DE1816280A1 - Washing, bleaching and cleaning agents - Google Patents

Description

It is known that detergents and cleaning agents, especially those that contain bleaching agents containing active oxygen, complexing aminopolycarboxylic acids or their alkali salts, such as nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA) or diethylenetriaminepentaacetic acid (DTPA) add to the stability of the bleach to increase or the optical brighteners contained in the detergents against the attack of the oxidizing agent to protect. However, these means have certain disadvantages. NTA is capable of the optical brighteners against oxidative ones Insufficient protection against attack, while EDTA and DTPA are not sufficiently resistant to oxidizing agents and are oxidized to inactive compounds. The compounds mentioned increase the cleaning power detergents, but are inferior to the known inorganic building blocks, in particular the polymer phosphates.

In the German Auslegeschrift 1 060 849 or the essentially identical British patent 866 492 are used as stabilizers for perborate or perborate Polyaminopolycarboxylic acids with a complexing effect on detergents and bleaches suggested formula below

HOOC-CH ₁ .
HOOC - CEr /

CH, -CH ₁ - / N — CH _a —CHA—

(I VCH.-COOH J _n

.CH, -COOH XH ₁ -COOH

009829/1565

obtained by reacting ethylene chloride with ammonia and subsequent carboxymethylation of the resulting polyamines. According to DAS 1 "060 849 the number η should be 1 to 10. In the corresponding British patent it is shown, however, that the resistance of the compounds described to oxidizing agents is greatest in the case of diethylenetriaminepentaacetic acid (DTPA) and triethylenetetraminehexaacetic acid (TTHA) and with Polymers in which the number η is greater than 3 do not differ significantly from EDTA in terms of their resistance to oxidation. The cleaning-enhancing properties of these compounds in detergents and cleaning agents show a very similar curve of a "builder effect ^11" - reaches the highest value with EDTA and DTPA and decreases again with increasing molecular weight. It had to be assumed, therefore, that the structure of polyaminocarboxylic acids produced by other means and only slightly different from the compounds described behave in a very similar manner, ie that the resistance to oxidizing agents and the builder effect would also decrease with increasing molecular weight. It was of the opinion that DTPA and TTHA represent an optimum in terms of their properties within the known aminopolycarboxylic acids.

The applicant has set himself the task of cleaning and bleaching agents with a complexing content to develop active substances, which are more resistant than the known agents against oxidizing substances, improved cleaning power and more effective stabilization of the optical Mark up brighteners.

009829/1565

ORIGlNALiNSPECTEO

The invention relates to detergents, bleaches and cleaning agents, characterized by a content of linear poly (N-acetic acid) ethylene imines of the formula

HOOc-CH ₂ -NH-CH ₂ -CH ₂ -

N-CH ₂ -CH ₂ CH ₂ -COOH

-NH-CH ^ -COOH

in which η represents an integer from J to 50. Preferably the poly (N-acetic acid) ethyleneimines are in the form of alkali metal, ammonium or organic ammonium salts before. (

Although the polymer to be used according to the invention N-acetic acid ethylene imines from the. known polyaminopolycarboxylic acids differ only in that there is an acetic acid group on each of the two terminal nitrogen atoms is replaced by hydrogen, they are the known agents in their resistance to oxidizing agents, their cleaning properties and their complexing ability considerably superior. This is all the more surprising since it is known that in comparable cases, e.g. Iminodiacetic acid and nitrilotriacetic acid, the replacement of an acetic acid group by hydrogen with a very sharp decline in cleaning properties and complexing capacity connected is.

The poly (N-acetic acid) ethyleneimines or their salts are obtainable by polymerizing an ester, amide or Nitrile of N-acetic acid aziridine and subsequent saponification to carboxylic acid salts. Suitable starting materials are in particular the lower alkyl esters, e.g. the methyl, ethyl, propyl, i-propyl and butyl esters of N-acetic acid aziridine. The polymerization takes place in the presence of LEWIS acids, e.g. neutral sulfuric acid esters,

«4 -009829/1565

ORIGINAL INSPECTED

such as dimethyl sulfate, diethyl sulfate, dipropyl sulfate and Dibutyl sulfate or sulfonic acid ester ^ such as the methyl •, Ethyl, propyl or butyl esters of methanesulfonic acid, Benzenesulfonic acid and p-toluenesulfonic acid. It can also be in the presence of solvents, in particular lower halogenated hydrocarbons. The polymerization time is generally at 2 to 60 hours., The reaction temperature is expediently by cooling to a temperature of JO held up to 90 C. The polymers obtained are saponified in a known manner, for example by heating with aqueous sodium or potassium hydroxide solution. The emerging The alkali salt can be converted into the free acid by treatment with ion exchangers or by subsequent neutralization with ammonia or organic ammonium bases, such as mono-, di- or triethanolamine, morpholine or N-methylmorpholine, converted into the corresponding ammonium salts.

