US 3650963 A
Abstract available in
Claims available in
Description (OCR text may contain errors)
7 us. c1. 252- 102 3,650,963 WASHING, BLEACHING AND CLEANSING AGENTS CONTAINING POLY-(N-ACETIC ACID)-ETHYLENEIMINES Achim Werdehausen, Monheim, and Manfred Dohr, Dusseldorf-Holthausen, Germany, assignors to Henkel & Cie GmbH, Dusseldorf, Germany No Drawing. Filed Dec. 1, 1969, Ser. No. 881,301 Claims priority, application Germany, Dec. 21, 1968, P 18 16 280.6 Int. Cl. Clld 7/54 4 Claims ABSTRACT OF THE DISCLOSURE 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 polyethyleneimine selected from the group consisting of (1) linear poly-(N-acetic acid)-polyethyleneimines of the formula wherein n is an integer from 3 to 50 and (2) their alkali metal, ammonium and organic ammonium salts.
THE PRIOR ART It has been common in the prior art to add to washing and cleansing agents, particularly those which contain bleaching compounds having active oxygen, complexing aminopolycarboxylic acids or their alkali salts, such as nitrioltriacetic acid (NTA), ethylenediamine tetraacetic acid (EDTA), or diethylenetriamine pentaacetic acid (DTPA), in order to increase the stability of the bleaching agent, or to protect the optical brighteners contained in the detergents against an attack by the oxidizing agents. These compounds have, however, certain disadvantages. NTA can protect the optical brighteners only insufliciently from an oxidizing attack, while EDTA and DTPA are not completely stable against oxidizing agents and are oxidized to inactive compounds. The compounds named indeed increase the cleaning properties of washing agents. They are, however, in this respect inferior to the known inorganic builders, particularly to the polymeric phosphates.
In the German Auslegeschrift 1,060,849, as well as the essentially identical British Pat. 866,492, there is suggested as stabilizing agents for perborates or for washing and bleaching agents containing perborates, in additional to DTPA, where n is 1, complexing polyaminopolycarboxylic acids of the formula as are obtained by the reaction of ethylene chloride with ammonia and a subsequent carboxymethylation of the reseulting polyamines. In German Auslegeschrift 1,060,849, 11 is indicated as being 1 to 10.
In the corresponding British patent, however, it is shown that the stability of the described compounds against oxidizing agents is the best with the diethylenetriamine pentaacetic acid (DTPA) and triethylenetetramine hexaacetic acid (TTHA) and decreases again with increasing molecular weight. Polymers in which the number n is greater than 3 differ unessentially from EDTA in their stability against oxygen. A similar behavior is shown by these compounds in washing and ice cleansing agents in regard to their property of increasing the cleaning properties. The increase in cleaning property, also often called the builder eifect, attains its highest value with EDTA and DTPA and thereafter decreases with increasing molecular weight. It had to be assumed, therefore, that polyamino carboxylic acids prepared in another way but whose structure differed little from the deescribed compounds, would behave quite similarly and that the stability against oxidizing agents and the builder effect would also decrease with increasing molecular weight. One skilled in the art would assume that DTPA and TTHA represent anoptimum within the known aminopolycarboxylic acids in regard to their properties.
OBJECTS OF THE INVENTION An object of the present invention is the obtaining of washing, bleaching and cleansing agents which have incorporated therein complexing aminopolycarboxylic acids or their salts which increase the stability and cleaning properties of the washing agents and stabilize the optiical brighteners present.
Another object of the invention is the obtaining of 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 polyethyleneimine selected from the group consisting of 1) linear poly-(N-acetic acid)-polyethyleneimines of the formula wherein n is an integer from 3 to S0 and (2) their alkali metal, ammonium and organic ammonium salts.
These and other objects of the invention will become more apparent as the description thereof proceeds.
DESCRIPTION OF THE INVENTION It has now been discovered that complexing aminopolycarboxylic acids or their salts of linear poly-(N- acetic acid)-ethyleneimines of the formula wherein n is a number between 3 and 50, are complexing compounds for washing, bleaching and cleansing agents which, incorporated in said agents, are distinguished by a good stability against oxidizing substances, by an improved cleaning property, and by an effective stabilizing of the optical brighteners.
