DE2043088A1 - Low-foaming washing, cleaning and softening agent - Google Patents

Description

Hang! & CSe GmbH Düsseldorf, Aug 27, 1970

_n ι, Henkelstr. 67

Patent department

Dr. Wa / Ml 2043088

Patent registration

D 4145

"Foaming detergent, cleaning agent and softening agent"

Low-foaming detergents and cleaning agents are known which contain nonionic active washing substances of the polyglycol ether type as washing active substances. The foam-suppressing properties of these compounds are not sufficient λ However, many of which contain the foam development of such agents that high-foaming surfactants of the sulfate or SuIfonattyp to damp enough, which is why fatty acids has been proposed, with more than l8 carbon atoms to add them as anti-foaming agents. However, the effect of these fatty acids is limited to surfactants of the sulfonate type and also depends on the hardness of the water used to prepare the cleaning solution. The silicones, which are widely used as foam suppressants, are less suitable for detergents and cleaning agents, since they can make the cleaned objects water-repellent and are difficult to remove from the substrate. ·

Even when using surfactant-free, complexing agents Containing polymer phosphates or organic complexing agents Softening agents for removing incrustations from textiles and washing machines, supply lines and Water heaters used can be significant Disturbances occur through foam development. As the cause for the foam formation, deposited organic impurities v / ground, such as protein or fatty substances, lime soap residues or traces of active washing substances.

BAD ORiGINAL 209810/1696

Henkel & Cie GmbH Sa »·

The applicant has set itself the task of finding a means to develop that does not have the disadvantages mentioned and its shock-dampening effect regardless of nature and composition of the foaming compounds as well as the water hardness does not have any negative effects on the cleaning result or shows the utility value of the cleaned items and is effective even in low concentrations is. -

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

R ₁ -NC-NH-R-NH-CNR

J- J Il Il I j

R ₂ 0 0 R4

in which R is a hydrocarbon radical with 2 to 20 carbon atoms, R, and R_ hydrocarbon radicals with 8 to 50 carbon atoms, Rp and R ^, hydrogen or carbonate water7 Represent radicals with 1 to 30 carbon atoms.

The radicals R, R, and R-, or Rp and Rj, can be straight-chain or branched, saturated or unsaturated or also cycloaliphatic or aromatic. Those compounds are preferably used in which H and R, straight-chain, saturated or monounsaturated hydrocarbon radicals with 10 to 24 carbon atoms, the radicals Rg and R _{2 |} _ Water-

- 3 "209 8 TO / 159 S BAD ORIGINAL

Henkel & Cie GmbH Sei! O3 for patent application D 4143

Substance or likewise straight-chain, saturated or monounsaturated alkyl radicals with 1 to 24 carbon atoms.

The foam-suppressing alkylene or aralkylene diuretic compounds are available in a known manner, for example by mixing diamines of the formula R, HN-R ~ NHR_ with isocyanates of the formula H ₁ -N = C = O or IU- N = C = O or starts from diisocyanates of the formula O = C = NRN = C = O and allows these to react with primary or secondary amines of the formula R, R ^ NH or R-JRJMH.

The alkyl radicals R- and R- can be derived from fatty acids of natural or synthetic origin. Examples of these are octyl, decyl, lauryl, myristyl, cetyl, stearyl, arachyl, behenyl, lignoceryl, palmitoleyl and oleyl radicals, as well as their mixtures, such as those in coconut, tallow, beetroot '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 be derived from paraffinic hydrocarbons, olefin polymers such as polyethylene, polypropylene and polybutylene, and from compounds obtainable by oxo synthesis. The radicals R _p and R ₂ can also have the aforementioned structures or be in the form of methyl, ethyl, propyl and isopropyl radicals or straight-chain or branched alkyl, alkylaryl and cycloalkyl radicals with the specified number of carbon atoms.

It has been shown that those foam-inhibiting compounds in which the alkyl radicals 10 to 14 Containing carbon atoms, their optimal effect in the temperature range from 20 ° to 60 ° C. If the alkyl groups have 16 or more, in particular 18 to 22 carbon atoms, the maximum foam damping shifts in the range from 60 ° to 100 ° C. By appropriate selection or Combination of foam inhibitors with different ones

2098 10/1595 ■. BATH ORIGINAL

Henkel & Cie GmbH So »e

Alkyl groups can therefore affect the sanitary behavior of washing, Cleaning and softening agents can be controlled as required and adapted to the respective requirements.

