US 3686128 A
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AU 165 EX 3,686,128 Patented Aug. 22, 1972 OBJECTS OF THE INVENTION 7 3,686,128 An object of the present invention is the obtaining WASHING, BLEACHING AND CLEANSING AGENTS CONTAINING POLY (N-TRI- CARBALLYLIC AClD)-ALKYLENEIMINES Achim Werdehausen, Monheim, and Peter Krings, Kre- 5 acids or their salts which i r e stability d cleanfeld, Germany, assignors to Henkel & Cie GmbH, Dus mg properties of the washing agents and stabilize the seldorf-Holthausen, Germany optical brighteners present.
N0 DfaWillg- Filed 1, 1969, 3 Another object of the invention is the obtaining of a Claim! P y, application Germany, May 1 s 1969 washing, bleaching and cleansing agent having a content P 19 24 300-6; July 1969, P 19 33 10 of from 50% to 99.9%, by weight, of customary com- US CL 25% C11! 7/56 7 Cl ponents of washing, bleaching and cleansing agents and from 0.1% to 50%, by weight, of salts of poly-(N-alkylcarboxylic acid)-alkyleneimines having an average molec- TRQ THE ISCI uilar weight of from 430 to 500,000 in which at least one CT OF D 0S 15 third of the recurring substituted alkyleneimine groups A washing, bleaching and cleansing agent having a have the following formula content of from 50% to 99.9%, by weight, of customary components of washing, bleaching and cleansing agents and from 0.1% to 50%, by weight, of salts of poly-(N- R alkylcar-boxylic y ha g an av g and the remainder of the recurring substituted alkylenemolecular weight of from 430 to 500,000 in which at least i i groups ha the following formula one third of the recurring substituted alkyleneimine groups have the following formula I i Y R wherein, in both formulas, R represents a member selected X R from the group consisting of hydrogen and methyl, X and the remainder of the recurring substituted alkylenerepresents imine groups have the following formula CH CH OOH ('lOOH (3003 Y R and Y represents a member selected from the group conwherein, in both formulas, R represents a member selectsisting of hydrogen,
ed from the group consisting of hydrogen and methyl, X
CH-CHCHI x R Y B boon boon boon and Y represents a member selected from the group and Y represents a member selected from the group conconslstmg of hydrogen and sisting of hydrogen 40 Ir X R B These and other objects of the invention will become and Y represents a member selected from the group con- 5 more apparent as the descnptlon theuof proceeds sisting of hydrogen and THE It has now been discovered that complexing amino- 3 polycarboxylic acids or their salts of poly-(N-tricarbal- X R lylic acid)-alkyleneimine having an average molecular weight of from 430 to 500,000, are complexing compounds for washing, bleaching and cleansing agents which, incorporated in said agents are distinguished by a THE PRIOR ART good stability against oxidizing substances, by an im- It has been common in the prior art to add to washing proved p s p p and y an effective stabilizing and cleansing agents, particularly those which contain of the optlcalbl'lghtenersbleaching compounds having active y e p -s The invention therefore comprises a washing, bleachammopolyocarboxylic acids or their alkali salts, such as, ing d l an in agent havin a ontent of from 50% uitrilotriacetic acid (NTA), ethylenediamine tetraacetic to 99.9%, by weight, of customary components of washacid (EDTA), or diethylenetriamine pentaacetic acid ing, bleaching and cleansing agents and from 0.1% to (DT'PA), in order to increase the stability of the bleach- 50%, lf f g Salts of P y-( ing agent, or to protect the optical brighteners contained alkyle e havms an average molecular y s of in the detergents against an attack by the oxidizing agents. from G t0 590,000 f 193511 One thud of These compounds have, however, certain disadvantages. recqmng substltuted alkylenelmln groups have the NTA can protect the optical brighteners only insufficient- 5 lowmg Formula I ly from an oxidizing attack, while EDTA and DTPA are -IIICH:CH
not completely stable against oxidizing agents and are x I 'f q to macuve comPounds' h compomfds named and the remainder of the recurring substituted alkyleneindeed increase the cleaning properties of washing agents. imine groups the f ll i .Fomula H They are, however, in this respect inferior to the known inorganic builders, particularly to the polymeric phosphates.
of washing, bleaching and cleansing agents which have incorporated therein complexing aminopolycarboxylic wherein, in both formulas, R represents a member selected from the group consisting of hydrogen and methyl, X represents CHCHCH:
COOH COOH COOH Y represents a member selected from the group consisting of hydrogen,
NCHr(IJH- and -NCH:([3H- X R Y R and Y represents a member selected from the group consisting of hydrogen and --NCH:CIJH- x R The amino groups present in the polyalkyleneimines can be completely or partially substituted by tricarballylic groups. Completely substituted polyalkyleneimines contain only the recurring groups according to Formula I and have a linear structure of the Formula III XNH-C.Hg(I?H[III-CHT(IJH NHX R x R 1, 111 wherein X and R are defined above and n is an integer from 2 to 130, preferably from 3 to 85, corresponding to a molecular weight of from 430 to 15,000, preferably from 500 to 10,000.
Such polymers in which only a part, for example, at least 33%% and less than 100% of the amino groups carry a tricarballylic group are mixed polymers which are built from the groups of the Formulas -I and II. Usually they contain branched chains and are partially illustrated by the following Formula IV wherein X and R are defined above. The branched and/ or mixed polymers have average molecular weights of from 430 to 500,000.
Preferably such alkylcarboxylic acid derivatives of polyethyleneimine or polypropyleneimine are used in which from 50% to 100% of the primary and secondary amino groups in the polyalkylenei'mine molecule carry tricarballylic acid groups. Of particular practical interest are the N-tricarballylic acid derivatives of polyetbyleneimines.
