Washing, Bleaching And Cleansing Agents Containing Copolymeric N-alkylcarboxylic Acid Alkyleneimines

Abstract

A washing, bleaching and cleansing agent having a content of from 50 to 99.9 percent, by weight, of customary components of washing, bleaching and cleansing agents and from 0.1 to 50 percent, by weight, of salts of at least one copolymeric N-alkylcarboxylic acid-alkyleneimine, said copolymeric N-alkylcarboxylic acid-alkyleneimine having an average molecular weight of from 500 to 500,000 and the recurring N-alkylcarboxylic acid-alkyleneimine units are of different structure of the formulas I and II where R represents a member selected from the group consisting of H and CH.sub.3, R' represents a member selected from the group consisting of H and CH.sub.3, X represents a member selected from the group consisting of H and --CH.sub.2 -- COOH, Y represents a member selected from the group consisting of H, --CH.sub.2 --COOH and --CH.sub.2 --CH.sub.2 COOH and n represents an integer of from one to two, the ratio of recurring N-alkylcarboxylic acid-alkyleneimine units of formula I to those of formula II being from one to 100 to 100 to one.

Description

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 nitrilotriacetic 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 insufficiently 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.

OBJECTS OF THE INVENTION

An object of the present invention is the obtaining of washing, bleaching and cleansing agents which have incorporated therein complexing compounds which have an increased stability against oxidizing agents, give an increased cleaning property to the washing agents and stabilize the optical 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 percent by weight of customary components of washing, bleaching and cleansing agents and from 0.1 to 50 percent by weight of salts of at least one copolymeric N-alkylcarboxylic acid-alkyleneimine, said copolymeric N-alkylcarboxylic acid-alkyleneimine having an average molecular weight of from 500 to 500,000 and the recurring N-alkylcarboxylic acid-alkyleneimine units are of different structure of the formulas I and II

wherein R represents a member selected from the group consisting of H and CH.sub. 3, R' represents a member selected from the group consisting of H and CH.sub. 3, X represents a member selected from the group consisting of H and --CH.sub. 2 -COOH, Y represents a member selected from the group consisting of H, --CH.sub. 2 -COOH and --CH.sub. 2 -CH.sub. 2 -COOH and n represents an integer of from one to two, the ratio of recurring N-alkyl-carboxylic acid-alkyleneimine units of formula I to those of formula II being from 1:100 to 100:1.

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 salts of copolymeric N-alkylcarboxylic acid-alkyleneimines having an average molecular weight of from 500 to 500,000, 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 percent by weight, of customary components of washing, bleaching and cleansing agents and from 0.1 to 50 percent, by weight, of salts of at least one copolymeric N-alkyl-carboxylic acid-alkyleneimine having an average molecular weight of from 500 to 500,000 and the recurring N-alkyl-carboxylic acid-alkyleneimine units are of different structure of the formula I and II

wherein R represents a member selected from the group consisting of H and CH.sub. 3, R' represents a member selected from the group consisting of H and CH.sub. 3, X represents a member selected from the group consisting of H and --CH.sub. 2 --COOH, Y represents a member selected from the group consisting of H, --CH.sub. 2 -COOH and --CH.sub. 2 -CH.sub. 2 -COOH and n represents an integer of from one to two, the ratio of recurring N-alkyl-carboxylic acid-alkyleneimine units of formula I to those of formula II being from one to 100 to 100 to one.

The copolymers are derived from derivatives of ethyleneimine (R=R'=H), propyleneimine (R=R'=CH.sub. 3) or from their mixtures (R and R' are not identical). Preferably the copolymers are derived from derivatives of ethyleneimine. The copolymers concerned with, according to the invention, can have the following composition:

1. Copolymers of N-succinic acid-ethyleneimine (R=H, X=H) with:

a. N-acetic acid-ethyleneimine (R'=H, Y=H, n=1)

b. N-propionic acid-ethyleneimine (R'=H, Y=H, n=2)

c. N-methylenesuccinic acid-ethyleneimine (R'=H, Y= --CH.sub. 2 -COOH, n= 2)

d. N-methyleneglutaric acid-ethyleneimine (R'=H, Y= --CH.sub. 2 -CH.sub. 2 -COOH, n= 2).