The amounts of foam inhibitors to be used depend on the amount of foaming or detergent substance as well as the size of the desired effect. The concentrations that are important for practical use range from 0.1 up to 10, preferably 0.2 to 5 percent by weight, based on the particulate matter. It is of course possible with to work even larger amounts, for example up to 25 percent by weight and more, but this is not in practice necessary.

The foam suppressants can be mixed with the other washing, cleaning and descaling agents in the usual way mixed and processed together with them, e.g. spray-dried or granulated or converted into solid, liquid or pasty mixtures by other known processes will. The compounds can also be in molten or dissolved form with those in the form of powders or granules Mix other ingredients of the agent or spray them on or granulate them.

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 complexing or chelating agents. In addition, other non-surface-active Build-up salts, oxygen-containing bleaches and others usually contained in such agents Additives be present.

- 5 -209810/1595

Hang! & Cie GmbH Soito J to Palontanmelduno D

The mixtures used as washing and cleaning agents can contain anionic washing raw materials of the sulfonate or sulfate type. Primarily alkylbenzenesulfonates, for example n-dodecylbenzenesulfonate, are suitable, furthermore olefin sulfonates such as are obtained, for example, by sulfonation of primary or secondary aliphatic monoolefins with gaseous sulfur trioxide and subsequent alkali or acidic hydrolysis, and also alkyl sulfonates such as those obtained from n-chloroalkanes by sulfonation or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfotaddition with olefins. Suitable 'are further {α-sulfo fatty acid esters, primary and secondary alkyl sulfates and 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 weight sulfated partial ethers and partial esters of polyhydric alcohols, such as the alkali salts of monoalkyl ethers or the monofatty acid esters of glycerol monosulfuric acid ester or 1,2-dihydroxypropanesulfonic acid. Furthermore, sulfates of ethoxylated or propoxylated fatty acid amides and alkylphenols as well as fatty acid taurides and fatty acid isethionates are possible.

Alkali soaps are further suitable anionic detergent raw materials of fatty acids of natural or synthetic origin, e.g. the sodium soaps from oocos, palm kernel or Tallow fatty acids. As zwitterionic washing raw materials, alkyl betaines and especially alkyl sulfobetaines come into question, e.g. 5- (NiN-dimethyl-N-alkylammonium) propane-1-sulfonate and 3- (N, N-dimethyl-N-alkylammonium) -2-hydroxypropane-isulfonate.

09810/1695

The anionic raw materials can be used in the form of sodium, Potassium and ammonium salts as well as salts of organic bases, such as mono-, di- or triethanolamine, are present. If the anionic and zwitterionic compounds mentioned are 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 contain the preferably unbranched alkyl chains on average β 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 radical are primarily suitable as nonionic surface-active washing active substances. Particularly suitable are poly · glycol ether derivatives, in which, the number of Athylenglykoläthergruppen 5 to 15 and the hydrocarbon residues are derived from straight-chain, primary alcohols having 12 to 18 carbon atoms or of alkyl phenols having a straight-chain, from 6 to I ¹ I carbon atoms having Alleylkette. By adding 3 to 15 moles of propylene oxide to the last-mentioned polyethylene glycol ethers or by converting them into the acetals, detergents are obtained which are characterized by a particularly low foaming power.

Further suitable non-ionic 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 alley chain. The namedon Compounds usually contain per propylene glycol unit 1 to 5 ethylene glycol units. Also non-ionic compounds of the amine oxide and sulfoxide type, which can optionally also be ethoxylated oil can be used,

209810/1595

BATH ORIGINAL

Henkel & Cie GmbH So », / xur Pai.ntanm.iduns d <■> ■> <+ -> ZUHOUQG

Preferred components of the mixture are also condensed Phosphates, such as pyrophosphates, triphosphates, tetraphosphates, trimetaphosphates and tetrametaphosphates in the form of the neutral ones or acidic sodium or potassium salts. Preferably will Pentasodium triphosphate and its mixtures with tetrasodium pyrophosphate used.