The average molecular weights of the polymeric N-acetic acid ethylene imines obtained in this way are between 500 and 2000. By separating off the low molecular weight fractions mostly contained in the mixture, for example by gel chromatography on polymerized dextrans (e.g. Sephadex ^), polymers with a average molecular weight of 1500 to 5000 obtained. However, since the low molecular weight fractions do not interfere with the application according to the invention, they can be present in the product remain. It is therefore preferable to use those polymeric N-acetic acid ethylene imines which have an average molecular weight from 600 to 2000.

The polymeric N-acetic acid ethylene imines can wash, Bleaching agents and cleaning agents in the form of salts or free acids are added, provided that in the latter case the agent has an alkaline reaction in sufficient quantities

0 098.29 / 156 S V

Amount contains, so when dissolving the funds in water neutralization of the free acid groups takes place.

The agents according to the invention also contain at least another cleaning or bleaching compound, such as nonionic, anionic and zwitterionic washing active substances, inorganic and organic synthesis salts, oxygen-containing bleaches and common detergents and Detergent ingredients.

As surface-active detergent substances, in those cases where value is placed on low foam development, primarily nonionic compounds, including, for example, the polyglycol ether derivatives of alcohols, fatty acids and alkylphenols, which contain 2 to ^ O glycol ether groups and 8 to 20 carbon atoms Contain hydrocarbon residue. Particularly suitable are polyglycol ether derivatives, in which the number of Äthy-] lenglykoläthergruppen is 5 to 15 and their carbon j hydrogen radicals from straight-chain, primary Aikoholen having from 12 to l8 carbon atoms or of alkyl phenols having a straight-chain, from 6 to 14 carbon atoms having Alky! Chain derive '. The addition of 3 to 15 mol of propylene oxide to the last-mentioned polyethylene glycol ethers or conversion into the acetals gives detergents which are distinguished by a particularly low foaming power.

Other suitable nonionic washing raw materials are the water-soluble 20 to 250 ethylene glycol ether groups and from 10 to 100 polyethylene oxide adducts containing propylene glycol ether groups with polypropylene glycol, ethylene diamino polypropylene glycol and alkyl polypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The mentioned Compounds usually contain per propylene

- 6 -009829/1565 originally inspected

glycol unit 1 to 5 ethylene glycol units. Not even r Ionic compounds of the amine oxide and sulfoxide type, which may also be ethoxylated, can be used.

The detergents and cleaning agents can also contain anionic washing raw materials of the sulfate or sulfate type. Primarily alkylbenzenesulfonates, for example n-dodecylbenzenesulfonate, come into consideration, furthermore olefin sulfonates, such as, for example, by sulfonation of primary or secondary aliphatic monoolefins with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis are obtained, as well as alkyl sulfonates, as they are obtained from n-alkanes by suIf © chlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. Also suitable are ot-sulfo fatty acid esters, primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated higher molecular weight alcohols. Further Compounds of this class, which may possibly be present in the detergents, are the higher molecular sulfated ones Partial ethers and partial esters of polyhydric alcohols, such as the alkali salts of monoalkyl ethers or mono fatty acid esters of the glycerol monosulfuric acid ester or the 1,2-dihydroxypropanesulfonic acid. Sulphates also come from ethoxylated or propoxylated fatty acid amides and alkylphenols and fatty acid taurides and fatty acid isethionates in question.

Alkali soaps are further suitable anionic Wasohrohstoffe of fatty acids of natural or synthetic origin, e.g. the sodium soaps from coconut, palm kernel or Tallow fatty acids. As zwitterionic detergent raw materials, alkyl betaines and especially alkyl sulfobetaines come into question, e.g. 5- (N, N-dimethyl-N-alkylammonium) -2-hydroxypropane-isulphonate.