2. Copolymers of N-tricarballylic acid-ethyleneimine (R=H, X= --CH.sub. 2 -COOH) with:

(a) N-acetic acid-ethyleneimine (R'=H, Y=H, n=1)

(b) N-propionic acid-ethyleneimine (R'=H, Y-H, n=2)

(c) N-methylenesuccinic acid-ethyleneimine (R'=H, Y= --CH.sub. 2 -COOH, n= 2)

(d) N-methyleneglutaric acid-ethyleneimine (R'=H, Y= --CH.sub. 2 -CH.sub. 2 -COOH, n= 2)

(e) N-succinic acid-ethyleneimine (R'=H, Y= --CH.sub. 2 -COOH, n= 1).

The polymeric (N-alkylcarboxylic 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-toluenesulfonic acid.

The preparation of the polymeric (N-alkylcarboxylic acid)-alkyleneimines can be done according to various known methods. For the synthesis of linear polymers, first monomeric ethyleneimine (aziridine) or propyleneimine is alkylated on the nitrogen atom according to the principles of the Michael-Addition, with derivatives of olefinic-unsaturated carboxylic acids, such as esters, amides and nitriles. Instead of olefinic-unsaturated carboxylic derivatives, also derivatives of halogenated carboxylic acids can be used for the alkylation on the nitrogen atom. Examples of suitable carboxylic acid derivatives and their reaction products with monomeric alkyleneimines are summarized in the following Table I.

table i

carboxylic Acid Derivatives Suitable for Reaction With Alkyleneimine Alkyleneimine Derivatives a. Ester, amide, or nitrile N-acetic acid derivative of chloro- or bromo acetic acid b. Ester, amide, or nitrile N-.beta.-propionic acid deriva of acrylic, .beta.-chloro tive propionic acid or .beta.- bromopropionic acid c. Diester, diamide, or N-methylenesuccinic acid dinitrile of itaconic derivative acid d. Diester, diamide or N-methyleneglutaric acid dinitrile of .alpha.-methyl derivative eneglutaric acid e. Diester, diamide, or N-succinic acid derivative dinitrile of maleic, fumaric, or monobromo succinic acid f. Triester of cis- or N-tricarballylic acid trans-aconitic acid derivative

Before the copolymerization one of the derivatives named under (a) to (d) is mixed with the derivative named under (e), or one of the derivatives named under (a) to (e) is mixed with the derivative named under (f), where the molar ratio may be 1:100 to 100:1, preferably 1:10 to 10:1. The copolymerization which may be carried out in the presence or absence of inert solvents, is catalyzed by 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 alkanol esters of alkylsulfonic acids and arylsulfonic acids, 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.degree. and 90.degree. C by cooling. The ester, amide or nitrile derivatives of the copolymeric (N-alkyl carboxylic 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-, di- or triethanolamine, morpholine, or N-methylmorpholine, the free acids can be converted to the corresponding organic ammonium salts, or by neutralization with strong acids, the free acids can be converted to the corresponding acid salts.

The average molecular weights of the copolymeric (N-alkylcarboxylic 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"), polymers with varied average molecular weight can be obtained. Since the low molecular components do not disturb, they can remain in the product.

If the N-alkylcarboxylic acid-alkyleneimines used in the copolymerization still contain unsubstituted ethyleneimine or propyleneimine, during the polymerization, copolymers are obtained which are more or less branched depending on the amount of the unsubstituted alkyleneimines present. The amount of the unsubstituted alkyleneimines in the starting material should not surpass 50 mol percent and preferably should be less than 30 mol percent.

A further method of preparation of the salts of the copolymeric (N-alkylcarboxylic acid)-alkyleneimines starts from preformed polyalkyleneimines 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 the above-indicated unsaturated carboxylic acids, or halogenated carboxylic acids. The carboxylic acids or their derivatives can be reacted simultaneously or successively with the polyalkyleneimine. In the reaction, the amount of the carboxylic acids or their derivatives or salts should be selected in order that least 50 percent and preferably more than 70 percent of the primary and secondary amino groups in the preformed polyalkyleneimines are substituted. The compounds prepared from preformed polyalkyleneimines are usually more or less highly branched. Their average molecular weight depends upon the degree of polymerization of the preformed polyethyleneimines 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 copolymeric (N-alkylcarboxylic acid)-alkyleneimines.