The condensed phosphates can also be wholly or partially be replaced by organic, complexing aminopolycarboxylic acids. These include in particular the alkali salts the nitrilotriacetic acid and Ä'thylendiaminotetraessig- ■ 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 carboxylic acid 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. Further suitable aminopolycarboxylic acids are poly (N-succinic acid) ethyleneimines and poly (N-tricarballylic acid) ethyleneimines from the average molecular weight 500 to 500,000, which are analogous to the. N-acetic acid derivatives are available.

Further 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, itaconic 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, for example, ethylenically unsaturated hydrocarbons such as ethylene, propylene, isobutylene and styrene, with ethylenically ' _f . unsaturated monocarboxylic acids, such as acrylic acid, methacrylic

- ^-: -:> ll '> ■■■ - 8 - -;.. 209810 / T6 & 5 .V. \ "* ^Il

Henkel & Cie GmbH s «n» 8 * ur Poicnionmoiduna d 4145

acid. Crotonic acid and 3-butene carboxylic acid or other ethylenically unsaturated alcohols, ethers, esters, amides and nitriles, such as vinyl alcohol, allyl alcohol, vinyl methyl ether, acrolein, vinyl acetate, acrylamide and acrylonitrile, can be used. Copolymers of ethylenically unsaturated mono-, di- and tricarboxylic acids and several ethylenically unsaturated compounds of different structure are also suitable. The polymers and copolymers have an average degree of polymerization of j5 to 6000 and are based on j5 monomer units, 1 to 9 »preferably contain from 2 to 9 carboxyl groups capable of salt formation.

The homopolymers and copolymers capable of salt formation Polycarboxylic acids as defined above can be represented by the following formula:

m + 1

R ₁ «H or -CH ₃ , ·

R ₂ * H or -CBL,

R ,, «H, -CH ,, -Phenyl, -OH, -CH ₀ OH, -OCH. ,, -0-C-CH ,,

-CHO, -COOH, -CONH ₂ , -CN, °

X = H or -COOH,
γ »H, -COOH or -CHgCOOH,

where X and Y should not represent -COOH at the same time, Z = H or (if X = COOH and Y «H) also -CIL, m = any numerical value from 0 to 2, η * an integer between 3 and 6000.

The value of m is not restricted to integer values, but can take on any numerical value, including fractions of whole numbers from 0 to 2.

^209810/1595 BADORiGINAL

Henkel & Cie GmbH ropes 9 "" patent application D 4 ^

Furthermore, complexing-acting phosphorus-containing polycarboxylic acid salts may be present, e.g. the alkali salts of aminopolyphosphonic acids, in particular aminotri (methylenephosphonic acid), Kthylenediamino-tetra-methylene phosphonic acid), 1-hydroxyethane-l, 1-diphosphonic acid, methylenephosphonic acid, Ethylenediphosphonic acid and salts of the higher homologues of the polyphosphonic acids mentioned. Mixtures of the abovementioned complexing agents can also be used.

Alkali silicates, in particular sodium silicate, in which the ratio of Na ₂ O: SiOp is 1: 3.5 to 1: 1, are suitable as further synthesis salts. 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 bleaching agents, such as alkali metal perborates, alkali percarbonates, perpyrophosphates and persilicates, and urea perhydrate, may be used as a further constituent of the mixture. Sodium perborate tetrahydrate is preferably used. In order to stabilize the per compounds, the agents can contain magnesium silicate, for example in amounts of from 5 to 20% by weight, based on the amount of perborate. For TeX tilwäsche at temperatures below 7O ⁰ C agents to be applied, so-called cold detergent bleach activators, particularly tetraacetyl containing a powder component. The powder particles consisting of the bleach activator or the per compound can be coated with coating substances such as water-soluble polymers, fatty acids or granulated salts such as alkali silicates, sodium sulfate or disodium hydrogen phosphate, in order to avoid interaction between the per compound and the activator during storage.