- 7 -009829/1565

The anionic detergent raw materials can be in the form of Na-. trium-, potassium and ammonium salts as well as salts of organic "\ shear bases such as mono-, di- or triethanolamine. If the called washing-active nonionic, anionic, and zwitterionic compounds have a long-chain aliphatic hydrocarbon residue, this should be preferably straight-chain and 8 to 22 carbon atoms In the compounds with araliphatic hydrocarbon radicals, the preferably unbranched alkyl chains contain on average 6 to Vo carbon atoms

Suitable components of the mixture are also inorganic synthesis salts, in particular condensed phosphates, such as pyrophosphates, triphosphates, tetraphosphates, trimetaphosphates, tetrametaphosphates and more highly condensed phosphates in the form of the neutral or acidic sodium, potassium or ammonium salts. Alkali metal triphosphates and their mixtures with pyrophosphates are preferably used. The condensed phosphates can also be completely or partially replaced by phosphorus and nitrogen-containing organic complexing "These include the alkali metal or ammonium salts of Aminopolyphosphon- like acids, particularly amino tri-Cmethylenphosphonsäure) Ä * thylendiamintetra- (methylene), 1-hydroxyethane-1, 1-diphosphonic acid, methylenediphosphonic acid, ethylene diphosphonic acid and the higher homologues of the polyphosphonic acids mentioned, also the alkali metal or ammonium salts of low molecular weight aminopolycarboxylic acids, such as NTA and EDTA. Silicates, in particular sodium silicate, in which the ratio of Na ₂ OiSiO _{2 is} 1: 2.5 to 1: 1, are suitable as further synthesis salts.

009829/1565

Neutral salts, such as sodium sulfate and sodium chloride, and substances for regulating the pH fourth, such as bicarbonates, carbonates, borates and hydroxides of sodium or potassium, and acids such as lactic acid and citric acid are also suitable as components of the mixture. The amount of alkaline substances, including alkali silicates and phosphates, should be such that the pH value of a usable lye is 9 to 12 for coarse laundry and 6 to 9 for delicate laundry.

Through a suitable combination of different surface-active Detergent raw materials or synthesis salts with one another can in many cases increase the effectiveness, for example a improved detergency or reduced foaming power can be achieved. Such improvements are for example possible by combining anionic with nonionic and / or zwitterionic compounds with one another, by combining different nonionic compounds with one another or by mixtures of Washing raw materials of the same type, which differ in terms of the number of carbon atoms or the number and position of Distinguish double bonds or chain branches in the hydrocarbon. They can also act synergistically Mixtures of inorganic and organic synthesis salts used or combined with the mixtures mentioned above will.

Depending on their intended use, the agents can contain oxygen-releasing bleaching agents, such as hydrogen peroxide, alkali perborates, alkali percarbonates, alkali perphosphates, urea perhydrate and alkali persulfates or compounds containing active chlorine, such as alkali hypochlorites, chlorinated trisodium phosphate and chlorinated cyanuric acid or their alkali salts. The per compounds can be mixed with bleach activators and stabilizers, such as magnesium silicate, are present.

009829/1565 ^? BATH

Optical brighteners suitable for cellulose fibers are those of the diaminostilbene sulfonic acid type of the formula:

in which X and Y have the following meanings: NH _? , NH-CH ,, NH-CH ₂ -CH ₂ OH, CH ₃ -N-CH ₂ -CH ₂ OH, .N (CH ₂ -CH ₂ OH) _2,. Morpliolino, ä Dime thy lmorpholino, NH-C ₆ H ₅ , NH-C ₆ H ₂ ^ -SO ₃ H, OCH ₃ , Cl, where X and Y can be the same or different. Compounds in which X is an anilino and Y is a diethanolamino or morpholino group are particularly suitable.

As optical brighteners for polyamide fibers, those come from Type of diarylpyrazoline of the following formula in question:

Ar - C. - CH ₀
"II I ²

^N n ^CH 2
Ar

In this formula, Ar and "Ar ¹ " mean aryl radicals, such as phenyl, "diphenyl or naphthyl, which can carry further substituents, such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, sulfonic acid and Sulfonamide groups or halogen atoms. A 1,5-diarylpyrazoline derivative is preferably used in which the radical Ar represents a p-sulfonamidophenyl group and the radical Ar ′ represents a p-chlorophenyl group. In addition, whiteners suitable for lightening other types of fibers can also be present, for example those of the naphthotriazole stilbene sulfonate, ethylene-bis-benzimidazole, ethylene-bis-benzoxazole, thlophen-bis-benzoxazole, dialkylaminocoumarins and cyanoanthracene type. These brighteners or their mixtures can be used in the agents in amounts of 0.01 to 1.5 wt .- ^, preferably 0.1

up to 1 wt.

