DE2043086A1 - Low-foaming washing, cleaning and softening agent - Google Patents

Description

Henkel & Cie GmbH Düsseldorf, August 27, 1970

HenkeIstr. 67

Patent department
Dr. Via / Ml

Patent application D 4157

"Visibly foaming detergent, cleaning agent and softening agent"

Low-foaming detergents and cleaning agents are known which, as active washing substances, contain non-ionic active washing substances of the polyglycol ether type. The foam-suppressing properties of these compounds are sufficient However, in many cases it is not enough to prevent the foam development of such agents, the high-foaming surfactants of the sulfate or sulfonate type contain sufficient steaming, which is why it has been proposed to use fatty acids with more than 18 carbon atoms as Adding foam suppressants. The effect of these fatty acids however, is limited to surfactants of the sulfonate type and also depends on the hardness of the Cleaning solution. As a hemostatic agent Often used silicones are less suitable for detergents and cleaning agents because they are a Can cause hydrophobization of the cleaned objects and difficult to remove from the substrate again permit.

Also when using surfactant-free, complexing polymer phosphates or containing organic complexing agents Softening agents for removing incrustations from textiles and washing machines, supply lines and Water heaters are used, considerable malfunctions can occur due to foam developments · As a cause For the foam formation, deposited organic impurities such as protein or fatty substances, lime soap residues are used or traces of washing active substances are responsible.

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Henkel & Cie GmbH s. ». 2 »r rai.manm.id _U n ₃ d 4157

The applicant has set itself the task of finding a means to develop that does not have the disadvantages mentioned and its foam-suppressing 'effect regardless of the The nature and composition of the foaming compounds, as well as the hardness of the water, have no negative effects indicates the cleaning result or the utility value of the cleaned items and even in low concentrations is effective.

The invention relates to foam-regulated washing, cleaning and softening agents containing at least one cleaning or complexing compound from the class of anionic, zwitterionic and nonionic washing active substances, polymer phosphates and complexing agents, characterized in that they, based on the amount of the aforementioned cleaning and complexing compounds, 0.1 to 10 wt .- # contain at least one foam-suppressing compound of the following formulas:

I) R ₁ -OC-NH-R-HN-COR ^
0 0

II) R ₁ -HN-COROC-NH-R ₀

JM Il d.

O 0

in which R is a hydrocarbon radical with 2 to 20 carbon atoms, R, and Rp represent hydrocarbon radicals with 8 to JO carbon atoms.

The radicals R, R and R ₂ can be straight-chain or branched, saturated or unsaturated, or else cycloaliphatic or aromatic. Those compounds are preferably used in which the radical R is an aliphatic radical having 2 to 10 carbon atoms and the radicals R ₁ and Rg are straight-chain, saturated or monounsaturated hydrocarbon radicals having 12 to 2 carbon atoms.

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Henkel * CIe GmbH β ·· * 5 »'-ί» ^ 157

The schaumdärapfend acting alkylated alkylene or arylene-di-urethanes are obtainable in a known manner, for example by reacting diisocyanates of the formula O = C = CNRN "O with primary or secondary alcohols of the formula R, OH or ^R o ^0H reacted. In this case, compounds of the formula I. Diurethanes of the formula II can be obtained by reacting dihydric alcohols or phenols with isocyanates of the formula R ₁ -N = C = O or R ₂ -N = C «0.

The alkyl radicals R 1 and R «can be derived from natural fatty acids or derived from synthetic origin. Examples are octyl, decyl, lauryl, myrlstyl, cetyl, stearyl, Arachyl, behenyl, lignoceryl, palmitoleyl and oleyl radicals, also mixtures of these, such as those found in coconut, tallow, rapeseed oil, Palm kernel oil, soybean oil, cottonseed oil, tall oil, peanut oil or fish oil fatty acids or their hydrogenation products are present. The residues can also consist of paraffinic hydrocarbons, olefin polymers such as polyethylene, polypropylene and Polybutylene, as well as compounds obtainable by oxo synthesis derive.

