DE1816348A1 - Washing, bleaching and cleaning agents - Google Patents

Description

Henkel & Cie GmbH Düsseldorf, on. 18-. Dec 1968

Patent department Henkelstr. 67

Dr. Walther / «! 181634 8

Γ patent registration

D 3648
"Detergents, bleaches and cleaning agents"

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

In the German Auslegeschrift 1 ΟβΟ 849 as stabilizing λ lisierungsmittel for perborate or perborathaltige V / a schund bleaching agent in addition to DTPA also such complex i er end v / irkenden compounds proposed by the reaction of ethylene chloride with ammonia and subsequent carbon oxy in et hy .1 ~ atation of the resulting polyamines can be obtained. The carboxymethylation products of the polyamines should contain up to 11 ethylenic groups, which corresponds to a maximum molecular weight of 1220. It can be shown, however, that these complexing agents, contrary to the assertion made in German Auslegeschrift 1 060 849, are also rapidly oxidized by per compounds and

009826/2003

8AD ORIGINAL

that, moreover, their cleaning power is even less than that of EDTA.

The applicant has set himself the task of adding agents containing complexing substances which develop through good resistance to oxidizing substances, improved cleaning power and are characterized by an effective stabilization of the optical brighteners.

The invention relates to detergents, bleaches and cleaning agents, characterized by a content of branched poly (N-acetic acid) ethylene imines of average molecular weight 2000 to 200,000 or their alkali metal, ammonium or organic ammonium salts.

The preparation of the branched polymeric N-acetic acid ethylene imines or their salts are carried out by known processes, for example by using branched polyethyleneimines from an average molecular weight of 1200 to 120,000 in an aqueous alkaline medium with chloroacetic acid or bromoacetic acid Reacts alkali metal salts. By treatment with ion exchangers, the alkali metal salts obtained can be converted into the free acids or by subsequent neutralization with ammonia or organic ammonium bases, such as mono-, dioder Triethanolamine, morpholine and N-methylmorpholine, in the corresponding ammonium salts are transferred.

The molecular structure of the branched poly (N-acetic acid) ethyleneimines can be represented by the following scheme:

. N-CH ₀ -CH ₀ -N-CH ₀ -CH ₀ -N-CH ₀ -Ch ₀ -N-CH ₀ -CH ₀ -N-

t dd \ dd ι dd \ dd A CH ₀ A CH ₀

! d I 2

CH ₂ CH ₂

HN-CH ₂ -CH ₂ NA ₂ AN

00 9826/2003

where A stands for the radical -CHg-COOH. Depending on the degree of alkylation, the polymers can accordingly also contain unsubstituted primary or secondary amino groups. Quaternary ammonium groups can also be present in products with a high degree of alkylation. Such products are suitable for use in the invention is primarily suitable in which _s in the starting material -the existing primary: secondary amino groups and 50 to 100 ·;>, preferably 60 to 98% carboxymethylated ¹ are.

The cleaning properties of the polymers increase with increasing molecular weight, which is why they are preferably used which have an average molecular weight of at least 4,000, for example 4,000 to 150,000.

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 contains alkaline compounds in sufficient quantity so that when the agent is dissolved in V-acser neutralization of the free acid groups takes place.

The agents according to the invention also contain at least another compound with a cleansing or bleaching effect, itfie non-icnic, anjonic and r .-. vitterionic V. 'ash-active substances, inorganic uni organic synthesis salts, oxygen-containing bleach so ;; ie usual detergents and Detergent ingredients.

BAO ORIGINAL

The surface-active washing active substances are used in those cases in which there is little foam development Value is placed primarily on non-ionic compounds, including, for example, the polyglycol ether derivatives of alcohols, fatty acids and alkyl phenols that have 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the. Contain hydrocarbon residue. Particularly ■ Polyglycol ether derivatives in which the number of ethylene glycol ether groups is 5 to 15 and their are suitable Hydrocarbon radicals are derived from straight-chain, primary alcohols with 12 to 18 carbon atoms or from alkylphenols derive with a straight-chain alkyl chain having 6 to 14 carbon atoms. By attachment from 2 to 15 moles of propylene oxide to the latter Polyethylene glycol ether or by converting it into the acetals detergents are obtained which are characterized by a particularly low foaming power.