209810/159 5 " ¹⁰ "

Since · Iv lor Polonlunmildunj D 'J- O

The detergents can also contain optical brighteners, in particular derivatives of diaminostilbene disulfonic acid or their alkali metal salts of the formula:

in which X and Y have the following meanings: NH ₂ , NH-CH- ,, NH-CH ₂ -CH ₂ OH, CH ₃ -N-CH ₂ -CH ₂ OH, N (CH ₂ -CH ₂ OH) ₂ , Morpholino, Dimethylmorpholino, NH-C ₆ H ₅ , NH-C ₆ H ₄ -SO H, OCH ₃ , Cl, 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 of the diarylpyrazoline type of the formula below are also suitable

Al * "~ * O HIM

- Ii 1 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. Further suitable whiteners are those of the naphthotriazole stilbene sulfonate, ethylene-bis-benzimidazole, ethylene-bis-benzoxazole, thiophene-bis-benzoxazole, dialkylaminocoumarine and cyanoanthracene type. Chemicals of optical brighteners can also be used.

209810/1

Henkel & Cie GmbH since 11 lut Palunlanmildung D 4145

Other suitable ingredients in the mixture are graying inhibitors, e.g. sodium cellulose glycolate, as well as the water-soluble alkali salts of synthetic polymers, the free Contain carboxyl groups. These include the polyesters or polyamides made from tricarboxylic and tetracarboxylic acids and divalent ones Alcohols or diarains.

The agents can also contain enzymes from the class of proteases, lipases and amylases or mixtures thereof. The enzymes can be of animal and vegetable origin, e.g. obtained from digestive enzymes or yeast, such as pepsin,,

Pancreatin, trypsin, papain, catalase and diastase. Preferred " It is wise to earth enzymatic substances obtained from bacterial strains or fungi such as Bacillus subtilis and Streptomyces griseus Active ingredients are used that are relatively resistant to alkali, per-compounds and anionic washing active substances and not even at temperatures between 50 ° and 70 ° C are significantly inactivated.

Other ingredients which may be included in the inventive compositions are neutral salts, especially sodium sulfate, bacteriostatic substances, such as halogenated phenolic ether and thioether, halogenated carbanilides and A-licylanilide and halogenated diphenyl methanes, further similar dyes and fragrances.

The agents according to the invention are distinguished by their high washing power. They are outstandingly suitable for use in automatic drum washing machines, since they ^{do not tend to over-foam even at temperatures above 90 °} C. or when the washing liquor is boiled. The foam inhibitors according to the invention also have the advantage over numerous other foam-suppressing substances that their action does not diminish even if they are dispersed in a paste-like detergent concentrate and spray-dried together with it.

- 12 -

20981 0/1595

Henkel & Cie GmbH page 12 * ur Palent application D 4145

Softeners primarily contain sodium or potassium polymer phosphates, e.g. pentana trium triphosphate, Hexasodium tetraphosphate and mixtures thereof with polyphosphates of the formula Ma / p \ P 0 / -. , -i \> where η stands for integers from 5 to 20, furthermore sodium or potassium metaphosphates, e.g. sodium trimetaphosphate, sodium tetrametaphosphate and sodium polymetaphosphates of the formula (NaPO-,), where m is an integer from 5 to 30. The condensed Phosphates can also be wholly or partially replaced by the aforementioned complexing agents from the class of aminopolycarboxylic acids, Alkane dl phosphonic acids, hydroxyalkanediphosphonic acids and aminoalkanepolyphosphonic acids.

The aforementioned detergent, cleaning and softening agents may contain other known foam suppressants, such as saturated fatty acids or their alkali metal soaps with 20 to 24 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 cleaning and complexing components that do not consist of the foam suppressant, as well as the other additives, largely depends on the specific field of application of the agent and, in the case of the technically important detergents and cleaning agents, corresponds to the following scheme (data in percent by weight):

2098 10/1595

Sill · ljjlur PalonlonmeliiunB D

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

10 to 80 $ of at least one non-surface-active, cleaning-enhancing or complexing building salt j

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 contain up to 100 %, preferably 25 to 95 %, from alkali metal triphosphates and mixtures thereof 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, ethylenediaminotetraacetic acid and up to 100%, preferably 5 to 75% of at least one encryption \ bond be composed of the class of alkali metal 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 5%, and also the enzymes which in an amount up to 5 # * preferably 0.2 to 3% may be graying and whose share can be up to 5% "preferably 0.2 to 3 $> be.