The inner salts of the copolymers 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 predominantly in water, but are readily soluble in acids and bases. From the inner salts, the corresponding ammonium salts can be prepared by neutralization with 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 copolymeric (N-alkylcarboxylic acid)-alkyleneimines or their salts.

The agents according to the invention contain at least one other cleaning or bleaching component, such as non-ionic, anionic and amphoteric surface-active materials, inorganic or organic builders, oxygen-containing bleaching agents, as well as other conventional washing and cleansing ingredients. The copolymeric (N-alkylcarboxylic 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.

The washing and cleansing agents can also contain anionic basic washing components of the sulfonate or sulfate type. Primarily alkylbenzene sulfonates, such as dodecyl-benzene 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 .alpha.-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-dihydroxy-propane-sulfonic acid. Also sulfates of ethoxylated or propoxylated fatty acid amides and alkyl phenols as well as fatty acid taurides and fatty acid isothionates 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-1-sulfonate and 3-(N,N-dimethyl-N-alkylammonium)-2-hydroxypropane-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 anionic and amphoteric compounds have a long-chain aliphatic hydrocarbon radical, the latter should preferably be straightchained and should have from eight to 22 carbon atoms. In the compounds with araliphatic hydrocarbon radicals the preferred straight alkyl chains contain an average of from six to 16 carbon atoms.

As non-ionic basic washing components are, in the first place, the polyalkylene-glycolether derivatives of alcohols, fatty acids and alkylphenols which contain three to 30 ethyleneglycolether groups and eight to 20 carbon atoms in the hydrocarbon radical. Particularly suitable are polyalkyleneglycolether derivatives in which the number of oxyethylene groups is from five 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 six to 14 carbon atoms. By the addition of three 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 non-ionic basic washing components are the water-soluble polyethylene oxide adducts, adducted to polypropyleneglycol, ethylenediamine-polypropyleneglycol and alkylpolypropyleneglycol with one to 10 carbon atoms in the alkyl chain. Preferably, these adducts contain from 20 to 250 oxyethylene groups and 10 to 100 oxypropylene groups in the molecule. The named compounds contain usually one to five oxyethylene units per oxypropylene unit. Also non-ionic compounds of the type of aminooxides and sulfoxides which, if necessary, can also be ethoxylated, are usable.

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 compounds including alkali metal silicates and phosphates should be calculated so that the pH of a serviceable washing liquor for coarse laundry is nine to 12 and for fine laundry six to nine.

Appropriate mixture ingredients 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 amino-tri-(methylenephosphonic acid), ethylenediaminetetra-(methylenephosphonic acid), 1-hydroxyethane-1,1-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 amino-polycarboxylic acids, such as NTA and EDTA. As other builders, alkali metal silicates are suitable, particularly sodium silicate in which the ratio Na.sub. 2 O:SiO.sub. 2 is 1:3.5 to 1:1.

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 non-ionic and/or amphoteric compounds, by combination of various non-ionic compounds with each other or also by mixtures 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 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: ##SPC1##

in which X and Y have the following meanings: NH.sub. 2, NH-CH.sub. 3, NH-CH.sub. 2 -CH.sub. 2 OH, CH.sub. 3 - N-CH.sub. 2 -CH.sub. 2 OH, N(CH.sub. 2 -CH.sub. 2 OH).sub. 2, morpholino, dimethylmorpholino, NH-C.sub. 6 H.sub. 5, NH-C.sub. 6 H.sub. 4 SO.sub. 3 H, OCH.sub. 3, Cl where X and Y can be the same or not. Particularly suitable are those compounds in which X is an anilino and Y is a diethanolamino, or a morpholino group.

As optical brighteners also 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-bis-benzoxazoles, thiophene-bis-benzoxazoles, dialkylamino-coumarins, and the cyanoanthracenes. These brighteners or their mixtures can be present in the washing agents in amounts of from 0.01 to 1.5 percent by weight, preferably from 0.1 to 1 percent by weight.

Further suitable mixture ingredients for the washing agents of the invention are greying-inhibiting compounds, such as sodium cellulose glycolate, as well as the water-soluble alkali metal 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.

