US3789002A - Solid, pulverulent to granular compositions containing bleaching activators - Google Patents

Abstract

SOLID, PULVERULENT TO GRANULAR COMPOSITIONS USEFUL FOR THE PREPARATION OF AQUEOUS COLD-BLEACHING BATHS, ESPECIALLY COLD-BLEACHING WASHING LIQUORS FOR TEXTILES COMPRISING (A) FROM 5% TO 100% BY WEIGHT OF AN ACTIVATOR COMPONENT CONSISTING OF AN ACTIVATOR FOR PRE-COMPOUNDS IN THE FORM OF PARTICLES SURROUNDED WITH A COATING SUBSTANCE INERT TO THE ACTIVATOR, SELECTED FROM THE GROUP CONSISTING OF WATER-SOLUBLE COMPOUNDS AND WATER-INSOLUBLE COMPOUNDS, SAID ACTIVATOR CONSTITUTING FROM 5% TO 50%, PREFERABLE 15% TO 40% BY WEIGHT, AND SAID COATING SUBSTANCE CONSTITUTING FROM 50% TO 95%, PREFERABLY 60% TO 85% BY WEIGHT, OF THE ACTIVATOR COMPONENT, AND (B) FROM 0 TO 95% BY WEIGHT OF OTHER CUSTOMARY CONSTITUENTS OF BLEACHING AGENTS OR WASHING COMPOSITIONS WITH BLEACHING ACTION; AS WELL AS THE METHOD OF PRODUCING THE COATED ACTIVATOR COMPONENT.

Description

Mn. 29, 1974 WEBER ETAL 501110, PULVERULENT TO GRANULAR 'COMIOSL'JII'ONS CONTAINING BLBACHING 'ACTIVATORS Flled Sept 22, 1971 INVENTORS V RUDOLF WEBER BY ANGELIKA OPGENQORTH ATTORNEYS United States Patent 7 3,789,002 SOLID, PULVERULENT TO GRANULAR COMPOSI- TIONS CONTAINING BLEACHING ACTIVATORS Rudolf Weber, Dusseldorf-Holthausen, and Angelika Opgenoorth, Dusseldorf, Germany,'assignors to Henkel 8: Cie GmbH, Dusseldorf, Germany Filed Sept. 22, 1971, Ser. No. 182,748 Claims priority, application Germany, Oct. 1, 1970, P 20 48 331.2 Int. Cl. Clld 7/56 US. Cl. 252-99 12 Claims ABSTRACT OF THE DISCLOSURE Solid, pulverulent to granular compositions useful for the preparation of aqueous cold-bleaching baths, especially cold-bleaching washing liquors for textiles comprising (A) from to 100% by weight of an activator component consisting of an activator for per-compounds in the form of particles surrounded with a coating substance inert to the activator, selected from the group consisting of water-soluble compounds and water-insoluble compounds, said activator constituting from 5% to 50%, preferably 15% to 40% by weight, and said coating substance constituting from 50% to 95%, preferably 60% to 85% by weight, of the activator component, and (B) from 0 to 95% by weight of other customary constituents of bleaching agents or washing compositions with bleaching action; as well as the method of producing the coated activator component.

THE PRIOR ART Inorganic percompounds, especially perborates, are known as the active component of numerous bleaching agents, for example those used for the bleaching and possibly for the simultaneous washing of textiles. Such bleaching agents have the disadvantage, however, that their bleaching action at temperatures below 80 C. is relatively low. The addition of organic activators to such bleaching agents containing percompounds is known. These activators act in such a manner that the active oxygen of the percompound also becomes effective at tem peratures below 80 C.

The organic activators used are generally compounds which contain N-acyl or O-acyl residues in the molecule, and which exert their activating action on the organic percompounds on contact with these in the washing liquor. The exact mode of action of the activators is not known, but it is assumed that organic per-acids are formed by reaction of the organic activators with the inorganic percompounds, which acids then liberate active oxygen by decomposition. Since this action occurs in the presence of water, compositions containing inorganic percompounds and activator combined must be kept under substantially anhydrous conditions.

OBJECTS OF THE INVENTION An object of the invention is the preparation of solid, pulverulent to granular compositions useful in the preparation of cold-bleaching liquors, especially of coldbleaching washing liquors which are stable on storage under humid conditions.

Another object of the invention is the preparation of solid, pulverulent to granular activator component compositions useful in the preparation of aqueous cold-bleaching baths consisting essentially of an activator for active oxygen derived from compounds yielding H 0 in aqueous solution, said activator being in the form of particles substantially surrounded with an at least water-dispersible coating substance inert to said activator selected from the group consisting of water-soluble compounds and 3,789,002 Patented Jan. 29,, 1974 water-insoluble compounds, said activator constituting from 5% to 50% by weight and said coating substance constituting from 50% to by weight, of the activator component.

A further object of the present invention is the development of a process for the production of solid, pulverulent to granular activator component composition useful in the preparation of aqueous cold-bleaching baths consisting of, in any sequence, wetting a solid, pulverulent to granular activator, for active oxygen derived from compounds yielding H 0 in aqueous solution with an aqueous liquid and admixing an at least water-dispersible, solid coating substance inert to said activator therewith, the relative proportions of said activator, said aqueous liquid and said solid coating substance being selected so that the water present is bound by forces selected from the group consisting of surface forces and water of crystallization, and said activator constitutes from 5% to 50% by weight and said coating substance including bound water constitutes from 50% to 95% by weight, of the activator component.

A yet further object of the present invention is the preparation of solid, pulverulent to granular compositions 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 of an activator component consisting of an activator for active oxygen derived from compounds yielding H 0 in aqueous solution, being in the form of particles substantially surrounded with with an at least Water-dispersible coating substance inert to said activator selected from the group consisting of water-soluble compounds and Water insoluble compounds, said activator constituting from 5% to 50% by weight and said coating substance constituting from 50% to 95 by weight, of the activator component, and (II) from 5% to 95 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, nonionic surface-active compounds and amphoteric surface-active compounds, ((1 optical brighteners, (e) water-soluble organic builder salts, (f) antimicrobial agents, (g) soil suspension agents, (h) enzymes, (i) foam stabilizers, (j) non-surface-active foam inhibitors, (k) textile softeners, (l) corrosion inhibitors, and (to) water.

These and other objects of the invention will become more apparent as the description thereof proceeds.

THE DRAWING FIG. 1 is a flow diagram of one embodiment of the process of coating the activator.

DESCRIPTION OF THE INVENTION The invention relates to agents for the preparation of cold-bleaching liquors, particularly cold-bleaching active washing liquors.

In one aspect, therefore, the present invention provides a solid pulverulent or granular composition useful for the preparation of cold-bleaching baths, especially coldbleaching washing liquor, comprising:

% to 5% by weight of an activator component comprising an activator for percompounds in the form of particles which are surrounded with a coating of a water-soluble and/or water-insoluble substance inert to the activator, while the activator constitutes 5% to 50%, preferably 15% to 40%, by weight and the coating material constitutes 95 to 50%, preferably 85% to 60%, by Weight of the activator component, and to 95% by weight of other customary constituents of bleaching agents or bleaching washing compositions.

The coated activators according to the invention are specially suitable for the preparation of bleaching and washing compositions containing percompounds, which thereby attain a considerably improved stability during storage.

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 (1), which have an activation value for compounds in the Per-Acid Formation Test of at least 3, preferably at least 4.5.