Further suitable nonionic detergent raw materials are the water-soluble 20 to 250 ethylene glycol ether groups and polyethylene oxide adducts containing 10 to 100 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 1 to 5 ethylene glycol units per propylene glycol unit. Also non-ionic compounds of the amine oxide and sulfoxide type, which can optionally also be ethoxylated can be used.

009826/2003

SAO

The detergents and cleaning agents can also contain anionic washing raw materials of the sulfonate or sulfate type: First and foremost come alkylbenzenesulfonates, for example n-Dodecylbenzenesulfonate, into consideration, also 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 made from n-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. Also suitable are o ^ -Sulfofettsäureester, primary and secondary alkyl sulfates and the sulfates of ethoxylated ones or propoxylated higher molecular weight alcohols. Other compounds of this class that may be used in detergents are the higher molecular weight sulfated partial ethers and partial esters of polyhydric alcohols, like the alkali salts of the monoalkyl ethers or the monofatty acid esters of glycerol monosulfuric acid ester or 1,2-dihydroxypropanesulfonic acid. Sulphates also come from ethoxylated or propoxylated fatty acid amides and alkylphenols as well as fatty acid taurides and fatty acid ethionates in question.

Other suitable anionic washing raw materials are alkali soaps of fatty acids of natural or synthetic origin, E.g. the sodium soaps made from coconut, palm kernel or tallow fatty acids. As zwitterionic washing raw materials There come alkyl betaines and, in particular, alky sulfobetaines. question, e.g. 3- (N, N-dimethyl-N ~ alkylammonium) -propane-1-sulfonate and 5- (N, N-dimethyl-N-alkylammonium) -2-hydroxypropane-1-sulf onat. "

0 0 9.82672003

The anionic detergent raw materials can be in the form of the sodium, potassium and ammonium salts as well as organic salts Bases such as mono-, di- or triethanolamine are present. Provided that the washing-active nonionic, anionic ones mentioned and zwitterionic compounds have a long-chain aliphatic hydrocarbon radical, this should preferably be straight-chain and have 8 to 22 carbon atoms. In connections with araliphatic hydrocarbon radicals contain the preferably unbranched alkyl chains on average β to 16 carbon atoms.

Suitable components of the mixture are also inorganic synthesis salts, in particular condensed phosphates, v / ie 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 wholly or partially replaced by phosphorus-containing and nitrogen-containing organic complexing agents. These include the alkali metal or ammonium salts of aminopolyphosphonic acids, in particular aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, methylenediphosphonic acid, ethylenediphosphonic acid and the higher homologues of the polyphosphonic acids mentioned Alkali metal or ammonium salts of low molecular weight amiriopolycarboxylic acids such as NTA and EDTA. Silicates, in particular sodium silicate, in which the ratio ¹ of Na ₂ OrSiO _{2 is} 1: 3.5 to 1: 1, are suitable as further synthesis salts.

-T-

009826/2003 8AD ORIGINAL

Ie substances for regulating the PLL VJertes into account ₃ ■ such as bicarbonates, carbonates, borates, and hydroxides of sodium or potassium, further acids ^, such as lactic acid ur.d citric acid; as constituents of the mixture continue to come Neutralsalao such as sodium sulfate and sodium chloride, sov. The amount of alkaline substances including the alkali silicates and phosphates should be such that the pH value of a usable liquor is 9 to 12 for coarse laundry and β to 9 for delicate laundry.