209810/1595

Henkel Λ Cig GmbH ί.π, Ι ^ «p.,! ,, *,» ,,. «», »4l ^ 5

Be is ρ 1 e 1 ο

The following are some recipes that can be used have proven particularly effective in practice.

Λ. Powdered, low-foaming detergent:

J5 15 # Sulphonate detergent raw material from the class of Alkylbenzenesulfonates, olefin sulfonates and n-alkanesulfonates,

0.5 - 5 # alkyl polyglycol ether (C ₁₂ ~ C ₁₈ -alkyl) or alkylphenol polyglycol ether (Cg-C ₁ ^ -alkyl) with 5 to 10 ethylene glycol ether groups,

5 % soap C ₁₂ -C ₁₈ ,

0.2-5% foam suppressant according to the invention as / ie their mixtures with saturated fatty acids or their alkali soaps with 20-2h carbon atoms,

- 50 ^ of a condensed alkali metal phosphate from the

Class of pyro- or tripolyphosphates, 0.1 - 25 % sodium ethylendlaminotetraacetate or

Sodium nitrilotriacetate, -

5 # sodium silicate.,

- 35 % sodium perborate tetrahydrate, 5 % enzyme,

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

0.1 - 30 % of an inorganic salt from the class

the carbonates, bicarbonates, borates, sulfates and chlorides of alkali metals, 4 ^> magnesium silicate,

0.5-3 # sodium cellulose glycolate.

. - 15 -

209810/1595

2043G88

Henkel Λ Cio GmbH - <·; · ■ »15 ™ · vw« ™ '·'»" * ο 4145

D. Machine dishwashing detergent:

0.1 - 5 % compounds from the class of the alkyl polyglycol ethers (C ₁₂ -C ₁ Q-AlRyI), alkylphenol polyglycols (Cq-C ₁ Jj.-alkyl) with 5-'J) O ethylene and 5-50 propylene glycol ether groups and ethoxylated Polypropylene glycols,

^{0.1-5 r} / o foam suppressant according to the invention

- 90 % pentasodium triphosphate,

1 - 40 YES sodium silicafc (Na ₂ OcSiO ₂ = 1: 1 to 1: 3), 0 5 io 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 OrSiO ₂ = 1: 1 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.

D. Softener:

0.1 - 5 ^ foam suppressant according to the invention - 95 % fentasodium triphosphate 0 - 70 fo polymer phosphates of the formula

^Na (n ₊ 2) ^P n ° (3n.Kl) ^{with n} T ^{h bls 20} 0 - 40 % sodium hexametaphosphate 0 - 20 i> soda

0-5 % sodium sulfate.

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209810/1595 ORIGINAL BATHROOM

Henkel & Cie GmbH ropes l6 for patent application D

Examples 1 to 28

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 c * sulfofene acid ester acts it is the sulfonated one in the 06 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 = xethylene oxide groups.

The difference up to 100 # consisted of a mixture of the foam suppressant and sodium sulfate, which was mixed into the detergents as a dry powder. The composition and the percentage amount of foam inhibitor based on the total amount of detergent is given in Tables 2 and 3 refer to.

The foam behavior was measured in a commercially available, fully automatic Washing machine with a horizontally mounted drum tested as a function of the suds temperature. The machine was equipped with a round sight glass through which the foam level could be observed. For the evaluation of the Foam height was given the following grades:

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209 8 10/1595

Henkel & Cie GmbH string If "" Patontanm "ldung D 4 ^

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 β foaming over

The washing machine was loaded with 3 kg of clean laundry. The detergent concentration was 5 g / l, the weight ratio from textile to washing liquor 1:15 · The degrees of hardness of the water are 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 wash liquor foamed over in all temperature ranges.

- 18 -

20981Q / 159

Henkel & Cie GmbH

Since · XO _Iur patent application D> -L "^

The acid inhibitors used in the formula R ₁ -NC-NH-R-NH-CNR.

