US3730902A

US3730902A - Scouring agents with a bleaching and disinfecting action

Info

Publication number: US3730902A
Application number: US00076612A
Authority: US
Inventors: K Disch; P Krings; D Kuehling; H Bellinger; J Perner
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1969-10-01
Filing date: 1970-09-29
Publication date: 1973-05-01
Anticipated expiration: 1990-05-01
Also published as: NL7012930A; DE1949561C3; FR2064075A1; FR2064075B1; AT305075B; BE756848A; GB1321874A; CH552671A; DE1949561B2; ES384117A1; DE1949561A1; TR16936A

Abstract

SCORING AGENTS HAVING A BLEACHING AND DESINFECTING ACTION COMPRISING A MAJOR AMOUNT OF WATER-INSOLUBLE SCOURING COMPONENTS AND A MINOR AMOUNT OF ESSENTIALLY WATER-SOLUBLE COMPONENTS INCLUDING A SOLID WATER-SOLUBLE PER-COMPOUND AND AN EFFECTIVE AMOUNT OF ACYLATED ACTIVATOR COMPOUNDS WHEREIN THE ACYL IS SELECTED FROM THE GROUP CONSISTING OF ALKANOYL HAVING 2 TO 4 CARBON ATOMS, BENZOYL AND SUBSTITUTED BENZOYL, SAID ACYLATED COMPOUNDS ARE SELECTED FROM THE GROUP CONSISTING OF NACYL COMPOUNDS, O-ACYL COMPOUNDS, CARBONIC ACID ESTERS AND PYROCARBONIC ACID ESTERS.

Description

United States Patent 3,730,902 SCOURING AGENTS WITH A BLEACHING AND DISINFECTING ACTION Karlheinz Disch, Hilden, Peter Krings, Krefeld, Dieter Kiihling, Monheim, Horst Bellinger, Dusseldorf, and Johannes Jiirgen Perner, Neustadt, Germany, assignors to Henkel & Cie GmbH, Dusseldorf, Germany No Drawing. Filed Sept. 29, 1970, Ser. No. 76,612 Claims priority, application Germany, Oct. 1, 1969,

P 19 49 561.5 The portion of the term of the patent subsequent to Dec. 28, 1988, has been disclaimed Int. Cl. (111d 7/54 US. Cl. 252-99 9 Claims ABSTRACT OF THE DISCLOSURE Scouring agents having a bleaching and disinfecting action comprising a major amount of water-insoluble scouring components and a minor amount of essentially Water-soluble components including a solid water-soluble per-compound and an effective amount of acylated activator compounds wherein the acyl is selected from the group consisting of alkanoyl having 2 to 4 carbon atoms, benzoyl and substituted benzoyl, said acylated compounds are selected from the group consisting of N- acyl compounds, O-acyl compounds, carbonic acid esters and pyrocarbonic acid esters.

Cleaning and securing agents which contain an additive with both a bleaching and disinfecting action are known already. In particular, bleaching and disinfecting detergents and scouring agents with a content of active chlorine-liberating compounds have been described. However, since such substances have the disadvantage of emitting an unpleasant and lasting chlorine odor, it has already been suggested to replace the active chlorineliberating compounds by an odor-free active oxygen-liberating compound. This substitution, however, gives rise to the necessity of adding an activator for the liberating of the active oxygen from the corresponding compound, since mostly such cleaning and scouring agents are sup posed to display their entire effectiveness at low temperatures. All storable per-compounds which come into consideration as bleaching and disinfectant additives do not liberate suflicient active oxygen at these low temperatures. Therefore, cleaning and scouring agents with a content of per-compounds and an activator for the percompound have already become known.

In accordance with German Auslegeschrift 1,280,456 the addition of an inert carrier substance impregnated with solutions of metal ions, particularly Co Mn Ni, Cr, Mo, Cu is recommended. The disadvantages of these activators is that on the one hand, a sequestration agent is required simultaneously, in order to avoid undesired discolorations caused by the mentioned metal ions, and on the other hand, those condensated phosphates normally employed in cleaners, owing to their satisfactory cleansing action, with the exception of hexametaphosphate, decrease the catalytic effectiveness of the activator.

OBJECTS OF THE INVENTION An object of the present invention is the obtention of scouring agents having a bleaching and disinfecting action comprising a major amount of water-insoluble scouring components and a minor amount of essentially Water-soluble components including a solid water-soluble percompound and an effective amount of an acylated activa tor compound wherein the acyl is selected from the group consisting of alkanoyl having 2 to 4 carbon atoms, benzoyl and substituted benzoyl, said acylated compounds are selected from the group consisting of N-acyl compounds, O-acyl compounds, carbonic acid esters and pyrocarbonic acid esters.