By suitable combination of various surface active detergent bases and salts build with each other, for example, an M improved washing power or a reduced foaming power can in many cases increases in effect, be achieved. " Improvements of this kind are possible, for example, by combining anionic with nonionic and / or zwitterionic compounds with one another, by combining various 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 double bonds or chain branching in the hydrocarbon unterscheidenο mixtures synergistic can ¹ of inorganic and organic salts used bzwο structure with the aforementioned mixtures combined Berten. %

The detergents may contain releasing bleaching agents such as hydrogen peroxide, alkali perborates "Älkalipercarbona" e, Alkaliperphosphate ,, urea perhydrate and alkali persulfates or active chlorine compounds, "t ^ ie alkaline hypochlorous it e, ■ ehloriertes Trinatriurnphosphat and chlorinated cyanuric acid hEWo alkali metal salts thereof entsprechend- their intended use oxygen. The per compounds can be mixed in as bleach activators and stabilizers, such as mag-

present »

co Q ca »

0098 28/2003

Ιλ & γ ^ ο \ ifiji

Optical brighteners suitable for cellulose fibers are those of the diaminostilbene disulfonic acid type of the formula «; X

in which X and Y have the following meanings: NH ₂ , NH-CH ₅ , NH-CH ₂ -CH ₂ OH, CH ₅ -N-CK ₂ -CH ₂ OH, N (CH ₂ -CH ₂ OH) ₂ , Morpholino, Damn thy imorpholino, NH-CgH ₅ , NH-CgH ^ -SO ₅ H, OCH ₅ , Ci; where X and Y can be the same or different. Those compounds in which X is an anilino and Y is a diethanolamino or morpholino group are particularly suitable.

Optical brighteners for polyamide fibers are those of the diarylpyrazoline type of the formula below

Ar-C-CH ₀ *

"I i ² · ''

N CH ₀

Ar

In this formula, Ar and Ar ¹ denote 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 1,3-diarylpyrazoline derivative is preferably used in which the radical Ar represents a p-sulfonamidophenyl group and the radical Ar ^{1 represents} a p-chlorophenyl group. In addition, white tones suitable for lightening other types of fibers may also be present, for example those of the naphthotriazole stilbene sulfonate, ethylene-bis-benzimidazole, ethylene-bis-benzoxazole, thiophene-bis-benzoxazole, dialkylaminocoumarin and cyanoanthracene type. These brighteners or their mixtures can be contained in the agents in amounts of 0.01 to 3.5 wt .-%, preferably 0.1 to 1 wt .- ^.

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BAD OHiGiNAL

Other suitable ingredients in the mixture are graying inhibitors, for example sodium cellulose glycolate, as well as the "· water-soluble alkali salts of synthetic polymers which contain free carboxyl groups. , Methacrylic « _s maleic», fumaric, itaconic, citraconic and aoonitic acid and the copolymers of the unsaturated carboxylic acids mentioned or their copolymers with olefins and vinyl ethers.

Preparations intended for use in drum washing machines suitably contain known foam suppressants, such as saturated fatty acids or their alkali soaps with 20 to 24 carbon atoms or triazine derivatives, the reaction of 1 mole of cyanuric chloride with 2 to 3 moles of an aliphatic, straight-chain, branched or eye · « llschen primary monoamines or by propoxylation or Butoxylation of melamine are available «,

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 or vegetable origin, ZoB. be obtained from digestive enzymes or yeasts, such as pepsin, pancreatin ^ trypsin, papain _fl catalase and diastase. Enzymes obtained from bacterial strains or fungi, such as Bacillus gubtilis and Streptomyces griseus, are preferably used, which are relatively resistant to alkali, percompounds, and monosonic washing active substances. Temperatures between 45 ° and 7O ⁰ C can not be significantly inactivated.

■ λ ¹ - '- ίο -

..I: ' ¹ : "00982S / 2003

BATH

The detergents and cleaning agents can be used in liquid, pasty or solid, for example powdery, granulated or lumpy form. Liquid Preparations can contain water-miscible solvents, in particular ethanol and i-propanol as well as solubilizers, such as the alkali salts of benzene, toluene, xylene or ethylbenzenesulfonic acid. 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 contain dyes and fragrances, bactericidal agents, Contain enhancing substances and fillers, for example urea.