Washing agents intended for 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 1 mol cyanuric chloride with two to three 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 Streptomyces griseus which are relatively stable against alkalis, peroxide compounds and anionic detergents and essentially not inactivated even at temperatures between 45.degree. and 70.degree. 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 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 non-ionic 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 the salts of the copolymeric (N-alkylcar-boxylic acid)-alkyleneimine amounts to from about 0.1 to 50 percent, preferably 0.2 to 25 percent by weight. The difference to 100 percent 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 percent of at least one compound from the class of the anionic, non-ionic and amphoteric detergents;

0 to 80 percent, preferably,

10 to 80 percent of at least one non-surface-active cleaning, intensifying or complexing builder;

0 to 50 percent, preferably 10 to 50 percent, of a per-compound, especially sodium perborate, with or without water of crystallization, as well as their mixtures with stabilizers and activators;

0 to 60 percent, preferably 0.1 to 20 percent, of other auxiliary and supplementary substances.

The detergent substances can consist of up to 100 percent, preferably from 5 to 70 percent, of compounds of the sulfonate and/or the sulfate type, up to 100 percent, preferably from 5 to 40 percent, of compounds of the non-ionic polyglycolether type, and up to 100 percent, preferably from 10 to 50 percent, of soaps. The builders can consist of up to 100 percent, preferably from 25 to 95 percent, of alkali metal triphosphates and their mixtures with alkali metal pyrophosphates, up to 100 percent, preferably from 5 to 50 percent, of an alkali salt of a complexing agent from the class of polyphosphonic acids, nitrilotriacetic acid, ethylenediaminetetraacetic acid, and up to 100percent, preferably from 5 to 75 percent, 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 percent, preferably from 0.2 to 3 percent; also the enzymes which can be present in an amount up to 5 percent, preferably from 0.2 to 3 percent; and the graying inhibitors which can be present in an amount up to 5 percent, preferably from 0.2 to 3 percent.

The copolymeric (N-alkylcarboxylic 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 15 percent of a sulfonate basic washing component from the class of alkylbenzene sulfonates, olefin sulfonates and n-alkane sulfonates (sodium salts),

0.5 to 5 percent of an alkylpolyglycolether (alkyl C.sub. 12 to C.sub. 18) or alkylphenolpolyglycolether (alkyl C.sub. 8 to C.sub. 14) with five to 10 oxyethylene groups,

0 to 5 percent of a C.sub. 12 to C.sub. 18 soap (sodium salt),

0.2 to 5 percent 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 percent of a condensed alkali metal phosphate from the class of the pyrophosphates or the tripolyphosphates,

0.1 to 25 percent of the copolymeric (N-alkylcarboxylic acid)-alkyleneimines or their alkali metal salt,

1 to 5 percent of sodium silicate,

10 to 35 percent of sodium perborate tetrahydrate,

0 to 5 percent of enzymes,

0.05 to 1 percent of at least one optical brightener from the class of diaminostilbene disulfonic acid or diarylpyrazoline derivatives,

0.1 to 30 percent of an inorganic alkali metal salt from the class of the carbonates, bicarbonates, borates, sulfates and chlorides,

0 to 4 percent of magnesium silicate,

0.5 to 3 percent of sodium celluloseglycolate.

B. powdery Foaming Fine Washing Agent

1 to 30 percent of a sulfonate basic washing component (sodium salt),

0.5 to 10 percent of alkylpolyglycolether sulfate (alkyl C.sub. 8 to C.sub. 16, one to five oxyethylene groups),

0 to 20 percent of an alkylpolyglycolether (alkyl C.sub. 10 to C.sub. 18) or alkylphenolpolyglycolether (alkyl C.sub. 8 to C.sub. 12), with five to 12 oxyethylene groups,

0.2 to 25 percent of the copolymeric (N-alkylcarboxylic acid)-alkyleneimines or their alkali metal salt,

0 to 5 percent of a higher fatty acid ethanolamide or diethanolamide,

0 to 20 percent of sodium tripolyphosphate,

0 to 1 percent of a brightener from the class of the diarylpyrazoline derivatives and its mixtures with polyester brighteners,

3 to 70 percent of sodium sulfate.