The polymeric(N tricarballylic acid) ethyleneimines are amphoteric substances. They can, therefore, depending upon the alkalinity or acidity of the washing, bleaching, and cleansing agents, be present as salts of alkali metals and ammonium salts, especially salts of sodium and potassium, and as salts of organic ammonium bases, as inner salts, or as salts of strong acids, for example, mineral acids such as sulfuric acid and organic acids such as p-toluene sulfonic acid.
The preparation of the polymeric (N-tricarballylic acid)-alkyleneimines can be done according to various known methods. For the synthesis of linear polymers, first monomeric ethyleneimine or propyleneimine is alkylated on the nitrogen atom according to the principles of the Michael-Addition, with derivatives of cisor trans-aconitic acids, such as, esters, amides and nitriles. Instead of olefinic-unsaturated carboxylic derivatives, also derivatives of halogenated tricarballylic acid can be used for the alkylation on the nitrogen atom.
Suitable starting materials are especially the lower alkyl esters, such as the methyl, ethyl, propyl, isopropyl and butyl esters of (N-tricarballylic acid)-aziridine. The plymerization takes place in the presence of Lewis type acids, for example, neutral sulfuric acid esters, preferably di-lower alkyl sulfates, such as dimethyl sulfate, diethyl sulfate, dipropyl sulfate, and dibutyl sulfate, or sulfonic acid esters, preferably lower alkylsulfonates and arylsulfonates, such as the methyl, ethyl, propyl and butyl esters of methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. The polymerization can also be conducted in the presence of solvents, especially of the lower halogenated hydrocarbons. The polymerization time is usually 2 to 60 hours. The reaction temperature is appropriately held between 30 and C. by cooling. The ester, amide or nitrile derivatives of the polymeric (N tricarballylic acid) alkyleneimines obtained are saponified in a known manner, for example, by heating with an alkali metal hydroxide solution such as aqueous sodium or potassium hydroxide. The alkali metal salts formed can be converted into the free acids by treating with ion-exchange resins. By subsequent neutralization with ammonia or organic ammonium bases, such as mono-, dior triethanolamine, morpholine, or N-methylmorpholine, the free acids can be converted to the corresponding acid salts.
The average molecular weights of the polymeric (N- tricarballylic acid)-alkyleneimines obtained in this way can vary within wide limits depending upon the type and amount of the polymerization catalyst used, the polymerization temperature, and the reaction time. In general, the average molecular weight of such linear polymers is between 500 and 10,000. By separating out the low molecular components often present in the mixture, for example, by gel-chromatography on polymerized dextranes (Sephadex), poymers with varied average molecular weight can be obtained. Since the low molecular components do not disturb, they can remain in the product.
If the polymerization of the (N-tricarballylic acid)- alkylenimine is conducted in the presence of unsubstituted monomeric ethyleneimine or propyleneimine, mixed polymers are formed which are built from groups of the Formulas I and II, and are more or less highly branched, as indicated in Formula IV. The ratio between substituted and unsubstituted monomeric ethyleneimine or propyleneimine is hereby selected in such a way that at least one third, preferably 50 to of the alkylenimine present 'in the polymerization mixture are substituted by alkylcarboxylic acids, to obtain polymeric (N-tricarballylic acid)-alkyleneimines which are preferably from 50% to 100% substituted on the amino groups.
A further method of preparation of the salts of the polymeric(N-tricarballylic acid)-alkyleneimines starts from preformed polyalkyleneirnines having an average molecular weight of from 300 to 150,000. The polyalkyleneimines are then reacted in alkaline aqueous medium with the derivatives or salts, preferably the alkali metal salts, of aconitic acid, or halogenated tricarballylic acids. Here the amount of carboxylic acid derivative should be selected in order that at least one third, preferably at least 50% of the primary and secondary amino groups in the preformed polyalkyleneimines are substituted. The compounds prepared from performed polyalkyleneimines are usually more or less highly branched. Their average molecular weight depends upon the degree of polymerization of the preformed polyethyleneirnines or polypropyleneimines, and can be from 500 to 500,000. In their performance, particularly in case of their use in washing, bleaching, and cleansing agents there is no essential difference between the linear and the branched polymeric(N-tricarballylic acid)-alkyleneimines.
The inner salts of the polymers can be obtained from the aqueous solutions by precipitation with mineral acids at the isoelectric point or by treating with ion-exchange resins. The inner salts are amorphous substances in solid form, which are insoluble in organic solvents and also predominately in water, but are readily soluble in acids and bases. From the free acids or inner salts, the corresponding ammonium salts can be prepared by neutralization vu'th ammonia or organic ammonium bases, such as, mono-, di-, or triethanolamine, morpholine, or N- methylmorpholine. The washing, bleaching and cleansing agents according to the invention can also contain mixtures of different polymeric (N-tricarballylic acid)- alkyleneimines or their salts.
The preferably used poly-(N-carballylic acid)-ethylene imines have an average molecular weight of 430 to 500,000.
The agents according to the invention contain at least one other cleaning or bleaching component, such as nonionic, anionic and amphoteric surface-active materials, inorganic or organic builders, oxygen-containing bleaching agents, as well as other conventional washing and cleansing ingredients. The polymeric (N-tricarballylic acid)-alkyleneimines or their salts, particularly the sodium salt, can be added to these ingredients in the form of their solutions or in solid form after previous drying.