The preparation of the agents according to the invention can be carried out in a conventional manner Alternatively by mixing, granulating or spray drying. If enzymes are used, it is recommended that to mix these with nonionic detergent raw materials and possibly fragrances or in the melt of a one containing water of crystallization Disperse salt, e.g. Glauber's salt, and then mix these premixes with the remaining powder components unite. As a result, the enzymes are cemented to the remaining powder particles, 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 the 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 "as well as any additional cleaning-enhancing building salts to be used. The qualitative and quantitative composition of these additional components depends on the special field of application of the agent. In the case of the technically particularly important detergents and cleaning agents according to the following scheme

(Data in percent by weight)! 009826/2003

-Xl -lORIGINAL

1 to 40 % of at least one compound from the class of anionic, nonionic and zwitterionic detergent substances,

10 to 80 SI * at least one non-surface-active, cleaning-enhancing or complexing building salt,

10 to 50 $ of a per compound, especially one containing water of crystallization or anhydrous sodium perborate, as well as their mixtures with stabilizers and activators, 0.1 to 20 # other auxiliaries and additives.

The active washing substances can contain up to 100 %, preferably M 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% consist of up to 50 % soap. The synthesis salts can contain up to 100%, preferably 25 to 95 % of alkali metal triphosphates and mixtures thereof, up to 100 %, preferably 5 to 50%, of an alkali metal salt of a complexing agent from the class of polyphosphonic acids, nitrilotriacetic acid, sthylenediamino tetraacetic acid and up to 100% , preferably 5 to 75 % composed 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 that may be f preferably in an amount of 0.2 to 5% in the inventive compositions in an amount up to 5 $ present »also the enzymes in an amount up to 5% "may preferably be 0.2 to 3 j6 and the antiredeposition agents, the proportion of up to 5 £ t may preferably be 0.2 to 3 f.

-12 009826/2003

In the following some recipes are given that have proven particularly effective in practice.

Examples

A. Powdered, low-foaming detergent:

- 15 % sulfonate detergent raw material from the class of

Alkylbenzenesulfonates, olefin sulfonates and ■ n-alkanesulfonates,

0.5 - 5 % alkyl polyglycol ether (C ₁₂ -C ₁ Q-AIlCyI) or "alkylphenol polyglycol ether (Cq-C ^ -alkyl) with 5 to 10 ethylene glycol ether groups," 0 - 5 % soap C ₁₂ -C ₁ Q,

0.2 - 5 % foam suppressant from the class of

Trialkylmelamines and saturated fatty acids or their alkali soaps with 20 - 24 Carbon atoms,

a condensed alkali phosphate from the class of pyro- or tripolyphosphates, poly- (N-acetic acid) -ethyleneimine or its alkali salts,
Sodium silicate,
Sodium perborate tetrahydrate, enzyme,

at least one optical brightening agent from the class of diaminostilbene disulfonic acid " or diarylpyrazoline derivatives,

0.1 - 50 % of an inorganic salt from the class

the carbonates, bicarbonates, borates, sulfates and chlorides of alkali metals,

0 4 # magnesium silicate, '■

$ 0.5-2> Sodium Cellulose Glycolate.

• 009826/2003 '" ¹ ^"

10 1 -. 50 % 0, - 25 % 1 - 5 % 10 - 55 % 0 05 5% 0, T et

ORIGlNAL BATHROOM

B. Powdered, foaming mild detergent:

1 - 30% sulfonate detergent 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-AIlCyI) 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

pyrazoline derivatives and mixtures thereof with

Polyester brighteners, 3 - 70 % 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 amide glycol ether condensate

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

1 - 10 % solubilizer from the alkali class

salts of benzene, toluene or xylene sulfonic acid;

0 - jJO ¹ Jo neutral or acidic potassium pyrophosphate,

0 - 10 % organic solvents from the class of Cp-C - * alcohols and ether alcohols,

0 »1 % optical brighteners from the class of diaminostilbene disulfonic acid and diarylpyrazoline derivatives,

The rest is water, fragrances, colorings, preservatives. .

