DE1792186A1 - Low-foaming detergents, dishwashing detergents and cleaning agents - Google Patents

Description

3s it is known that non-ionic detergents, dishwashing detergents and cleaning agents, in particular those based on polyglycol ether, have good cleaning power and low foaming power and are also suitable for dampening the foaming of anionic laundry raw materials. These properties are particular in the case of such detergents and cleaning agents of importance, those for use in drum washing machines and automatic dishwashers are determined.

The present invention is based on the object of developing detergents, dishwashing detergents and cleaning agents, which in comparison with the known agents, an even lower tendency to foam or, compared with foaming detergent raw materials, an improved foam-dampening Have an effect and are also characterized by a high washing and cleaning power. Subject of Invention are low-foaming detergents, dishwashing detergents and cleaning agents, characterized by a content of ethoxylated alkyl urea derivatives the formula

R ₁ -N- (C ₂ H ₄ O) _x -H

C = O
R ₂ -N- (C ₂ H ₄ O) -H

109842/1770

in the rule an alkyl radical with 8 to 24 carbon atoms, R ₂ a hydrogen atom, the group - (CpH ^ O) -H or an alkyl radical with 1 to 24 carbon atoms and the sum of x, y and ζ a number of 5 to 50 mean.

The ethoxylated alkyl urea derivatives referred to above are represented in a known manner. The Monoalky example, can be made by reacting Alkylaminhydrochloriden with alkali metal cyanates and subsequent ethoxylation manufacturing W! Connections. The N, N'-dialkylurea derivatives are obtainable, for example, by reacting alkylamines with urea and then ethoxylating.

The alkyl groups present in the ethoxylated urea derivatives can be of synthetic or natural origin, for example from petroleum, through oxo synthesis or olefin polymerisation or obtained from fats or their mixtures and be straight-chain, branched, saturated or unsaturated and the * have the usual composition for technical mixtures. Examples these are those of coconut, palm kernel, tallow, cottonseed, peanut, soy, rapeseed, sperm or fish oils or their Compounds derived from hydrogenation products.

Among the monohydric urine derivatives, those j are preferably used in which R 1 denotes a straight-chain alkyl radical having 10 to 20 carbon atoms and the sum of the glycine groups is 8 to 55. Also those in the dialkylurea derivatives

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The alkyl groups R ₁ and R 4 present, which may be the same or different, should preferably be straight-chain and have 10 to 20 carbon atoms. The sum of the glycol ether groups in the dialkyl urea derivatives should preferably be 15 to 40.

The monoalkyl derivatives have a slightly increased detergency compared to the dialkyl derivatives, while the dialkyl derivatives have an even lower foaming power than the monoalkyl derivatives. By mixing the two compounds, the properties the detergent can be adapted to the intended use.

The new detergents and cleaning agents can, depending on their intended use, contain other customary constituents, such as pyrophosphates, triphosphates and more highly condensed phosphates in the form of the sodium, potassium or ammonium salts. Furthermore, silicates can be present, in particular sodium silicate, in which the ratio of Na _p 0: SiOp is 1: 3.5 to 1: 1. Oxygen-releasing or active chlorine-containing bleaches such as alkali perborates, alkali percarbonates, urea perhydrate, alkali hypochlorites and chlorinated cyanuric acid or its alkali salts, stabilizers such as magnesium silicate and neural salts such as sodium sulfate or sodium chloride can also be present as constituents of the mixture.

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BATH ORIGINAL * ¹ '"*

Furthermore, complexing agents can be present, in particular Alkali salts of aminopolycarboxylic acids and / or aminopolyphosphonic acids, such as the sodium or potassium salts of aminotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminopentaacetic acid, Triethylenetetraminohexaacetic acid and its higher homologues, A'thylenediaminohydroxyäthantriessigsäure, Aminotri- (methylenephosphonic acid), ethylenediaminotetra- (methylenephosphonic acid), l-hydroxyethane-l, l ~ diphosphonic acid and the higher homologues of the polyphosphonic acids mentioned.

Substances are also regulated as components of the mixture of the pH value into consideration, such as bicarbonates, carbonates, hydroxides and borates of sodium or potassium, also lactic acid and citric acid. The amount of alkaline substances including the alkali silicates and phosphates should be dimensioned so that the pH value of a usable lye for machine Rinsing and cleaning is 10 to 14, for coarse laundry 9 to 12 and for delicates 6 to 9. For hair washing or body care Certain preparations or detergents also preferably have a weakly acidic, neutral or weakly basic one Reaction to.

