Chemicals Limited Particulate sodium perborate monohydrate containing adsorbed activator
US4681695A (en) * 1984-09-01 1987-07-21 The Procter & Gamble Company Bleach compositions
US4988451A (en) * 1989-06-14 1991-01-29 Lever Brothers Company, Division Of Conopco, Inc. Stabilization of particles containing quaternary ammonium bleach precursors
US5002691A (en) * 1986-11-06 1991-03-26 The Clorox Company Oxidant detergent containing stable bleach activator granules
US5055217A (en) * 1990-11-20 1991-10-08 Lever Brothers Company, Division Of Conopco, Inc. Polymer protected bleach precursors
US5112514A (en) * 1986-11-06 1992-05-12 The Clorox Company Oxidant detergent containing stable bleach activator granules
US5269962A (en) * 1988-10-14 1993-12-14 The Clorox Company Oxidant composition containing stable bleach activator granules
US20050065054A1 (en) * 2003-05-30 2005-03-24 Manske Scott D. Detergent formulations containing alkaline peroxide salts and organic acids

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IE49996B1 (en) * 1979-07-06 1986-01-22 Unilever Ltd Particulate bleach compositions
US4333844A (en) * 1979-11-12 1982-06-08 Lever Brothers Company Detergent compositions
IE51848B1 (en) * 1980-11-06 1987-04-15 Procter & Gamble Bleach activator compositions,preparation thereof and use in granular detergent compositions
ATE12517T1 (de) 1980-12-09 1985-04-15 Unilever Nv Bleichmittelaktivatorgranulate.
FR2519035A1 (fr) * 1981-12-28 1983-07-01 Rhone Poulenc Fibres Produit textile type file de fibres, procede et dispositif pour sa fabrication
ZA851897B (en) * 1984-04-02 1986-10-29 Colgate Palmolive Co Non-caking bleaching detergent composition containing a lower hydrate of sodium perborate
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
US5905067A (en) * 1997-02-10 1999-05-18 Procter & Gamble Company System for delivering hydrophobic liquid bleach activators

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3925234A (en) * 1972-07-31 1975-12-09 Henkel & Cie Gmbh Coated bleach activator
US3975280A (en) * 1974-03-21 1976-08-17 Henkel & Cie G.M.B.H. Storage-stable, readily-soluble detergent additives, coating compositions and process
US4003841A (en) * 1974-08-14 1977-01-18 Henkel & Cie G.M.B.H. Coated stabilized bleach activators, process and washing compositions
US4078099A (en) * 1976-08-25 1978-03-07 Lever Brothers Company Encapsulated bleaches and methods for their preparation
US4290903A (en) * 1978-06-26 1981-09-22 The Procter & Gamble Company Packaged free flowing bleach activator product
US4457858A (en) * 1981-07-17 1984-07-03 Henkel Kommanditgesellschaft Auf Aktien Method of making coated granular bleach activators by spray drying
US4545784A (en) * 1983-04-14 1985-10-08 Interox Chemicals Limited Particulate sodium perborate monohydrate containing adsorbed activator
US4681695A (en) * 1984-09-01 1987-07-21 The Procter & Gamble Company Bleach compositions
US5002691A (en) * 1986-11-06 1991-03-26 The Clorox Company Oxidant detergent containing stable bleach activator granules
US5112514A (en) * 1986-11-06 1992-05-12 The Clorox Company Oxidant detergent containing stable bleach activator granules
US5269962A (en) * 1988-10-14 1993-12-14 The Clorox Company Oxidant composition containing stable bleach activator granules
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
US20050065054A1 (en) * 2003-05-30 2005-03-24 Manske Scott D. Detergent formulations containing alkaline peroxide salts and organic acids

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CA991363A (en) 1976-06-22
AT326612B (de) 1975-12-29
AR192661A1 (es) 1973-02-28
DE2138584C3 (de) 1980-08-28
FR2148203B1 (en:Method) 1976-05-14
DE2138584B2 (de) 1980-01-03
IT965731B (it) 1974-02-11
CH579146A5 (en:Method) 1976-08-31
BE786985A (fr) 1973-01-31
DE2138584A1 (de) 1973-02-22
GB1398785A (en) 1975-06-25
NL7209314A (en:Method) 1973-02-06
DE2207974A1 (de) 1973-09-06
ATA664272A (de) 1975-03-15
FR2148203A1 (en:Method) 1973-03-11
SE415034B (sv) 1980-09-01

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