- 14 -

"009826/2003

10 - 50 1 - 5th 0, - 5th 0 - 5th

D. Soaking and prewash detergent:

0.5 - 5 % sulfonate detergent raw material - 3 % compounds from the class of alkyl

polyglycol ether (C. ₂ -C, g-alkyl) and alkylphenol polyglycol _{ether (Cg-C 12} with 5-12 ethylene glycol ether groups,

0.1-10 # poly (N-acetic acid) ethyleneimine or its Alkali salts,. .

Soda,

Water glass,
Magnesium silicate, enzyme.

E. Machine dishwashing detergent:

0.1 - 3 % compounds from the class of alkyl polyglycol ethers (C ^ -Cjg-alkyl), alkylphenol polyglycol ethers (Cg-C ^ .- alkyl) with 5-30 ethylene and 5-30 propylene glycol ether groups and ethoxylated polypropylene glycols, 0.2 - 25 % poly (N-acetic acid) -äthylenirain or its

Alkali salts,
- 95 % pentasodium triphosphate,

1 - 40 % sodium silicate (Na ₂ O: SiO ₂ = 1: 1 to 1: 3), 0 - 5 % potassium dichloroisocyanurate,

- 2 % foam suppressant.

F. Liquid dishwashing detergent and cleaning agent - 30 % sulfonate detergent raw material,

2 - 15 % alkyl polyglycol ether sulfate (Cg-C./-- alkyl,

1-5 ethylene glycol ether groups,

0.2 - 10 $> Alkaline salts of poly (N-acetic acid) ethylene imine

0 - 20 % organic solvents from the class of

C ₂ -C -, - alcohols and ether alcohols,

1 - 10 % solubilizer, such as toluene sulfonate, xylene

sulfonate and urea,

The rest is water, fragrances, colorings, preservatives.
009826/2003 _Ί _

G. Bleachί

0.2 - 25 $> poly (N-acetic acid) ethyleneimine or:

its alkali salts, 10 - 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.

Ho Alkaline Cleaner:

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

Alkali salts

0.5-50 %. Sodium silicate (Na ₃ OtSiO ₂ = IjI up to 1: 3),

0.5 - 80 % sodium hydroxide,

0 - 40 % trisodium phosphate,

0 - 40 % condensed alkali phosphate,

0 - 40 % soda,

0 - 10 % hydroxyethane diphosphonate, -

0 - 5 % anionic and / or nonionic

Washing active substance.

I. Abrasives:

1 - 10 % anionic and / or nonionic washing

raw material,

0.1 - 5 % alkali salt of poly (N-acetic acid) -ethylene-

imins,
- 95 % abrasives,

0 - 10 % cleaning salts from the class of alkali polymer phosphates, alkali silicates, alkali borates and alkali carbonates,

0 - 10 # alkali dichloroisocyanurate.

0098 26/2003 "16-

Examples 1 to ^

The cleaning effect of detergents containing one part by weight of an anionic detergent raw material (Na-n-dodecylbenzenesulfonate and 2 parts by weight of builder salts) was compared with one another. wherein said wash liquor is heated to 90 ⁰ C within 15 minutes of 20 ° and a further 15 minutes was maintained at 90 ⁰ C. the Waschmittelkonzentratj on the water hardness was 3 g / l> 1.6 ° dH, the weight ratio 'of the textile material to V / aschflotte 1: 12. this was followed by four mil; rinsed water and spun the fabric and dried, the (fi = 0 _t = 100 ^ original fabric brightening soiled fabric) is measured using a photometer certain percentage whitening, as well as the composition of the agent.. , can be found in the following table.