009829/1565 -10-

-ίο - ■■■ '"■

Other suitable ingredients in the mixture are gray scale inhibitors, e.g. sodium cellulose glycolate, as well as the water-soluble alkali salts of synthetic polymers, which contain free carboxyl groups. These include the polyesters or polyamides made from tri and tetracarboxylic acids and dihydric alcohols or diamines, also polymeric 'acrylic, methacrylic, maleic, pumar, itacon, citracon and aconitic acid and the copolymers of the unsaturated carboxylic acids mentioned or their copolymers with olefins and vinyl ethers.

Agents intended for use in drum washing machines suitably contain known foam-suppressing agents, for example saturated fatty acids or their alkali soaps with 20 to 2k carbon atoms or triazine derivatives, which are obtained by reacting 1 mole of cyanuric chloride with 2 to 3 moles of an aliphatic, straight-chain, branched one or cyclic primary monoamine or by propoxylation or butoxylation of melamine.

To further improve the soil-releasing properties of the agents according to the invention, they can also contain enzymes from the class of proteases, lipases and amylases. The enzymes can be of animal and vegetable origin, for example from digestive enzymes or yeasts, such as pepsin, pancreatin, trypsin, papain, catalase and diastase. Preferably from Bakterienstänmen or fungi such as Bacillus subtilis and Streptomyces griseus, obtained enzymatlsche agents used, which are relatively resistant to alkali compounds and anionic detersive active ingredients and will not be inactivated appreciably at temperatures between 45 ° and 70 ⁰ C.

009829/1585

The detergents and cleaning agents can be liquid, pasty or solid, for example powdery, granulated or lumpy form. Liquid preparations can contain solvents miscible with water, in particular ethanol and i-propanol as well as solubilizers, such as the alkali salts of benzene, toluene, xylene or Kthylbenzenesulfonsäure contain. To increase the foaming power and to improve skin tolerance, alkylolamides such as fatty acid mono- and diethanolamides are added. In addition, the mixtures can dyes and fragrances, bactericidal active ™

contain substances, substances with a finishing effect and fillers, for example urea.

The preparation of the agents according to the invention can be carried out in a conventional manner Way by mixing, granulating or spray drying. If enzymes are used, it is recommended that these with non-ionic detergent raw materials and possibly fragrances to mix or to disperse in the melt of a salt containing water of crystallization, e.g. Glauber's salt, and this Then combine the premixes with the remaining powder components. This will make the enzymes with the rest Powder particles cemented, so that the mixtures do not {tend to form dust or not to separate.

The poly (N-acetic acid) ethyleneimine content or its salts in washing, bleaching and cleaning agents is 0.1 to 50, preferably 0.2 to weight percent, depending on the area of application. The difference of up to 100 % is due to the aforementioned substances with a washing and bleaching effect and any additional cleaning-enhancing building salts that may be used. The qualitative and quantitative composition of these additional components depends largely on the specific field of application of the agents. In the case of the technically particularly important detergents and cleaning agents, it corresponds to the following scheme

(Data in percent by weight):

009829/1565

1 to 40 % of at least one compound from the class of anionic, nonionic and zwitterlonlscheii washing active substances,

10 to 80 % of at least one non-surface-active, cleaning enhancer or complexing building salt,

10 to 50% of a peroxy compound, in particular containing water of crystallization or anhydrous sodium perborate, and mixtures thereof with stabilizers and activators, from 0.1 to 20 $ other auxiliaries and additives.

The washing active substances can contain up to 100 % , preferably 5 to 70% from compounds of the sulfonate and / or sulfate type, up to 100 %, preferably 5 to 40 % from nonionic compounds of the polyglycol ether type and up to 100 % preferably 10 to 50% > consist of soap. The synthesis salts can consist of up to 100 %, preferably 25 to 95 %, from alkali metal triphosphates and their mixtures with alkali metal pyrophosphates, up to 100%, preferably 5 to 50% from an alkali metal salt of a complexing agent from the class of polyphosphonic acids, nitrilotriacetic acid, ethylenediamine tetraacetic acid and up to 100 % , preferably 5 to 75 % of at least one compound from the class of alkali metal silicates, alkali metal carbonates and alkali metal borates.

To the other excipients and additives include in addition to the optical brighteners in particular the foam inhibitors, the 5 to $> may be present in the inventive compositions in an amount up * preferably in an amount of 0.2 to 5%, and also the enzymes that can be present in an amount of up to 5 %, preferably 0.2 to 5 % , and the graying inhibitors, the proportion of which can be up to 5 %, preferably 0.2 to 5 % .

- 15 009829/1565

Some recipes are given below, which have particularly proven themselves in practice.