The invention, therefore, comprises a washing, bleaching and cleansing agent having a content of from 50% to 99.9%, by weight, of customary components of wasl1- ing, bleaching and cleansing agents and from 0.1% to 50%, by weight, of a polyethyleneimine selected from the group consisting of (1) linear poly-(N-acetic acid)-polyethyleneimines of the formula wherein n is an integer from 3 to 50 and (2) their alkali metal, ammonium and organic ammonium salts.
Although the polymeric (N-acetic acid)-ethyleneimines, to be used according to the invention, differ from the known polyamino carboxylic acids only in that both terminal nitrogen atoms each time a single acetic acid group is replaced by hydrogen, they are considerably superior to the known agents in their stability against oxidizing agents, their cleaning properties and their complexing properties. This is the more surprising as it is known that in comparative cases, such as that of iminodiacetic acid and nitrilo triacetic acid, the replacement in NTA of an acetic acid group by hydrogen is connected with a very considerable decrease of the cleaning properties and of the complexing properties.
The linear poly-(N-acetic acid)-ethyleneimines or their salts utilized in the invention can be obtained by polymerization of an ester, amide or nitrile of (N-acetic acid)- aziridine and subsequent saponification to the carboxylic acid salts. Suitable starting materials are especially the lower alkyl esters, such as the methyl, ethyl, propyl, isopropyl and butyl esters of the (N-acetic acid)-aziridine. The polymerization 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 alkyl alkylsulfonates and arylsulfonates, such as the methyl, ethyl, propyl and butyl esters of methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acidfThe 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 90 C. by cooling. The polymers 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 and by subsequent neutralization with ammonia or organic ammonium bases, such as mono, di or triethanolamine, morpholine, or N-methylmorpholine. The free acids can be converted to the corresponding organic ammonium salts.
The average molecular weights of the polymeric (N- acetic acid)-ethyleneimines obtained in this way are between 500 and 2,000. By separating out the low molecular component often present in the mixture, for example, by gel-chromatography on polymerized dext'ranes ('Sephadex), polymers with an average molecular weight of 1,500 to 5,000 are obtained. Since the low molecular components do not disturb, they can remain in the product. Preferably such polymeric -(N-acetic acid)-ethyleneimines are used which have an average molecular weight of 600 to 2,000.
The polymeric (N-acetic acid)-ethyleneimines can be added to the washing, bleaching, and cleansing agents in forms of salts or the free acid, if, in the latter case, the substrate contains sufficient amounts of alkaline reacting compounds so that on dissolving the agents in water a neutralization of the free acid groups takes place. 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.
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 alkyleneglycolether groups and 8 to 20 carbon atoms in the hydrocarbon radical. Particularly suitable are polyalkyleneglycolether derivatives in which the number of oxyethylene groups is from to 15 and whose hydrocarbon radicals are derived from straight-chain 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 w foaming power.
Other suitable nonionic basic washing components are the water soluble polyethylene oxide addducts, adducted to polypropyleneglycol, ethylenediamine-polypropyleneglycol and alkylpolypropyleneglycol with 1 to 10 carbon atoms in the alkyl chain. Preferably, these adducts contain from 20 to 250 oxyethylene groups and 10 to 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 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 pri mary and secondary aliphatic monoolefins with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis, as well as alkylsulfonates obtainable from n-al-kanes by sulfochlorination or sulfoxidation and subsequent hydrolysis, or neutralization, or by addition of bisulfite to olefins are also suitable. Also asulfo 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 dihydroxypropanesulfonic 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-alkyl-ammonium)-2-hydroxypropane-l-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 salts, 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)ethylenediamino-tetra- (methylenephosphonic acid), 1-hydroxyethane-1,1 diphosphonic acid, methylene diphosphonic acid, ethylene diphosphonic 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 effectiveness, such as a higher cleaning 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 mixtures of basic washing components of the same type which dilfer 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 perphosphates, 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:
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, OCH Cl where X and Y can be the same or not. Particularly suitable are those compounds in which X is an anilino and Y a diethylamino, 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 diarylpyrazoline derivative in which the radical Ar is a p-sulfonamidophenyl group and the radical Ar is a p-chlorophenyl 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-bis-benzimidazoles, ethylene-bisbenzoxazoles, 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 polyamides of tri and tetracarboxylic acids and dihydric alcohols or diamines, and also polymeric acrylic acid, methacrylic 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 and vinylethers.