C. liquid Washing Agent

0.5 to 10 percent of a sulfonate basic washing component (potassium salt),

0 to 10 percent of alkylpolyglycolether sulfate (alkyl C.sub. 8 to C.sub. 16, 1 to 5 oxyethylene groups),

0.2 to 25 percent of the copolymeric (N-alkylcarboxylic acid)-alkyleneimines or their alkali metal salts,

0.1 to 5 percent of fatty acid amide-glycolether condensate (alkyl C.sub. 10 to C.sub. 18, 1 to 10 oxyethylene groups),

1 to 10 percent of solution aids from the class of the alkali metal salts of benzene, toluene, or xylene sulfonic acids,

0 to 30 percent of neutral or acid potassium pyrophosphate,

0 to 10 percent of organic solvent media from the class of the C.sub. 2 to C.sub. 3 alcohols and ether alcohols,

0 to 1 percent of optical brighteners from the class of of the diaminostilbene disulfonic acids and diarylpyrazoline derivatives,

0 to 5 percent of hydrogen peroxide,

Residue: Water, perfumes, dyes, preservatives.

D. steeping and Pre-Washing Agent

0.5 to 5 percent of sulfonate basic washing component (sodium salt),

0 to 3 percent of compounds from the class of alkylpolyglycolethers (alkyl C.sub. 12 to C.sub. 18) and alkylphenolpolyglycolethers (alkyl C.sub. 8 to C.sub. 12) with five to 12 oxyethylene groups,

0.1 to 10 percent of the copolymeric (N-alkylcarboxylic acid)-alkyleneimines or their alkali metal salts,

10 to 50 percent of sodium carbonate,

1 to 5 percent of water glass,

0 to 5 percent of magnesium silicate,

0 to 5 percent of enzymes.

E. dishwashing-Machine Washing Agents

0.1 to 3 percent of compounds from the class of the alkylpolyglycolether (alkyl C.sub. 12 to C.sub. 18), alkylphenolpolyglycolether (alkyl C.sub. 8 to C.sub. 14) with five to 30 oxyethylene groups and five to 30 oxypropylene groups, and ethoxylated polypropyleneglycols,

0.2 to 25 percent of the copolymeric (N-alkylcarboxylic acid)-alkyleneimines or their alkali metal salts,

45 to 95 percent of pentasodium triphosphate,

1 to 40 percent of sodium silicate (Na.sub. 2 O:SiO.sub. 2 = 1:1 to 1:3),

0 to 5 percent of potossium dichloroisocyanurate,

0 to 2 percent of foaming inhibitors.

F. liquid Rinsing and Cleansing Agent:

5 to 30 percent of a sulfonate basic washing component (potassium salt),

2 to 15 percent of alkylpolyglycolether sulfate (alkyl C.sub. 8 to C.sub. 16, one to five oxyethylene groups),

0.2 to 10 percent of alkali metal salts of the copolymeric (N-alkylcarboxylic acid)-alkyleneimines,

0 to 20 percent of organic solvents from the class of C.sub. 2 to C.sub. 3 alcohols and ether alcohols,

1 to 10 percent 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 percent of the copolymeric (N-alkylcarboxylic acid)-alkyleneimines or their alkali metal salts,

10 to 95 percent of per-compounds,

0 to 50 percent of alkaline reacting compounds from the class of alkali metal hydroxides, carbonates, silicates and phosphates,

0 to 50 percent of bleaching activators,

0 to 5 percent of anionic and/or non-ionic detergents,

0 to 10 percent of other ingredients, such as corrosion inhibitors, optical brighteners, neutral salts, magnesium silicate.

H. alkaline Cleansers:

0.1 to 25 percent of the copolymer (N-alkylcarboxylic acid)-alkyleneimines or their alkali metal salts,

0.5 to 50 percent of sodium silicate (Na.sub. 2 O:SiO.sub. 2 = 1:1 to 1:3),

0.5 to 80 percent of sodium hydroxide,

0 to 40 percent of trisodium phosphate,

0 to 40 percent of condensed alkali metal phosphates,

0 to 40 percent of sodium carbonate,

0 to 10 percent of hydroxyethane diphosphonate (sodium salts),

0 to 5 percent of anionic and/or non-ionic detergents.