Among the surface-active materials present as a component in the washing, bleaching and cleansing agents of the invention are, in the case where little foaming is essential, nonionic compounds, such as the polyalkyleneglycolether derivatives of alcohols, fatty acids and alkylphenols which contain 3 to 30 ethyleneglycolether groups and 8 to 20 carbon atoms in the hydrocarbon radical. Particularly suitable are polyethyleneglycolether derivatives in which the number of oxyethylene groups is from 5 to and whose hydrocarbon radicals are derived from straightchain primary alcohols with 12 to 18 carbon atoms, or from alkylphenols with a straight-chain alkyl chain of 6 to 14 carbon atoms. By the addition of 3 to 15 mols of propylene oxide to the last-named polyethyleneglycolethers, or by converting them into acetals, detergents are obtained which are distinguished by a specially low-foaming power.
Other suitable nonionic basic washing components with low-foaming properties are the water soluble polyethylene oxide adducts, adducted to polypropyleneglycol, ethylenediamine-polypropyleneglycol and alkylpolypropyleneglycol with 1 to 10 carbon atoms in the alkyl chain. Preferably, these adducts contain from to 250 oxyethylene groups and 10 to 100 oxypropylene groups in the molecule. The named compounds contain usually 1 to 5 oxyethylene units per oxypropylene unit. Also nonionic compounds of the type of aminooxides and sulfoxides containing at least one hydrocarbon radical with 10 to 20 carbon atoms which, if necessary, can also be ethoxylated, are usable.
The washing and cleansing agents can also contain anionic basic washing components of the sulfonate or sulfate type. Primarily alkylbenzene sulfonates, such as dodecylbenzene sulfonate are suitable. However, olefin sulfonates, such as, are obtained by sulfonation of primary and secondary aliphatic monoolefins with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis, as well as alkylsulfonates obtainable from n-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis, or neutralization, or by addition of bisulfite to olefins are also suitable. Also a-sulfo fatty acid esters, primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated higher alcohols are suitable. Other compounds of this class which can be occasionally present in the detergents are the higher molecular weight sulfated partial ethers and partial esters of polyhydric alcohols, such as, the alkali metal salts of the monoalkyl ethers, or mono-fatty acid esters of the glycerine monosulfuric acid esters, or, of 1,2 dihydroxypropane-sulfonic acid. Also sulfates of ethoxylated or propoxylated fatty acid amides and alkyl phenols as well as fatty acid taurides and fatty acid isethionates are suitable.
Other appropriate anionic basic washing components are alkali metal soaps of natural or synthetic fatty acids, such as, sodium soaps of coconut, palm kernel, or tallow fatty acids. As amphoteric basic washing components,
alkylbetaines and, particularly, alkylsulfobetaines are suitable, for example, 3-(N,N-dimethyl-N-alkylammonium)-propane-l-sulfonate and 3-(N,N-dimethyl-N-alkylammonium)-2-hydroxy-propane-1 sulfonate, preferably Where alkyl is a lower alkyl such as methyl or ethyl.
The anionic basic washing components can be present in the form of the alkali metal salts such as the sodium and potassium salts as well as the ammonium salt, or as salts of organic bases, such as mono, di, and triethanolamine. Where the named surface-active nonionic, anionic and amphoteric compounds have a long-chain aliphatic hydrocarbon radical, the latter should preferably be straight-chained and should have from 8 to 22 carbon atoms. In the compounds with araliphatic hydrocarbon radicals the preferred straight alkyl chains contain an average of from 6 to 16 carbon atoms.
Appropriate mixture ingredients in addition to the above are also inorganic builders, particularly condensed phosphates, such as, pyrophosphates, triphosphates tetraphosphates, trimetaphosphates, tetrametaphosphates as well as more highly condensed phosphates in the form of the neutral or acidic alkali metal salts such as the sodium and potassium salts as well as the ammonium salt. Preferably alkali metal triphosphates and their mixture with pyrophosphates are used. The condensed phosphates can also be partly or completely substituted by organic complexing agents containing phosphorus or nitrogen atoms. Such compounds are the alkali metal or ammonium salts of aminopolyphosphonic acids, particularly aminotri-(methylenephosphonic acid), ethylenediaminetetra-(methylenephosphonic acid), l-hydroxyethane-l,l-diphosphonic acid, methylenediphosphonic acid, ethylenediphosphonic acid as well as the higher homologs of the named polyphosphonic acids, as well as the alkali metal or ammonium salts of low-molecular-weight aminopolycarboxylic acids, such as, NTA and EDTA. As other builders, alkali metal silicates are suitable, particularly sodium silicate in which the ratio Na,O:SiO, is 123.5 to 1:1.
As further mixture ingredients are neutral salts, such as, sodium sulfate and sodium chloride, as well as compounds for adjustment of the pH, such as bicarbonates, carbonates, borates and hydroxides of sodium and potassium and acids, such as, lactic and citric acid. The amount of the alkaline reacting substances should be calculated so that the pH of a serviceable washing liquor for coarse laundry is 9 to 12 and for fine laundry 6 to 9.
By appropriate combination of various surface-active basic washing components or builders with each other, in many cases increased elfectiveness, such as a higher clean ing property or lower foaming power can be attained. Such improvements are possible, for example, by combination together of anionic with nonionic and/or amphoteric compounds, by combination of various nonionic compounds with each other or also by mixture of basic washing components of the same type which differ in regard to the number of carbon atoms or the number and position of double bonds or branched chains in the hydrocarbon. Synergistically effective mixtures of inorganic and organic builders can also be used or combined with the precedingly named mixtures.
Depending upon their respective use, the washing agents of the invention can contain oxygen-releasing bleaching compounds, such as, hydrogen peroxide, alkali metal perborates, alkali metal percarbonates, alkali metal perphos- .phates, urea hydrogen peroxide and alkali metal persulfates or active-chlorine compounds, such as, alkali metal hypochlorites, chlorinated trisodium phosphate and chlorinated cyanuric acid, or its alkali metal salts. The peroxide compounds can be present in a mixture with bleaching activators and stabilizers, such as, magnesium silicate.