The detergents and cleaning agents can also contain enzymes from the Contain class of proteases, lipases and amylases, which are of animal and vegetable origin, e.g. from digestive enzymes or yeast can be obtained, v / ie pepsin, pancreatin, trypsin, Papain and diastase. Preferably from bacterial strains or fungi, such as Bacillus subtllis and Streptomyces griseus,

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BATH ORIGINAL

recovered enzymatic active ingredients used, which compared to the The first-mentioned enzymes have the advantage that they have the advantage over alkali, per-compounds and anionic washing active substances are relatively stable and are not noticeably inactivated even at temperatures between 45 and 70 C. Her The relatively high resistance to oxidizing agents is possibly due to the low content of free sulfhydryl groups.

Skin protection substances such as fatty acid mono- and dialkylolamides can also be present as components of the mixture. Agents intended for use in washing machines can contain additional foam inhibitors, for example fatty acids or their alkali soaps with 20 to 2k carbon atoms or triazine derivatives, which are obtainable by reacting 1 mole of cyanuric chloride with 2 to 5 moles of an aliphatic, straight-chain, branched or cyclic primary monoamine . In addition, graying inhibitors such as sodium cellulose glycolate, disinfecting and finishing agents, fillers such as urea, abrasives and dyes and fragrances can be present.

The agents can also contain optical brighteners, for example those of the diaminostilbene disulfonic acid type according to the following formula:

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in which X and Y have the following meanings : NH , NH-CH ,,,

NH-CH ₂ -CH ₂ OH, CH-N-CH ₂ -CH ₂ OH, N (CH ₂ -CH ₂ OH ^ ₂ , morpholino, dimethylnorpholino, NH-CgH, NH-CgH ₂ ^ -SO H, OCH ₃ , Cl, where X and Y can be the same or different. Particularly suitable are those compounds in which X is an anilino and Y is a diethanolamino or

Represent morpholino group.

Optical brighteners of the diarylpyrazoline type according to the following formula can also be present:

Ar '- C CIU

! I I

N CHR N

I Ar

In this formula mean R is a hydrogen atom, an alkyl radical or aryl radical,

which may be substituted,

Ar + Ar ¹ aryl radicals, such as phenyl, diphenyl or naphthyl, which can carry further substituents, such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylaraino, acylamino, carboxyl, sulphonic acid «M sulfo« aBiidgruppen

or Halogenaton ».

109 «42/1770" ⁷ "

Preference is given to using 1,3-diarylpyrazolines in which R represents a hydrogen atom.

Other low-foaming washing raw materials can also be added to the detergents and cleaning agents, including, in particular, the nonionic polyglycol ether derivatives of alcohols, fatty acids and alkylphenols which contain> up to 30 glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon radical. Polyglycol ether derivatives in which the number of ethylene glycol ether groups is 5 to 15 and whose hydrocarbon radicals are derived from straight-chain, primary alcohols with 12 to 18 carbon atoms or from alkylphenols with a straight-chain alkyl chain containing 6 to 14 carbon atoms are particularly suitable. 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 distinguished by a particularly low foaming power.

Other low-foaming compounds are water-soluble, 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups Containing polyethylene oxide adducts with polypropylene glycol, ethylene diamine polypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain are possible. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

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Detergents and cleaning agents that produce a slight amount of foam does not bother, anionic detergent raw materials can also be used of the sulfonate or sulfate type. Examples of such washing raw materials are olefin sulfonates, such as those by Sulphonation of primary or secondary aliphatic monoolefins with gaseous sulfur trioxide and then alkaline or acid hydrolysis, also alkylbenzenesulfonates and alkylsulfonates, such as those obtained from n-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. Suitable are also c-c-sulfofatty acid esters, primary and secondary Alkyl sulfates and the sulfates of ethoxylated or propoxylated alcohols. Further compounds of this class, which may be may be present in the 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-dioxypropanesulfonic acid. There are also sulfates of ethoxylated or propoxylated fatty acid amides and alkylphenols and fatty acid taurides and Fatty acid ethers in question.

Except for the mentioned washing raw materials of the sulfonate and sulfate type The agents can also contain alkali soaps of fatty acids, ampholytes, such as alkyl betaines and alky sulfobetaines and nonionic surfactants of the type of amine oxides and sulfoxides.

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The anionic detergent raw materials can be in the form of sodium, Potassium and ammonium salts as well as salts of organic bases such as mono-, di- or triethanolamine are present. Unless the mentioned Active washing compounds have an aliphatic hydrocarbon radical, this should preferably be straight-chain and have 8 to 22 carbon atoms. Contained in the compounds with araliphatic hydrocarbon radicals the preferably unbranched alkyl chains have an average of 6 to 16 carbon atoms.