I. scouring Agent:

1 to 10 percent of anionic and/or non-ionic basic washing components,

0.1 to 5 percent of alkali metal salts of the copolymeric (N-alkylcarboxylic acid)-alkyleneimines,

80 to 95 percent of abrasive agents,

0 to 10 percent or cleansing salts of the class of alkali metal polyphosphates, alkali metal silicates, alkali metal borates, and alkali metal carbonates,

0 to 10 percent of alkali metal dichloroisocyanurate.

PREPARATION OF THE MONOMERIC STARTING MATERIALS AND OF THE MIXED POLYMERS

For the preparation of the monomeric N-succinic ester-ethyleneimine, dibutyl maleate and aziridine in a mol ratio of 1:2 were heated for 24 hours at 30.degree. to 40.degree. C in the presence of 1 mol percent of sodium methylate. The N-(dibutylsuccinate)-aziridine was then isolated from the reaction mixture by fractionate distillation (boiling point 122.degree. C at 0.4 mm Hg). For the preparation of monomeric N-tricarballylic acid ester-ethyleneimine, dibutyl aconitate and aziridine in a mol ratio of 1:1 were heated for 24 hours at 30.degree. to 40.degree. C in the presence of 1 mol percent of sodium methylate. The product obtained was used without intermediary purification. In an analogous manner aziridine was heated with methyl acrylate, dimethyl itaconate, or .alpha.-methyleneglutaric ester in a mol ratio of 1:1, in the presence of 1 mol percent of sodium methylate and thereby the propionic acid ester, methylenesuccinic acid ester, and methyleneglutaric acid ester derivatives were obtained. The N-(methyl acetate)-ethyleneimine was obtained by condensation of methyl chloroacetate with aziridine in the presence of aqueous alkali.

The monomeric ethyleneimine derivatives were mixed according to the mol ratios listed in the following examples and polymerized by the stepwise addition of 1 to 5 mol percent diethyl sulfate in an inert gas atmosphere within 5 to 48 hours at a temperature not higher than 50.degree. C. For the saponification the copolymers, dissolved in methanol, were treated with the equivalent amount of 20 percent aqueous sodium hydroxide solution. The solution was heated to 80.degree. to 85.degree. C and the methanol was removed by distillation. After heating for 5 to 10 hours, with frequent addition of water, the saponification was completed and the sodium salts of the linear copolymers were then isolated by spray drying.

For the preparation of the branched copolymer, containing succinic acid and acetic acid groups, polyethyleneimines of an average molecular weight of 1,800, 15,000 and 40,000 were heated for 24 hours at 80.degree. to 90.degree. C in a 20 percent aqueous solution with 50 percent of the stoichiometric amount, required for a 100 percent N-alkylation, of maleic acid. The pH was adjusted to 10 to 11 by addition of sodium hydroxide during the reaction. Subsequently, the reaction was completed on addition of 55 mol percent of sodium chloroacetate by heating for 5 hours at 80.degree. to 90.degree. C with addition of sodium hydroxide to maintain a pH of 10 to 11. The solution was freed of salts by the use of anionic and cationic exchange resins. The copolymers were converted to the sodium salts by neutralization with sodium hydroxide.

EXAMPLES 1 TO 13

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 one of the linear copolymeric N-alkylcarboxylic acid-ethyleneimines in the form of its sodium salt, as listed in Table II, 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 machine where the washing liquor was heated from 20.degree. to 90.degree. C within 15 minutes and kept at 90.degree. C for another 15 minutes. The washing agent concentration was 3 gm/1. The water hardness was 16.degree. 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 percent, original cloth 100 percent) and is shown in the following Table II as well as the composition of the washing agents.

The results of the washing tests of Table II show that the copolymeric (N-alkylcarboxylic acid)-ethyleneimines are superior to the other known builders, among them sodium ethylenediaminetetraacetate.

