WO2014053365A1 - Performance-enhanced detergents or cleaning agents comprising complexing agents i - Google Patents

Abstract

Disclosed are detergents or cleaning agents containing at least one compound of formula (I), where R¹, R² and R³ independently represent –H, -CH₃, -CH₂-CH₃, -(CH₂)₂-CH₃, -CH-(CH₃)₂ or –(CH2)_n-CH₃, where n = 3, 4, 5, 6, 7, 8, 9, 10 or 11; X represents a hydrogen atom, a monovalent cation or the n^th portion of an n-valent cation. Said detergents and cleaning agents have an improved cleaning performance, in particular on enzymatic dirt.

Description

 "Performance Enhanced Detergents or Detergents with Complexing Agents I"

The invention relates to performance-enhanced detergents or cleaners that certain

Complexing agent included.

The most important constituents of the water hardness are salts of calcium and magnesium, in particular chlorides, sulfates and bicarbonates, which are known as so-called hardness images. Since the bicarbonates are converted into carbonates under thermal stress, a part of the calcium salts precipitates as poorly soluble CaC0 ₃ , especially in washing and cleaning operations at elevated temperatures. At high magnesium concentrations, basic magnesium carbonates are also formed. Contain the detergents and cleaning agents themselves carbonates, for example in the form of alkali metal carbonates or other precursors such

For example, percarbonates, which can release carbonate during the washing process, this carbonate content promotes the formation of insoluble calcium and magnesium carbonate residues.

The removal of hardness-forming Ca / Mg ions from aqueous solutions by ion exchange or complexation is therefore an important step in washing and cleaning processes.

Conventional complexing agents commonly used in detergents and cleaners are

Phosphonates, polycarboxylates, gluconates, NTA and EDTA. These products are not or only partially produced on the basis of renewable raw materials, which phosphonates, NTA and EDTA can still lead to an environmentally harmful contamination of the wastewater.

For some complexing agents, it has been demonstrated that they can increase the cleaning performance of detergents and cleaners. For example, EP 0 970 167 B1 discloses processes for improved cleaning of hard and textile surfaces by using tetrasodiumiminodisuccinate (also: iminodisuccinate tetrasodium salt, Λ- (1,2-dicarboxyethyl) aspartic acid tetrasodium salt, and the salts are also called iminodisuccinates (IDS) ).

Fabric detergents which contain 0.5 to 5% by weight of alkali metal salts as bleaching agents and 0.05 to 5% by weight of IDS or OH-substituted IDS (HIDS) are disclosed in WO 2001/88077 A1. This paper also mentions the bleach-stabilizing effect of IDS.

Despite these findings, detergents containing IDS or HIDS are still

improvement. In particular, so-called "enzymatic soiling" (ie Stains that are removed by enzymes such as milk, egg, starch, etc.) are still in need of improvement.

It is an object of the present invention to provide washing and cleaning compositions which have a further improved washing performance and in particular support the action of enzymes.

Surprisingly, it has now been found that molecules lacking a complexing COOH grouping in comparison with IDS and HIDS are distinguished, in particular, by enzymatic soiling by improved complex formation and improved cleaning performance.

The present invention is in a first embodiment washing or

Cleaning agent containing at least one compound of the formula (I)

in the

R ¹ , R ² and R ^{3 are} independently -H, -CH ₃ , -CH ₂ -CH ₃ , - (CH ₂ ) ₂ -CH ₃ , -CH- (CH ₃ ) ₂ or - (CH ₂ ) _n -CH ₃ with n = 3, 4, 5, 6, 7, 8, 9, 10 or 11;

 X represents a hydrogen atom, a monovalent cation or the nth part of an n-valent cation.

The compounds of the formula (I) are preferably employed in the compositions according to the invention in amounts of up to 10% by weight, based in each case on the weight of the composition. preferred

Detergents or cleaning agents according to the invention are characterized in that the compound of the formula (I) is used in an amount of from 0.1 to 5% by weight, preferably from 0.2 to 3% by weight, more preferably from 0.3 to 2.5 wt .-%, even more preferably from 0.4 to 2 wt .-% and in particular from 0.5 to 1, 5 wt .-%, in each case based on the weight of the washing or cleaning agent is included.

In formula (I), X represents a hydrogen atom, a monovalent cation or the n-th part of an n-valent cation. Depending on the pH of the agent or the subsequent application liquor, the acid groups may be completely or partially neutralized. It is preferred to use the alkali metal salts of the compounds of the formula (I) in the preparation of the detergents or cleaners, the sodium salts and, among these, the trisodium salts being particularly preferred. In liquid washing or Depending on the pH, the acids (X = H) or dissociated disodium salts or monosodium salts may also be present in detergents or in the application liquor.