The washing and cleaning agents can be liquid or pasty or solid, for example powder, granulated or lumpy form. Liquid preparations can be used for the purpose better solubility with water-miscible solvents, in particular ethanol and i-propanol and solubilizers such as Alkali salts of benzene, toluene, xylene or ethylbenzenesulfonic acid contain.

As far as detergents and cleaning agents are composed of two or more components, they should contain the ethoxylated mono- or dialkylurea derivatives according to the invention or their mixtures in amounts of 0.1 to 80% by weight, preferably 0.5 to 50% wt -.,% by weight.

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Ira following are some compositions for the invention Detergents, dishwashing detergents and cleaning agents are listed. However, the invention is not limited to the following mixtures limited, but these can be modified in many ways or supplemented by the additives listed in the description. The sulfate and sulfonate detergent raw materials and soaps are generally used as the sodium salts. As far as liquid preparations are concerned, the anionic Active washing substances are advantageously used in the form of the mono-, di- or triethano-ammonium salts.

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1. Powdery, slightly foaming ^{V. 7 a schmitt el:}

0.1 - 10 £ ethoxylated mono- or dialkyl urea,

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

- 5 % alkyl polyglycol ether (Cp-Co-alkyl) or alkylphenol polyglycol ether (Co-Ch-alkyl) with 5 to 10 ethylene glycol ether groups,

0 - 5 % soap ^c ₁₂ ~ ^c i8 *

8 % of a foam suppressant from the class

of fatty acids or their alkali soaps with 20 - 24 carbon atoms or triazine derivatives, obtainable by reacting 1 mole of cyanuric chloride with 2-3 moles of an alkylamine 4 to 20 carbon atoms,

- 50 % of a condensed alkali phosphate from the class of pyro- or tripolyphosphates,

0.1 - 20 % complexing agents from the class of alkali salts of aminopolycarboxylic acids, aminoalkylenepolyphosphonic acids and hydroxyalkanephosphonic acids,

1 - 5 % sodium silicate,

10 - 35 % sodium perborate tetrahydrate 0 - 5 % enzyme,

0.05 - 1 % of an optical brightening agent from the class of the diaminostilbene disulfonic acid derivatives,

0.1 - 30 % of an inorganic salt from the class of carbonates, bicarbonates, borates, sulfates and chlorides of alkali metals,

0.5-4 % magnesium silicate, 0.5-3 % sodium cellulose glycolate.

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2. Machine dishwashing detergent:

0.1 - 5 % ethoxylated mono- or dialy urea 0 5 % alkyl polyglycol ether (C ₁₂ -C 12 -alkyl) or

Alkylphenol polyglycol ether (Cg-C ^ -alkyl) with 5-50 ethylene and 5-50 propylene glycol ether groups,

0 5 % ethoxylated polypropylene glycol ether or

ethoxylated ethylenediamine polypropylene glycol ether,

50 - 95 % pentasodium triphosphate,

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

0 5 % potassium dichloroisocyanurate

5.Liquid detergent, dishwashing detergent and cleaning agent:

1 50 % ethoxylated mono- or dialkyl urea 0 - 10 % sulfonate detergent raw material

0 - 10 % alkyl polyglycol ether sulfate (Cg-Cg-alkyl, 1-5 ethylene glycol ether groups),

0.1 - 5 % fatty acid amide glycol ether condensate

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

0 - 10 % solubilizer from the class of alkali salts of benzene, toluene or xylene sulfonic acid,

0 - 50 % neutral or acidic potassium pyrophosphate, 0 - 10 % organic solvents from the class of

Cp-C, alcohols and ether alcohols,
0 1 fo optical brightener

The rest is water, fragrances, dyes, preservatives.

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4. Powdered mild detergent:

5 - 50 % ethoxylated mono- or dialkyl urea, 0 - 20 % sulfonate detergent raw material

0 - 10 % alkyl polyglycol ether sulfate (Cg-C ^ g-alkyl, 1-5 ethylene glycol ether groups,

_0-20 % alkyl polyglycol ether (C ₁₀ -C 18 alkyl, 5-12 ethylene glycol ether groups),

0 5 % fatty acid ethanolamide or diethanolamide, 0 - 10 % alkali tripolyphosphate,

0 - 20 % complexing agent from the class of the alkali salts of aminotrlacetic acid, ethylenediaminotetraacetic acid, hydroxyathane diphosphonic acid and aminoalkylenephosphonic acids,

3 - 70 % sodium sulfate.