Optical brighteners suitable for cellulosic fibers used in the washing agents of the invention are those of the diaminostilbene disulfonic acid type of the formula:
i N N -t- N 1 1 is u Y 80; SO;- Y
in which X and Y have the following meanings: NH NHCH NHCH CH=OH,
N(CH --CH OH) morpholino, dimethylmorpholino, NH-C H NH- c,H,so,H, out, or where X and Y can be the same or not. Particularly suitable are those compounds in which X is an anilino and Y a diethanolamino, or a morpholino group.
As optical brighteners for polyamide fibers suitable for use in the washing agents of the invention are those of the diarylpyrazoline type of the following formula:
In this formula Ar and Ar are aryl radicals, such as, phenyl, diphenyl, or naphthyl which can have further substituents, such as, hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, sulfonic acid, and sulfonamide groups, or halogen atoms. Preferred is a 1,3 di arylpyrazoline derivative in which the radical Ar is a psulfonarnidophenyl group and the radical Ar is a pchlorophenyl group. In addition to the brighteners, whiteners suitable for the brightening of other fiber types can be present, for example, compounds of the type of naphthotriazolestilbene sulfonates, ethylene-bisbenzimidazoles, ethylene-bis-benzoxazoles, thiophene-bis-benzoxazoles, dialkylaminocoumarins, and the cyanoanthracenes. These brighteners or their mixtures can be present in the washing agents in amounts of from 0.01% to 1.5% by weight, preferably from 0.1% to 1% by weight.
Further suitable mixture ingredients for the washing agents of the invention are greying-inhibiting compounds, such as sodium celluloseglycolate, as well as the water soluble sodium salts of synthetic polymers which contain free carboxylic groups. These latter include the polyesters or the po'lyamides of triand tetracarboxylic acids and dihydric alcohols or diamines, and also polymeric acrylic acid, methaerylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and aconitic acid as well as the mixed polymerizates of the named unsaturated carboxylic acids, or their mixed polymerizates with olefins.
Washing agents intended for the use in drum-washing machines contain appropriately known foam-suppressing substances such as saturated fatty acids with 20 to 24 carbon atoms, or their alkali metal soaps, or triazine derivatives which can be obtained by reacting one mol cyanuric chloride with 2 to 3 mols of aliphatic, straight-chained, branched-chained or cyclic primary monoamines or by propoxylating, or, butoxylating melamine.
For a further improvement of the dirt-loosening properties of the washing agents according to the invention they can also contain enzymes from the class of proteases, lipases, or amylases. These enzymes can be of animal or plant origin, for example, those obtained from digestive ferments or yeasts, such as pepsin, pancreatin, trypsin, papain, catalase and diastase. Preferably used are enzymatic active substances obtained from bacterial strains or molds, such as, Bacillus subtilis and Slreptomyces griseus which are relatively stable against alkalis, peroxide compounds and anionic detergents and essentially not inactivated even at temperatures between 45 C. and 70 C.
The washing and cleansing agents can be present in liquid, pasty or solid form, as powder, granules or lumps.
Liquid preparations may contain water-miscible solvents, particularly lower alkanols such as ethanol and isopropanol, as well as dissolving aids, such as, the alkali metal salts of benzene, toluene, xylene, or ethylbenzene sulfonic acids. For increasing of the foaming power and for the improvement of the skin compatibility alkylolamides, such as, fatty acid mono, or diethanolamides may, if necessary, be added. The mixture can also contain dyes or odorizing substances, bactericidally-active materials, activators as well as fillers, for example, urea.
The preparation of the agents according to the invention can be done in customary manner by mixing, granulating or spray-drying. Insofar as enzymes are used, it is recommended to mix them with the nonionic basic washing components and, if necessary, odorizing substances, or to disperse them in the melt of a salt containing water of crystallization, such as Glaubers salt, and to combine these premixtures with the other powdery ingredients. By this procedure, the enzymes are cemented with the other powder particles so that the mixtures do not tend to dust or separate.
The content of the washing, bleaching and cleansing agents of poly-(N-tricarballylic acid)-alkyleneimine or its alkali metal salts amounts from about 0.1% to 50% preferably 0.2% to 25% by weight, depending upon their use. The difference to 100% is taken up by the previously named detergent and bleaching active substances as well as, if necessary, the additional builders to improve the cleaning power. The qualitative and quantitative composition of these additional ingredients depend widely upon the special use of these agents. It corresponds in the case of the technically particular important washing and cleansing agents to the following recipe: (data in percent by weight) 1% to 40% of at least one compound from the class of the anionic, nonionic, and amphoteric detergents. 0 to preferably 10% to 80% of at least one non-surface-active cleaning intensifying or complexing builder. 0 to 50%, preferably 10% to 50% of a percompound, especially sodium perborate, with or without water of crystallization, as well as their mixtures with stabilizers and activators. 0 to 60%, preferably 0.1% to 20% of other auxiliary and supplementary substances.
The detergent substances can consist of up to 100%, preferably from 5% to 70%, of compounds of the sulfonate and/or the sulfate type, up to 100%, preferably from 5% to 40% of the nonionic polyglycolether type, and up to 100%, preferably from 10% to 50% of soaps. The builders can consist of up to 100%, preferably from 25% to of alkali metal triphosphates and their mixtures with alkali metal pyrophosphates, up to preferably from 5% to 50%, of an alkali salt of a complexing agent from the class of polyphosphonic acids, nitrilotriacetic acid, ethylene'diaminetetraacetic acid, and up to 100%, preferably from 5% to 75% of at least one compound of the class of alkali metal silicates, alkali metal carbonates and alkali metal borates.