It has been shown that those foam-inhibiting compounds in which the alkyl radicals contain 10 to Ik carbon atoms develop their optimum effect in the temperature range from 20 ° to 60 ° C. Provided that the alkyl groups of 16 or more, in particular 18 to 22 carbon atoms, the maximum of the foam dampening shifts in the range from 60 ° to 100 ⁰ C. By appropriate selection or combination of foam inhibitors with different alkyl groups can therefore show Raver holding the washing, cleaning - and softening agents can be controlled as required and adapted to the Jev / urgent requirements.

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Henkel & Cie GmbH see 4 ■ »Μ« * »« «! ·! .. ·« d 4157

The amounts of foam inhibitors to be used depend on the amount of foaming or more active substance Substance as well as the size of the desired effect. The application concentrations that are important for practice range from 0.1 to 10, preferably 0.2 to 5 percent by weight, based on the solid substance. It goes without saying possible to work with even larger amounts, for example up to 25 percent by weight and more, however this is not necessary in practice.

The foam suppressants can be mixed with the rest of the washing, cleaning and descaling agents in the usual way mixed and processed together with them, e.g. spray-dried or granulated or according to other known processes be converted into solid, liquid or pasty mixtures. The compounds can also be melted or in dissolved form with the other ingredients of the agent, which are available as powder or granules or spray it on or granulate it.

These other ingredients consist of at least one washing or complexing compound from the class the anionic, nonionic or zwitterionic surface-active substances, polymer phosphates and complex or Chelating agents. In addition, other non-surface-active builder salts, oxygen-containing bleaches and other additives usually contained in such agents may be present.

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Henkel & Cia GmbH s · »· 5« r fcttmanmtijun, d 4157

The mixtures used as detergents and cleaning agents can contain anionic detergent raw materials of the sulfonate or sulfate type. First and foremost come alkylbenzenesulfonates, for example n-Dodecylbenzenesulfonate, also possible, olefin sulfonates, such as, for example, by sulfonating primary or secondary aliphatic monoolefins with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis can be obtained, as well as alkyl sulfonates such as them from n-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulf otaddition to olefins are available. Also suitable are ot-sulfo fatty acid esters, primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated higher molecular alcohols. More connections of this class, which may possibly be present in the detergents, are the higher-molecular sulfated partial ethers and partial esters of polyhydric alcohols, such as the alkali salts of the monoalkyl ethers or the monofatty acid esters of the glycerol monosulfuric acid ester or 1,2-dihydroxypropanesulfonic acid. There are also sulfates of ethoxylated or propoxylated fatty acid amides and alkylphenols and fatty acid taurides and fatty acid ethers.

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. Come as zwitterionic washing raw materials Alkylbetaines and in particular alkylsulfobetaines in question, e.g. 3- (N, N-dimethyl-N-alkylaniraoniuni) -propane-l-sulfonate and ^ - (NiN-diraethyl-N-alkylammoniuraJ-S-hydroxypropane-isulphonate.

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Henkel Λ Cio GmbH Son «6« _t pc »«! O «i» «iJi» ii-i ο "157

The anionic washing raw materials can be used in the form of sodium, Potassium and ammonium salts as well as organic salts BaGen, such as mono-, di- or triethanolamine, are present. Unless the aforementioned anionic and zwitterionic Compounds an aliphatic hydrocarbon radical own, this should preferably be straight-chain and have 8 to 22 carbon atoms. In the connections with an araliphatic hydrocarbon radical, the ν or ζ ugs contain unbranched alkyl chains on average 6 to 16 carbon atoms.

™ Polyglycol ether derivatives of alcohols, fatty acids and alkylphenols, which contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon residue, are primarily used as nonionic surface-active detergent substances. Particularly suitable are polyglycol ether derivatives in which, the number of Äthylenglykoläthergruppen 5 to 15 and the hydrocarbon radicals are comprising of straight chain, primary alcohols having from 12 to l8 carbon atoms or of alkyl phenols having a straight-chain, from 6 to l * l · carbon atoms

Derive alleyl chain. W by addition of 3-15 mol of propylene oxide to the latter polyethylene glycol ether or converted into the acetals are detergent

obtained, which is characterized by a particularly low foaming power distinguish.

Other suitable nonionic detergent raw materials are the water-soluble, 20 to 250 ethylene glycol ether groups and 10 to 3 100 propylene glycol ether groups containing polyethylene oxide adducts with polypropylene glycol, ethylene diamino polypropylene glycol and Λ Iky! Polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol per propylene glycol unit. Aucl | Non- toxic compounds of the amine oxide and sulfox type, which can also be thoxylated, and are vulnerable.