For the preparation of the branched poly- (N ~ acetic acid) -äthylenimines branched "polyamines with average molecular weight 2500.5CCn _U r..i γο 000 in 20.'IiV ^ r aqueous solution with in each case GO ^ - the rtochicrnetrisehen amount, which for an IOC '.- ige carbonic acid; Solution was kept constant to a value of IC up to 11 eir.f ^ i ;. By treatment with anion and non-ion exchangers, the reaction products were desalted or iu di-: free acid transferred and then neutralized with sodium hydroxide solution.

. The Ergebnir '; e ö.er ./aschversuche zeiren that the polymeric IJ ^ Essig.Täurc thylonimirie other known builder salts, including d' - w.. air, nohr known effective pentasodium triphosphate, in: hroi · Reini £ i.ungsi '/ 5rkunß are superior.

- 17 009826/200 3

ORIGINAL

Example: builder salts % lightening

Sodium salts of branched
Poly (N-acetic acid) ethylene
Inside 73.0 1 average Molecular weight 5,000 73.3 2 ¹¹ "10,000 74.0 . 3 "" '. 140,000 72.7 _ Pentasodium triphosphate 72.0 - Na ethylenediaminetetraacetate 67.2 Na salt of a carboxymethylated
Polyamines according to DAS 1 0β0 849
(Molecular weight 900)

Examples 4 to 6

A detergent of the following composition was used (Data in percent by weight):

8 Jfj- Na-n-Dodeoylbenzenesulfonat 5 % sodium soap of fatty acids C ₁₂ -Cg ₂

3 % oleyl alcohol polyglycol ether (10 ethylene glycol

groups)
% Pentasodium triphosphate 5 % sodium silicate (Na ₂ O. 3,3 SiO ₂ )

2 % magnesium silicate 1 % sodium cellulose glycolate% sodium perborate tetrahydrate 8 % water

0.8 % pyrazoline-type brightening agent 0.2. ίο Diaminostilbene-type whitening agents

-18 -

0098 26/2003

8AD OBlGINAL

The lightening agents had the following structure:

Cl-

Pyrazole type

2 Gew .- ^ of the Na.triumsalzes of a branched poly (N-acetic acid) -äthylenimins were added to this agent, which in Example 4 has an average molecular weight of 5,000, in Example 5 an average molecular weight of 10,000 and in Example 6 had one of 140,000. A detergent was used for comparison, to which 2 % sodium nitrilotriacetate (NTA) or 2% sodium ethylenediaminetetraacetate (EDTA) had been added instead of the polymers according to the invention.

- 19 -

009826/2001

6AD ORIGINAL

By these means were washed textiles made of polyamide fiber (Perlon®) in a Laboratoriumswasehmaschine, wherein the wash liquor is heated over 15 minutes from 20 ⁰ C to 60 ° C and left stirring continued for 15 minutes at this temperature. The detergent concentration was 5 g / l and the weight ratio of textiles to ash liquor 1:50. The water used had a hardness of 16 dH and a content of 10 "* KoI per liter of copper ions. The degree of whiteness of the four times rinsed and then dried laundry was determined photometrically, and the results are compiled in the table below, which show the superiority of the compounds to be used according to the invention.

Ex. Na-poly-CN-acetic acid / ethyleneimine Whiteness
1 wash after
5 washing k Molecular weight 5GOO 105 112 5 ¹¹ 10,000 106 115 6th "IiIOOOO 107 115 . - Na nitrilotriacetate 100 104 - Na ethylenediaminetetraacetate 103 110

- 2o -

0 0 9 8 2 6/2 00 3

EDTA
DTPA

Carboxymethylated polyamine according to DAS 1 ΟβΟ 849 from Molecular weight 900

without addition 35 18 8

73 56 40 24 15th 75 60 43 29 21 52 26th 10 • 40 15th 5 2 - 48 2? Q 5

- 21 -

Examples 7 and 8

From a bleaching agent consisting of 154 g of sodium perborate and 124 g of the sodium salt of a by reaction of ver * · '* branched polyethylene with tiloroacetic acid (1 mol of chloroacetic acid «· '-;' acid per ethyleneimine unit) produced poly * (N-acetic