Washing agents intended for the use in drum-washing machines contain appropriately known foam-suppressing substances such as saturated fatty acids with 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, straightchained, 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 diastease. Preferably used are enzymatic active substances obtained from bacterial strains or molds, such as, Bacillus subrilis and Streptomyces 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 asids, 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-acetic acid)-ethyleneimine 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 of at least one compound from the class of the anionic, nonionic, and amphoteric detergents.
0 to 80%, preferably 10% to 80% of at least one non-surface-active cleaning intensifying or complexing builder.
0 to preferably 10% to 50% of a per-compound, especially sodium perborate, with or without water or crystallization, as well as their mixtures with stabilizers and activators.
to 60%, preferably 0.1% to 20% of other auxiliary and supplementary substances.
The detergent substances can consist of up to 100%, preferably from to 70%, of compounds of the sulfonate and/ or sulfate type, up to 100%, preferably from 5% to 40% of the nonionic polyglycolether type, and up to 100%, preferably from to 50% of soaps. The builders can consist of up to 100%, preferably from 25% to 95%, of alkali metal triphosphates and their mixtures with alkali metal pyrophosphates, up to 100%, preferably from 5% to 50%, of an alkali salt of a complexing agent from the class of polyphosphonic acids, nitrilotriacetic acid, ethylenediaminetetraacetic 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, es pecially 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 3%.
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 pyrophosphates or the tripolyphosphates.
0.1% to 25% of poly-(N-acetic acid)-ethyleneimine 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 oxyethylene groups 0.2% to 25% of poly-(N-acetic acid)-ethyleneimine or its alkali metal salt 0 to 5% of a higher fatty acid ethanolamide or diethanolamide 8 0 to 20% of sodium tripolyphosphate 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-acetic acid)-ethyleneimine or its alkali metal salts 0.1% to 5% of fatty amide-glycolether condensate (alkyl C to C 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 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 clas 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-acetic acid)-ethyleneimine 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 polypropyleneglycols 0.2% to 25% of poly-(N-acetic acid)-ethyleneimine 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 (G) Bleaching agents 0.2% to 25% of poly-(N-acetic acid)-ethyleneimine or its alkali metal salts 10% to 95% of percompounds 0 to 50% of alkaline reacting compounds from the class of alkali metal hydroxides, carbonate, silicates and phosphates 0 to 5 0% of bleaching activators 0 to 5% of anionic and/ or nonionic detergents 0 to 10% of other ingredients, such as, corrosion inhibitors, optical brighteners, neutral salts, magnesium silicate.
9 (H) Alkaline cleansers 0.1% to 25% of poly-(N-acetic acid)-ethyleneimine or its alkali metal salts 0.5% to 50% of sodium silicate (Na O:SiO =1.1 to
10 2% Magnesium silicate 1% Sodium celluloseglycolate 25% Sodium perborate-tetrahydrate 8% Water 13) 5 0.8% Brightener of the pyraz oline type 05 to 80% of Sodium hydroxide 0.2% Brlghtener of the diaminostllbene type. to 40% of trisodium phosphate The brighteners had the following structures: 0 to 40% of condensed alkali metal phosphates 0 to 40% of sodium carbonate 2 0 to 10% of hydroxyethanc diphosphonate (sodium salts) 10 ii (311: 0 to 5% of anionic and/or nonionic detergents (I) Scouring agent 1% to of anionic and/or nonionic basic washing components 0.1% to 5% of alkali metal salts of poly-(N-acetic acid) ethyleneimine l 80% to 95% of abrasive agents SO2NH2 0 to 10% of cleansing salts of the class of alkali metal Pyrazohnetype polyphosphate's, alkali metal silicates, alkali metal borates, and alkali metal carbonates 0 to 10% of alkali metal dichloroisocyanurate. =K EXAMPLE 1 E The cleaning action of washing agents that contained S I I( 2H10H)z 2 an anionic basic washing