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Honke! Λ. Cie GmbH ϊλ. 7th

Preferred components of the mixture are also condensed phosphates, such as pyrophosphates, triphosphates, tetraphosphates, Tr! Metaphosphate and tetrameta phosphate in the form of the neutral or acidic sodium or potassium salts. Pentasodium triphosphate and its mixtures with tetrasodium pyrophosphate are preferred used.

The condensed phosphates can also be completely or partially replaced by organic, complexing aminopolyearboxylic acids be replaced. These include in particular the alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid. The salts of diethylenetriaminopentaacetic acid are also suitable and the higher homologues of the aminopolycarboxylic acids mentioned. These homologues can, for example, by Polymerization of an ester, amide or nitrile of N-acetic acid aziridine and subsequent saponification to give carboxylic acids. Salts or by reacting polyamines with a molecular weight from 500 to 100,000 made with chloroacetic acid or bromoacetic acid salts in an alkaline medium will. Other suitable aminopolycarboxylic acids are poly (N-succinic acid) ethyleneimines and poly (N-tricarballyic acid) ethylene imines with an average molecular weight of 500 to 500,000, which are obtainable analogously to the N-acetic acid derivatives.

Other suitable synthesis salts are the complexing water-soluble potassium and especially sodium salts of higher molecular weight polycarboxylic acids, for example of polymers of ethylenically unsaturated mono-, di- and Tricarboxylic acids such as acrylic acid, maleic acid, fumaric acid, itaeonic acid, citric acid, mesaconic acid, aconitic acid and Methylenemalonic acid. Copolymers of these carboxylic acids with one another or with other copolymerizable substances, such as ethylenically unsaturated hydrocarbons, such as ethylene, propylene, isobutylene and styrene, with ethylenic unsaturated monocarboxylic acids, such as acrylic acid, methacrylic

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BATH ORIGINAL

Honkol (\ Cio GmbH s.> I «8« «r« iMM «m.ijuni, ο 4157

acid, crotonic acid and J-butenoarbori.'w'uro or nri.t others Ethylenically unsaturated alcohols, ethers, esters, amides and nitriles, such as vinyl alcohol, allyl alcohol, vinyl methyl ether, Acrolein, vinyl acetate, acrylamide and acrylonitrile are useful. Ethylenic copolymers are also used unsaturated mono-, di- and tricarboxylic acids and several ethylenically unsaturated compounds of different Structure suitable. The polymers and copolymers have an average degree of polymerization of from 1 to 6,000 on and should, based on j5 monomer units, 1 to 9 * preferably contain 2 to 9 carboxyl groups capable of salt formation.

The homopolymers and copolymers capable of salt formation Leave polycarboxylic acids as defined above represented by the following formula:

- CII -

^ m +1

R, = H or -CH ,,
R ₂ = H or -CH ^,
R, = H, -CH ^, -Phenyl, -OH, -CHgOH, -OCH ,, -OC-CH ,,

-CHO, -COOH, -CONH ₂ , -CN, °

X = H odor -COOH,
Y => H, -COOH or -CHgCOOH,

where X and Y should not represent -COOH at the same time, Z = H or (if X * COOII and Y »H) also -OIL ·, m = any number from 0 to 2, η = an integer between j5 and 6000.

The word of m is not restricted to whole number words, ■ but can have any numerical value, including Bruoh words p; anzei · numbers from 0 to ?. accept.

7Ü98U / 1286 ^ßAD

• Phosphorus-containing compounds with a Koniplexicrend can also be used polycarboxylic acid salts may be present, e.g. the alkali metal salts of aminopolyphosphonic acids, in particular aminotri "(non-ethylene phosphonic acid), Xthylenediaminotetra- (methylenephosphonic acid), 1-Hydroxyathaη-1,1-diphosphonic acid, methylenephosphonic acid, Ethylenediphosphonic acid and salts of the higher homologues of the polyphosphonic acids mentioned. Also mixtures of the aforementioned Complexing agents can be used.