To the additional auxiliary and supplementary substances belong, in addition to the optical brighteners, especially the foam inhibitors which can be present in the agents according to the invention in an amount of up to 5%, preferably from 0.2% to 3%; also the enzymes which can be present in an amount up to 5%, preferably from 0.2% to 3%; and the greying-inhibitors which can be present in an amount up to 5%, preferably from 0.2% to In particular, poly-(N-tricarballylic acid)-ethyleneimine is suitable for the preparation of clear aqueous detergent concentrates without the use of organic solvents or hydrotropic compounds. Such hydrotropic substances as well as the water mixable solvents have, as it is known, no detergent properties. Since their use makes the preparation of liquid detergents more expensive without any gain in detergent power, there is a special interest for such liquid products in which all ingredients have cleansing properties.
A clear liquid concentrate, stable on storage, consists essentially of 5% to 40%, preferably 15% to 30%, by weight, of alkali metal salts of poly (N-tricarballylic acid)-ethyleneimine, 3% to 30%, preferably 5% to 15%, of a primary and/or secondary olefinsulfonate with 8 to 24 carbon atoms in the form of its alkali metal, ammonium, or organic ammonium salts, and 50% to 92% by weight of water. In addition to the precedingly named ingredients, such agents can also contain up to 10%, preferably not more than by weight, of anionic or nonionic detergents which have good solubility in water. Examples of these detergents are the alkali metal salts of alkanesulfonic acids, and lower alkyl esters of atsulfofatty acids, particularly the methyl, ethyl, propyl and butyl esters of a-sulfonated saturated fatty acids having from 8 to 20 carbon atoms, also the sulfated ethoxylated products of alkanols, alkylphenols, amines, fatty acids and fatty amides which contain a hydrophobic hydrocarbon radical with 8 to 20 carbon atoms and from 1 to oxyethylene units, as well as the corresponding non-sulfated polyglycolether derivatives, in which the ratio of the number of carbon atoms in the hydrophobic hydrocarbon radical to the number of oxyethylene units is between 2:1 and 1:2 as an average.
The poly-(N-tricarballylic acid)-alkyleneimines and their salts impart to the washing, cleansing and bleaching agents, according to the invention, a high washing and cleansing power, as well as improved dirt-carrying power. They are effective stabilizers for peroxide compounds and are less attacked by peroxide compounds than known complexing agents. They are, therefore, suitable for the stabilization of liquid bleaching detergents, such as those containing hydrogen peroxide and compounded liquid bleaching agents. The preparation of such agents has failed so far because of the low storage-stability of the peroxide compounds. The new compounds protect, in addition, the oxygen-sensitive ingredients of washing agents, particularly the optical brighteners and enzymes effectively against oxidative destruction. In contrast to many known oxidation inhibitors they do not diminish the bleaching power of the agents. The agents can be easily degraded biologically and have the advantage that they can replace completely or partially the polymeric phosphates which have previously necessarily been present in washing agents, so that because of a lesser amount of phosphate ions in the sewage they do not promote the growth of algae in rivers and lakes.
The following examples are illustrative of the practice of the invention without being limitative. In the following, some recipes are given which have proven particularly good in practice.
EXAMPLES (A) Powdery, low-foaming washing agent 3% to of a sulfonate basic washing component from the class of alkylbenzene sulfonates, olefin sulfonates and n-alkane sulfonates (sodium salts) 0.5% to 5% of an alkylpolyglycolether (alkyl C to C or alkylphenolpolyglycolether (alkyl C; to C with 5 to 10 oxyethylene groups 0 to 5% of a C to C soap (sodium salt) 0.2% to 5% of foam inhibitors from the class of trialkylmelamines and saturated fatty acids with 20 to 24 carbon atoms, or their alkali metal soaps 10% to 50% of a condensed alkali metal phosphate from the class of the pyrophosphatcs or the tripolyphosphates 0.1% to 25% of poly-(N-tricarballylic acid)-alkyleneimine or its alkali metal salt 1% to 5% of sodium silicate 10% to of sodium perborate tetrahydrate 0 to 5% of enzymes 0.05% to 1% of at least one optical brightener from the class of diaminostilbenedisulfonic acid or diarylpyrazoline derivatives 0.1% to 30% of an inorganic alkali metal salt from the class of the carbonates, bicarbonates, borates, sulfates and chlorides 0 to 4% of magnesium silicate 0.5% to 3% of sodium celluloseglycolate (B) Powdery foaming fine washing agent 1% to 30% of a sulfonate basic washing component (sodium salt) 0.5% to 10% of alkylpolyglycolether sulfate (alkyl C;
to C 1 to 5 oxyethylene groups) 0 to 20% of an alkylpolyglycolether (alkyl C to C or alkylphenolpolyglycolether (alkyl C, to C with 5 to 12 oxyethyene groups 0.2% to 25% of poly-(N-tricarballylic acidhalkyleneimine or its alkali metal salt 0 to 5% of a higher fatty acid ethanolamide or diethanolamide 0 to 20% of sodium tripolyphospate 0 to 1% of a brightener from the class of the diarylpyrazoline derivatives and its mixtures with polyester brighteners 3% to 70% of sodium sulfate (C) Liquid washing agent 0.5% to 10% of a sulfonate basic washing component (potassium salt) 0 to 10% of alkylpolyglycolether sulfate (alkyl C; to C 1 to 5 oxyethylene groups) 0.2% to 25% of poly-(N-tricarballylic acid)-alkyleneimine or its alkali metal salts 0.1% to 5% of fatty amide-glycolether condensate (alkyl C to C1 1 to 10 oxyethylene groups) 1% to 10% of solution aids from the class of the alkali metal salts of benzene, toluene, or xylene sulfonic acids.
