Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3723—Polyamines or polyalkyleneimines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines
  • C08G73/0206—Polyalkylene(poly)amines

Definitions

• 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-alkyleneirnine 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 ll where R represents a member selected from the group consisting of H and CH R represents a member selected from the group consisting of H and CH X represents a member selected from the group consisting of H and -Cl-I -COO H, Y represents a member selected from the group consisting of H, CH COOH and -CH
• N0 Drawings WASHING BLEACHING AND CLEANSING AGENTS CONTAINING COPOLYMERIC N- ALKYLCARBOXYLIC ACID ALKYLENEIMINES THE PRIOR ART
• washing and cleansing agents particularly those which contain bleaching compounds having active oxygen, complexing aminopolycarboxylie acids or their alkali salts, such as nitrilotriacetic acid (NTA), ethylenediamine tetraacetic acid (EDTA), or diethylenetriamine pentaacetic acid (DTPA)
• NTA nitrilotriacetic acid
• EDTA ethylenediamine tetraacetic acid
• DTPA diethylenetriamine pentaacetic acid
• 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.
• 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 con- I CH-COOH
• R represents a member selected from the group consisting of H and CH
• X represents a member selected from the group consisting of H and -CH,-COOH
• Y represents a member selected from the group consisting of H, CH,-COOH and -CH,-CH,-COOH
• 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 11 being from 1:100 to 100:1.
• 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 R represents a member selected from the group consisting of H and CH,, X represents a member selected from the group consisting of H and -CH COOH, Y represents a member selected from the group consisting of H, -CH -COOH and -CH -CH -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
• the copolymers are derived from derivatives of ethyleneimine.
• the copolymers concerned with, according to the invention can have the following composition:
• 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,
• the preparation of the polymeric (N-alkylcarboxylic acid)-alkyleneimines can be done according to various known methods.
• 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.
• 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.
• Triester of cisor 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 :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.
• Lewis-type acids for example, neutral sulfuric acid esters, preferably di-lower alkyl sulfates, such as dimethyl sulfate, diethyl sulfate, dipropyl sulf
• 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 90 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.
• 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.
• ammonia or organic ammonium bases such as mono-, dior triethanolamine, morpholine, or N- methylmorpholine
• 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.
• polymers with varied average molecular weight can be obtained. Since the low molecular components do not disturb, they can remain in the product.
• 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.
• the amount of the carboxylic acids or their derivatives or salts should be selected in order that least 50 percent and preferably more than 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.
• the corresponding ammonium salts can be prepared by neutralization with ammonia or organic ammonium bases, such as mono-, dior triethanolamine, morpholine, or N-methylmorpholine.
• the washing, bleaching and cleansing agents according to the invention can also contain mixtures of different copolymcric (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.
• alkylbenzene sulfonates such as dodecyl-benzene sulfonate are suitable.
• 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.
• 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 monofatty acid esters of the glycerine monosulfuric acid esters, or of 1,2-dihydroxy-propane-sulfonic acid.
• sulfates of ethoxylated or propoxylated fatty acid amides and alkyl phenols as well as fatty acid taurides and fatty acid isothionates are suitable.
• 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-hydroxypropanel -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-, diand triethanolamine.
• 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.
• the preferred straight alkyl chains contain an average of from six to 16 carbon atoms.
• 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 and whose hydrocarbon radicals are derived from straight-chain primary alcohols with 12 to l8 carbon atoms, or from alkylphenols with a straight-chain alkyl chain of six to l4 carbon atoms.
• non-ionic basic washing components are the water-soluble polyethylene oxide adducts, adducted to polypropyleneglycol, ethylenediaminepolypropyleneglycol and alkylpolypropyleneglycol with one to 10 carbon atoms in the alkyl chain.
• these adducts contain from 20 to 250 oxyethylene groups and 10 to oxypropylene groups in the molecule.
• the named compounds contain usually one to five oxyethylene units per oxypropylene unit.
• non-ionic compounds of the type of aminooxides and sulfoxides which, if necessary, can also be ethoxylated, are usable.
• 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.
• neutral salts such as sodium sulfate and sodium chloride
• 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, 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.
• condensed phosphates such as pyrophosphates, triphosphates, 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.
• 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,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 amino-polycarboxylic acids, such as NTA and EDTA.
• alkali metal silicates are suitable, particularly sodium silicate in which the ratio Na ozSio is 1:3.5 to
• fective mixtures of inorganic and organic builders can also be used or combined with the precedingly named mixtures.