As v / urther structure salts, alkali metal silicates are suitable, especially sodium silicate, in which the ratio of Na ₀ O: 3.5 to 1 i 1: SiO _Q. 1 To regulate the pH, carbonates, bicarbonates and borates of sodium or potassium, and also acids, such as lactic acid and citric acid, can also be added. 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.

Oxygen-releasing bleaches, such as alkali perborates, alkali percarbonates and perpyrophosphates, are a further constituent of the mixture and persilicates as well as urea perhydrate are possible. Sodium perborate tetrahydrate is preferably used. In order to stabilize the per compounds, the agents Magnesium silicate contain, for example in amounts of 3 to 20 wt .- ^, based on the amount of perborate. For washing textiles Agents to be used at temperatures below 70 ° C, so-called cold washing agents, can be bleach activators, especially tetraacetylglycoluril, contained as a powder component. The one from the bleach activator or from the porous compound existing powder particles can be mixed with auxiliary substances, v / ic water-soluble polymers, fatty acids or aui'granullerten Salts, such as alkali silicates, sodium sulphate or din tri-hydrogen phosphate, excessive no, to have a Weehno! effect between The preparation of the porch and the active laboratory during flor /. 'ornng V'ii'mr:! .Den.

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BATH ORIGINAL

Henkel & CIo GmbH

ι »» · 10 _no Γοΐ. · υ «·« ι <ι «« «ο 4 157

20 A 3086

The detergents contain fornor optical brighteners, in particular derivatives of diamino-tilbene disulfonic acid or their alkali metal salts of the formula:

in which X and Y have the following meanings: NH ₂ , NH-CH- ,, NH-CII ₂ -CH ₂ OH / CH ₅ -N-CH ₂ -CH ₂ OH, N (CH ₂ -CH ₂ OH) ₂ , Morpholine *, Dimethy lmorpholino, NH-C ₆ H ₅ , NH-CgH ^ -SO H, OCH ₃ , Cl, where X and Y can be the same or different. Particularly suitable compounds are those in which X is an alino group and Y is a diethanolamino or morpholino group.

Optical brighteners of the diarylpyrazoline type with the following formula are also suitable:

Ar - C I.

CH

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, sulphonic acid and sulphonamide groups or halogen atoms. Preference is given to using a 1,3-diarylpyrazole derivative in which the root Ar is a p-oulfonamidophenyl group and the radical Ar 'is a p-chlorophenyl group ! it. V / urther suitable V / are eißtöner .Such the type of Haphthotriazol.stilbnnrjulfonato, Ä'thylenbL ^c j-benziniLda :: oLo, Äthylon-bL: - benzoxazoles, Thiüi) hen-BIU iMjiK'.oxazole, Diaiky Laininucumar Ltio and dor, cyanoan incense. Also f'rcmi.scho from opbi.ichon Aui'lu; 1. lc.vn r, Lud '/..rv/ondbar.

2 0 ij 8 U / 1 7 R Γ,

BATH ORIGINAL

Henkel & Cic GmbH * · »« YY- «« Ραΐ «« · ο * »· ι << Μ-9 ο i {

Older fjoeii ^ neto Mischun ^ ahcstandtclle are graying inhibitors, E.g. sodium chloride glycolate, ie the water-soluble ones Alkali salts of synthetic polymers that remove free carboxyl groups. These include the polyester or Polyamides made from tri- and tetracarboxylic acids and dihydric alcohols or diamines.

The agents can also include enzymes from the class of proteases, Contain lipases and amylases or mixtures thereof. The enzymes can be of animal and vegetable origin, e.g. from Digestive ferments or yeasts such as pepsin, pancreatin, trypsin, papain, catalase and diastase. Preferably earth from bacterial strains or fungi, v / ie Bacillus subtilis and Streptomyces griseus, obtained enzymatic Active ingredients are used that are relatively resistant to alkali, per-compounds and anionic washing active substances and are not significantly inactivated even at temperatures between 50 ° and 70 ° C.

Other ingredients that can be contained in the agents according to the invention are neutral salts, especially sodium sulfate, bacteriostatic substances such as halogenated phenol ethers and thioethers, halogenated carbanilides and A-lieyl anillides and halogenated diphenylmethanes, as well as dyes and fragrances.

The agents according to the invention are characterized by a high Washing power off. They are ideal for use in automatic drum washing machines because they are also at high temperatures Do not tend to foam over above 90 ° C or when the detergent solution is boiled.