Per-acid formation test The activation value (=titre) for the activators is determined in the following way:

Solutions which contain 0.615 gm./ liter of NaB O H O 3H O (4 mol/liter) and 2.5 gm./liter of Na P O -10H O, are heated to 60 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 gm. of ice and 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. Under the given experimental conditions, for a 100% activation of the peroxide used, 8.0 ml. of thiosulfate solution are con-' sumed, the titre is 8.0. This maximum value is of course seldom attained. Good activators have a titre of at least 4.5, preferably from 5 to 7. Useful results are often obtained with activators having a titre of at least 3.0.-

Activators of the N-acyl or O-acyl compounds type contain an acyl residue RCO-, 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 are C alkoxy groups, halogen atoms, nitro or nitrile groups; when R is an aroamtic residue it may be chloroand/or nitro-substituted, especially m-chloro or mor p-nitro-substituted. Such substituents are, for example, chloroalkyl having 1 to 3 carbon atoms, m-chlorophenyl, p-nitrophenyl, and p-methoxyphenyl.

Of the activators described below, compounds with a melting point of at least 70 0., preferably at least 100 C. and especially at least 150 C., are specially suitable. Further the equivalent weight of these compounds should be not more than 170, preferably not more than 130 and especially not more than 110 (the equivalent weight is here the quotient of the molecular weight and the number of RCO- residues present in the molecule where the compound is N-acylated or O-acylated).

The types of compound mentioned under (a) to (j) are useful activators according to the invention. In the formulae the numbered residues R have the meaning given for R above unless specifically otherwise indicated. If several residues R are present in a molecule, they may be the same or different.

(a) N-diacylated amines of the Formula I, in which I X represents a residue R or one of the residues Ia, lb,

From this class of compounds, N,N,N',N-tetraacetyl-' methylenediamiue (melting point 9295 C.), N,N,N', N'-tetraacetylethylenediamine, N,N-diacetylaniline and N,N-diacetyl-p-toluidine are named as examples.

(b) N-alkyl-N-sulfonyl-carbonamides of Formula II, which R preferably signifies a C alkyl residue.

Suitable compounds are, for example, 1,3-diacetyl-5,5- dimethylhydantoin, 1,3 dipropionylhydantoin (M.P.

104.5 to 106? C.) and 3-benzoylhydantoin-l-acetic acid ethyl ester.

v ((1) 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.

C}|IC 0 Ru (1 V A suitable compound is, for example, mono-acetyl-maleic acid hydrazide.

(e) Carbonic acid esters of Formula V, in which X representsv'an electron-attracting residue, preferably selected from the group p-carboxyphenyl, p-sulfophenyl or alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy group: I

X -OCOOR For example, p-ethoxycarbonyloxy-benzoic acid (M.P.

.157" C.) is utilizable.

(f) Pyrocarbonic acid esters of C to C alkanols as, for example, pyrocarbonic acid ethyl ester. (g) Triacyl-cyanurates of Formula VI For example, triacetylor tribenzoyl-cyanurate.

(h) Optionally substituted anhydrides of benzoic or phthalic acids, especially beuzoic anhydride itself or mchloro-benzoic anhydride (M.P. 95 C.).

(i) 0,N,N-trisubstituted hydroxylamines of Formula VII, in which R represents a residue R, preferably a methyl or ethyl residue, an optionally substituted aryl residue or the group VIIa, while X and X represent one of the residues R-CO--, 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-l39 C.), O-acetyl- N,N-succinyl-hydroxylamine (M.P. 132-134 C.), O-pmethoxybenzoyl N,N succinyl-hydroxylamine (M.P. l42145 C.), O-p-nitrobenzoyl-N,N-succinyl-hydroxylamine (M.P. 212215 C.) and O,N,N-triacetyl-hydroxylamine.

(l) N,N' diacyl sulfurylamides of Formula VIII, in which R and R preferably represent C alkyl residues or aryl residues such as phenyl, while R and R preferably represent C alkyl residues, especially C alkyl residues.

R es

N,N'-dimethyl-N,N'-diacetyl-sulfurylamide (M.P. 58 to 60 C.) and N,N'-diethyl-N,N'-dipropionyl-sulfurylamine (M.P. 95-97 C.) may be mentioned as examples.

(k) 1,3-diacy1-4,5-diacyloxy-imidazolidines of Formula IX, in which X represents hydrogen or R, and R and R represent hydrogen or R.

O C-Rs4 (VIII) O Ros (IX) To these belong: 1,3-diformyl-4,5-diacetoxy-imidazolidine (M.P. 160 -165.5 C.), l,3-diacetyl-4,5-diacetoxy-imidazolidine (M.P. 139-1405 C.), 1,3-diacetyl-4,5dipropionyloxy-imidazolidine (M.P. 85-87 C.).

(l) Acylated glycolurils of the general Formula X, in which X represents the residue R or RCO.

It is often sufficient to activate only a part of the activeoxygen present. For this, additions of activator of at least 0.1, preferably of a least 0.2 mol of activator per gram-atom of active oxygen are sufficient. If the greatest possible activation of the active oxygen is required, the addition of activator can be increased up to 4 mols, preferably up to 3 mols. However, it is preferred to work with 0.3 to 2 mols of activator per gram-atom of active oxygen. These amounts can, of course, be varied according to the activity of the particular activator used.

The activator component according to the invention is present in a pulverulent to granular state, i.e. in a particle size range of 0.1 to 3 mm., preferably to at least 70% in a particle size range of 0.3 to 2 mm. The expression pulverulent to granular is here in its general meaning, as it is ordinarily used in connection with washing, bleaching and cleaning compositions, so that particle sizes of fine powdered to coarsely granular inclusive of granulates or agglomerates are included.

Suitable coating materials for coating the activators are water-soluble partly hydratable salts and/ or water-insoluble inorganic or organic pulverulent materials with a large surface area. The coatings may also contain the below described water-soluble or water-dispersible cellulose, protein and starch derivatives, alkali metal silicates, surface-active compounds and dispersing agents.

The invention also relates to a. process for the preparation of the solid pulverulent to granular activator component substances which are suitable for the production of cold-acting bleaching baths. This process is characterized in that the activator is wetted with aqueous liquids and then mixed with solid coating substances in any sequence, the relative proportions of activator, aqueous liquid and solid coating substance being chosen so that the water present is bound by surface forces and/or as water of crystallization, and the granulate or agglomerate thus obtained is admixed with the further constituents optionally contained in the compositions according to the invention, possibly after an additional drying.

The most important solid coating substance for the process of the invention are calcined water-soluble inorganic salts which are able to crystallize with the binding of Water of crystallization, for example, the carbonates, ortho-, pyroand poly-phosphates, and the sulfates of the alkali metals, especially of sodium and potassium. Mixtures of different salts can also be used, and the mixtures may contain the same or different cations and/or the same or different anions. Watersoluble salts are preferably used which form the usual constituents of bleaching agents, especially bleaching washing compositions and washing assistants, and which are further described in detail below as builder salts for washing compositions. The water-insoluble coating substances of inorganic or organic pulverulent materials with an large active surface are, for example, inorganic materials such as microcrystalline silicic acid, magnesium oxide, magnesium silicate, tin oxide, tin silicates, or titanium dioxide, and also organic plastic powders such as, polyethylene and polypropylene powders. Here also coating substances are preferred which are the usual washing composition constituents, for example the said oxides and silicates serving as water-insoluble stabilizers for percompounds which are also described in more detail later.