A further object of the present invention is the obtention of scouring agents having a bleaching and disinfecting action consisting essentially of (A) from 60% to by weight of water-insoluble scouring components having a mechanical cleaning action and (B) from 40% to 5% by weight of essentially water-soluble components consisting essentially of (1) from 5% to by weight, of said water-soluble components, of a combination of a solid, water-soluble per-compound containing bound H 0 and a water-soluble acylated activator compound in a ratio such that from 10 to 0.l acyl groups are present per molecule of bound H 0 said acylated activator compound is selected from the group consisting of:

(a) N-diacylated amines having the formula wherein R and R are selected from the group consisting of alkyl having 1 to 3 carbon atoms and phenyl, and X is selected from the group consisting of alkyl having 1 to 3 carbon atoms, phenyl and COR (CH2)m-N COR wherein R and R have the above-assigned values and m is an integer from 0 to 2,

(b) N-a'lkyl-N-sulfonyl-carbonamides having the formula SOzRza wherein R is selected from the group consisting of alkyl having 1 to 3 carbon atoms and haloalkyl having 1 to 3 carbon atoms, R is alkyl having 1 to 3 carbon atoms and R is selected from the group consisting of alkyl having 1 to 8 carbon atoms and phenyl,

(c) N-acyl-hydantoins having the formula wherein R and R are selected from the group consisting of hydrogen and alkyl having 1 to 2 carbon atoms. R is selected from the group consisting of alkanoyl having 2 to 4 carbon atoms, alkyl having 1 to 4 carbon atoms, phenyl, and benzoyl, and R is selected from the group consisting of alkanoyl having 2 to 4 carbon atoms, alkyl having 1 to 4 carbon atoms, phenyl, carboxymethyl and alkoxycarbomethyl wherein the alkoxy has 1 to 3 carbon atoms, with the proviso that at least one of R and R is alkanoyl,

( d) N-acyl-imides having the formula CH-GO CHE-CO N-Ru the group consisting of alkanoyl having 2 to 4 carbon atoms, benzoyl, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy, alkylsulfonyl having 1 to 4 carbon atoms and benzenesulfonyl,

(e) Cyclic N-acyl-hydrazides having the formula wherein R is alkanoyl having 2 to 4 carbon atoms,

(g) Phenyl esters having the formula wherein R is selected from the group consisting of alkyl having 1 to 4 carbon atoms and phenyl,

(h) Acylated polyhydroxy compounds having the formula wherein Y is selected from the group consisting of a mono-saccharide residue, a di-saccharide residue and a lower alkanepolyol having at least 3 hydroxyl groups, R is alkyl having 1 to 4 carbon atoms and n is an integer of at least 3,

(i) Carbonic acid esters having the formula R -OCOOR wherein R is selected from the group consisting of p-carboxyphenyl, sodium-p-sulfophenyl and alkoxycarbonyl having 1 to 4 carbons in the alkoxy, and R is selected from the group consisting of alkyl having 1 to 4 r carbon atoms, phenyl and cycloalkyl having 5 to 6 carbon atoms,

(j) Triacyl cyanurates having the formula wherein R is alkanoyl having 2 to 3 carbon atoms,

(k) Benzoic acid anhydride, and

(l) Phthalic acid anhydride, and (2) from 0 to 95% by weight, of said water-soluble components, of watersoluble scouring components selected from the group consisting of surface-active anionic compounds, surface-active non-ionic compounds, surface-active amphoteric compounds, inorganic builders, organic complex-forming compounds, dirt carriers, antimicrobial compounds, skin protecting compounds, superfatting compounds, corrosion in hibitors, enzymes, dyestuffs and perfumes.

Another object of the invention is the combination of solid, water-soluble per-compounds containing bound H 0 and the water-soluble acylated activator compounds.

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

DESCRIPTION OF THE INVENTION The present invention provides scouring agents having a bleaching and disinfecting action comprising a major amount of water-insoluble scouring components and a minor amount of essentially Water-soluble components including a solid water-soluble per-compound and an effective amount of acylated activator compounds.

The following N-acyl or O-acyl compounds, or carbonic acid or pyrocarbonic acid esters can be used as water-soluble organic acylated activators according to the invention:

(a) N-diacylated amines of Formula I:

COR XN\ COR];

in which R and R represent an alkyl residue with 1 to 3 carbon atoms, or an optionally substituted aryl residue, preferably phenyl, and X represents an alkyl residue having 1 to 3 carbon atoms, an aryl residue, preferably phenyl, or one of the groups COR1 COR COR" or CH2OH2N or -N\ COR CORn com;

such as N,N-diacetyl-ethylamine, N,N-dipropionylphenylamine, tetraacetyl-methylenediamine, tetraacetylethylenediamine, tetrapropionyl-ethylenediamine and tetraacetylhydrazine;

(b) N-alkyl-N-sulfonyl-carbonamides of Formula II:

in which R represents an alkyl residue or halogenated alkyl residue having 1 to 3 carbon atoms or an optionally substituted aryl residue, preferably phenyl, R represents an alkyl residue having 1 to 3 carbon atoms, and R represents an alkyl residue having 1 to 8 carbon atoms or an optionally substituted aryl residue, preferably phenyl, such as N-methyl-N-benzene-sulfonyl-acetamide, N-ethyl- N-ethanesulfonyl-propionamide, N-methyl-N-methanesulfonyl-acetamide and N-methyl-N-methanesulfonyl-benzamide;