component, Na-n-dodecylben- Diaminostilbene type zene sulfonate) and different builder components were To this agent were added each time 2%, by weight of conpared- With Washing agents grey co tton S P the linear Na poly-(N-acetic acid)-ethyleneimine. The which had been so1led with a synthetic so1l containing linear polymeric carboxylic acids were prepared by 1 sootglron oXldF and 3km fat was W e a laboratory erization of (N-acetic acid)-aziridine in the presence of washing machine where the Washing 11qu0r Was heated dipropyl sulfate and had, in Example 2, an average molecfrom 20 to 90 wlthm 15 mmlltes and kept at 900 ular weight of 870; in Example 3, 1230, and in Example 4, for another 15 minutes. The washing agent concentra- 1720 As comparison, the washing agent was utilized to tion was 3 grn./l. The water hardness was 16 dH. The which instead of the linear polymers according to the inweight ratio of textile to liquor Was 1:12. Subsequently, vehtioh, f Na nitrolotriacetate (NTA), or 2% f the textiles were rinsed with Water four times, centrif uged Na ethylenediaminetetraacetate (ED-TA) were added. and dried. The percent whiteness was determined with a w these washing agents, textiles of polyamide fibers photometer (soiled cloth 0%, onginal cloth 100%) a (Perlon) were washed in a laboratory washing machine 18 shown In Table L a Well as the composltlcn of the where the washing liquor was heated from 20 C. to 60 agents- C. within 15 minutes and was kept at this temperature for t f Salt of the P y f acld)ethyl an additional 15 minutes. The washing agent concentraenelmlne Utlllled, Was P p y heatlng 130 05 tion was 5 gm./l. and the weight ratio of textiles to liquor N-(methylcafbethoXy)-aZiridi1'1B and of p py was 1:30. The water used had a hardness of 16 dH as sulfate in 1500 ml. of 1,2dichloroethane for 3 hours in Well as a copper ion content f 05 mols per m The the absence of air. Thereafter, the solvent was separated degrees of whiteness of h f mi i d d h aI 1d the Polymerizate W Saponified y heating to dried wash was determined by a photometer. The results Wlth 3 N NaOH for 3 hours- The Polymer had an average are summarized in Table II. These results demonstrate the molecular weight of 1230. The results of Table I show superiority of the compounds used according to the inthat the linear poly-(N-acetic acid)-ethyleneimine of the ti invention is superior in its cleaning properties to other TABLE H known builders, among them pentasodium triphosphate which is known for its effectiveness. g ffi Addition (2% by Weight to the TABLE I Example washing agent) 1 wash 5washings 2 Poly-(N-aceticacid)-ethyleneimine 105 114 3 "do! 106 114 Amounts in gm./liter 4 "(10. 106 115 NTA 100 104 E EDTA 103 110 Composition: ample Comparisons 1 Average molecular weight 870. Na-N-dodeeylbenzene sulfonate 1 1 1 1 2 Average molecular weight 1,230. N a poly-(ljl-acetio1 acigr-eglgiylltlahfiso) 2 3 Average molecular weight 1,720. gfiaalfifi figfifi hm.E. EXAMPLES 5 AND 6 N a tfiiiiiiiaii'aetaseta An aqueous solution containing 0.62 gm./l. sodium per- Pemnt bnghtemng borate was prepared from a bleaching agent composition 65 consisting of 154 gm. of sodium perborate and of 124 gm. EXAMPLES 2 TO 4 of a sodium salt of a linear poly-(N-acetic acid)-ethylene- A washing agent of the following composition was mum of: used (data in weight percent): in Example 5, an average molecular weight of 810, 8% Na n dodecylbenzene sulfonate in Example 6, an average molecular weight of 1500. 5% Sodium soap of C to C fatty acids The sodium salt of linear poly-(N-acetic acid)-ethyl- 3% Oleyl alcohol polyethyleneglycol ether (10 oxyethyleneimine was prepared by polymerization of (N-methylene units) carbomethoxy)-aziridine in the presence of diethylsulfate, 40% Pentasodium triphosphate saponification of the polymerizate with sodium hydroxide, 5% Sodium silicate (Na O.3.3 SiO and adjustment to a pH of 10 with dilute sodium hydroxide. The decrease of the active-oxygen content of this solution at 90 C. was determined every 30 minutes by iodometric titration. For comparison the determination was repeated with equal amounts of known perborate stabilizers. The results are summarized in Table III. These results demonstrate the superiority of the agents according to the invention.