1 I H Il I J

R ₂ 0 0 R ₄

Substituents contained are listed in Table 1.

Designation
tion R. R ₁ , R ₃ ^R ₂ * R4 Ethylene Octadecyl hydrogen ^s a
^S 3 dd
It Tallow alkyl,
hydrogenated
Behenyl It
ti ^S 4 Hexamethylene Hexadeoyl η ^S 5 H Octadecyl ti ³ 6 It Mixture of
equal parts
Coconut alkyl
Tallow alkyl and
saturated
C ₂₀ -C ₂₂ alkyl Il ^S 7 It Dodecyl Dodecyl ^S 8 Octamethylene Octadecyl hydrogen ^S 9 p-phenylene - Octadecyl Methyl-

Tab. 1

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209810/1595

Henkel & Cie GmbH

S «lt · Xy door Folanlanmdldung O ^ l'I-5

f ι - .. ι E. F. G H J K L. η-dodecyl benzosulfonate 7.5 - - - 5.0 5.0 4.0 ctf-olefin sulfonate ( ^{C 15-18} - - 7.0 3.0 - - n-alkanesulfonate (C) - - m 8.0 - 3.0 - ct-sulfo fatty acid ester - 7.5 - m - 4.0 Alkyl polyglycol ether (9 AO groups) 2.5 2.5 - 2.0 3.5 - - Nonylphenol polyglycol ether
(9 ÄO groups) - ^m 3.0 - - 3.0 2.0 Soap C ₁₂ -C ₁₈ , 4.0 2.5 3.0 4.0 1.0 2.0 3.0 -. - - - . "-... ,,, -", 0.5 - - Pentasodium triphosphate 40.0 25.0 40.0 40.0 40.0 40.0 30.0 Tetrasodium pyrophcapba t 5.0 - 5.0 5.0 5.0 5.0 - Sodium silicate
(Na Qi SiO = 1: 3.3} 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Magnesium silicate 2.5 2.5 2.5 2.5 2.5 2.5 2.5 sodium - 10.0 - - ■ - - - Sodium perborate 25.0 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 0.5 CMC ■ - 1.0 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 0.5 opt. Aüfllicher, Faib-,
Fragrances 0.5 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 8.0 7.0

Tab. 2

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20,9,8 10/159 5

20A308.8

Henkel & CIe GmbH S · »· 20 iur Pol« ntanm «ldung O

Ex. Washing
middle Foaming
hibitor 1 YoS ₁ % S 0 O 7th 5 5 hardness
° dH 30 ° 0
50 Foam note
70 ° 90 ° 2 95 ° 1 E. 1 \ % s Y ₀ S ₈ 5
5 16 3 0 0 4th 3 2 1 * ^S 9 6th 3 3 1 0 1 4th 3 1 ⁷ IoS
5 ^ s ₆ 16. 3 2 0 1 1 4th 5 YoS ₁ % s ₇ 16 3 1 ■■ 0 '. 1 • 2 5 1 ' ^{% S} 3 16 3 1 0 1 3 6th ¹ ' -55, S ₃ 16 3 0 ; ο 2 1 7th 1 ° i JO S
3 3 3 1 ■ 0 1 2 8th ι ' 16 2 1 0 0 ! 1 9 1 16 3 1 0 0 "3 10 1 % S
O 16 3 0 Ό 2 1 11 YoS ₁₇ 16 3 1 0 0 3 12th F. ι - mixture
0.3 "fts 16 0 1 0 2 1 13th 1 0.3 3, 1 . 1 '0 '<■ 0 . 3 14th ι 16. 1 0 0 2 1 15th 0.5 3 ¹ 1 0 1 .0.
1 2 16
1
17th 0.5 16
16, 0
2 0
; ι ο ο 1 1
2 18th 1 Ιβ, 1 0 0 0 1 19th 1 '3 1 0 0 0 1 20th 1 16 0 0 0 1 2 21st G \ 16 3 2 0 1 3 22nd H ι ' 16: 3 2 - ο 1 2 23 J 1 1 16 3 1 <f 0 2 24 K • 0.5 16 3 2 0 1 2 25th L. 0.5 16 3 1 0 1 3 26th 0.5 16 2 1 0 1 2 27 16 2 1 θ 1 3 28 E. 16 2 1 0 2