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Henkel & Cio GmbH s.iu 12 mr Poteni <in., MMu, ij d 4157

Softeners primarily contain sodium or potassium polymer phosphates, e.g. pentasodium triphosphate, Hexasodium tetraphosphate and their mixtures with poly-

phosphates of the formula ^ (η, ^^ η ^^ η + ΐ) ' ^{where n stands} for integers from 5 to 20, furthermore sodium odor potassium metaphosphates, e.g. sodium trimetaphosphate, sodium tetrametaphosphate and sodium polynetaphosphates of the formula (NaPO,), in which m stands for whole numbers from 5 to j50. The condensed phosphates can also, if appropriate, completely or partially by the aforementioned complexing agents from the class of the aminopoly-P carboxylic acids, alkanediphosphonic acids, hydroxyalkanediphosphonic

acids and aminoalkanepolyphosphonic acids be replaced.

The aforementioned washing, cleaning and softening agents can optionally contain other known foam suppressants, such as saturated fatty acids or their alkali metal soaps with 20 to 2h carbon atoms, higher molecular weight fatty acid esters or triglycerides or trialkylmelamines. Such additives can often have a synergistic effect.

The qualitative and quantitative composition of the detergent and complexing ingredients that do not consist of the foam suppressant, as well as the other additives, largely depends on the specific field of application of the detergents and, in the case of the technically particularly important detergents and cleaning agents, corresponds to the following scheme (data in percent by weight) :

BATH ORIGINAL

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Henkel & Cio GmbH "su 1 jj i" rp _a . _Un : o _n m.Mun ₃ ο 4157 ZlM J UG

1 to 40 $> at least one compound from the class of anionic non-ionic and hybrid detergent active substances, ■

IO to 80 ii at least one non-surface-active, cleaning-enhancing or complexing building salt.,

10 to 50 # of a per compound, in particular sodium perborate ¹ containing water of crystallization or anhydrous, as well as their equipment with stabilizers and activators, 0.1 to 20 % other auxiliaries and additives.

The washing-active substances can be up to $ 100, preferably 5 to 70% of compounds of sulphonate and or or sulfate type, up to 100 ^, preferably 5 to 40 i> of non-ionic compounds from Polyglykoläthertyp and up to 100 Ji, preferably 10 to 50 % consist of soap. The synthesis salts can contain up to 100 %, preferably 25 to 95 % from Altojlimetalltriphosphaten and mixtures thereof with Alka lime tallpyrophosphaten, up to 100 $, preferably 5 to 50 % from an alkali metal salt of a complexing agent from the class of polyphosphoric acids, · = Nitrilotriacetic acid, ethylenediamino tetraacetic acid up to 100 %, preferably 5 to 75 #, be composed of at least one compound from the class of the alkali metal filler silicates, alkali metal carbonates and alkali metal borates

The other auxiliaries and additives include, in addition to the optical brighteners, in particular the foam inhibitors, which can be present in the agents according to the invention in an amount of up to 5 % , preferably in an amount of 0.2 to 3%, forner the enzymes , which can be present in an amount bio of 5 %, preferably 0.2 to 3 % , and the graying inhibitors, the proportion of which can be up to 5 %, preferably 0.2 to 3 % .

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Honknl A Cio tv.mbH:,: ΐι1'Ι-. _u , ρ.ι - ,. μ ,,,,, ι) ^, d 4157

B ο i π ρ le I ₁ e

In the following some recipes are given that are Particularly in practice ::; have bgwiihrt.

Λ. Powdered, foaming detergent:

- 15 $> sulfonate detergent raw material from the class of alkylbenzenesulfonates, olefin sulfonates and n-alkanesulfonates,

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

- 5 % soap C ₁₂ -C ₁₈ ,

0.2-5% foam dampening agent according to the invention and their mixtures with saturated fatty acids or their alkali soaps with 20-24 carbon atoms,.

- 50 % of a condensed alkali metal phosphate from the

Class of pyro- or tripolyphosphates,

0.1 - 25 % sodium ethylenediaminotetraacetafc or

Sodium nitrilotriacetate, -

1-5 $ sodium silicate,. . .

- 35 # sodium perborate tetrahydrate,. .