0 to 30% of neutral or acid potassium pyrophosphate 0 to 10% of organic solvent media from the class of the C, to C alcohols and ether alcohols 0 to 1% of optical brighteners from the class of the diaminostilbene disulfonic acids and diarylpyrazoline derivatives 0 to 5% of hydrogen peroxide Residue: Water, perfumes, dyes, preservatives (D) Steeping and pre-washing agent 0.5% to 5% of sulfonate basic washing component (sodium salt) 0 to 3% of compounds from the class of alkylpolyglycolethers (alkyl C to C and alkylphenolpolyglycolethers (alkyl C to C with 5 to 12 oxyethylene groups 0.1% to 10% of poly-(N-tricarballylic acid)-a1kyleneimine or its alkali metal salts 10% to 50% of sodium carbonate 1% to 5% of water glass 0 to 5% of magnesium silicate 0 to 5% of enzymes (E) Dishwashing-machine washing agents 0.1% to 3% of compounds from the class of the alkylpolyglycolether (alkyl C to C alkylphenolpolyglycolether (alkyl C; to C with 5 to 30 oxyethylene groups and 5 to 30 oxypropylene groups, and ethoxylated polypropylencglycols 0.2% to 25% of poly-(N-tricarballylic acid)-alkyleneimine or its alkali metal salts 45% to of pentasodium triphosphate 1% to 40% of sodium silicate (Na O:SiO,=1:1 to 1:3)
0 to 5% of potassium dichloroisocyanurate 0 to 2% of foaming inhibitors (F) Liquid rinsing and cleansing agent 5% to 30% of a sulfonate basic washing component (potassium salt) 2% to 15% of alkylpolyglycolether sulfate (alkyl C; to
C16. 1 to 5 oxyethylene groups) 0.2% to 10% of alkali metal salts of poly-(N-tricarballylic acid)-al-kyleneimine 0 to 20% of organic solvents from the class C; to C alcohols and ether alcohols 1 1 1% to 10% of solution aids such as sodium toluene sulfonate, sodium xylene sulfonate and urea Residue: Water, perfumes, dyes, preservatives (G) Bleaching agents 0.2% to 25% of poly-(N-tricarballylic acid)-alkyleneimine or its alkali metal salts 10% to 95% of percompounds to 50% of alkaline reacting compounds from the class of alkali metal hydroxides, carbonate, silicates and phosphates 0 to 50% of bleaching activators 0 to of anionic and/or nonionic detergents 0 to l0% of other ingredients, such as, corrosion inhibitors, optical brighteners, neutral salts, magnesium silicate.
(H) Alkaline cleansers 0.1% to 25 of poly-(N-tricarballylic acid)-alkyleneimine or its alkali metal salts 0.5% to 50% of sodium silicate (N O:SiO =1 :1 to 1:3)
0.5% to 80% of sodium hydroxide 0 to 40% of trisodium phosphate 0 to 40% of condensed alkali metal phosphates 0 to 40% of sodium carbonate 0 to of hydroxyethane diphosphonate (sodium salts) 0 to 5% of anionic and/o1- nonionic detergents (I) Scouting agent 1% to 10% of anionic and/0r nonionic basic washing components 0.1% to 5% of alkali metal satls of poly-(N-tricarballylic acid)-alkyleneimine 80% to 95% of abrasive agents 0 to 10% of cleansing salts of the class of alkali metal polyphosphates, alkali metal silicates, alkali metal borates, and alkali metal carbonates 0 to 10% of alkali metal dichloroisocyanurate EXAMPLES 1 TO 3 The cleaning action of washing agents that contained one part by weight of an anionic basic washing component (Na-n-dodecylbenzene sulfonate) and two parts by weight of builder components were compared. With these washing agents, cotton cloth which had been soiled with a synthetic soil containing soot, iron oxide and cutaneous fat was washed in a laboratory washing ma chine where the washing liquor was heated from 20 C. to 90 C. within minutes and kept at 90 C. for another 15 minutes. The washing agent concentration was 3 gm./l. The water hardness was 16 dH. The weight ratio of textile to liquor was 1:12. Subsequently, the washed cloth was rinsed with water four times, centrifuged and dried. The percent of whiteness was determined with a photometer (soiled cloth 0%, original cloth 100%) and is shown in the following Table I as well as the composition of the washing agents.
For the preparation of the polymeric (N-tricanballylic acid)-ethyleneimine, dibutyl aconitate and aziridine in a mol ratio of 1:1 were heated in the persence of 1 mol percent of sodium methylate for 24 hours at 30 to 40 C. After addition of 1 mol percent of diethyl sulfate, the N- (tricarballylic acid tributyl ester)-aziridine formed was polymerized in an inert atmosphere for 5 to 10 hours at a temperature not higher than 40 C. Subsequently, the polymer was dissolved in methanol and then treated with an equivalent amount of sodium hydroxide. The solution was heated to 80 of 85 C., and the methanol removed by distillation. After 5 hours of heating with water being repeatedly added, the saponification was completed. The sodium salt of the polymerizate was isolated by spray drying.
The results of the washing tests of Table I show that the polymeric (N-tricarballylic acid)-ethyleneimines are superior to the other known builders, among them the pentasodium triphosphate which is known as being very effective, in the cleaning property.