Examples

A. Powdered, low-foaming detergent:

J5 - 15 % sulfonate washing raw material from the class of

Alkylbenzenesulfonates, olefin sulfonates and | η-alkanesulfonates,

0.5 - 5 % alkyl polyglycol ether (C ^ -C ^ g-alkyl) or alkylphenol polyglycol ether (Cg-Ch-alkyl) with 5 to 10 ethylene glycol ether groups,

0 - 5 % soap C ₁₂ -C ₁ Q,

0.2 - 5 % foam suppressants from the class of trialkylamines and saturated fatty acids or their alkali soaps with 20 carbon atoms,
- 50 % of a condensed alkali metal phosphate

the class of pyro- or tripolyphosphates,

0.1 - 25 % poly (N-acetic acid) ethyleneimine or similar

its alkali salts,

1 5 % sodium silicate,

- j55 % sodium perborate tetrahydrate, 5% enzyme,
0.05-1 % of at least one optical brightening agent

from the class of the diaminostilbene disulfone

acid or diarylpyrazoline derivatives, 0.1 - J> 0% of an inorganic salt from the class

of carbonates, bicarbonates, borates, sulfates

and chlorides of alkali metals, 0.4 % magnesium silicate, 0.5-5 % sodium cellulose glycolate.

- 14 009829/1565

• Β. Powdered, foaming mild detergent:

1 - 50 % sulfonate detergent raw material 0.5 - 10 % alkyl polyglycol ether sulfate (Cg-C ^

1-5 ethylene glycol ether groups, 0-20 % alkyl polyglycol ether (C ₁₀ -C ₁ Q-AlKyI) or

Alkylphenol polyglycol ether (Cg-C ^ -alkyl) with

5-12 ethylene glycol ether groups, 0.2 - 25 $> poly (N-acetic acid) ethylene imine or its

Alkali salts,

0 - 5 % fatty acid ethanolamide or diethanolamide, 0 - 20 % sodium tripolyphosphate, 0 - 1 $ of a brightener from the class of diaryl

Pyrazoünderivate and its mixtures with

Polyester brighteners, 3 - 70 fo sodium sulfate.

C. Liquid detergent:

0.5 - 10 % sulfonate detergent raw material

0 - 10 % alkyl polyglycol ether sulfate (Cg-C ^ -alkyl,

1-5 ethylene glycol ether groups), 0.2 - 25 % poly (N-acetic acid) ethylene imine or its

Alkali salts 0.1 - 5 % fatty acid amd glycol ether condensate

(C ₁₀ -C ₁ Q-AIkYl, 1-10 ethylene glycol ether groups),

1 - 10 % solubilizer from the alkali class

salts of benzene, toluene or xylene sulfone

acid,

0 - 30 % neutral or acidic potassium pyrophosphate, 0 - 10 % organic solvents from the class of

Co-Cx alcohols and ether alcohols, 0 - 1 % optical brighteners from the class of diamino

stilbene disulfonic acid and diarylpyrazoline

father,
Remaining water, fragrances, colorings, preservatives

funds.

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009829/1585

10 - 50 fo 1 - 5th fo 0. - 5th % 0 - 5th

D. Soaking and prewash detergent:. 0.5 - 5 f>. Sulphonate detergent raw material

0 - 3 % compounds from the "class of alkyl

polyglycol ether (C, ^ - C.ο-alkyl) and alkylphenol polyglycol _{ether (Cg-C 12} -alkyl) with 5-12 ethylene glycol ether groups,

O ₅ I - 10 fo poly (N-acetic acid) ethylene imine or its alkali salts, ·
Soda,

Water glass,

Magnesium silicate,

Enzyme.

E. Machine dishwashing detergent:

0.1 - 3 f> compounds from the class of alkyl polyglycol ethers (C ₁₂ -C ₃ Q-AIlCyI), alkylphenol polyglycol ethers (Cg-C ^ -alkyl) with 5-30 ethylene and 5-30 propylene glycol ether groups and ethoxylated polypropylene glycols,

0.2 -25/5 poly (N-acetic acid) ethyleneimine or its Alkali salts,

45 - 90 fo pent ana tr iumtr! Phosphate,

- 40 % sodium silicate (Na ₂ OrSiO ₃ «1: 1 to 1: 3),

- 5 % potassium dichloroisocyanurate, %

0 - 2 fo foam suppressant,

F. Liquid dishwashing detergent and cleaning agent: 5 - 30 fo sulfonate detergent raw material,

- 15 % alkyl polyglycol ether sulfate (Cg-C, g-alkyl,

1-5 ethylene glycol ether groups,

0.2 - 10 % alkali metal salts of poly (I-acetic acid) ethylene imine

- 20 fo organic solvents from the class of

C ₂ -Cz alcohols and ether alcohols,

- 10 fo solubilizers, such as toluene sulfonate, xylene

sulfonate and urea,
Rest of water, fragrances, dyes, preservatives

-reans.