Suitable aqueous liquids, with which the activator is wetted are pure water; aqueous solutions preferably saturated, of the above-mentioned water-soluble salts, prefably binding Water of crystallization; aqueous solutions or dispersions of colloidal adhesives such as cellulose derivatives as for example, carboxymethylcellulose, methylor hydroxy-ethyl-cellulose, protein and starch derivatives such as, for example, gelatine, casin, egg albumen,

groundnut or soya bean proteins, dcxtrins, tragacanth,

pectin, agar-agar, alginates, etc; and aqueous solutions of the water-soluble alkali metal silicates. Also useful are 7 the queous dispersions or solutions of the usual surfaceactive compounds and dispersing agents known as constituents of washing compositions and described in more detail below, especially the non-ionic surface-active compounds and dispersing agents such as, for example, fatty alcohol polyglycol ethers, alkylaryl-polyglycol ethers, ethylene oxide-propylene oxide polymers, polyethylene gycols and polyvinyl alcohols.

When the above-mentioned water-soluble salts binding water of crystallization are used as coating substances according to the process of the invention, the amount of water to be used is such that the inorganic salts in the finished agglomerate have a degree of hydration of from to 90%, preferably from to 50%, of the highest possible hydration for the solid stable hydrate.

The partical size range of the particles of the activator and the solid coating substance to be processed lies in general in the range of 0.005 to 1 mm., preferably from 0.01 to 0.8 mm. but the process according to the invention is not restricted to the use of particles of the particle size range indicated.

The composition according to the invention prepared by use of water-soluble salts binding water of crystallization contains from 5% to 100% by weight of an activator component of the following composition:

5% to 50%, preferablyto 40% by weight of activator 95 to 30%, preferably 85% to 35% by weight of watersoluble salts containing water of crystallization with a degree of hydration of 5% to 90%, preferably 10% to 50%.

0% to 15%, preferably 1% to 10% by weight of the above-mentioned substances suitable for forming solutions or dispersions with water for wetting the activator.

The composition prepared by use of water-insoluble solid coating substances contains from 5% to 100% by weight of an activator component of the following composition:

5% to 50%, preferably 15% to 40% by weight of activator,

95% to preferably 82% to by weight of water-insoluble solid pulverulent coating substances, of large surface area,

0% to preferably 2% to 10% by weight of water,

0% to 20%, preferably 1% to 10% by weight of the above-mentioned substances forming together with water suitable solutions or dispersions for wetting the activator.

According to a preferred form of the process of the invention, acylated glycolurils, especially tetraacetyl-glycoluril, are used as the activator. Water and calcined sodium tripolyphosphate or aqueous gelatine solution and calcined sodium tripolyphosphate or aqueous carboxymethyl-cellulose solution and pulverulent magnesium oxide have been found particularly good for the granulation coating of these glycolurils.

For carrying out the process of the invention an apnozzles are shaped as far as possible so that the sprayed liquid is distributed as evenly as possible over the surface occupied by the moving mass of particles. Moreover,

nozzles which send out a fan-shaped jet of liquid have proved satisfactory. In such case the fan of sprayed liquid should suitably form a right angle with the direction of movement of the material.

. The apparatus may be provided with stationary or rotating fittings, which however should proceed largely in the direction of the movement of the material to be granulated, so that as little friction as possible with the material passing through occurs, the continuous run through of the material is favored and contact of already formed granules with fresh or only partly granulated material is largely prevented. Such fittings are, for example, screw conveyors, stripping or guiding plates extending in the direction of movement of the material on which the material slides past. These fittings ensure that the time each particle remains in the apparatus is as near as possible to the average time of the whole material therein. The time of the material may vary within wide limits from, for example, 5 to 200 seconds.

If it is desired to cool the granules, this may be effected in any known apparatus, as for example cooling towers and cooling drums. Cooling of the material whirled up or conveyed with or against a stream of air has proved specially suitable. The material to be cooled can also be allowed to trickle down a vertical tube or tower and cold air blown against it with a speed which is a little less than the speed of fall of the granules. In this way the cooling of the granules can be combined with an air separation of the fines.

An apparatus for carrying out the process according to the invention is shown in FIG. 1. The activator to be granulated is in the stock vessel 1 and runs via the dosing device 2 into the funnel 3, which conveys it to the granulating device 4, which is an obliquely positioned rotating disc. The solid coating substance to be used in the granulation is in the stock vessel 5 and is conveyed via the dosing device 6 into the funnel 3, where it is mixed with the activator. The aqueous liquid used for wetting is in the pressure vessel 7 and, as described, comprises either of water, a solution of the salt crystallizing with binding of water of crystallization present in the stock vessel5 or of another, or of a solution or dispersion of a surface.- active compound or dispersing agent. The vessel 7 is via the line 8 and the reducing valve 9 put under pressure by a gas so that the liquid arrives at the nozzle 12 via the line 10 which may be provided with a heating arrangement 11, and is sprayed on the granulation disc 4. The granulated material runs over the edge of the disc into the funnel 13, and from there into the pipe 14 and the vessel 15. Air is forced into this vessel 15 from the fan 16 via the line 17 and the throttle valve 18. Part of this air flows into the pipe 14 into the just formed granulate in countercurrent at such a speed that the speed of fall of the granulate in the pipe 14 is greatly reduced, the granulate being cooled at the same time. The granulate falls to the bottom of the container 15 and in the lower funnel-shaped part of the vessel 15 is conveyed by the remainder of the air forced into this vessel into the descending line 19, which is connected with the lower part of the rising line 20. Air from the fan 27 is sucked through the lower open end of the rising line 20 at such speed that the whole of the granulate is lifted through this rising line into the separator 21. The air leaves the separator through the line 22 and goes to the cyclone 23, where the fine, ungranulated or not sufficiently granulated particles and particles entrained by the stream ofair are separated and are returned through the line 24 to the funnel 3. The stream of air is sucked out of the cyclone through the fan 27, the throttle valve 26 and the line 25. The granulate separated in the container 21 leaves the separator at its bottom opening and falls on the shaking screen 28. The material which falls through the shaking screen is the granulate of the desiredgrain size and is removed through the line 29. The coarse-grained material remaining on the screen 28 is carefully comminuted in the mill 30. The line 31 conveys the material issuing from the mill back into the separator under the reduced pressure prevailing in the separator 21, where the particles of dust are separated.

The granulation may also be egected in a rotating drum. The material to be granulated is in this case passed into the drum via a funnel and a tube. There it is partly lifted from the rotating drum and forms therein a continuously moving mass. A stripper prevents the material from being lifted too far and caking of the particles sprayed against the wall of the drum. The solution used for the spraying is introduced through a pipe into the drum and is there converted by nozzles into radiating sprays. The solid coating substance used for the coating is passed into the drum through a second funnel.

The granulation process may be carried out discontinuously or continuously in the described apparatus.

The size of the granulates prepared by the process of the invention may vary within very wide limits according to the existing requirements. In general, granulates of grain size over 5 mm. are only needed in special cases. For use in washing compositions, granulates of grain size from 2 down to 0.3 mm. have particular importance, while the granulates may also contain constituents of other grain sizes, the fraction of 2 to 0.3 mm. generally constituting at least 50% by weight of the total granulate. In the granulate of the activator component prepared by the above described process of the invention the organic activator is present substantially in the form of solid coated particles, possibly combined with one another to give agglomerates, the nuclei of these particles consist of the solid activator, and these nuclei are coated with a layer consisting of partly hydrated salts which bind water in the form of water of crystallization and/or surfaceactive powders and possibly film-forming colloids and/r surface-active compounds or dispersing agents. Thus in the granulates of the activator component the water used for coating the activator in the above described granulation process is in practice bound by surface forces and/ or as water of crystallization. The coated activator particles are in this form largely screened from the attack of undesired reactive substances, above all against the moisture of the air and the water possibly in the preparations which is not bound as water of crystallization, as well as from the inorganic percompounds possibly present in the preparations, especially perborate. The solid pnlverulent to granular preparations according to the invention therefore also have excellent storage properties.