(c) N-acyl-hydantoins of Formula III:

sa CO-R34 RazI I N-Rs;

O i) (III) in which R represents an alkanoyl residue having 2 to 4 carbon atoms, an alkyl residue having 1 to 4 carbon atoms, an optionally substituted benzoyl residue, or an aryl residue, preferably phenyl, R represents an alkanoyl residue having 2 to 4 carbon atoms, an alkyl residue having 1 to 4 carbon atoms, an aryl residue, preferably phenyl, or an optionally esterified carboxymethyl residue, preferably carboxymethyl or alkoxycarbomethyl having 1 to 4 carbon atoms in the alkoxy, while in the compounds of Formula III at least one of the residues R and R represents an alkanoyl group, and R and R represent hydrogen or an alkyl residue having 1 or 2 carbon atoms, such as 1,3-dipropionyl-hydantoin, l-ethyl-3-butyryl-5,S-dimethyl-hydantoin, 1-methyl-3-benzoylhydantoin, 1-propionyl-3-phenyl hydantoin, and l-rnethoxycarbomethyl-3-propionyl-hydantoin;

(d) N-acyl-suc'cinimides and maleic acid imides of Formula IVa or IVb:

in which R and R represent an alkanoyl residue having 2 to 4 carbon atoms, an optionally substituted benzoyl residue, an alkoxycarbonyl residue having 1 to 4 carbon atoms in the alkyl residue or an alkane-sulony residue having 1 to 4 carbon atoms, or an optionally substituted benzenesulfonyl residue, such as N-acetyl-succinimide, N-propionyl-maleic acid imide, N-benzoylmaleic acid imide, N-ethoxycarbonyl-succinimide, N-benzenesulfonyl-maleic acid imide and N-methanesulfonylsuccinimide;

(e) Cyclic N-acylhydrazides of Formula V:

in which P represents an alkanoyl residue having 2 to 4 carbon atoms, such as l,4-diformyl-2,3,5,6-tetraacetoxyprperazme;

(g) Phenol esters, optionally substituted in the phenol residue, of Formula VII:

(VII) in which R represents an optionally substituted alkyl,

preferably having 1 to 4 carbon atoms or aryl residue, preferably phenyl, such as phenyl acetate and phenyl benzoates;

(h) O-acyl derivatives of monoand di-saccharides and of aliphatic polyhydroxyoxyalcohols of Formula VIII:

a1)11 (VIII) in which Y represents a monoor di-saccharide residue or the residue of an aliphatic polyhydroxyalcohol, preferably a lower alkanepolyol having at least 3 hydroxyl groups, R represents an alkyl residue having 1 to 4 carbon atoms, preferably a methyl residue, and n is at least the number 3 and at most the number corresponding to the per-O-acyl compound, such as glucose pentaacetate and pentaerythritol tetraacetate;

(i) Carbonic acid esters of Formula IX:

in which R represents an electron-attracting residue, preferably from the group of p-carboxyphenyl, sodium p-sulfophenyl and alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy, and R represents an optionally substituted alkyl, aryl, preferably phenyl, or cycloalkyl residue, such as diethyl pyrocarbonate, O-p-carboxyphenyl-O-ethyl-carbonate, O sodium-p-sulfophenyl-O-cyclohexyl-carbonate, etc.;

(j) Triacyl-cyanuric acids of Formula X:

RIUI 'O (E\ in which R represents an alkanoyl residue having 2 to 3 carbon atoms, such as triacetyl-cyanuric acid and tripropionyl-cyanuric acid, and l (k) Optionally substituted benzoic or phthalic anhydrides such as benzoic acid anhydride and phthalic acid anhydride.

On moistening, the compositions according to the invention already develop at normal temperatures an excellent odorless bleaching and disinfectant action, since organic per-acids with a bleaching and disinfecting action are formed from the organic activators and the percompounds.

The above-mentioned compounds (a) to (j) of Formulas I to X, as well as compound (k), which may be used in the compositions, according to the invention, and their preparation are described in the literature.

The quantitative ratio between the acylated activator and the per-compound should be selected so that from 10 to 0.1, particularly from 4 to 0.5, acyl groups are available per molecule of organically or inorganically bound H202.

The composition of the scouring agents of the invention preferably lie within the scope of the following general recipe.

60% to 95%, preferably to by weight of water-insoluble scouring components having a mechanical cleaning action,

40% to 5%, preferably 20% to 10%, by weight of an essentially water-soluble mixture consisting of:

5% to 100%, preferably 10% to 50%, by weight of a combination of per-compound and activator of the above-specified constitution, whereby the quantitative ratio between per-compound and ac tivator lies within the above range,

0 to preferably 50% to 90%, by weight of other usual components in the substantially watersoluble cleaning compositions.