5. Soaking and pre-wash detergent:

0.1 - 5 % ethoxylated mono- or dialkyl urea, 0 - 5 % sulfonate detergent raw material

0 - 3 <fo alkyl polyglycol ether (C ^ -C ^ g-alkyl,

5-12 ethylene glycol ether groups), - 50 % soda,

1 - 5 % water glass,

0 - 5 % magnesium silicate,
0-5 % enzyme.

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β. Abrasives:

0.2 - 5 / S ethoxylated mono- or dialy! Urea,

0.1 - 5% sulfonate raw material,

0.5 - 10 % soda, sodium sesquicarbonate, notrium bicarbonate,

0 -5/0 ortho-, pyro- or polyphosphate,

70 - 95% abrasives,

0-2 % sodium dichloroisocyanurate, 0.1-5 % sodium sulfate.

¹ J. Cold detergent and bleach:

1 - 15 % ethoxylated mono- or dialky urea, 0.1 - 15 % sulfonate detergent raw material

0 --10Ji alkyl polyglycol ether (C ₁₂ -C ₁ Q-AIlCyI) or alkylphenol polyglycol ether (Co-Cw-alkyl) rait ^ 5 to 10 ethylene glycol ether groups,

- 50 % of a condensed alkali phosphate from the class of pyro- or tripolyphosphates,

0 - 25 % complexing agents from the class of alkali salts of aminopolycarboxylic acids, aminoalkylenepolyphosphonic acids and hydroxyalkanephosphonic acids,

0 - 5 % sodium silicate,

1 - 20 % sodium dichloroisocyanurate, 0.1 - 2 % optical brightener,

0.1 - 50 % of an inorganic salt from the class of carbonates, bicarbonates, borates, sulfates and chlorides of alkali metals.

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1G98U / 1770

Examples 1-8

A detergent was prepared by mixing 5 parts by weight of sodium sulfate and 1 part by weight of ethoxylated mono- or dialkylureas. To test the washing power, artificially soiled wool was ^{washed for 15 minutes at JO 0} C in a wash liquor with a weight ratio of wool to wash liquor of 1:50 and a water hardness of ΐβ dH. The composition of the washing raw materials, the concentration of the washing liquor and the percentage brightening measured on photometric Viege are shown in the table below. The abbreviation Ä "0 means ethylene oxide groups. The foaming power of the washing liquor was determined in accordance with DIN 53 902. The test series labeled A and B are listed for comparison comparable well-known products.

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109842/1770

laundry detergent % Brightening 2 g / l 3 g / l Foaming ability 2 g / l 3 g / l Ex. (3 parts Na ₉ SO., 1 part washing 1 g / l 32 53 1 g / l 50 60 raw material) ^ ^H 22nd 53 64 30th 10 20th ι
1 N-tetradecylurea + 10 AO 34 69 66 5 60 70 2 N-hexadecylurea + 10 AO 61 61 69 40 30th 40 3 N-hexadecylurea + 20 AO 38 58 70 20th 35 40 4th N-octadecylurea + 20 AO 43 60 68 30th 40 50 5 N-octadecylurea + 30 AO 35 45 61 30th 20th 30th 6th N-coconut alkyl urea + 15 AO 27 49 57 10 20th 30th 7th Ν, Ν'-ditetradecylurea + 30 AO 33 24 27 10 140 160 8th N, N'-dihexadecylurea + 20 AO 14th 6th 6th 95 140 160 A. Coconut alcohol + 12 ÄO 4th 100 B. Coconut alcohol + 20 ÄO

CQ K) "a

Example 9

By spray drying an aqueous concentrate and then By adding sodium perborate, a loose, hollow ball powder was produced with the following composition:

14 % Na-n-Dodecylbenzenesulfonate

2.5 % oleyl alcohol + 10 AO

5.5- fo dihexadecylurea + 20 AO

4] 5 % pentasodium triphosphate

16 % sodium perborate

4 fo water glass (Na ₃ O: SiO ₃ = 1: 3.3)

8 % sodium sulfate

9 % V / water, opt. Brightener.

In a drum washing machine with a sight glass, clean V / ase was made with an alkali concentration of 5 g / l> a water hardness of 16 ° dH and a weight ratio of textile to washing liquor of 1:10 at temperatures between 20 and 97 ° C, without that it came to a disturbing foam development.

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In the following table are some formulations according to the invention Detergents and cleaning agents compiled for the following areas of application:

low-foam heavy duty detergent

Cold detergent

Liquid detergent

Wool detergent

Soaking agent

Foam-retardant detergent for colored laundry

liquid dishwashing detergent

Cleaner for coarse soiling

Abrasives.