It has surprisingly been found that the activity of the activator is not affected by the water bound by surface forces and/or as water of crystallization. This applies especially when acylated glycolurils, especially tetraacetylglycoluril, are used as activators.

Therefore, a reaction of the organic activator with the inorganic percompound in practice does not occur until the preparation is dissolved or dispersed in baths containing water or percompounds for the preparation of a cold-bleaching bath.

Preparations which comprise substantially the granulated activator component, are suitable for use in the textile industry or in industrial laundries, where they are used together with hydrogen peroxide or solid percompounds and possibly the usual additions for the preparation of the bleaching baths and bleaching washing baths.

If, in addition to the activator component according to the invention, the 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:

5% to 95%, preferably 7% to 50% by weight of an activator component defined above,

95% to 5%, preferably 93% to 50% 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.

When in the above formulation the inorganic builder salts are wholly or partly replaced and present as percompounds yielding H 0 in aqueous solution, the preparations according to the invention represent specially interesting bleaching compositions for practical purposes, which on dissolving in water give cold-bleaching washing liquors, in which the active oxygen is already effective at temperatures from 20 to 70 (3., especially 30 to 60 C.

In such bleaching compositions the ratio of the activator in the activator component of the invention to the percompound is always such that from 0.05 to 2 mols, preferably 0.1 to 1 mol of activator is present per gramatom of active oxygen of the percompound.

When such bleaching compositions contain more than 40% by weight of activator and percompound, this quantity relating to the pure activator and the pure percompound without the other constituents of the activator component, these preparations are preferably used as bleaching agent concentrates in the textile industry or in industrial laundries.

When the bleaching compositions of the invention contain up to 40% 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 therefore represent a preferred field of application of the present invention. In such bleaching washing compositions and washing assistants, the proportions of activator and percompound constitute together mostly from 5% to 40%, especially from 10% to 35% 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:

5% to 40%, preferably 7% to 30% by weight of a surface active component, containing at least one surfaceactive compound of the type of the sulfonates, soaps, non-ionics, and, optionally, one or more of the following substances:

0 to 10%, preferably 0.5% to 8% by weight of foam stabiilzers,

0 to 10%, preferably 0.5% to 8% by weight of nonsurface-active foam inhibitors,

5% to 40%, preferably 10% to 35% by weight of pure activator and percompound,

10% to preferably 35% to 75% by weight of builder salts these substances being preferably alkaline-reacting and the amount of these substances preferably constituting 0.5 to 7 times, and especially 1 to 5 times, the total amount of surface-active compounds, and

0% to 30%, preferably 3% to 15% by weight of other bleaching and washing composition constituents such as, for example, soil suspension agents, textile softeners, enzymes, optical brighteners, dyestuffs and perfumes, water,

while the activator of the above-defined activator component 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.

In this general formulation are also included bleaching fine washing compositions to be used at temperatures up to 70 C., the surface-active compound content of which is generally in the range from 8% to 40%, preferably from to 40% by weight. Provided 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% 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% to 30% by weight; these mostly contain at least one of the following two types of surface-active compound in the amounts there indicated:

15% to 100%, preferably 35% to 90% by weight of a sulfonate and/or a sulfate with preferably 8 to 18 carbon atoms in the hydrophobic residue,

10% to 60%, preferably 10% to 50% by weight of nonionics and optionally one or more of the following substances:

% to 70%, preferably to 60% by weight of a soap,

0% to 10%, preferably 0.5% to 8% by weight of a foam stabilizer,

0% to 10%, preferably 0.5% to 8% by weight of a nonsurface-active foam inhibitor,

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-surfaceactive foam inhibitors.

The said bleaching washing compositions are generally prepared by mixing the activator component according to the invention with washing compositions containing percompounds, which have usually been obtained by admixing a washing composiiton powder prepared by hot drying with a percompound. Such cold-bleaching washing compositions are marked by a good stability on storage.

The further constituents of the compositions according to the invention are described below in more detail according to the class of substance.

The anionic, amphoteric or nonionic 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 nonionic 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 0 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.

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.

Of the synthetic anionic surface-active compounds, 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 10 to 14 carbon atoms, by chlorinating and alkylating benzene or from corresponding terminal or non-terminal olefins by alkylation of benzene and sulfonation of the alkylbenzenes obtained. Further, 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. As aliphatic sulfonates, mixtures containing alkene sulfonates, hydroxyalkane sulfonates and disulfonates are useful, which are obtained from terminal or non-terminal C and preferably C1248 olefins by sulfonation with sulfur trioxide and acid or alkaline hydrolysis of the sulfonation products. In the aliphatic sulfonates thus prepared, 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 bisufite can also be used.

Furthermore, salts, preferably dialkali metal salts of ozsulfo-fatty acids, and salts of esters of these acids with monoor poly-hydric alcohol containing 1 to 4, and preferably 1 to 2 carbon atoms belong to the sulfonates to be used according to the invention.

Further useful 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.

As tensides of the sulfate type are 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 resi dues, 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.

The nonionic surface-active compounds, here called nonionics, 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.

The products obtainable by addition of ethylene oxide and/ or glycide to fatty alcohols, alkylphenols, fatty acids, 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.

Further, products known by the trade name of Pluronics or Tetronics belong to the nonionics. 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 nonionics 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 nonionics.

The nonionics 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 nonionic dispersing agents are possibly nonsurface-active water-soluble compounds or compounds emulsifiable or dispersible in water, such as, for example, fatty acid partial 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 oxide adducts of glycerine and other polyalcohols.

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.

The foaming power of the surface-active compounds can be increased or reduced by combination of suitable types of surface-active compounds, just as it can be changed by additions of non-surface-active organic substances.

Suitable foam stabilizers, above all in the case of surface-active compounds of the sulfonate or sulfate type, are surface-active carboxy or sulfo-betaines and also the above-mentioned non-ionics of the alkylolamide type. Moreover, fatty alcohols or higher terminal diols can be utilized for this purpose.

Products with a reduced foaming power are primarily intended for use in washing-and dishwashing machines, where sometimes a limited repression of foam is sufiicient while in other cases a stronger foam repression may be desired. Products which foam in the middle range of temperature up to about 65 C. but at higher temperatures (70 C. to 100 C.) develop less and less foam, are of special practical importance.

A reduced foaming power is frequently obtained with combinations of different types of surface-active compounds, especially with combinations of synthetic anionic surface-active compounds, particularly of (1) sulfates and/or sulfonates or of (2) nonionics on the one hand and (3) soaps on the other hand. With combinations of the components (1) and (2) or (1), (2) and (3), the foaming power can be affected by the particular soap used. The inhibition of foam is smaller with soaps from preferably saturated fatty acids with 12 to 18 carbon atoms, while a greater inhibition of foaming, particularly in the higher temperature range, is obtained by soaps from saturated fatty acid mixtures having 20 to 26, preferably 20 to 22 carbon atoms, used in an amount of from at least 5%, preferably at least by weight of the total soap fraction present in the combination of surface-active compounds.

The foaming power of the surface-active compounds can also be reduced, by the addition of known, non-surface-active foam inhibitors. These include optionally chlorine-containing N-alkylated aminotriazines, which are obtained by reacting 1 mol of cyanuric cloride with 2 to 3 mols of a monoand/or di-alkylamine having 6 to 20, preferably 8 to 18 carbon atoms in the alkyl residue. Aminotriazine or melamine derivatives which contain propylene glycol or butylene glycol ether chains, in an amount of 10 to 100 of such glycol residues per molecule, have a similar action. Such compounds are obtained, for example, by addition of corresponding amounts of propylene and/or butylene oxide to aminotriazine, especially to melamine. The reaction products from 1 mol of melamine with at least 20 mol of propylene oxide or at least 10 mol of butylene oxide are preferred. Products which are obtained by addition of 5 to 10 mol of propylene oxide to 1 mol of melamine and further addition of 10 to 50 mol of butylene oxide to this propylene oxide derivative have proved particularly effective.