The other usual components in substantially watersoluble cleaning compositions are principally surfaceactive compounds and/or neutral to alkaline reacting builders. Such other usual water-soluble cleaning components may comprise:

0 to 95 preferably 10 %to 60%, by weight of anionic, nonanionic and/ or amphoteric surface-active agents,

0 to 95 preferably 10% to 50%, by weight of alkalinereacting inorganic builders and organic complex formers,

0 to 20%, preferably 1% to 10%, by weight of other common scouring agent components, such as, for example, dirt carriers, antimicrobial substances, skin-protecting substances and superfatting agents, corrosion inhibitors, enzymes possibly coated or stabilized, and dyestuils and perfumes.

Useful as water-insoluble scouring components having a mechanical cleaning action are finely ground mineral abrasive materials such as quartz, feldspar, marble or finer-spar powder, kaolin and pumice stone. In place of mineral abrasives, finely ground synthetic resin granulates or their mixtures with mineral scouring components may be used. Also mineral abrasives coated with a synthetic resin film may be used.

The per-compounds used in the scouring agents of the invention may be of an organic or inorganic nature and preferably contain bound H 0 Suitable are, for instance,

per-compounds such as urea and melamine per-hydrates and, in particular, inorganic per-salts, such as, for instance, alkali metal perborates, percarbonates, perpyrophosphates and persilicates. Among the preferable inorganic per-salts containing bound H to be used, sodium perborate tetrahydrate is of specific practical importance. Instead, partially or completely dehydrated perborates may be used as well, that is, dehydrated to the approximate composition: NaBO -H O Finally, borates containing active oxygen, NaBO -H O in which the proportions Na O:B O is less than 0.5 :1 and is preferably in the range from 0.4 to 0.15:1, and in which the proportions H O :Na is in the range from 0.5 to 4:1 are also useful. These products are described in German Pat. No. 901,287 and in United States Pat. No. 2,491,789.

The perborates may be wholly or partly replaced by the above-identified inorganic per-compounds. These peroxyhydrates are preferably soluble in water and are ordinarily utilized in the form of their alkali metal salts, such as their sodium salts.

The anionic, amphoteric or nonionic surface-active compounds contain in the molecule at least one hydrophobic residue containing 8 to 26, preferably to 20, and in particular, 12 to 18 carbon atoms and at least one anionic or nonionic or amphoteric water-solubilizing group. The preferably saturated hydrophobic residue may be of aliphatic or alicyclic nature, and be combined with the water-solubilizing groups directly or through intermediate members. Suitable intermediate members are, for example, benzene rings, carboxylic acid ester or carbonamide groups, ether or ester-like bound residues of polyvalent alcohols, such as ethylene glycol or propylene glycol, glycerine or corresponding polyether residues.

The hydrophobic residue is preferably an aliphatic hydrocarbon residue with 10 to 18 carbon atoms, preferably 12 to 18 carbon atoms, but deviations from this preferred carbon range are possible depending on the nature of the surface-active compound in question.

Soaps are useful as anionic detergents which are derived from natural or synthetic fatty acids, and possibly also from resin or naphthenic acids, particularly if these acids have iodine numbers of 30 at the most and preferably of less than 10.

Of the synthetic anionic surface-active compounds, the sulfonates and sulfates are of special practical importance.

The sulfonates include, for example, the alkylaryl sulfonates, especially the alkylbenzene sulfonates, which are obtained among others from preferably straight-chain aliphatic hydrocarbons with 9 to 15, preferably 10 to 14, carbon atoms by chlorination and alkylation of ben- Zene or from corresponding olefins with terminal or nonterminal double bonds by alkylation of benzene and sulfonation of the alkylbenzenes obtained. Further, aliphatic sulfonates are of interest, such as, for example, as are obtainable from preferably saturated hydrocarbons containing 8 to 18 and preferably 12 to 18 carbon atoms in the molecule by sulfochlorination with sulfur diOXide and oxygen and conversion of the products thereby obtained into the sulfonates. Furthermore, mixtures of alkenesulfonates, hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from terminal or central C C and preferably G -C olefins by sulfonation with sulfur trioxide and acid or alkaline hydrolysis of the sulfonation products, are utilizable as aliphatic sulfonates. In the aliphatic sulfonates so prepared, the sulfonate group is often found on a secondary carbon atom, but by reacting terminal olefins with bisulfite, sulfonates with terminal sulfonate groups may be prepared.

Salts, preferably dialkali salt of a-sulfo-fatty acids as well as salts of esters of these acids with alcohols containing 1 to 4 and preferably 1 or 2 carbon atoms also belong to the sulfonates to be used according to the invention.

Further utilizable sulfonates are the fatty acid esters of hydroxyethanesulfonic acid and dihydroxypropanesulfonic acid, the salts of fatty alcohol esters of lower aliphatic or aromatic sulfo-monoand di-carboxylic acids containing 1 to 8 carbon atoms, the alkylglycerylethersulfonates, as well as the salts of the amide-like condensation products of fatty acids or sulfonic acids with aminoethane-sulfonic acid.