- 5/6 enzyme,

0.05 - 1 % of at least one optical brightening agent from the class of the diaminostilbene disulfonic acid or diaryipyrazoline derivative,

0.1-30 $ of an inorganic salt from the class

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

¹ % magnesia filler, ·

0.5-3 % sodium cellulose glycolate.

BATH ORIGINAL

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H'Mifiol C /. "Cici C? ItnbH s ^-; >« 15 '«' -w ¹ '" « ¹ '! '») ¹ ' 4157

B. Machine dishwashing detergent:

0.1 - 5 % compounds from the clause of alkyl polyglycol ethers (G ₁₂ -C ₁ Q-AlRyI), alkylphonol polyglycol ethers (CQ-Cj ^ -alkyl) with 5-30 ethylene and 5-20 propylene glycol ether groups and ethoxylated polypropylene glycols,

0.1-5% foam suppressant according to the invention

- 90 ^ pentasodium triphosphate,

1 - 40 % sodium silicate (Na ₂ OtSiO ₂ = 1: 1 to 1

0 '- 5 % potassium dichloroisocyanurate,

0 - 2 % foam suppressant.

C. Alkaline detergent and bottle washing agent:

0.1-5% foam suppressant according to the invention

0.5 - 50 % sodium silicate (Na ₂ OcSiO ₂ = 1: 1 to 1

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.

D. Softener:

0.1. - 5 $ foam suppressant according to the invention - 95 i> pentasodium triphosphate 0 - 70 / ^ polymer phosphates of the formula

^Na (n «-2) ^P n ⁰ (3nfl) ^{with ne} ' ^{4 to 20} 0 - 40 % sodium hexametaphosphate 0 - 20 $> Soda

0-5 % sodium sulfate. ·

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Henkel & Cie GmbH so "· l6" r rotontonmtiduna ο ^ 157

Examples 1 to 26

The detergents listed in Table 2 were used, the numbers being percentages by weight. The sulfonate detergents and soaps came as sodium salts to use. The o * -sulf © fatty acid ester acts it is the sulfonated one in the ct position to the ester group Methyl ester of a hydrogenated tallow fatty acid. The abbreviations mean

NTA = sodium nitrilotriacetate

EDTA = sodium ethylenediaminetetraacetate

CMC = sodium salt of carboxymethyl cellulose

ÄO = »ethylene oxide groups.

The difference up to 100 % consisted of a mixture of the foam suppressant and sodium sulfate, which was added to the detergents as a dry powder. The composition and the percentage, based on the total amount of detergent, of the foam inhibitor can be found in Tables 2 and 3.

The foaming behavior was tested in a commercially available, fully automatic washing machine with a horizontally mounted drum as a function of the caustic temperature. The machine was equipped with a round sight glass through which the foam level could be observed. The following grades were given for the evaluation of the foam height:

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Henkel & CIe GmbH se »· 1 ( «> r Paioniunnn l

Note Maximum height of the foam level

0 no foam

1 1/4 of the sight glass

2 1/2 of the sight glass

3 3/4 of the sight glass

4 4/4 of the sight glass

5 foam visible in the filler neck

6 foaming over

The washing machine was loaded with 3 kg of clean laundry, The detergent concentration was 5 g / l, and the weight ratio of textile material to washing liquor was 1: 15. The degrees of hardness of the water were given in German degrees of hardness (1 ° dH corresponds to 1 mg CaO in 100 ml water).

In the absence of a foam inhibitor, the V / ash liquor foamed over in all temperature ranges.

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Henkel & CIe GmbH s.it. 18 i ", ραΐ · ι>» αη * .ι <ΐυηβ ο

The foam inhibitors identified below with S. to S. are compiled in Table 1. The types S < to S [- are derived from diurethanes of formula II, types Sg to Sq from those of the formula lab.