Other non-surface-active water-insoluble organic compounds, such as parafiins or halogenated paraffins with melting points below C., aliphatic C to C ketones and aliphatic carboxylic acid esters, which contain at least 18 carbon atoms in the acid or alcohol residue, possibly also in both of these two residues (for example triglycerides or fatty acid-fatty alcohol esters), can be used as foam inhibitors, particularly in combinations of anionic synthetic surface-active compounds and soaps.

The non-surface-active foam inhiibtors are frequently only completely effective at temperatures at which they are present in the liquid state, so that the foaming behavior of the products can be controlled by choice of suitable foam inhibitors in a similar way to that by the choice of soaps from fatty acids of suitable chain lengths.

When foam stabilizers are combined with foam inhibitors dependent upon temperature, good foaming products are obtained at lower temperatures which, as the temperature approaches the boiling temperature, foam less and less.

Suitable Weakly-foaming nonionics, which can be used both alone and in combination with anionic, amphoteric and nonionic surface-active compounds and which reduce the foaming power of more strongly foaming surfaceactive compounds, are products of addition of propylene oxide to the above-described surface-active polyethylene glycol ethers as well as the also above-described Pluronic, Tetronic and Ucon-Fluid types.

Suitable builders are weakly acid, neutral and alkaline reacting inorganic or organic salts, especially inorganic or organic complex-foaming substances.

Useful, weakly acid, neutral or alkaline-reacting salts according to the invention are, for example, the alkali metal bicarbonates, carbonates, borates or silicates, mono-, dior tri-alkali metal orthophosphates, dior tetraalkali metal pyrophosphates, alkali metal metaphosphates known as complex-forming substances, alkali metal sulfates and the alkali metal salts of organic, non-surfaceactive sulfonic acids, carboxylic acids and sulfocarboxylic acids containing 1 to 8 carbon atoms. These include, for example, water-soluble salts of benzene-, tolueneor xylene-sulfonic acid, water-soluble salts of sulfoacetic acid, sulfobenzoic acid or salts of sulfodicarboxylic acids and the salts of acetic acid, lactic acid, citric acid and tartaric acid.

Further, the water soluble salts of higher molecular weight polycarboxylic acids are utilizable as builders, especially polymerizates of maleic acid, itaconic acid, mesaconic, fumaric acid, aconitic acid, methylenemalonic acid and citraconic acid. Copolymerizates of these acids With one another or with other polymerizable substances, as for example, with ethylene, propylene, acrylic acid, methacrylic acid, crotonic acid, 3 butenecarboxylic acid, 3- methyl 3 butenecarboxylic acid and with vinyl methyl ether, vinyl acetate, isobutylene, acrylamide and styrene, are utilizable.

Suitable complex-forming builders are also the weakly acid reacting metaphosphates and the alkaline reacting polyphosphates, especially tripolyphosphate, in the form of their alkali metal salts. They may be wholly or partly replaced by organic complex forming substances.

The organic complex-forming substances include, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N hydroxyethyl ethylenediaminetriacetic acid, polyalkylene-polyamine-N-polycarboxylic acids and other known organic complex-forming substances, while combinations of diiferent complex-forming substances may a 15 also be 'used. Diand poly-phosphonic acids of the following constitutions also belong to the other known complex-forming substances:

OH X OH OH X OH I X OH Germain. o=l .t l=o N t l=o] dnfrn dnzn irbnr X OH HO X X OH N: auto] assists [she] 14... Hit. M14...

in which R represents alkyl and R alkylene radicals with l to 8, preferably 1 to 4 carbon atoms, X and Y represent hydrogen or alkyl radicals with l to 4 carbon atoms and Z represents --OH, ---NH; or NXR. For a practical application above all the following compounds are considered: methylenedisphosphonic acid, l-hydroxyethane- 1,1-diphosphonic acid, l-aminoethane-1,1-diphosphonic acid, amino-tri-(methylenephosphonic acid), methylaminoor ethyla-mino-di-((methylenephosphonic acid as well as ethylenediamine tetra (methylenephosphonic acid). All these complexing compounds may be present as free acids or preferably as the alkali metal salts.

Further, soil suspending agents or greying inhibitors may be contained in the preparations according to the invention, which hold the dirt loosened from the fiber suspended in the bath and thus prevent greying. Watersoluble colloids of mostly organic nature are suitable for this purpose, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatine, salts of ether-carboxylic acids or ether-sulfonic acids of starch or cellulose or salts of acid sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acid groups are also suitable for this purpose. Furthermore, soluble starch preparations and starch products other than those mentioned above can be used, for example, degraded starch, and aldehyde starches. Polyvinylpyrrolidone is also useful.

The constituents of the treatment compositions according to the invention, especially washing compositions and washing assistants of this kind, and particularly the builder substances, are usually chosen so that the preparations have a neutral to distinctly alkaline reaction, so that the pH value of a 1% solution of the preparations mostly lie in the region from 7 to 12. Fine washing compositions usually have a neutral to weakly alkaline reaction (pH value 7 to 9.5, while soaking, prewashing and boiling washing compositions are adjusted to be more strongly alkaline (pH value 9.5 to 12, preferably 10 to 11.5). The action of the activators is combined with a certain consumption of alkali. Therefore, the builder substances present should be in an amount sufficient to prevent the pH value from falling below the given minimum values during the whole period of treatment.

Of the, preferably inorganic, per-compounds yielding H in aqueous solution, sodium perboate tetrahydrate (NaBO- .H O .3H O) is of special practical importance. Partly or completely dehydrated perborates, i.e., up to NaBO .H O may be used in its place. Borates such as NaBO .H O described in German Pat. 901,287 and US. Pat. 2,491,789, in which the ratio Na O:B 0 is less than than 0.5 :1 and preferably lies in the region of 0.4 to 0.15:1, while the ratio H O :Na lies in the region of 0.5 to 4:1 are also useful. All these perborates may be wholly or partly replaced by other inorganic per-compounds, especially by peroxyhydrates, such as the peroxyhydrates of ortho-, pyroor polyphosphates, especially of the tripolyphosphates, as well as the carbonates.

It is advisable to incorporate in the compositions from 0.25% to by weight of the usual water-soluble and/ or water-insoluble stabilizers for the stabilization of the pre-compounds. Suitable water-insoluble per-compound stabilizers which, for example, constitute 1% to 8%, preferably 2% to 7%, of the weight of the total preparation, are the magnesium silicates (MgO:SiO =4"to 1:4,

preferably 2:1 to 1:2 and especially 1:1), mostly obtained by precipitation from aqueous solutions. Other alkaline earth metal, cadmium or tin silicates of corresponding composition are utilizable in their place. Water-contain ing tin oxides are also suitable as stabilizers. Watersoluble stabilizers, which may be present together with water-insoluble stabilizers, are the organic complexforming substances the amount of which may constitute 0.25% 'to 5%, preferably 0.5% to 2.5% of the weight of the whole preparation. l

The enzymes to be used are mostly a mixture of different enzymic substances. They are called proteases, amylases, carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, layases, transferases, desmolases or nucleases, depending upon their action. The enzymic substances obtained from strains of bacteria or fungi such as Bacillus subtilis and Streptomyes griseus are of particular interest, especially proteases or amylases. Preparations obtained from Bacillus subtilis have the advantage compared with others that they are relatively stable towards alkali, per-compounds and anionic detergent substances and are still active at temperatures up to 70 C. l I

Enzyme preparations are usually marketed by the manufacturers as aqueous solutions of the active substances or with the addition of diluents, as powders. Suitable diluents are sodium sulfate, sodium chloride, alkali metal or'tho-, pyroor polyphosphates, especially tripolyphosphate. Frequently moist enzyme preparationsare mixed with calcined salts, which then bind Water of crystallization present and the enzymic substance, possibly with agglomeration of the particles to larger particles.