Suitable surface-active compound of the sulfate type are fatty alcohol sulfates, especially those derived from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol. Useful sulfonation products of the sulfate type can also be prepared from C to C olefins with terminal or non-terminal double bonds. Furthermore, this group of surface-active compounds includes sulfated fatty acid alkylolamides, sulfated monoglycerides and sulfated products of ethoxylated and/or propoxylated fatty alcohols, alkylphenols with 8 to 15 carbon atoms in the alkyl residue, fatty acid amides, fatty acid alkylolamides and so on, where 0.5 to 20, preferably 1 to 8, and especially 2 to 4 mols of ethylene oxide and/ or propylene oxide are added on to one mol of the said compounds to be ethoxylated and/or propoxylated.

Suitable as anionic surface-active agents of the carboxylate type are, for example, the fatty acid esters or fatty alcohol ethers of hydroxy carboxylic acids as well as the amide-like condensation products of fatty acids or sulfonic acids with amino carboxylic acids, for example, With glycocoll, sarcosine or albumin hydrolysates.

The nonionic surface-active agents useful in the scouring agents are the so-called Nonionics which are products which owe their water solubility to the presence of polyether chains, amine-oxide, sulfoxide or phosphineoxide groups, alkylolamide groupings as Well as in general to a large number of hydroxyl groups.

Of special practical interest are products which are obtainable through the addition of ethyleneoxide and/or glycide to fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid or sulfonic acid amides. These Nonionics may contain from 4 to 100, preferably 6 to 40 and especially 8 to 20, ether radicals, and above all, ethyleneglycol ether radicals per molecule. Furthermore, these polyether radicals may contain central or terminal propyleneor butylene-glycol ether radicals as polyether chains.

Products known by the trade names of Pluronics and Tetronics are also included among the nonionics. They are obtained from polypropylene glycols, themselves water-insoluble, or 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 derivative are converted into the said nonionics by ethoxylation until the product is soluble in water. Finally, the still water-soluble reaction products of the above mentioned aliphatic alcohols with propylene oxide known as Ucon-Fluid are also useful as nonionics.

Other suitable Nonionics" are fatty acid or sulfonic acid alkylolamides which are derived, for instance, from monoor diethanolamine, from dihydroxypropylamine or other polyhydroxyalkylamines, e.g., the glycamines. They may be replaced by amides from higher primary or secondary alkylamines and polyhydroxycarboxylic acids.

To the capillary active amineoxides belong, for instance, those products which are derived from higher tert. amines which possess a hydrophobic alkyl radical and two shorter alkyl and/or alkylol radicals with up to 4 carbon atoms.

Amphoteric surface-active agents contain both acid and basic hydrophilic groups in the molecule. Among the acid groups are carboxylic acid groups, sulfonic acid groups, sulfuric acid half-ester groups, phosphonic acid groups and phosphoric acid partial ester groups. Among the basic groups are primary, secondary, tertiary and quaternary ammonium groupings. Amphoteric compounds with quaternary ammonium groups belong to the betaine type.

Owing to their good compatibility with other surfaceactive agents, carboxy, sulfate and sulfonate betaines are of special practical interest. Suitable sulfobetaines are obtained, for instance, through reaction of tert. amines, containing at least one hydrophobic alkyl radical, with sultones, for instance, propane or butane sultone. Corresponding carboxybetaines are obtained through reaction of the above-identified tert. amines with chloroacetic acid, its salts or with chloroacetic acid esters and cleavage of the ester bond.

The foaming properties of the surface-active agents may be increased or decreased by means of combination of suitable surface-active agent types as well as being modified by addition of non-surface-active organic substances. Particularly Well suited as foam stabilizers for surface-active agents of the sulfonate or sulfate type are capillary active carboxy or sulfobetaines as well as the above-mentioned nonionics of the alkylolamide type. Equally well suited for this purpose are fatty alcohols or higher terminal alkanediols.

Suitable builders are weakly acid, neutral and alkalinereacting inorganic or organic salts, especially inorganic or organic cmplex-forming substances.

Weakly acid, neutral or alkaline reacting salts utilizable in the compositions of the present invention are, for example, the borates, bicarbonates, carbonates or silicates of the alkali metals, and mono-, dior tri-alkali metal orthophosphates, dior tetra-alkali metal pyrophosphates, and metaphosphates known as complexforming substances, alkali metal sulfates and the alkali metal salts of organic, non-surface-active sulfonic acids, carboxylic acids and sulfocarboxylic acids containing 1 to 8 carbon atoms. These include, for example, watersoluble salts of benzene-, tolueneor xylene-sulfonic acids, water-soluble salts of sulfoacetic acid, sulfobenzoic acid or salts of sulfodicarboxylic acids, as well as the salts of acetic acid, lactic acid, citric acid and tartaric acid.