Abbreviation foam inhibitor

S .. ethylene di- (N-octadecyl urethane)

Sg ethylene-di- (N-docosyl-urethane)

S-, hexamethylene-di- (N-ootadecyl-urethane)

Su hexamethylene di- (N-tallow alkyl urethane)

W (tallow alkyl = saturated C-jg-Cjg-alkyl mixture)

Sc decamethylene di-iN-octadecyl urethane

Sg hexamethylene-di-CO-dodecyl-urethane)

S "hexamethylene-di-iO-octadecyl-urethane)

Sg 2,4 ~ toluylene-di- (0-octadecyl-urethane)

Sg 2,4-toluylene-di- (0-dodecyl-urethane)

Tab. 1

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Henkel & CIo GmbH

S «it« I9 «· '

and

i [\ 5T

(—- ■ E. F. G H . J * 25.0 K L. n-dodecylbenzenesulfonate 7.5 - m m 5.0 - 5.0 4.0 c * -olefin sulfonate (cis-ia * - - 7.0 m 3.0 0.5 - - n-alkanesulfonate (C J
14-lT - - - 8.0 1.0 3.0 - ■ ot-5ulfofe «acid esters * T. 5 - - 0.5 4.0 Alkyl polyglycol ether (9 Xo groups) 2.5 2.5 «I 2.0 3.5 0.5 - - '· Nonylphenol polyglycol ether
(9 Xo groups) - 3.0 8.0 3.0 2.0 ^{Soap 0} I ₂ - ⁰ I ₈ 4.0 2.5 3.0 4.0 1.0 2.0 3.0 ^SoapC 20- ° 22 - - - 0.5 - - Pentasodium triphosphate 40.0 25.0 40.0 40.0 40.0 40.0 30.0 Tettanatiium pyiophosphate 5.0 - 5.0 5.0 5.0 5.0 - Sodium silicate ^.
(Na I): SiO = 1: 3.39 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Magnesian silicate 2.5 2.5 2.5 2.5 2.5 2.5 2.5 sodium - 10.0 M. m - Sodium perborate 25.0 25.0 \ 25.0 25.0 25.0 25.0 NTA - 12.0 « - - 15.0 EDTA 0.5 - 0.5 0.5 0.5 0.5 CMC 1.0 1.0 1.0 1.0 1.0 1.0 Enzyme concentrate 0.5 0.5 0.5 0.5 0.5 0.5 opt. Brightener, FaA-,
Fragrances 0.5 0.5 0.5 0.5 0.5 0.5 Difference up to 100 * 7.0 8.0 8.0 7.0 8.0 7.0.

T * b. 2

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Henkel & Cie GmbH Since 20 for patent application O 41 57

at Washing Foam- lärt 30 ° 50 Foam note 90 ° 95 ° C game middle inhibi-
gate ^ö dH 3 3 ° 70 ° 3 4th 1 E. 1 ? 16 3 1 0 1 2 2 1 ° / 16 3 1 0 2 3 3 1 5 3 3 2 0 2 4th 4th 1 ? 16 2 1 0 1 2 5 2 9 16 3 2 0 0 2 6th 1 7 16 1 0 0 1 2 7th 1 5 16 1 1 0 3 3 8th 1 / 3 0 0 2 0 1 9 1 / 16 0 1 0 2 2 10 1 ° / 3 2 2 1 0 1 11 F. 1 / 16 2 2 0 0 0 12th 1 / 16 2 2 0 1 2 13th 1 ° / 3 1 1 1 0 2 14th 1 ? 16 0 0 0 2 4th 15th 1 5 16 0 0 0 0 2 16 1 ^c , 16 0 0 0 2 3 17th 1 5 3 0 0 1 0 1 18th 1 / 16 0 0 0 * 1 2 19th 0.5 5 16 0 0 1 1 1 20th $ 1 16 0 2 1 1 2 21st 2 5 16 3 2 1 1 CVJ 22nd G 1 5 16 2 1 0 1 2 23 H 1 < 16 2 1 0 2 2 24 I. 1 ; 16 2 1 0 0 2 25th K 1 ; 16 0 0 0 0 1 26th L. 1 5 16 0 £ S ₁ δ S ₂ t> S ₂ £ s. ^f ° S ₄ 6S ₆ SS ₆ 6 S _? 6 p δ s ₂ δ S ₂ 6 S ^ 6 S ₅ ^ s ₆ « ^S 6 6 S ₇ 6 p * ^S 8 <S ₉ £ s _? ί S ^ £ S ₇ £ S ₇ ί S ₇

Tab. 3

2098U / 1286

Henkel & Cio GmbH

21 * ^ur PotenlunneMurtfl D r J. J ^) f

Examples 27 to? 1

The following table 4 shows examples of softening and descaling agents. The foam inhibitors were added in solid form to the granular polyphosphate mixtures using a powerful compulsory mixer. The agents are suitable for pre-washing or descrusting of textiles, as an additive to washing and caustic solutions when using hard water and for removing limescale deposits in washing machines and water heaters. A foaming of the treatment solutions, their concentration 0.5 to 5 g / l. was, occurred at the arrival. In no case turn on.