EXAMPLES 4 AND 5 A washing agent of the following composition was used (data in percent by weight):
8% Nan-dodecylbenzene sulfonate 5% sodium soap of C to C fatty acids 5% sodium salt of C to C fatty acids 40% pentasodium triphosphate 5% sodium silicate (Na O.3.3SiO
2% magnesium silicate 1% sodium cellulose glycolate 25% sodium perborate-tetrahydrate 8% water 0.8% brightener of the pyrazoline type 0.2% brightener of the diaminostilbene type The brighteners had the following structures: cio -cn. HN-O IE 6H2 NZK =ii N H H I S OJNB N(C;H4OH)2 2 Diaminostilbene type I SOzNH:
Pyrazoline type To this agent were added each time 2% by Weight of the sodium salt of the poly-(N-tricarballylic acid)-ethyleneimine listed in the following Table II. For comparative purposes, a washing agent was used which, instead of the polymers according to the invention, 2% of sodium nitrilotriacetate (NTA) or 2% of Na ethylenediamine tetraacetate (EDTA) was added.
With these agents, textiles of polyamide fiber (Perlon, registered trademark)were washed in a laboratory washing machine where the washing liquor was heated from 20 C. to 60 C. within 15 minutes and was kept at this temperature for additional 15 minutes. The washing agent concentration was 5 gm./l. and the weight ratio of textiles to liquor was 1:30. The water used had a hardness of 16 dH as well as a copper ion content of 10 mols per liter. The degree of whiteness of the four times rinsed and then dried wash was determined by photometer. The results are summarized in Table IV. These results demonstrate the superiority of the use of the polymers of the present invention.
the washing agents listed in the Examples 4 and 5 with addition of 2% by weight of polymeric (N-tricarballylic acid)-ethyleneimines for 30 minutes at a temperature of 90 C. The concentration of the washing agent was 5 gm./l. The weight ratio of textile to washing liquor was 1 to and the hardness of the tap water was 16 dH. The reflection values of the three times rinsed and dried samples, determined photometrically, are summarized in the following Table III.
TABLE III Percent reflection Molec- Unbleached ular Cotton cotton Ex. Addition weight fabric cloth 6. Poly-(N-tricarballylic acid)- 2, 040 87. 9 78. 6
ethyleueimine. Na ethylenedtamlne tetra- 85. 7 75. 8
acetate. Na nitrilotriacetate 86. 4 76. 8
EXAMPLE 7 An aqueous solution containing 0.62 gm./l. of sodium perborate was prepared from a bleaching agent consisting of 1 mol (154 gm.) of sodium perborate and one monomeric unit (217 gm.) of a poly-(N-tricarballylic acid)-ethyleneimine having an average molecular weight of 2040. The pH of the solution was adjusted to 10 with dilute sodium hydroxide. Another bleaching solution, also adjusted to a pH of 10 with dilute sodium hydroxide, contained, per liter, 4 millimols (0.136 gm.) of hydrogen peroxide and 4 millimols (0.87 gm.) of complexing agent.
The decrease of the active-oxygen content of these solutions at 100 C. was determined every 30 minutes by iodometric titration. For comparison the determination was repeated with equimolecular amounts of known perborate stabilizers (ethylened-iamine-tetraacetic acid, nitrilotriacetic acid). The results are summarized in the following Table IV. They show the particular stability of the agents according to the invention.
EXAMPLES 8 to 10 In the following examples, sodium salts of branched poly-(N-tricarballylic acid)-ethyleneimines were used. These polymers were prepared as follows. Aqueous solutions containing by weight of polyethyleneimines having average molecular weights of 5,000, 25,000, and 70,000 were separately heated to 80 C. to 90 C., each time with 80% of the stoichiometric amount required for complete N-alkylation, of aconitic acid while the pH was adjusted to 10 to 11 by addition of sodium hydroxide. The reaction product was separated by hot spraying. Based on free acid content, the polymers had average molecular weights respectively of 20,000, 100,000, and 280,000.
The compounds were added to the washing agent compositions used in Examples 4 and 5, in place of the linear polymeric aminocarboxylic acids described there, in amounts of 2% by weight, and the textile samples of polyamide fabric were subsequently washed and examined in the same way. The degree of whiteness of the samples is given in the following Table V:
TABLE V Degree of whiteness Molecular atter w. of the Example polymer 1 washing 5 washings 8- 20,000 109 116 9 100,000 110 116 10 280,000 109 115 NTA 104 EDTA 103 EXAMPLES 11 to 17 The folowing mixtures were prepared using linear-aolefinsulfonates. The sulfonates were used as the sodium salts. For the sodium salt of the linear poly-(N-tricarballylic acid)-ethyleneimine the abbreviation PTE was used. The indicated molecular weight refers to free PTE, not to the sodium salt. The optical brightener was a pyrazoline compound of the following formula The percent data given is percent by weight.
Example 11 10% olefinsulfonate (chain length C C 20% PTE (mol. weight 2040) Residue water Example 12 10% olefinsulfonate (chain length O -C 20% PTE (mol. weight 3500) 0.12% optical brightener Residue water Example 13 15% olefinsulfonate (chain length C 43 15% PTE (mol. weight 1430) 0.1% optical brightener Residue water Example 14 5% olefinsulfonate (chain length C15C18) 30% PTE (mol. weight 2040) Residue water Example 15 7.5% olefinsulfonate (chain length C C 2.5% salt of methyl a-sulfo-stearate 20% PTE (mol. weight 2040) 0.1% optical brightener Residue water Example 16 7.5 olefinsulfonate (chain length C -C 2.5% secondary alkanesulfonate (saponified sulfochlorination product, chain length C C 20% PTE (mol. weight 2040) 0.1% optical brightener Residue water Example 17 9% olefinsulfonate (chain length C -C 1% oleylalcohol polyglycolether (10 oxyethylene units) 20% PTE (mol. weight 2040) 0.1% optical brightener Residue water The solutions were stored at room temperature for sev eral weeks and no turbidity or separation occurred. When the a-olefinsulfonate was replaced by other known basic washing compounds, such as, n-dodecylbenzenesulfonate,
ethoxylated nonylphenol, or, ethoxylated oleyl alcohol with each having 8 oxyethylene units, laurylsulfate, lauryldiglycolether sulfate, methyl u-sulfo-stearate, or secondary alkanesulfonates, whereby the sulfonates and sulfates were used as sodium salts, turbidity and separation occurred within one day. The same negative result was obtained if PTE was replaced by other complexing agents, such as, Na nitrilotriacetate, Na ethylenediamiuetetraacetate, pentapotassium triphosphate, or tetrapotassium pyrophosphate.