Further, the water-soluble salts of higher molecular weight polycarboxylic acids are useful as builders, especially polymerizates of maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, methylenemalonic acid and citraconic acid. Copolymerizates of these acids with one another or with other polymerizable monomers as, for example, ethylene, prop'ylene, acrylic acid, methacrylic acid, crotonic acid, 3-butene-carboxy1ic acid, 3-methy1-B-butene-carboxylic acid and also vinylmethylether, vinyl acetate, isobutylene, acrylamide and styrene are also utilizable.

Other suitable complex-forming builders are the weakly acid-reacting metaphosphates, as well as the alkaline-reacting pol'yphosphates, especially tripolyphosphate. They may be wholly or partly replaced by organic complex-forming substances.

Usable organic complex-forming compounds are the alkali metal salts of nitrolotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid, polyalkylene-polyamine-N-polycarboxylic acids as well as other known organic complex-forming compounds. Combinations of several complex-forming compounds may be employed as well. Diand poly-phosphonic acids of the following constitutions also belong to the other known complex-forming compounds:

in which R represents alkyl and R represents alkylene residues with 1 to 8, preferably 1 to 4, carbon atoms,

10 X and Y represent hydrogen atoms or alkyl residues with 1 to 4 carbon atoms and Z represents the groups -OH, -N=H or -NXR. For practical use the following compounds are of particular value:

methylene-diphosphonic acid l-hydroxyethane-1,1-diphosphonic acid l-aminoethane-l,l-diphosphonic acid amino-tri-(methylene-phosphonic acid) methylaminoor ethylamino-di-(methylene-phosphonic acid) as well as ethylenediamino-tetra-(methylene-phosphonic acid).

All these complex-forming compounds may be present as the free acids, but preferably as the alkali metal salts.

The said inorganic builders and organic complex-forming substances may be replaced partly by neutral-reacting diluents or blending agents, for example, sodium sulfate or sodium chloride. Other scouring agent components comprise antimicrobial substances, skin-protective substances or super-fatting agents, corrosion inhibitors, enzymes possibly coated or stabilized as well as dyestuffs and perfumes.

The scouring compositions according to the invention may be prepared by mixing the solid constituents in the usual way, or by preparing first a pulverulent product in known way from the water-soluble constitutents suitable for spray drying and admixing with the other solid constituents of the composition, or by mixing the solid constituents and spraying on the solid particles of the mixture any liquid or pasty constituents possibly present in known way, owing to which the preparations have excellent non-dust-producing properties.

The compositions of some of the preparations of the present invention will be further described by way of reference to the following examples. These are, however, not to be deemed limitative in any respct.

EXAMPLES The salt components, salt of surface-active agents, other organic salts as well as inorganic salts which are contained therein, are sodium salts. The terms used in the examples are as follows:

Alkylbenzenesulfonate represents the sodium salt of an alkylbenzenesulfonic acid with from 10 to 15, preferably 11 to 13, carbon atoms in the alkyl chain which is obtained by condensation of straight-chain olefins with benzene and sulfonation of the thus obtained alkylbenzene.

Fatty alcohol+EO represents the addition products of ethylene oxide (E0) to technical oleyl alcohol. The number indicates the molar amount of ethylene oxide added per 1 mol of alcohol.

Olefinsulfonate represents a sulfonate obtained from olefin mixtures with from 12 to 18 carbon atoms through sulfonation with S0 and hydrolyzation of the sulfona tion product with sodium hydroxide solution. This sulfonate mainly consists of al-kenesulfonates and hydroxyalkanesulfonates as well as small amounts of disulfonates. Each of the olefinsulfonate-comaining preparations was prepared from two diiferent olefinsulfonate types. One of these had been prepared from a mixture of straight-chain terminal olefins, the other from a mixture of nonterminal olefins.

Fatty alcohol2 EO-sulfate represents a sulfated addition product of 2 mols of ethyleneoxide to 1 mol of coconut fatty alcohol.

Fatty alcohol sulfate represents a sulfated coconut fatty alcohol.

Fatty acid diethanol amide represents the amide from coconut fatty acid and diethanolamine.

Alkanesulfonate represents a sulfonate obtained from paraffins with from 12 to 16 carbon atoms by means of sulfoxidation.

Soap represents the sodium salts of a fatty acid mixture of the following composition:

Perborate represents an approximate 10% active oxygen containing product of the approximate NaBO -H O 'SH O The explanations for the remaining terms can be taken from the above context whereby the expression fatty acid is always to be interpreted as coconut fatty acid mixture.

TABLE I Percent y weight Ingrcdient Alkylbenzenesulfonate.

Fatty alcohol plus 10 E0.

Sodium pyrophosphate.

Sodium carbonate.

Perborate.

Tetraacctyl-methylcncdiamine (Formula I).

Quartz flour.

Alkylbenzenesulfonatc.

Fatty alcohol sulfate.