When the enzymic substances are present as dry powders, liquid, paste-like and possibly also solid, nonionic, preferably surface-active, organic compounds especially the above-described non-ionics, can be used at the usual room temperatures to bind the enzymes to the powders of the washing compositions or washing assistants. For this purpose a mixture of the respectiveproduct and the enzymic substance is preferably sprayed with the abovementioned nonionic substances, or the enzyme preparations is dispersed in the said nonionic substance and this dispersion is united with the other constituents of the product. When these other constituents are solids, the dispersion of the enzymic substances in the non-ionic component can also be sprayed on the other solid constituents.

The enzymes, or combinations of enzymes with different actions, are generally used in quantities such that the finished products have protease activities of 50 to 5000, preferably to 2500 LVE/ g. and/or amylases activities of 20 to 5000, preferably 50 to 2000 SKBE/g. and/or lipase activities of 2 to 1000, preferably 5 to 500 IE/g.

These data on enzyme activities result from the activities of those enzyme preparations which at the present time seem to be suitable from the economic standpoint for use in the washing composition field. From the chemical-technical standpoint the enzyme activities of the preparations can be increased as desired, so that the activities in the case of proteases and amylases may be raised, for example, up to five times, and in the case of lipases, for example, up to ten times, the highest values given above. If, therefore, in the future preparations with such high activities should be available which also economically appear appropriate for the use in the application fields, named at the beginning, products with respective higher enzyme activities can be prepared.

With reference to the determination of the enzyme activities, the following literature references are given: Determination of the activity of proteases according to Lohlein-Volhardz A. Kunzel, Chemical Tanning Pocketbook, 6th ed., Dresden and Leipzig, 1955; determination of the activity of amylases: J. Wohlgemuth, Biochemische Zeitschrift, vol. 9, (1908), pp. 1-9; R. M. Sandstedt et 'al., Cereal'Chemistry, vol. 16, (1939), pp. 712-723; deter- 17 mination of the activity oflipases: R. Willst'atter et al., Hoppe-Seylers Zeitschrift fiir Physiologiche Chemie, vol. 125 (1923), pp. 110-117; R. Boissonas, Helvetica Chimica Acta, vol. 31 (1948), pp. 1571-1576.

The products according to the invention may also contain antimicrobial substances. As such, the 2-hydroxy- 2',4,4-trichloro-diphenylether has been proven good.

Particularly import representative of optical brighteners are the diaminostilbene sulfonic acid derivatives of the general formula J ll 1' 1 N N n o a Rn H S og 03 H R:

wherein R and R may represent halogen atoms, lower alkoxy groups, theamino 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 carbonatoms, while the heterocyclic ring systems are primarily rings with 5 or 6 members. As 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 represents the residue morpholino-, -NH--C H NHC H SO H, --OCH Some of the brighteners are, in regard to their fiber afiinity, to be considered as transitional types to the polyamide brighteners, such as thebrightener with R -NH-C H To the cotton brighteners of the diaminostilbene sulfonicacid type also belongs the compound 4,4-bis-(4-phenyl vicinal-triazolyl-2) stil'bene disulfonic acid-2,2.

These 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.

The present invention will be further described with reference to the following specific examples which are not to be deemed limitative of the invention.

EXAMPLES Examples V1 to V3 describe the preparation of the activator component according to the invention.

Example V1 An apparatus illustrated in FIG. 1 with a granulating disc served for carrying out the process. 50 kg./hr. of

tetraacetylglycoluril of a particle size range between 0.08 and 0.2 mm. and 70 kg./hr. of calcined sodium tripolyphosphate of substantially the same particle size range were passed on to the granulating disc, the size, inclination and speed of rotation of which were such that the average duration of the mixture thereon was 60 to 80 seconds. 15 kg./hr. of a solution of sodium tripolyphosphate saturated at room temperature were sprayed by means of a nozzle on the activator-tripolyphosphate mixture. The finished granulate was allowed to flow for 5 seconds through a countercurrent of air at a temperature of about 15 C. The" activator component thus obtained had a particle size range in the region of 0.3 to 2.5 mm. I

1 8 Example V2 25 kg./hr. of tetraacetylglycoluril, of a particle size range of 0.08 to 0.2 mm., were sprayed in a rotating drum with 60 kg./hr. of a hot 10% aqueous gelatine solution in the first third of the length of the drum. 50 kg./hr. of calcined sodium tripolyphosphate of a particle size range of 0.1 to 2.2 mm. were fed into the last third of the drum, and the average duration of time of the activator in the drum was to 100 seconds. The granulate thus obtained, after running through a countercurrent stream of air at 22 C. had a particle size range of between 0.3 and 3.5 mm.

Example V3 1.5 kg. of tetraacetylglycoluril, particle size range of 0.08 to 0.2 mm., was placed in a rotating drum and sprayed with 0.8 kg. of a 5% carboxymethylcellulose solution, in a discontinuous operation. 1.7 kg. of magnesium oxide, particle size range of 0.008 to 0.12 mm., was added to this mixture in a period of 15 minutes and the mixing was continued for a further 15 minutes. The granulate obtained had a particle size range in the region of 0.2 to 3 mm.

Example M1 7 To determine the stability on storage of the preparations according to the invention, a bleaching agent of the following composition was prepared.

80% by weight of an activator component consisting of:

25% by weight of tetraacetylglycoluril, 5% by weight of gelatine, 50% by weight of sodium tripolyphosphate, 20% by weight of water and 20% by weight of sodium perborate tetrahydrate.

TABLE I Residual perborate content in percent after- 10 days 30 days 50 days Bleaching agent Example M1 98 32 Sample for comparison 57 16 2 The perborate content of the test samples were determined by the following method:

In each case 100 g. of the samples were added to about 0.5 liters of 10% sulfuric acid in a 1-liter measuring flask. After dissolution had taken place, the flask was filled up to the calibration mark with 10% sulfuric acid. 10 ml. of this solution were removed, treated with about 10 ml. of a 10% potassium iodide solution and, after addition of a few drops of a saturated solution of ammonium molybdate, titrated with 0.1 N sodium thiosulfate solution until a light yellow coloration was obtained. Then a few drops of a starch solution were added and the solution was further titrated until decolorization occurred. The residual perborate was then determined according to the following formula Residual perborate content in percent [m1. 0.1 N thiosulfate]-0.77-l00 Init,ial perborate content in percent 19 agent according to the invention has a distinctly better stability on storage.

The following specific examples describe the composition of further preparations of the invention. The saltlike constituents contained therein such as salt-like surface-active compounds, other organic salts as well as inorganic salts are present as sodium salts, if not expressly stated otherwise. The other terms and abbreviations used have the following meanings:

ABS is the salt of an alkylbenzenesulfonic acid with 10 to 15, essentially 11 to 13 carbon atoms in the alkyl chain obtained by condensing straight-chain olefins with benzene and sulfonation of the alkylbenzene thus formed.