009829/1565 - 16 ~

G. Bleach:

0.2 - 25 % poly (N-acetic acid) ethyleneimine or its alkali salts, - 95 % per compound, 0 - 50 % alkaline compounds

the class of hydroxides, carbonates, silicates and phosphates of alkali metals,

0 - 50 % bleach activators,

0 - 5 % anionic and / or nonionic washing active substance,

0 - 10 % other components, such as corrosion inhibitors, optical brighteners, neutral salts, magnesium silicate.

H. Alkaline cleaner:

0.1 - 25 % poly (N-acetic acid) ethyleneimine or its

Alkali salts

0.5 - 50 % sodium silicate (Na ₂ O: SiO ₂ = 1: 1 to 1: 3),

0.5 - 80 fo sodium hydroxide,

0 - 40 % trisodium phosphate,

0 - 40 % condensed alkali phosphate,

0 - 40 % soda,

O - 10 fo Hy dr oxy ä t ha nd i ph ο s ph ona t,

0 - 5 % anionic and / or nonionic

Washing active substance.

I. Abrasives:

1 - 10 % anionic and / or nonionic washing raw material,
0.1-5 %. Poly (N-Acetic Acid) Ethylene Alkali Salt

imins,

80 - 95 % abrasives,
0 - 10 fo cleaning salts from the class of alkali

polymer phosphates, alkali silicates, alkali borates

and alkali carbonates, 0-10? o alkali dichloroisocyanurate.

0 098 297156 5

example 1

The cleaning effect of detergents that contained a builder substance in addition to an anionic detergent raw material (Na-n-dodecylbenzenesulfonate) was compared with one another. With these V / aschmitteln was sisal fabric which had been soiled with carbon black, iron oxide and skin fat, washed in a laboratory washing machine, said wash liquor is heated over 15 minutes from 20 ° to 90 ⁰ C and another 15 minutes was maintained at 90 ⁰ C. The detergent concentration was 3 g / l> the water hardness 16 ° dH, the weight ratio of textiles to V / ash liquor 1:12. It was then rinsed four times with water and the textile material was spun and dried. The percentage lightening determined with a photometer (soiled fabric = 0 %, original fabric = 100 % lightening), as well as the composition of the agents, can be found in the following table.

The sodium salt of the polymeric N-acetic acid ethylene imine was by heating Γ? 0 g of N- (ethyl acetate) aziridine for three hours and 0.2 g of dipropyl sulfate in 1500 ml of 1,2-dichloroethane with exclusion of air, separation of the solvent and saponification of the polymer with 3 η NaOH for three hours Heating to 100 C has been established. The results show that the polymeric N-acetic acid ethylene imine is known to others Builder substances, including triphosphate, which is known to be very effective, surpasses its cleaning effect.

-18-

• j ΐ -ι.

composition Quantities in g / l
Example comparisons 1 1 2 - 1 Na-n-dodecylbenzenesulfonate 1 61.0 24.3 Na-poly (N-acetic acid) -
ethylene imine (molecular weight
weight 1250) 2 2 - Pentasodium triphosphate - - Sodium sulfate - 2 Na ethylenediaminetetraacetate - 59.5 % Brightening 61.8

Examples 2 Ms 4

A detergent with the following composition was used (data in percent by weight):

8 % Na-n-Dodecylbenzenesulfonate 5 # Sodium Elf of fatty acids Cjp-Cgp

3 % oleyl alcohol polyglycol ether (10 ethylene glycol groups)

40 % pentasodium triphosphate |

5 # sodium silicate (Na ₂ O. 3.3 SiO _g )

2% magnesium silicate

1 % sodium cellulose glycolate /

$ 25 Sodium Perborate Tetrahydrate

8 % water

. 0.6 % pyrazoline- type dissolving agent

0.2 fl on ft ollunemit te 1 of the diamino ti type rc. -

008829 / UÖS

The lightening agents had the following structure:

- C - CH

Pyrazoline type

Dlaminos t ilb entyp

This agent were each 2 wt -.% Na-poly (N-acetic acid) · ethyleneimine added. The polymeric carboxylic acids prepared by polymerizing N-acetic acid aziridine in the presence of dipropyl sulfate had an average molecular weight of 870 in Example 2, 125O in Example 3 and 1,720 in Example 4. For comparison used was a detergent, which had been added in place of the polymers of this invention 2% Na ~ nitrilotriacetat (NTA) or 2% Na-Ä'thylendiaminotetraazetat (EDTA).