Borax.

Perborate.

-p-carboxyphcnyl-O"ethyl-carbonate (Formula Marble dust.

Alkylbcnzcnesulfonate.

Fatty alcohol plus 2 EO-sulfate.

Fatty acid diethanolamide.

Nitrilotriacetate.

Perborate.

1,3-dipropionyl-hydanto1n (Formula III) Quartz flour.

Marble dust.

Soap.

Orthophosphate.

Perboratc.

Benzoic acid anhydride (k).

Alkanesulfonate.

Fatty alcohol plus 10 E0.

Bicarbonate.

Perboratc.

Triacetyl-cyanuric acid (Formula X).

Quartz flour.

Fatty alcohol sulfate.

Nonylphenol plus 3 EO-sulfatc.

Pyrophosphatc.

Sodium carbonate.

Perborate.

N-acetyl-maleic hydrazide (Formula V).

Marble dust.

Fatty alcohol plus 4 EO-sulfate.

Triphosphate.

Perborate.

1,4-diformyl-2,3,5,6-tetraacctoxy-piperazine (For mula V1).

Quartz flour.

Alkylbenzenesulfonate.

Triphosphatc.

Sodium sulfate.

Perborate.

Glucose pentaacctate (Formula VIII).

Example Of the above given examples, Examples 2, 3, 4, 5 and 8 are obtained by mixing the constituents, Examples 6 and 7 by mixing the first product prepared by spray drying the anionic surface-active compounds and pyrophosphate or triphosphate with the remaining constituents, and Example 1 by spraying the nonionic surface-active component on the remaining mixture.

EXAMPLE 9 Using a scouring composition according to Example 6, a dispersion is prepared which consists of 3 parts of scouring composition and 2 parts of water, In each case 3 gm. of this dispersion are applied to pottery dishes which have been artifically dirtied with coffee, tea and carrot juice, respectively. The bleaching treatment was effected at 20 C. After different times of action the scouring composition is rinsed off and the bleaching action expressed in test values. Value 1 is given for a complete bleaching action, and for an imperceptible bleaching action value 6 is given. The values given in the following Table II are average values from three individual determinations. A comparative experiment is carried out with a scouring composition of the same composition in which, however, the activator to be used according to the invention is replaced by the same amount by weight of pumice flour.

TABLE II Bleaching action Without activator Time of action in With Dirt minutes activator Carrots Carrots/oil EXAMPLE 10 Scouring compositions with various contents of perborate and activator are tested in comparison with corresponding mixtures without activator for their anti-microbial activity according to the surface disinfection test. For this purpose 6 x 6 cm. in size samples of rough wood or glazed tiles are uniformly infected with 3 drops of germ suspension and the suspension is allowed to dry. The germ suspensions are prepared by floating 24-hour old cultures on Merck Standard I agar in normal size Petri dishes with 5 ml. each of sterile Merck Standard I broth, shaking with sterile glass beads and filtering through sterile glass wool. The surfaces are then evenly moistened with the test product premixed with water at 20 C. (test dilution 5 gm. product +5 ml. water). The removal of the sample was effected by rubbing off in each case a quarter of the surface of the sample with a slightly moistened cotton plug, spreading this on Merck Standard I broth and inoculating the swab in broth. The incubation is carried out at 37 C. up to a maximum of 8 days. The test organisms used were Escherichia coli (bacterial count: ll7 10 /ml.), Pseudomonas aeruginosa and Staphylococcus aureus (122 X 10 ml.)

The following scouring compositions were tested:

(a) A scouring composition according to Example 3; (b) A scouring composition with:

1% by weight of perborate, 1% by weight of 1,3-dipropionyl-hydantoin, 2% by weight of quartz flour,

the remainder being of the same composition as the scouring composition according to Example 3;

(c) A scouring composition with:

0.5% by weight of perborate 0.5% by weight of 1,3-dipropionyl-hydantoin 3 by weight of quartz flour,

the remainder being of the same composition as the scouring composition according to Example 3.

Scouring compositions of the same composition in which, however, the activator was replaced by the same amounts by weight of quartz flour served as control. In the following Table IH the killing times for the test organisms used are given in minutes.

The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood, however, that other expedients known to those skilled in the art may be employed without departing from the spirit of the invention or the scope of the appended claims.