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 polyethyleneimine selected from the group consisting of (1) linear poly- (N-acetic acid)-polyethyleneimines of the formula TABLE III Percent active oxygen after- 30 60 90 120 150 Example Stabilizer min. min. min. min. min.
Poly-(N-acetic acid)ethylenelmine: 5 Average molecular weight 8l0 80 W 71 W 65 59 52 6 Average molecular weight 1,500.. 83 73 69 64 58 52 26 3 40 5 2 Oarboxymethylated polyamine ace cording to German Pat. 1,060,849 of an average molecular Weight of 900. 48 22 9 5 Without addition 35 is s 4 In the following Table IV are summarized some recipes N CH2 CH2 of washing, bleaching and cleansing agents accordmg to 1 000E] the invention for the following fields of application: 2- l 7 F h a 11.! ant wherein n is an integer from 3 to 50 and (2) their alkali i g? teavy w S 1 g ag metal, ammonium and organic ammonium salts with E f 5 agen t bases selected from the group consisting of mono-, di- 3 i agent and triethanolamine, morpholine and N-methyl morpho- E 00 mgtagen line, said customary components of washing, bleaching 12 i gi agen t and cleansing agents consisting essentially of from 1% gi t to 40% by weight of at least one compound selected Examp 1 g f from the group consisting of anionic, non-ionic and am- 15 S or eztwy Sol mg photeric surface-active basic washing components, from xamp e couring agen. 0% to 80% by weight of at least one builder selected The ingredients (a) to (d) and (f) to (i) were present from the group consisting of condensed inorganic phosas the sodium salts, the pyrophosphate [ingredient (k)] phate builders, alkali metal silicates, carbonates, bicarwas, in Example 9, the potassium salt, and in all other bonates, borates, sulfates and chlorides, alkali metal and examples, the sodium salt. As enzyme [ingredient (q)] ammonium salts of aminopolyphosphonic acids and lowa preparation (Maxatase) made from Bacillus subtilis, with an activity of 100,000 LVA/gm. was utilized. The foam suppressor [ingredient (v)] is a reaction product of 1 mol of cyanuric chloride with 2.7 mols of a primary n-alkylamine with a C to C chain length.
TABLE IV 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 Example (Data in weight percent) Ingredient 7 8 (a) n-Dodecylbenzene sulionate 012 to C olefin sulfouate (c) 014 to C17 alkane sulfonate (d) Coconut alcohol glycol ether sulfate (2 E0) (e) Oleyl alcohol polyglycol ether (10 E0) (f) 012 to Cnsoap (g) 02a to C22 soap-. (h) Poly-(N-aeetic acid) ethylene (i) Tripolyphosphate (k) Pyrophosphate (1) Sodium carbonate (n) Sodium sulfate t. (0) Sodium perborate (D) Magnesium silicate Na toluenesulfonate (t) Coconut fatty acid diethanolamide (u) Optical brightener (v) Foam suppressor (w) Water (x) Dichloroisocyanurate (y) Coloring and odorizing agent (2) Quartz powdsr N OTE.EO =oxyethylene units.
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.
phosphate and chlorinated cyanuric acid and its alkali metal salts, and mixtures thereof with magnesium silicates, and from 0% to of other auxilliary and supplementary components of washing agents selected from the group consisting of optical brighteners, greying-inhibi- 13 14 tors, foam-suppressors, enzymes, water-miscible solvents, 4. The washing, bleaching and cleansing agent of claim water and dissolving aids, said ingredients totalling 100% 3 wherein said average molecular Weight is from 600 by Weight of said customary components. to
References Cited 2. The Washing, bleaching and cleanslng agent of claim 5 1 wherein said polyethyleneimine is present in an amount FOREIGN PATENTS of fro 05% to 25% by weight 231,499 10/1960 Australia 252-102 3. The washing, bleaching and cleansing agent of claim 1 wherein said linear poly-(N-acetic acid)-polyethyleneimine has an average molecular weight of from 500 to 10 5,000. 252-486; 260-2 EN, 534 E MAYER WEINBLA'IT, Primary Examiner