-20 -

009829/1565

ORIGINAL INSPECTED

-2Ö -

With these means, textiles were made from polyamide fibers

(Perlon ^) washed in a laboratory washing machine,

o where the washing liquor was heated from 20 ° C. to 60 ° C. within 15 minutes and left at this temperature for a further 15 minutes. The detergent concentration was 5 g / l and the weight ratio of textile to washing liquor was 1:50. The water used had a hardness of 16 dH and a content of 10 ^J mol per liter of copper ions. The whiteness of the laundry, rinsed four times and then dried, was determined photometrically. The results are compiled in the table below. They show the superiority of the compounds to be used according to the invention.

additive Whiteness after Ex. Poly (N-acetic acid) - 1 wash 5 Washes 2 ethyleneimine 105 114 Molar weight 87Ο Poly (N-acetic acid) - ethyleneimine 106 114 Molecular weight 1250 Poly (N-acetic acid) - 4th ethyleneimine 106 115 Molecular weight 1720 NTA - EDTA 100 104 mm IO35 110

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009829/1565

Examples 5 and 6

From a bleaching agent consisting of 154 g of sodium perborate and 124 g of the sodium salt of a obtained by polymerizing N- (methyl acetate) aziridine in the presence of diethyl sulfate and saponification with sodium hydroxide solution produced poly- (N-acetic acid) -äthylenimines from the

Example 5) Molecular weight 810 Example 6) Molecular weight 1500,

an aqueous solution containing 0.62 g / l sodium perborate was prepared and diluted sodium hydroxide solution was added adjusted to a pH of 10. The decrease in the active oxygen content this solution at 90 ° C was added at intervals of 30 minutes by titration by iodometric method certainly. For comparison, the determination was repeated with the same amounts of known perborate stabilizers. The results are compiled in the following table. They show the superiority of the agents according to the invention.

% Active oxygen 60 90 120 150 min. stabilizer 30th 71
73 in σ \
VO VO 59
64 CVl OO
in in Poly (N-acetic acid) ethylene
1min
Molecular weight 810
Molecular weight I500 80
83 26th 10 3 - EDTA 52 15th VJl 2 - DTPA 40 22nd 9 5 Carboxymethylated polyamine
according to DAS 1 060 849 of
Molecular weight 900 48 18th 8th 4th - without addition 35,

- 22-

In the table below are some recipes about washing, bleaching and cleaning agents according to the invention compiled for the following areas of application:

low-foam heavy duty detergent

Cold detergent

Plus detergent

Wool detergent

Soaking agent

Bleach

liquid dishwashing detergent

Cleaner for coarse soiling

Abrasive «

Ingredients a through d and f through i were found as sodium salts before, the pyro phosphate (component k) came in Example 9 as the potassium salt, in all other examples as the sodium salt. A was used as the enzyme (component q) Maxatase ^ product obtained from Bacillus subtilis from Koninklijke Nederlandsche Gist en Spiritusfabriek N.V. Delft, with an activity of 100,000 LVU / g. In which Foam suppressant (component v) is a reaction product of 1 mol of cyanuric chloride with 2.7 mol of a primary n-alkylamine of chain length Cg-C.o

Example 7 8th It 9 Il 10 H 11th ft 12th M. 1? It 14th Il 15th Jt

O (O GO ro co

CJl σ »cn

a) I. W) component 7th Examples 8th 9 (Information in 11th Weight - *> * 14th 15th b) ro
I. x) 6th - 5 10 - 12th 13th 5.5 - 2.5 c) y) n-Dodecylbenzenesulfonate 3 - - 15th 3.5 - 15th - - d) z) C ^ -CjgOlefimellön « - 10 5 - - - - - - - e) C ₁₄ -C 7 alkanesulfonate • 2.3 5 - - 0.5 5 70 - - f) Coconut fatty alcohol glycol ether sulfate (2 AO) 3 4th - 10 - - 4th - 1 - G) Oleyl alcohol polyglycol ether (10 AO) 3 - - 5- . - - 0.1 2 - b) CJ ₂ -C ₁₈ soap - - - - - - - - ■ - - i) C _2o -C ₂₂ soap 25th 15th 1 - 0.2 - - 0.5 0.2 • k) Poly (N-acetic acid) ethyleneimine • ίο 20th - 5.5 - 1.5 1 10 - 1) Tripolyphosphate - - 20th - 20th - - 2 - ■ m) Pyrophosphate - 20th - - 35 - - 45 5 n) soda 5 5 - - 5 25th - 25th 1 O) Sodium silicate 4.4 - -. -. 18th 20th - - 1.2 P) Sodium sulfate 25th - - 45 - - 0.4 - - q) Sodium perborate 3 - - - 3 50 - - - r) Magnesium sludge 1.5 - - - 2 - - - - s) enzyme 1.5 - - - - - - - - t) Na cellulose gly colate - - 7 ' - - - - - - u) Na toluenesulfonate - - - - - - - - I ν) Coconut fatty acid diethanolamide 0.5 0.7 0.1 5 - - - - Optical brighteners 0.5 - - - - 0.5 - - Foam suppressants 8.5 7.9 56.7 - 13.3 - 13.4 - water - 15th - 14.5- - 2.5 1 4th Dichloroisocyanutate 0.1 0.1 0.2 - - - 0.1 0.1 Dyes and fragrances - - - - - - 86 Quartz flour -