• the washing agents of the invention can contain oxygemreleasing 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:
• X and Y have the following meanings: NI-I NI-I-CI-I NI-l-CI-I -CI-I OI-l, CH N-CI-I -CH OH, N(CH,-CH OH) morpholino, dimethylmorpholino, NI-I-C H NH-C H SO I-I, 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 is a diethanolamino, or a morpholino group.
• optical brighteners also suitable for use in the washing agents of the invention are those of the diary!- pyrazoline type of the following 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.
• 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, thiophenebis-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.
• 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 triand 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.
• 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.
• the washing agents 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.
• 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 and 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.
• alkylolamides such as fatty acid monoor 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.
• enzymes 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.
• 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-box ylic acid)-alkyleneimine amounts to from about 0.1 to 50 percent, preferably 0.2 to 25 percent by weight.
• the difference to 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):
• a percompound especially sodium perborate, with or without water of crystallization, as well as their mixtures with stabilizers and activators;
• the detergent substances can consist of up to 100 percent, preferably from 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 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.
• 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.
• 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.
• alkylpolyglycolether alkyl C to C or alkylphenolpolyglycolether (alkyl C to C with five to 10 oxyethylene groups
• foam inhibitors from the class of trialkylmelamines and saturated fatty acids with 20 to 24 carbon atoms, or their alkali metal soaps,
• optical brightener from the class of diaminostilbene disulfonic acid or diarylpyrazoline derivatives
• an inorganic alkali metal salt from the class of the carbonates, bicarbonates, borates, sulfates and chlorides,
• alkylpolyglycolether sulfate alkyl C to C one to five oxyethylene groups
• alkylpolyglycolether alkyl C to C or alkylphenolpolyglycolether (alkyl C to C with five to 12 oxyethylene groups
• Liquid Washing Agent 0.5 to 10 percent of a sulfonate basic washing component (potassium salt),
• alkylpolyglycolether sulfate alkyl C to C l to 5 oxyethylene groups
• optical brighteners from the class of of the diaminostilbene disulfonic acids and diarylpyrazoline derivatives
• Residue Water, perfumes, dyes, preservatives.
• alkylpolyglycolethers alkyl C to C and alkylphenolpolyglycolethers (alkyl C to C with five to 12 oxyethylene groups
• magnesium silicate 0 to 5 percent
• Dishwashing-Machine Washing Agents 0.1 to 3 percent of compounds from the class of the alkylpolyglycolether (alkyl C to C18), alkylphenolpolyglycolether (alkyl C to C with five to 30 oxyethylene groups and five to 30 oxypropylene groups, and ethoxylated polypropyleneglycols,
• alkylpolyglycolether sulfate alkyl C,, to C one to five oxyethylene groups
• solution aids such as sodium toluene sulfonate, sodium xylene sulfonate and urea
• Residue Water, perfumes, dyes, preservatives.
• alkaline reacting compounds from the class of alkali metal hydroxides, carbonates, silicates and phosphates,
• anionic and/or non-ionic detergents 0 to 5 percent of anionic and/or non-ionic detergents.
• alkali metal polyphosphates 0 to 10 percent or cleansing salts of the class of alkali metal polyphosphates, alkali metal silicates, alkali metal borates, and alkali metal carbonates,
• the monomeric ethyleneimine derivatives were mixed according to the mol ratios listed in the following examples and polymerized by the stepwise addition of l to 5 mol percent diethyl sulfate in an inert gas atmosphere within 5 to 48 hours at a temperature not higher than 50 C.
• the copolymers dissolved in methanol, were treated with the equivalent amount of 20 percent aqueous sodium hydroxide solution. The solution was heated to 80 to 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 iso- 5 lated by spray drying.
• 1,800, 15,000 and 40,000 wereheated for 24 hours at 80 to 90 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.
• the reaction was completed on addition of 55 mol percent of sodium chloroacetate by heating for hours at 80 to 90 C with addition of sodium hydroxide to maintain a pH of 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.
• 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 11 as well as the composition of the washing agents.
• 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.
• 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 dH.
• the reflection values, determined by photometer, of the three-times rinsed and dried textile samples are summarized in the following Table IV.
• 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.
• 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 (l 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 1 and II wherein R represents a member selected from the group consisting of H and CH R represents a member selected from the group consisting of H and CH X represents a member selected from the group consisting of H and CH COOH, Y represents a member selected from the group consisting of H, CH -COOH and CH -CH -COOH and n represents an integer of from one to two, with the proviso that when X is H, Y is H or --CH,-CH,-COOH, the ratio of recurring N-al
• copolymeric N-alkylcarboxylic acid-alkyleneimine contains less than 30 percent of unsubstituted recurring alkyleneimine units.

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