In the following experimental series, fabric samples of cotton, polyester and polyamide fibers were soiled with an artificial soil of cutaneous fat and soot and washed with tap water of 16 dB. The heating-up time of the washing liquor to the washing temperature and the duration of the treatment was 15 minutes each. For cotton, the washing temperature was 90 C. and the weight ratio of textile to washing liquor was 1 to 12. For the synthetics, these values were 60 C. and 1 to 30. After rinsing four times with water at 30 C., the degree of whiteness of the dried fabric was photometrically determined. The reflection values of the soiled samples, referred to pure magnesium oxide (=l% were for cotton 44.1%, for polyester 39.6%, and for polyamide 36.3%. In order to eliminate the influence of optical brighteners detergent mixtures free of them were used. For comparison a commercial liquid fine-washing agent, prepared with the aid of dissolving intermediaries, which had the following composition was tested under the same conditions:
14% Na-lauryl-diethyleneglycolether sulfate Na-dodecylbenzenesulfonate 1.5 Na-toluenesulfonate 2% pentasodium triphosphate Residue water.
This results can be seen from the following table. They show that the polymeric agents according to the invention are equally effective for fabrics of cotton, polyester, and polyamides while in the use of comparative agents each time only one or two of the named textile fabrics were cleaned satisfactorily.
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.
1. A washing, bleaching and cleansing agent having a content of from 50% to 99.9% by weight, of customary components of washing, bleaching and cleansing agents and from 0.1% to 50% by weight, of a polyalkyleneimine selected from the group consisting of (1) poly-(N-tricarballylic acid)-alkyleneimines having an average molecular weight of from 430 to 500,000 in which at least 33 /s% to 100% of the recurring substituted alkyleneimine groups have the following formula N-CH:CIH-
and the remainder of 0 to 66%% of the recurring substituted alkyleneimine groups having the following formula wherein, in both formulas, R represents a member selected from the group consisting of hydrogen and methyl, X rep resents CH-CHCH2 (IJOOH (10011 00011 and Y represents a member selected from the group consisting of hydrogen,
--NCHTCH and NCHTCH- t I t 1.
and Y represents a member selected from the group consisting of hydrogen and NCH2CH- and (2) their alkali metal, ammonium and organic ammonium salts with bases selected from the group consisting of mono-, diand triethanolamine, morpholine and N-methyl morpholine, said customary components or washing, bleaching and cleansing agents consisting essentially of from 0% to 40% by weight of at least one compound selected from the group consisting of anionic, nonionic and amphoteric surface-active basic washing components, from 0% to by weight of at least one builder selected from the group consisting of condensed inorganic phosphate builders, alkali metal silicates, carbonates, bicarbonates, borates, sulfates and chlorides, alkali metal and ammonium salts of aminopolyphosphonic acids and low-molecular-weight aminopolycarboxylic acids, from 0% to by weight of a bleaching compound selected from the group consisting of hydrogen peroxide, urea hydrogen peroxide, alkali metal perborates, percarbonates, perphosphates, persulfates, hypochlorites, chlorinated trisodium phosphate and chlorinated cyanuric acid and its alkali metal salts, and mixtures thereof with magnesium silicates, and from 0% to 60% of other auxiliary and supplementary components of washing agents selected from the group consisting of optical brighteners, greyinginhibitors, foam-suppressors, enzymes, water-miscible solvents, water and dissolving aids, said ingredients totaling 100% by weight of said customary components.
2. The washing, bleaching and cleansing agent of claim 1 wherein said polyalkyleneimines are present in an amount of from 0.5% to 25% by weight.
3. The washing, bleaching and cleansing agent of claim 1 wherein said polyalkyleneimines are branched poly-(N- tricarballylic acid)-alkyleneimines having the formula wherein R represents a member selected from the group consisting of hydrogen and methyl and X represents wherein R represents a member selected from the group consisting of hydrogen and methyl and X represents (?H (1H CH:
C OOH C OOH OOH and n is an integer from 3 to 35.
5. The washing, bleaching and cleansing agent of claim 4 wherein R is hydrogen.
6. The washing, bleaching and cleansing agent of claim 3 wherein R is hydrogen.
7. A stable, liquid washing and cleansing composition consisting essentially of from 5% to 40% by weight of an alkali metal salt of poly-(N-tricarballylic acid)-ethyleneimine having an average molecular weight of from 430 to 500,000, from 3% to 40% by weight of a sulfonate selected from the group consisting of alkal metal, ammonium and organic ammonium salts of primary and secondary olefinesulfonic acids having from 8 to 24 carbon atoms, and from 50% to 92% by weight of water.
References Cited UNITED STATES PATENTS 3,251,778 5/1966 Dickson et al 2602 EM 3,424,790 1/1969 Bond et al 260534 E MAYER WEINBLATI, Primary Examiner US. Cl. X.R.
25295; 2602 EM, 78, 534 E