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Claims (16)

Claims 1. Washing, bleaching and cleaning agents, characterized by a content of linear poly (N-acetic acid) -äthyleniminen the formula _l2 -vu ₂ j -NH-CH ₂ - η HOOC -CH ₂ -NH-CH ₂ - ^ ₂ -NH-CH ^ -COOH in which η represents a number from 5 to 50. 2. Agent according to claim 1, characterized by a content of alkali metal, ammonium or organic Ammonium salts of poly (N-acetic acid) ethylene amines. 3 · Means according to claim 1 and 2, characterized by a content of poly (N-acetic acid) ethylene imines with an average molecular weight of 500 to 5000 or its alkali metal, Ammonium or organic ammonium salts, obtainable by polymerizing an ester, amide or nitrile of N-acetic acid aziridine and subsequent saponification to carboxylic acid salts. 4. Composition according to claim 1, characterized by a content of poly (N-acetic acid) -äthyleniminen or their Salts with a molecular weight of 600 to 2000. 5. Composition according to claim 1 to 4, characterized by a content of 0.1 to 50 %, preferably 0.5 to 25 % poly (N-acetic acid) ethyleneimine or its salts and 50 to 99 * 9 .. £ “Preferably 75 to 99 * 5 %” consist of other detergents, cleaning agents and bleaching agents. - 25-0 09829/1565 6. Composition according to claim 1 to 5> wherein the other ingredients consist of 1 "to 40% of at least one compound from the class of anionic, nonionic and zwitterionic washing active substances. 7. Composition according to claim 1 to 6, wherein the other ingredients consist of 10 to 80% of at least one building salt. 8. Means according to claim 1 to 7> wherein the other constituents consist of 10 to 50% of a per compound and mixtures thereof with stabilizers and activators. 9. Means according to claim 1 to 8, wherein the washing active substances up to 100 %, preferably 25 to 70 $ from those of the sulfonate and / or sulfate type, up to 100 %, preferably 5 to 40 % from nonionic compounds of the polyglycol ether type and up 100 %, preferably 10 to 50 % of soap. 10. Means according to claim 1 to 9, wherein the building salt up to 100 %, preferably 25 to 95 % of alkali metal triphosphates and mixtures thereof with alkali metal pyrophosphates, up to 100 %, preferably 5 to 50 % of an alkali metal salt of a complexing agent from the class of polyphosphonic acids , Nitrilotriacetic acid, ethylenediaminotetraacetic acid and up to 100 %, preferably 5 to 75 %, of at least one compound from the class of alkali metal silicates, alkali metal carbonates and alkali metal borates. 11. Composition according to claim 1 to 10, wherein the per compound consists of anhydrous and / or sodium perborate containing water of crystallization. - 26 - 12. Composition according to claim 1 to H _1, characterized in that it contains up to 5 % » preferably 0.2 to 3 % of at least one foam inhibitor from the class of saturated fatty acids containing 20 to 22 carbon atoms and their alkali metal soaps, and the substituted triazines , obtainable by reacting 1 mole of cyanuric chloride with 2 to 3 moles of a primary monoamine or by propoxylation and / or butoxylation of melamine. 15. Agents according to Claims 1 to 12, characterized in that they contain up to 5%, preferably 0.2 to 3%, of enzymes. 14. Composition according to claim 1 to 13, characterized in that they contain up to 5% *, preferably 0.2 to 3 % , of graying inhibitors. 15. Composition according to claim 1 to 14, characterized in that they contain 0.01 to 1.5% of optical brighteners. 16. Agent according to example A to I. Henkel & Cie. GmbH, fix i.V. (Dr. Haas) (Dr. Nagel)