Alkanesulfonate is a sulfonate obtained from paraffins with 12 to 16 carbon atoms via the sulfoxidation method. 1 Fs-estersulfonate is a sulfonate obtained from the methyl ester of a hardened tallow fatty acid by sulfonation with S Olefinsulfonate is a sulfonate obtained from mixtures of olefins with 13 to 18 carbon atoms by sulfonation with S0 and hydrolysis of the sulfonation product with alkaline liquor, which sulfonate consists substantially of alkanesulfonate and hydroxyalkanesulfonate, but in addition still contains small amounts of disulfonates. Each olefinsulfonate-containing preparation was prepared with use of two diiferent types of olefinsulfonate; one was prepared from a mixture of straight-chain terminal olefins, and the other from a mixture of nonterminal olefins.

KA-Sulfate and TA-Sulfate are the salts of sulfated substantially saturated fatty alcohols prepared by reduction of coconut fatty acid and tallow fatty acid respectively.

KA-EO-Sulfate," TA-EO-Sulfate and OA-EO-Sulfate are the sulfated products of addition of 2 mols of ethylene oxide to 1 mol of coconut fatty alcohol, of 3 mols of ethylene oxide to 1 mol of tallow fatty alcohol and of 2 mols of ethylene oxide to 1 mol of oleyl alcohol respectively.

are the products of addition of ethylene oxide (E0) and propylene oxide (PO) to commercial oleyl alcohol (0A), and coconut alcohol (KA).

Perborate is a product containing about of active oxygen of the approximate composition NTA, EDTA and HEDP are the salts of nitrilotriacetic acid, ethylenediaminetetraacetic acid and by droxyethanediphosphonic acid respectively.

Soap A or B is a soap prepared from a fatty acid mixture of 9% by wt. C 14% by wt. C and 77% by wt. C (iodine value 3) (A); or 8% by wt. C 32% by wt. C 12% by wt. C and 48% by wt. C (iodine value 4) (B).

CMC is the salt of carboxymethylcellulose.

In theexamples a mixture of about 45% of a-N,N'-di- (alkylamino)-monochlorotriazine and about 55% of a N,N',N"-tri(alkylamino) -triazine was used as non-surfaceactive foam inhibitor. The alkyl residues in these triazine 4 derivatives are present as a mixture of homologswith 8 to 18 carbon atoms. The monochlorotriazine derivative or thhe trialkylaminotriazine could be used with a similar result. If the products described contain synthetic sulfates or sulfonates together with soap, the other non-surfaceactive foam inhibitors mentioned in the description may be used, for example paraflin oil or paraflin. In the production of the preparations the non-surface-active foam inhibitor dissolved in a suitable organic solvent or in molten state was sprayed by means of a nozzle on the moving pulverulent preparation.

In all the examples the amounts relates to the pure substances. These substances may contain impurities caused 20 a by the preparation such as, for example, water, sodium sulfate, sodium chloride, sodium carbonate, etc. Thus in the subsequent Table II, the sign in the line Na SO means that small amounts of sodium sulfate are present as impurity in the anionic surface-active compounds. Since such impurities do not impair the activity of the individual substances, they are not mentioned in the formulations. The expression residue therefore stands essentially for water and the above mentioned salts as well as for dyestuffs and perfiurmes.

Example M2 Bleaching activatorfor industrial laundries:

80.0% by weight of an activator component compris- 25% by weight tetraacetylglycoluril 6% by weight of gelatine 1 50% by weight sodium tripolyphosphate 19% by weight water 5.0% by weight Na O:3.3SiO

3.5% by weight OA-l-lO E0 2.5% by weight ABS Remainder sodium sulfate and water.

Example M3 Bleaching agent concentrate:

' 70.0% by weight of an activator component compris- 30% by weight tetraacetylglycoluril 5% by weight OA+5 E0 50% by weight sodium tripolyphosphate 15% by weight water 30.0% by weight perborate.

I I Example M4 Bleaching prewashing agent: 7

The following Examples M5 to M10 set forth in Table II describe bleaching washing compositions according to the invention, in which the following activator components prepared according to Examples used:

Activator component V1:

37.5% by weighttetraacetylglycoluril 55.0% by weight sodium tripolyphosphate 7.5% by weight water Activator component V2:

. 25% by weight tetraacetylglycoluril 6% by weight gelatine 50% by weight sodium tripolyphosphate 19% by weight water. J I l .Activator component V3:

" 37.5 by weight tetraacetylglycoluril 1.0% by weight CMC 42.5% by weight magnesium oxide 19.0% by weight water,

V1, V2 and V3 were.

TABLE H 1 wherein R here and hereafter is a member selected from the group consisting of methyl, ethyl, n-propyl, Percent fg f i fl isopropyl, phenyl, tolyl, xylyl and chloroalkyl having 1 to 3 carbon atoms and X represents a member Components of the preparation M5 M6 M7 M8 M9 M10 5 selected from the group consisting of ABS- 3.0 Alkanesulionate 4. 5 5. 5 Fs-estersulfonate. 2. 5 G 0-R C 0-3. 0 OR Olefinsulfonate. 5.4 6.0 KA-sulfate-.- 2 0 R, .CH:-N- v -CH2CHz-N and -N C O-R C O-R C OR (b) N-alkyl-N-sulfonyl-carbonamides having the formula zr-N S0R.flj

wherein R represents alkyl having 1 to 3 carbon atoms, R represents a member selected from the group consisting of R, p-nitrophenyl and p-methoxyphenyl and R represents R,

(c) N-acyl-hydantoins having the formula Ere CMC Y3 Brightener. Remainder wate C 0-( )'Y Xsz-IL' N-Xu N Instead of the activator components used in the washing A compositions of Table II, those in which the tetraacetylglycoluril is replaced by other glycolurils of Formula X or by activators of Formulae I to 1X may also be used with wherein at least one of X and X is RC0 and the a imilar result, 35 other is selected from the group consisting of RCO,

Cotton brighteners, polyamide brighteners, polyester R, carboxymethyl and carbethoxymethyl, and Y brighteners and their combinations may be used as optical and Y32 are selected from the group consisting of brighteners, depending upon the purpose for which the hydrogen and alkyl having 1 to 2 carbon atoms, washing composition according to the invention is to be (d)"cyclic-N-acyl-hydrazines having the formula used. a

In preparations containing enzymesare to be made, 7 to N 15% by weight of commercial products are used which, Where solid enzyme concentrates are concerned, are adhr-COR justed by the manufacturer to the following activities by addition of inorganic salts, mostly sodium sulfate or sowherein the two nitrogen atoms are part of a hetero dmm tripolyphosphate: 1 ring selected from the group consisting of maleic A protease with 125,000 DIE/g hydrazide, phthalic hydrazide, triazole and urazole,

An amylase with 75,000 SKBE/g (e) carbonic esters having the formula A lipase with 10,000 IE/ g.