We claim:

1. Scouring agents having a bleaching and disinfecting action consisting essentially of (A) from 60% to 95% by weight of water-insoluble, finely ground mineral scouring components having a mechanical cleaning action and (B). from 40% to by weight of essentially watersoluble components consisting essentially of (1) from 5% to 100% by weight, of said water-soluble components, of a combination of a solid, water-soluble per-compound containing bound H 0 and a water-soluble acylated activator compound in a ratio such that from to 0.1 acyl groups are present per molecule of bound H 0 said acylated activator compound is selected from the group consisting of:

(a) N-diacylated amines having the [formula COR CORn wherein R and R are selected from the group consisting of alkyl having 1 to 3 carbon atoms and phenyl, and X is selected from the group consisting of alkyl having 1 to 3 carbon atoms, phenyl and (cH2)m"'N COR]:

wherein R and R have the above-assigned values and m is an integer from 0 to 2, (b) N alkyl N sulfonyl-carbonamides having the formula R12 R2 CO-N S OzRza wherein R is selected from the group consisting of alkyl having 1 to 3 carbon atoms (and haloalkyl having 1 to 3 carbon atoms), R is alkyl having 1 to 3 carbon atoms and R is selected from the group consisting of alkyl having 1 to 8 carbon atoms and phenyl,

(c) N-acyl-hydantoins having the formula wherein R and R are selected [from the group consisting of hydrogen and alkyl having 1 to 2 carbon atoms, R is selected from the group consisting of alkanoyl having 2 to 4 carbon atoms, alkyl having 1 to 4 carbon atoms, phenyl, and benzoyl, and R is selected from the group consisting of alkanoyl having 2 to 4 carbon atoms, alkyl having 1 to 4 carbon atoms, phenyl, carboxymethyl and alkoxycarbomethyl wherein the alkoxy has 1 to 3 carbon atoms, with the proviso that at least one of R and R is alkanoyl,

(d) N-acyl-imides having the formula CH-CQ D N-Rn CH-CO wherein the two nitrogen atoms are part of a heterocyclic ring selected from the group consisting of maleic hydrazide, phthalyl hydrazide, triazole and urazole and R is selected from the group consisting of alkyl having 1 to 4 carbon atoms and phenyl,

(f) 1,4 diformyl 2,3,5,6 tetraalkanoyloxy-piperazines having the formula N-CHO wherein R is alkanoyl having 2 to 4 carbon atoms, (g) Phenyl esters having the formula wherein R- is selected from the group consisting of alkyl having 1 to 4 carbon atoms and phenyl,

(h) Acylated polyhydroxy compounds having the formula Y(COR81):1

wherein Y is selected from the group consisting of a mono-saccharide residue, a di-saccharide residue and a lower alkanepolyol having at least 3 hydroxyl groups, R is alkyl having 1 to 4 carbon atoms and n is an integer of at least 3,

(i) Carbonic acid esters having the formula wherein R is selected from the group consisting of p-carboxyphenyl, sodium-p-sulfophenyl and alkoxycarbonyl having 1 to 4 carbons in the alkoxy, and R is selected from the group consisting of alkyl having 1 to 4 carbon atoms, phenyl and cycloalkyl having 5 to 6 carbon atoms,

(j) Triacyl cyanurates having the formula R1o1-O-C /C0 1o1 wherein R is alkanoyl having 2 to 3 carbon atoms,

(k) benzoic acid anhydride, and (l) phthalic acid anhydride,

(2) from 0 to 95% by weight, of said water-soluble components, of surface-active agents selected from the group consisting of surface-active anionic compounds, surface-active non-ionic compounds, and surface-active amphoteric compounds, (3) from 0 to 95% by weight, of said water-soluble components, of inorganic builders selected from the group consisting of alkali metal bicarbonates, carbonates, borates, silicates, orthophosphates, pyrophosphates and metaphosphates and organic complex-forming compounds, and (4) from 0 to 20% by weight, of said water-soluble components, of neutral inorganic salts.

2. The scouring agent of claim 1 wherein said acylated activator compound is tetraacctyl-methylenediamine.

3. The scouring agent of claim 1 wherein said acylated activator compound is O-p-carboxyphenyl-O'-ethylcarbonate.

4. The scouring agent of claim 1 wherein said acylated activator compound is 1,3-propionyl-hydantoin.

5. The scouring agent of claim 1 wherein said acylated activator compound is benzoic acid anhydride.

6. The scouring agent of claim 1 wherein said acylated activator compound is triacetyl-cyanuric acid.

7. The scouring agent of claim 1 wherein said acylated activator compound is N-acetyl-maleic hydrazide.

8. The scouring agent of claim 1 wherein said acylated activator compound is 1,4-diformyl-2,3,5,6-tctraacctoxypiperazine.

9. The scouring agent of claim 1 wherein said acylated activator compound is glucose pentaacctate.

References Cited UNITED STATES PATENTS 3,630,921 12/1971 Disch et a1. 202- 3,058,916 10/1962 Sinner et a1. 25295 X 3,532,634 10/ 1970 Woods 25299 X 3,163,606 12/1964 Viveen et al. 25299 X 3,349,035 10/1967 Dithmar et a1 25299 3,272,750 9/1966 Chase 25299 3,256,198 6/1966 Matzner 25299 3,183,242 5/ 1965 Dithmar et al. 25299 X 3,177,148 4/1965 Bright et al. 25299 3,130,165 4/1964 Brocklehurst 25299 3,458,446 7/1969 Diaz 25299 MAYER WEINBLATI, Primary Examiner US. Cl. X.R. 25295, 186