TABLE II

Amount of the Carboxylic Acids in the Linear Molecular Brighten- Example Copolymer (Na-salt) Weight ing % __________________________________________________________________________ 1 50% succinic acid 850 78.6 2 50% acetic acid 1280 78.6 3 75%succinic acid 950 79.0 4 25%acetic acid 1420 79.2 5 50% succinic acid 50%methylenesuccinic 1680 79.1 acid 6 50% succinic acid 50% methyleneglutaric 2400 79.4 acid 7 50% tricarballylic acid 650 78.4 8 50% acetic acid 1760 78.8 9 90% tricarballylic acid 1450 80.3 10% acetic acid 10 60% tricarballylic acid 3400 78.2 40% propionic acid 11 50% tricarballylic acid 1380 79.8 12 50% succinic acid 2300 80.1 13 80% tricarballylic acid 980 80.5 20% succinic acid -- Na-ethylenediaminotetra- acetate -- 75.4 __________________________________________________________________________

EXAMPLES 14 TO 20

A washing agent of the following composition was used (data in percent by weight):

Percent 8.0 Na-n-dodecylbenzene sulfonate 5.0 Sodium soap of C.sub. 12 to C.sub. 22 fatty acids 3.0 Oleyl alcohol polyethyleneglycolether (10 oxyethylene groups) 40.0 Pentasodium triphosphate 5.0 Sodium silicate (Na.sub. 2 O.sup.. 3.sup.. 3 SiO.sub. 2) 2.0 Magnesium silicate 1.0 Sodium cellulose glycolate 25.0 Sodium perborate-tetrahydrate 8.0 Water 0.8 Brightener of the pyrazoline type 0.2 Brightener of the diaminostilbene type

The brighteners had the following structures: ##SPC2##

To this agent were added each time 2 percent by weight of the sodium salt of the copolymeric (N-alkylcarboxylic acid)-ethyleneimine listed in the following Table III. For comparative purposes, a washing agent was used which, instead of the polymers according to the invention, 2 percent of sodium nitrilotriacetate (NTA) or 2 percent of Na-ethylenediaminetetraacetate (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.degree. to 60.degree. C within 15 minutes and was kept at this temperature for an 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.degree. dH as well as a copper ion content of 10.sup..sup.- 5 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 III. These results demonstrate the superiority of the use of the polymers of the present invention.

The branched copolymers used in Examples 19 and 20 were obtained by reaction of preformed polyethyleneimine with maleic acid and chloroacetic acid in aqueous sodium hydroxide.

TABLE III

Degree of amount of the carboxylic whiteness acids in the copolymer molecular after Ex. (Na-salt) weight 1 wash 5 washes __________________________________________________________________________ 14 50% succinic acid 1,280 108 115 50% acetic acid 15 75% succinic acid 1,420 109 115 25% acetic acid 16 50% succinic acid 1,680 108 114 50% methylenesuccinic acid 17 50% tricarballylic acid 1,760 108 116 50% acetic acid 18 50% tricarballylic acid 1,380 110 117 50% succinic acid 19 40% branched succinic acid 6,400 107 115 50% acetic acid 10% unsubstituted 20 40% branched succinic acid 120,000 108 116 57% acetic acid 3% unsubstituted Na-Nitrilotriacetate -- 100 104 Na-ethylenediaminotetra- -- 103 110 acetate

EXAMPLES 21 TO 24

Textile samples of grey cotton cloth soiled with tea were washed by applying the washing agent used in Examples 14 to 20, with the addition of 2 percent by weight of copolymeric, linear N-alkylcarboxylic acid-ethyleneimines for 30 minutes at 90.degree. C. The concentration of the washing agent was 5 gm/l. The weight ratio of textile to washing liquid was 1:10 and the hardness of the tap water was 16.degree. dH. The reflection values, determined by photometer, of the three-times rinsed and dried textile samples are summarized in the following Table IV.

table iv

molecular % Re- Example Copolymers (Na-salt) Weight flection __________________________________________________________________________ 21 (50% succinic acid 1280 77.2 (50% acetic acid 22 (50% succinic acid 1680 77.1 (50% methylene succinic acid 23 (50% tricarballylic acid 1760 77.5 (50% acetic acid 24 (50% tricarballylic acid 2300 78.3 (50% succinic acid -- Na-ethylenediamine- -- 75.8 tetraacetate -- Na-nitrilotriacetate -- 76.8 __________________________________________________________________________