acid) -ethylenimine from

Example 7) Molecular Weight 4,200 "-

Example 8) Molecular Weight 15,000 / ·;

an aqueous solution containing 0.62 g / l sodium perborate was prepared and adjusted to a pH of 10 by adding dilute sodium hydroxide solution. The decrease of the Aktiy- ^! . '|. oxygen content of this solution at 90 ⁰ C was in Abstän · 'M to 30 minutes by titration to jodometrisohem way. -' certainly. For comparison, the determination was repeated with the same>< _t amounts of known perborate stabilizers. The results are summarized in the table below. They show the superiority of the agents according to the invention.

% Active oxygen after stabilizer 30 60 90 120 150 min.

Poly (N-acetic acid) ethyleneimine molecular weight 4,200 Molecular weight 15,000

009826/2003

example 7th If 8th ti 9 H- 10

The following table shows some formulations for washing, bleaching and cleaning agents according to the invention compiled for the following areas of application:

low-foam heavy duty detergent

Cold detergent

Liquid detergent

Wool detergent ". 11. Soaking agent ¹¹ 12 Bleaching agent ¹¹ Ij liquid dishwashing agent" 14 Cleaner for coarse soiling "15 Abrasive agent.

The components a to d and f to i were present as sodium salts, the pyrophosphate (component k) kar ”: in example 9 as potassium salt, in all other examples as sodium salt obtained preparation Maxatase ^ from Koninklijke Nederlandsche Gist en Spiritusfabriek NV Delft, with an activity of 100,000 LVU / g. The foam suppressant (component v) is a reaction product of 1 mol of cyanuric chloride with 2.7 mol of a primary η-alkyl! amines of chain length Co-C ₁ η

- 22 -

_v QQ9S £ 6 / 2QQ3

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component 7th Examples 8th 9 (Information in 11th Weight - *) 14th 15th φ - 6th - 5 10 - 12th 13th - 2.5 - a) n-Dodecy! benzenesulfonate 3 - - 15th 3.5 15th - - - b) ^c 12 " ^c 18 olefiosulfonate - 10 5 - - - - - - • - c) C ₁₄ -C 7 alkanesulfonate - 2.3 5 - - 0.5 5 - - - d) Cocci fatty alcohol glycol ether sulfate (2 ÄO) 3 4th - 10 - - 4th 1 - - e) Oleyl alcohol polyglycol ether (10 ÄO) 3 - 5- - - 2 - - t) C ₁₂ -C ^ ₈ soap - - - - - " - - - - 4th G) ^C 2o " ^C 22" ^soap 25th 15 ' 1 - 0.2 - - 0.5 0.2 0.1 H) Poly (N-acetic acid) ethyl imine 10 • 20th - 5.5 - 1.5 1 10 - • β i) Tripolyphosphate - - 20th - 20th - - 2 - k) Pyrophosphate 20th - - 35 - • - 45 5 D. soda 5 5 '- 5 25th - 25th 1 m) Sodium silicate 4.4 - - - 18th 20th - - 1.2 n) Sodium sulfate • 25 - - 45 - - 0.4 - - O) Sodium lumper borate 3 - - - 3 50 - - P) Magnesium silicate 1.5 - - - 2 - -. - enzyme 1.5 - - - - - - t) Na-celluloic glycolate - - 7th - - - - *) Na toluenesulfonate - - - - - - - - t) Coconut fatty acid diethanolamide 0.5 0.7 0.1 5 - - 5.5 - u) Optical brighteners 0.5 - - - - 0.5. - . - v) Foam suppressants 8.5 7.9 56.7 - 13.3 - - 13.4 W) water - 15th - 14.5 - 2.5 70 1 x) Dichloroisocyanurate 0.1 0.1 0.2 - - - - 0.1 y) Dyes and fragrances - - 0.1 Z) Quartz flour

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Claims (1)