Tab. 3

-209810/1595

Henkel & Cie GmbH

Seif · 21 »or Potentonnuldung 0 4145

Examples 29 to 33

The following table 4 shows examples of softening and descaling agents. The foam inhibitors the granular polyphosphate was mixed in solid form using a powerful compulsory mixer © mixed in. The agents are suitable for prewashing or de-encrusting textiles, as an additive to detergents and Flush soaps when using hard water and for removing limescale deposits in washing machines and water heaters. A foaming of the treatment solutions, the concentration of which was 0.5 to 5 g / l, occurred at the start. In no case turn on.

component 29 Shares in 0 50 0 51 Weight percent . 33 0.3 : , 5 , 3 32 0.5 Connection S, - 40. 7th 0.8 ^Na (n ₊ 2) ^P n ° 3n ₊ l 95.0 55, , 0 9 , 5 35.0 with η = 3 ν.- 4, • 0 65. , 0 35.0 15.0 with η = 4 to 9 - - 5 - , 0 15.0 - with η = 10 to 20 - - 30.5 Sodium hexa-
metaphosphate - · - - - - NTA - 10 - Sodium silicate
(Na ₂ OrSiO ₂ = - 2, 10 1: 3.3) - - 16, 2 15.0 soda - 0 - 4.0 Sodium sulfate 29.2

Tab. 4 200810/1595

-22 .-

Claims (8)

Henkel & Cie GmbH se »» 22 Iur Pot (> 1) lonm, lduna D 4145 P a t e η t a η s ρ r ü c h e 1. Foam-regulated washing, cleaning and softening agents contain 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 v / irkenden compounds, 0.1 to 10 wt -% of at least one foam-damping effect compound of the following formula.: R -N-C-NH-R-NH-C-N-R, XlH fl I J R ₂ 0 0 R ₂ ^ · in which R is a hydrocarbon radical with 2 to 20 carbon atoms, R-, and R., hydrocarbon radicals with 8 to 30 carbon atoms, R ₂ and R ₁ . Represent hydrogen or hydrocarbon radicals with 1 to 30 carbon atoms « 2. Means according to claim 1, characterized in that the radicals R-, and R, straight-chain, saturated or monounsaturated hydrocarbon radicals with 10 to 24 carbon atoms, the radicals R ₂ and R ^ represent hydrogen or straight-chain, saturated or monounsaturated alkyl radicals with 1 to 24 carbon atoms. 3 · Agents according to claim 1 and 2, characterized in that their content of the aforementioned foam inhibitors 0.2 to 5 wt. #. - 23 - 209810/1595 Henkel & CJe GmbH se »· - 23 ^IurPatent ° ^nmeldun e ^D 4145 4. Mattel according to claim 1 to J>, characterized in that the compounds mentioned under a) have the following composition: $ 1 to $ 40 at least one compound from the class of anionic, nonionic and zwitterionic washing active substances, . 10 to non-surface-active 80% of at least one cleaning bzw.komplexierend acting construction 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% of other auxiliaries and .Zusatzstoffe. / Λ 5. Means according to claim 4, wherein the washing active substances up to 100 %, preferably 25 to 70 % from those of the Sülfönat- 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. 6. 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 $, preferably 5 to 50 % of the sodium salt of a complexing agent from the class of nitrilotriacetic acid and ethylenediaminotetraacetic acid and up to 100% , preferably 5 to 50%, of the sodium salt of a polymeric carboxylic acid. 7. Means according to claim 1 to y, characterized in that that the complexing acting components of at least one compound from the class of the polymer phosphates of the formula ^ e # ₂ % P 0 / _,%, the metaphosphates of the formula () b ^ _1n exist, in which Me stands for Na or K, η for a number from 3 to 20 and m for a number from 5 to 50. - 24 - 209810/1595 Henkel & Cio GmbH s <-: i <>2't «τ Poieninnm-wung d μ '15 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 trialkylmelamines. 209810/1595