EXAMPLES 25 AND 26

An aqueous solution containing 0.62 gm/l of sodium perborate was prepared from a bleaching agent consisting of 154 gm (1 mol) of sodium perborate and 1 mol of a copolymeric N-alkylcarboxylic acid-ethleneimine (159 gm in Example 25 and 188 gm in Example 26) and adjusted to a pH of 10 by addition of dilute sodium hydroxide solution. Another bleaching solution, also adjusted to a pH of 10 with sodium hydroxide, contained per liter 5 millimol (0.136 gm) of hydrogen peroxide and 4 millimol (0.63 gm in Example 25 and 0.8 gm in Example 26) of the complexing agent. The decrease in the active-oxygen content of these solutions at 100.degree. C was determined every 30 minutes by iodometric titration. For comparison the determination was repeated with equimolar amounts of known perborate stabilizers (EDTA = ethylenediaminetetraacetic acid, NTA = nitrilotriacetic acid). The results are summarized in the following Table V. They show the particular stability of the agents, according to the invention to oxidizing agents.

TABLE V

Copolymer % Active Oxygen After According oxidizing 30 60 120 180 Example to example agent min min min min __________________________________________________________________________ 25 8 NaBO.sub. 3 80 66 40 24 H.sub. 2 O.sub. 2 84 70 43 26 26 11 NaBO.sub. 3 89 74 53 33 H.sub. 2 O.sub. 2 90 82 56 36 EDTA NaBO.sub. 3 28 2 H.sub. 2 O.sub. 2 25 3 NTA NaBO.sub. 3 68 47 18 11 H.sub. 2 O.sub. 2 67 46 18 12 No addi- NaBO.sub. 3 30 18 3 tion H.sub. 2 60sub. 2 31 7 4 __________________________________________________________________________

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.

Claims

We claim:

1. A washing, bleaching and cleansing agent having a content of from 50 to 99.9 percent, by weight, of customary components of washing, bleaching and cleansing agents and from 0.1 to 50 percent, by weight of a polyalkyleneimine selected from the group consisting of (1) copolymeric N-alkylcarboxylic acid-alkyleneimine having an average molecular weight of from 500 to 500,000 and recurring N-alkylcarboxylic acid-alkyleneimine units of different structure of the formulas I and II ##SPC3##

wherein R represents a member selected from the group consisting of H and CH.sub. 3, R' represents a member selected from the group consisting of H and CH.sub. 3, X represents a member selected from the group consisting of H and --CH.sub. 2 --COOH, Y represents a member selected from the group consisting of H, --CH.sub. 2 -COOH and --CH.sub. 2 -CH.sub. 2 -COOH and n represents an integer of from one to two, with the proviso that when X is H, Y is H or --CH.sub. 2 -CH.sub. 2 -COOH, the ratio of recurring N-alkylcarboxylic acid-alkyleneimine units of formula I to those of formula II being from one to 100 to 100 to one and (2) their alkali metal, ammonium and organic ammonium salts with bases selected from the group consisting of mono-, di- and triethanolamine, morpholine and N-methyl morpholine, said customary components of washing, bleaching and cleansing agents consisting essentially of from 0 to 40 percent by weight of at least one compound selected from the group consisting of anionic, non-ionic and amphoteric surface-active basic washing components, from 0 to 80 percent 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 100 percent 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 percent of other auxiliary and supplementary components of washing agents selected from the group consisting of optical brighteners, greying-inhibitors, foam-suppressors, enzymes, water-miscible solvents, water and dissolving aids, said ingredients totalling 100 percent by weight of said customary components.

2. The washing, bleaching and cleansing agent of claim 1 wherein said ratio of recurring N-alkylcarboxylic acid-alkyleneimine units of formula I to those of formula II is from one to 10 to 10 to one.

3. The washing, bleaching and cleansing agent of claim 1 wherein said polyalkyleneimines are present in an amount of from 0.5 to 25 percent by weight.

4. The washing, bleaching and cleansing agent of claim 1 wherein said copolymeric N-alkylcarboxylic acid-alkyleneimine contains less than 50 percent of unsubstituted recurring alkyleneimine units.

5. The washing, bleaching and cleansing agent of claim 4 wherein said copolymeric N-alkylcarboxylic acid-alkyleneimine contains less than 30 percent of unsubstituted recurring alkyleneimine units.

6. The washing, bleaching and cleansing agent of claim 1 wherein R and R' are hydrogen.