The PrFceding R are fllustratlve of wherein X represents an electron-attracting radical the practice of the invention. It is to be understood, howl ted from the group consisting of p-carboxyever, that other expedients known to those skllled 1n the phenyl, p sulfophenyl, and ethoxycarbonyl, art or disclo herein y 13% p y Without p (f) pyrocarbonic acid esters of alkanols having 1 to 4 ing from the spirit of the invention or the scope of the 5 carbon atoms, appended claims. (g) triacyl-cyanurates having the formula We claim:

1. A solid, pulverulent to granular activator compo- A V nent useful in the preparation of aqueous cold-bleaching 1 r I baths, said activator component being a granulate at least 50% of which has a particle size fraction of between 0.3

mm. and 2 mm., consisting of an activator for active oxygen derived from acompounds yielding H 0 in aquem ous solution, said activator having a melting point of at 1 V N least C. and an activating action of at least 3 in the Per-Acid Formation Test and is selected from the group consisting of (a) N-diacylated amines having the formula a wherein R-has the above-defined values, '(h) 0,N,N -trisubstituted hydroxylamines having the formula 23 7 wherein R represents a member selected from the group consisting of R and and the CO, succinyl and phthalyl, and n represents an integer from to 2, (i) N,N-diacyl-sulfurylamides having the formula wherein R and R represent alkyl having 1 to 3 carbon atoms and R and R represent alkyl having 1 to 4 carbon atoms and phenyl,

(j) 1,3-diacyl-4,S-diacyloxy-imidazolidines having the formula wherein X represents a member selected from the group consisting of R and hydrogen, and

(k) acylated glycolurils having the formula glycolurils having the formula wherein X represents a member selected from the group consisting of R-CO and R, I said activator being in the form of particles substantially surrounded with an at least water-dispersible coating substance inert to said activator and capable of binding water by forces selected from the group consisting of surface forces and water of crystallization, said coating substance containing bound water and being selected from the group consisting of (i) calcined water-soluble inorganic salts which are able to crystallize with the binding of water of crystallization, with a degree of hydration of from 5% to 90% of the highest possible hydration for the solid stable hydrate and (ii) water-insoluble inorganic and organic pulverulent materials with a large surface area selected from the group consisting of microcrystalline silicic acid, magnesium oxide, magnesium silicate, tin oxide, tin silicate, titanium dioxde, polyethylene powder and polypropylene powder, saidactivator constituting from 5% to 50% by weight and said coating substance constituting from 50% to 95% by weight, of the activator component.

2. The composition of claim 1 wherein said activator constitutes from to 40% by weight and said coating substance constitutes from 60% to 85% by weight of the activator component composition.

3. The compositionof claim 1 wherein said activator has an activating action of at least 4.5 in the Per-Acid Formation Test.

4. The composition of claim 1 wherein said at least water-dispersible coating substance has a'further content of from 1% to 20% by weight of the total activator component composition of at least one agglomeration agent selected from the group consisting of water-soluble to water-dispersible cellulose, protein and starch derivatives, water-soluble alkali metal silicates, surface-active compounds, surface-active dispersing agents and said bound water.

5. The composition of claim 1 consisting essentially of from 15 %'to 40% by weight of said activator, from 35% to 85 of a water-soluble salt capable of binding water as water of crystallization and being from 5% to 95% hydrated and from 0% to 15% by weight of an agglomeration agent forming with water a solution to dispersion suitable for wetting said activator.

6. The composition of claim 1 consisting essentially of from 15% to 40% by weight of said activator, from 25% to 82% by weight of a water-insoluble inorganic or organic pulverulent compound having a large surface area, from 2% to 20% of water bound by surface forces and from 0% to 20% by weight of an agglomeration agent forming with water a solution to dispersion suitable for wettingsaid activator. V v

7. The composition of claim 1 wherein said activator for active oxygen has the formula wherein R R and R represent a member selected from the group consisting of alkyl having 1 to 3 carbon atoms, phenyl, and phenylalkyl having 7 to 8 carbon atoms and X represents a member selected from the group consisting of R and R -CO.

8. The composition of claim 5 whereinsaid activator is tetraacetylglycoluril and said water-soluble salt is sodium tripolyphosphate.

9. The composition of claim 5 wherein said activator is tetraacetylglycoluril, said water-soluble salt is sodium tripolyphosphate and said agglomeration agent is present in an amount of from 1% to 10% by weight and is gelatine.

. 10. The composition of claim 6 wherein said activator is tetraacetylglycoluril, said water-insoluble pulverulent compound having a large surface is magnesium oxide and said agglomeration agent is present in an amount of from 1% to 10% by weight and is carboxymethylcellulose.

11. The composition of claim 7 wherein said activator for active oxygen is a member selected from the group consisting of tetraacetylglycoluril, tetrapropionylglycoluril, methyltriacetylglycoluriland diacetyldibenzoylglycoluril.

12. A process for the production of solid, pulverulent to granular activator component useful in the preparation of aqueous cold-bleaching baths, said activator component being a granulate at least 50% of which has a particle size fraction between 0.3 mm. and 2 mm., consisting of, in any sequence, wetting a solid, pulverulent to granular activator, for active oxygen derived from compounds yielding H 0 in aqueous solution as claimed in claim 1, with an aqueous liquid and admixing an at least waterdispersible solid pulverulent coating substance inert to forces selected from the group consisting of surface forces and water of crystallization, selected from the group consisting of (i) calcined water-soluble inorganic salts which are able to crystallize with the binding of water of crystallization and (ii) water-insoluble inorganic and organic pulverulent materials with a large surface area selected from the group consisting of microcrystalline silicic acid, magnesium oxide, magnesium silicate, tin oxide, tin silicatc, titanium dioxide, polyethylene powder and polypropylene powder, the relative proportions of said activator, said aqueous liquid and said solid coating substance being selected so that the water present is bound by forces selected from the group consisting of surface forces and water of crystallization and said activator constitutes from 5% to 50% by weight and said coating substance including bound water constitutes from 50% to 95% by weight, of the activator component.

References Cited UNITED STATES PATENTS Moyer et al 252-99 Disch et a1. 252-99 XR Derangeon et al. 25299 XR Corey et al. 252-99 Chase 25299 Maruta et a1 252-99 Cray 25299 Woods 252-99 XR MAYER WEINBLATT, Primary Examiner U.S. CI. XLR.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 5,789,002 Jan. 29, 197

Patent No. Dated lnv Rudolf Weber et a1.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

lat t. 9 1- 5:22:

1 #7 Change "555st" to Twists" 3 2 Change "mol/liter" to :nMol/liter 3 6 Change "(j)" to (l) I 9 l Change" "egected". to effected 39 After "sulfonate's; please insert su-lfates,

21 "In" should be If i 3 Delete the phrase glycolurlls having the formula" which was repeated in error. 7 i

l6 86 In original claim 7, now known as claim .5, delete l7 the words "and being from 5% to 95% hydrated".

This was cancelled as per Amendment Rule 116.

2 22 In original claim l0, 'now' known as claim 6,

I please change "a" to said as per A mend ment Role 116-. Signed and seale this 17th day of December 1974.

SEAL) fittest:

' McCOY M. GIBSONJR. I C. MARSHALL DANN attesting Officer Commissioner of Patents ORM PC7-1050 (10-69) USCOMM-DC 60376-P69 u 5 GOVERNMENT vnm'rma OFFICE: 930

5,789,002 Jan. 29,'197

Patent No. Dated Rudolf Weber et a1.

Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Feie ii l 7 Change "organic" to inorganic 3 2 Change "moi/liter" to. mMol/liter 3 62 Change ".(J) t v I I I 9 l Change ':'ejgected"j. to e fi'ecvced i0 39 After "sulfonate's; please: insert sulfates, 1 i "In" should be If V V 23 +2 Delete the phrase '.'g1ycolurils having the formula" which was repeated in error. Q I 2M 16 8c In original I claim 7, now known as claim 5, delete l7 the words "and hein from 5% to 95% hydrated".

This was cancelled as per Amendment Rule ll6. 22 In original claimlC), 'now Known as claim 6,

i please change; "a" to said as per: amendment RLile 116. v Signed and sealedthis 17x1; day of December 1W4.

(SEAL) fittest:

' MCCOY M. GIBSONJR. c. MARSHALL DANN Attesting Officer Commissioner of Patents ORM PO-OSO (10-69) USCOMM-DC 60376-5 69 u 5. GOVERNMENT rnmrmo OFFICE: 93 o

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