Component ^ - 0.3 Proportions in percent by weight
28 29 30 31 S. - 0.3 r 2.2 0.8 0.5 Connection 3j 95.0
4.7 0.5 7.5
9.0
65.0 16.0 35.0
15.0 35.0
15.0 ^Na (n ₊ 2) ^P n ° 3n + l
with η = 3
with η = 4 to 9
with η β 10 to 20 40.0
55.0
4.5 - 30.5 Sodium hexa-
metaphosphate - ■ - - 10 - NTA - «V 10 Sodium silicate
(Na ₂ OrSiO ₂ »
1: 3.3) - - 15.0 soda - 29.2 4.0 Sodium sulfate

Tab. 4

2098U / 1286

Claims (1)

Henkel & CIe GmbH s.it. 22 »rp _o t.nta-, _m .id _u « _a ο 4157 Claims 1. Foam-regulated washing, cleaning and softening agents with a content of at least one cleaning or complexing compound from the class of anionic, zwitterionic and nonionic washing active substances, polymer phosphates and complexing agents, characterized in that they based on the amount of the aforementioned cleansing and complexing compounds, 0.1 to 10 percent by weight contain at least one foam-suppressing compound of the following formulas: I) R ₁ -OC-NH-R-HN-COR ₀
0 0 ^IJ ) R ₁ -HM-COROC-NH-R ₀
I it it d 0 0 in which R represents a hydrocarbon radical with 2 to 20 carbon atoms, R ₁ and Rp represent hydrocarbon radicals with 8 to JO carbon atoms. 2. Agent according to claim 1, characterized in that the radical R is an aliphatic radical with 2 to 10 carbon atoms and the radicals R ₁ and Rp represent straight-chain, saturated or monounsaturated hydrocarbon radicals with 12 to 24 carbon atoms. 3. Composition according to claim 1 and 2, characterized in that its "content of the aforementioned foam inhibitors 0.2 to 5 wt -% by.. 2098UM286 Henkel & CiG GmbH s «uo 23 ^{lur PottntanmelJu} " «° 4-157 4. Means according to claim 1 to 3 * characterized in that the compounds mentioned under a) have the following composition: 1 to 40 % of at least one compound from the class of anionic, nonionic and zwitterionic Yiasch active substances, 10 to QO $> at least one non-surface-active, cleaning or complexing building salt., 10 to 50 % of a per-compound, in particular sodium perborate containing water of crystallization or anhydrous, and mixtures thereof with stabilizers and activators, 0.1 to 20% other auxiliaries and additives. ?. Agent according to claim 4, wherein the washing active substances are 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 to 100 %, preferably 10 to 50 % soap. 5. Agent according to claim 4, wherein the cleaning and complexing building salt up to 100 %, preferably 25 to 95 % of triphosphate and its mixtures with pyrophosphate, up to 100 % _t preferably 5 to 50 # from the sodium salt of a complexing agent from the class the nitrilotriacetic acid and ethylenediaminetetraacetic acid and up to 100 $>, preferably 5 to 50 $> from the sodium salt of a polymeric carboxylic acid. f, means according to claims 1 to 3 *, characterized in that the complexing components consist of at least one compound from the class of polymer phosphates of the formula "ei" \ Ρ.0 /,, w of the metaphosphates of the formula (MePO. *) , in which Me stands for Na or K, η for a number from 3 to 20 and m for a number from 5 to 30. 2098U / 1286 Henkel & CIe GmbH s.; R. 24 «.r Pct. Avoidance ο ^l \\ j ( 8. Composition according to claim 1 to 7, characterized in that they contain up to 5% of further foam inhibitors from the class of saturated fatty acids containing 20 to 24 carbon atoms and their alkali metal soaps, paraffins, triglycerides and trialkylamine. 209814/1286