The components C to F and H to K were present as sodium salts, the pyrophosphate (component L) came in Example 4 as Potassium salt, used in all other examples as the sodium salt. An enzyme from Bacillus sub Maxatase ^ from the Koninklijke Nederlandsche obtained from tilis Gist en Spiritusfabriek N.V., DeIft, with an activity of 100,000 LVE / g.

example 10 It 11 dd 12th dd 13th dd 14th dd 15th It 16 It 17th dd 18th

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T09842 / 1770

A) B) C) 0) E) F) G) H)

Component 1

Ci2 ~ Ci8 "monoalkyl urea + 20 Ä0 Ci2-Ci8-dialkylureaff 20 Ä0

n-dodccylbenzenesulfonate

Coconut fatty alcohol glycolity sulfate (2 Ä0) Nonylphenol polyglycol ether (10 ÄO)

C ₁₂ -C ₁₈ soap

co I) ^C 2o " ^c 22 soap CD K) Tripolyphosphate ro L) Pyrophosphate M) soda N) Sodium silicate • O) Sodium sulfate O P) Sodium perborate O) Magnesium silicate R) enzyme S) Na-ceulose glycolate Na aminotriacetate : u) Coconut fatty acid diethanolamide V) water W) K-dichloroisocyanurate X) Color, fragrance, opt. Brightener Y) Sodium toluene sulfonate ¹ Z) Quartz flour ro I ... O

11 Examples 13th (Declarations 5 - in Weight .-Ίο) 17th 5 18th 10 8th 12th 10 14th 5 13 15th 16 3. 1 2 - 10 5 1 - - 5 - 2.5 - - - - - 3. 5 - - - 3.5 - - - - 6th 5 - - 1.5 3.5 m - - 2 - - - - ■ 2.3 δ 10 m • δ • - - - δ - 15th - - - m - - 1. 5 - - 3 - - - - 4th - - - 1.3 26th - - 2 - 10 - 15th - - - - 45 - 2 1.4 5 15th 20th - 20th 8th - 45 5 - 5 - - 35 - - 25th 2 - 5 - - 45 5 3 - 1. - - - - - 18th 5. 5 0.4 - 25th - - - - - - - - 3 - - - 3 - - ■ - - 0.6 - - - 1 O, 5 - - - 1.5 20th - ' 2. 2 2. 5 - - - 20th - 1 5 10 - - 2 - - 7.9 - 17th - 3.5 12, 0 - 8.5 15th 57.2 - 8th. 0 71 1, 1 4th - 0.8 - - - - 0, 0.1 0.6 - 0.3 - o.i - _ - "6.5 -

86

ι- · VD

Claims (6)

Claims 1. Low-foaming detergents, dishwashing detergents and cleaning agents, marked by a content of ethoxylated alkyl urea derivatives of the formula R ₁ -N- (C ₂ H ₄ O) _x -H C = O
R ₂ -N- (C ₂ H ₄ O) _y -H in which R _{1 is} an alkyl radical with 8 to 24 carbon atoms, Rp is a hydrogen atom, the group - (CH ₄ O) -H or an alkyl radical with 1 to 24 carbon atoms and the sum of x, y and ζ is a number from 5 to 50 mean. 2. Agent according to claim 1, characterized in that R is a straight-chain alkyl radical having 10 to 20 carbon atoms, Rp is the group - (C ₂ H ₄ O) -H and the sum of x, y and z · 'is a number of 8 to mean 35. 3. Composition according to claim 1, characterized in that R ₁ and R _{2 are} straight-chain alkyl radicals having 10 to 20 carbon atoms and the sum of χ and y is a number from 15 to 40. 108842/1770 4. Low-foaming detergents, dishwashing detergents and cleaning agents, characterized in that they contain at least one compound according to Claims 1 to 3 and at least one compound from the class of anionic, zwitterionic and nonionic contain surface-active detergent raw materials or the inorganic and organic synthesis salts. 5 · agent according to claim 4, characterized in that it urea derivatives in amounts of from 0.1 to 80 percent by the ethoxylated alkylene -.% By weight. 6. A composition according to claim 4, characterized in that it urea derivatives in amounts of from 0.5 to 50 percent by the ethoxylated alkylene -.% By weight. 7. Agent according to one or more of the preceding claims, characterized in that it contains mixtures of ethoxylated mono- and dialkyl urea derivatives. Henkel & Cie. GmbH. (Dr. Haas) Gen. Volim. 8/1966 1G9842 / 1770