UL washing «* bleaches and cleaning agents, labeled. jtttroh contains branched poly (N-acetic acid) -. lenltoliieii 'with an average molecular weight of 2,000 to QOO * The agent according to claim 1, characterized by an oil content of alkali metal "ammonium" or organic ^{s [v} f | pi "biium" n of the poly (acetic acid) ethylene lraine. j ^ 'H »means HiOh claims 1 and 2 # characterized,''* ä & ß 50 am 100 % 9 Wfrfcugsweiee 6o to 98 % of the primary and secondary amino groups in the polyethylene: itein vorhaii $ ®2i @ n \ -.4. Means according to claim 1 to 'ß _ä characterized by . '''Iline content of poly (!! - acetic acid ^ lthylenimines or their.: "; ,, have a molecular weight of -4,000 to 150,000 _e '5' agent according to claims 1 to 4, characterized by a content of 0.1 to 50 % _s, preferably 0.5 to 25 % poly (N-acetic acid) -thylenimine or its salts, 6β agent according to claims 1 to 5 »characterized by a content of 0.1 to * 50 % _t, preferably 0.5 to 25 % poly-tN-acetic acid ethylenimine or its salts and 50 to 99.9 %» preferably 75 to 99 # 5 $ >> consist of other laundry detergents and bleach ingredients. 7. Agent according to claims 1 to 6, in which the other constituents consist of 1 to 40% of at least one compound from the class of anionic, nonionic and zwitterionic mesh active substances. - 2h 009826/2003 ORIGINAL INSPECTED Henkel & Cie GmbH - 2% - 1 B 1 6 3 4 8 Patent department D 2648 8. A composition according to claim 1 to 7 »wherein the other ingredients to 10 to 8ö fo of at least one salt structure exist. 9 »Means according to claim 1 to 8, wherein the other ingredients to 10 to 50 fj from a per connection as well order their equipment with stabilizers and activators. 10. Means according to claim 1 to 9 »wherein the iias chalet ivs punch up to 100 % _9, preferably 23 to 70 ^ from those of the sulfonate and / or sulfate type, up to 100 ^, preferably 5 to 40 $ from non-ionic Compounds of the polyglycol ether type and up to 100 %, preferably 10 to 50%, consist of soap. 11. Means according to claim 1 to 10, wherein the building salt up to 100 Z, preferably 25 to 95 ? ■ · from alkali metal triphosphates and mixtures thereof with alkali metal pyrophosphates, up to 100 ^ g preferably 5 to 50 ⁽ i from an alkali metal salt of a complexing agent from the Class of polyphosphoric acids, liitrilotriecsipsäuro, ithyler.diaminctetraessifsrure and up to 100 ^, preferably 5 to 75 ^ from at least one compound from the class of alkali metal silicates, allcalite metal carbonates and alkali metal bcrates, stands. 12. Hitt d according to claim 1 to 11, v: orin the per compound from va: ir- ^ rfreiera and / or water-of-crystalline sodium b ^^ at exists. 15 · Gown according to Claims 1 to 12, characterized in that it consists of up to 5 £> * preferably 0.2 to 3 ■ ' of at least one! ;; t'ehauminhibitor from the class of saturated fatty acids containing 20 to Zd carbon atoms and - 25 009828/2003 8AD ORIGINAL Patent department their alkali metal soaps, as many substituted triazines, obtainable by reacting 1 mole of cyanuric chloride with 2 to 5 parts of a primary monoamine hzvi. by propoxylation and / or butoxylation of melamine. 14. Composition according to claim 1 to Ij5, characterized in that they contain up to 5%, preferably 0.2 to 3 % , of enzymes. 15. Composition according to claim 1 to 14, characterized in that they contain up to 5 'p », preferably 0.2 to 3 % of graying inhibitors. 16. Composition according to claim 1 to 15, characterized in that they contain 0.01 to 1.5% of optical brighteners. 17. Means according to example A to I. Henkel & Cie. GmbH. i.V. (Dr. Haas) (Dr. ilagel) 009826/2003 ^ IKttao CMj SAD QfHOtNAL