R ¹ , R ² and R ³ in formula (I) independently of one another represent -H, -CH ₃ , -CH ₂ -CH ₃ , - (CH ₂ ) ₂ -CH ₃ , - (CH ₃ ) ₂ or - ( CH ₂ ) _n -CH ₃ with n = 3, 4, 5, 6, 7, 8, 9, 10 or 11. Among these radicals, -H, -CH ₃ , CH ₂ -CH ₃ , - (CH ₂ ) ₂ -CH _{3 are} particularly preferred.

 Preferred representatives of the formula (I) can be described by the formulas (1-1), (I-2), (I-3) and (I-4):

in which R and R ² independently of one another are -H, -CH ₃ , -CH ₂ -CH ₃ , - (CH ₂ ) ₂ -CH ₃ , -CH- (CH ₃ ) ₂ or - (CH ₂ ) _n -CH ₃ with n = 3, 4, 5, 6, 7, 8, 9, 10 or 11 and X represents a hydrogen atom, a monovalent cation or the n-th part of an n-valent cation. Representatives derived from formula (1-1) (R ³ = H) are particularly preferred. Very particular preferred compounds of formula (I) are those derived from formula (1-1) in which R and R ² independently of one another are -H, -CH ₃ , -CH ₂ -CH ₃ , - (CH ₂ ) 2-CH ₃ , -CH- (CH ₃ ) ₂ , for example the compounds



(I-1a23), (1-1 a24),

in which X represents a hydrogen atom, a monovalent cation or the nth part of an n-valent cation.

Most preferably, R and R ² independently of one another are -H or -CH ₃ .

Detergents or cleaning agents which are extremely preferred according to the invention are characterized in that they contain, based on their weight, from 0.1 to 5% by weight, preferably from 0.2 to 3% by weight, more preferably from 0.3 to 2, 5 wt .-%, more preferably from 0.4 to 2 wt .-% and in particular from 0.5 to 1, 5 wt .-% of a compound of formula (Ia)

where X is a hydrogen atom, a monovalent cation or the nth part of an n-valent cation.

The compound of formula (Ia) is N- (1,2-dicarboxy-2-hydroxyethyl) -sarcosine (DHES) and is characterized by an effective hardness reduction in a wide pH range as well as by an increase in the cleaning performance.

Further inventively extremely preferred detergents or cleaners are characterized in that they contain, based on their weight, from 0.1 to 5% by weight, preferably from 0.2 to 3% by weight, more preferably from 0.3 to 2 , 5 wt .-%, still more preferably from 0.4 to 2 wt .-% and in particular from 0.5 to 1, 5 wt .-% of a compound of formula (Ib)

where X is a hydrogen atom, a monovalent cation or the nth part of an n-valent cation.

The compound of the formula (Ib) is N- (1,2-dicarboxy-2-hydroxyethyl) glycine (DHEG) and is distinguished by a highly effective reduction of hardness in a broad pH range and by an increase in the cleaning performance, in particular of blood. Stains off.

Further inventively extremely preferred detergents or cleaners are characterized in that they contain, based on their weight, from 0.1 to 5% by weight, preferably from 0.2 to 3% by weight, more preferably from 0.3 to 2 , 5 wt .-%, even more preferably from 0.4 to 2 wt .-% and in particular from 0.5 to 1, 5 wt .-% of a compound of formula (Ic)

where X is a hydrogen atom, a monovalent cation or the nth part of an n-valent cation.

The compound of formula (Ic) is N- (1,2-dicarboxy-2-hydroxyethyl) alanine (DHEA) and is characterized by effective hardness reduction in a wide pH range as well as by an increase in cleaning performance.

Further inventively extremely preferred detergents or cleaners are characterized in that they contain, based on their weight, from 0.1 to 5% by weight, preferably from 0.2 to 3% by weight, more preferably from 0.3 to 2 , 5 wt .-%, even more preferably from 0.4 to 2 wt .-% and in particular from 0.5 to 1, 5 wt .-% of a compound of formula (Id)

where X is a monovalent cation or the nth part of an n-valent cation.

The compound of formula (Id) is N- (1,2-dicarboxy-2-hydroxyethyl) -alpha-methylaminopropionate (DHEMAP) and is characterized by an effective hardness reduction in a wide pH range as well as an increase in the cleaning performance.

As already mentioned, it is preferred to use the alkali metal salts of the compounds of the formula (I) in the preparation of the detergents or cleaners, the sodium salts and, among these, the trisodium salts being particularly preferred. According to the invention preferred washing or

Detergents are characterized in that X ⁺ in the formulas (I), (Ia), (Ib), (Ic), (Id) is Na ⁺ .

With regard to increasing the performance of enzymes, it is preferred that the

Detergents or cleaning agents according to the invention contain an enzyme or a mixture of enzymes. Particularly suitable are those from the class of the hydrolases such as the proteases, (poly) esterases, lipases, amylases, glycosyl hydrolases, cellulases, hemicellulases, cutinases, ß-glucanases, oxidases, peroxidases, pectate lyases, mannanases, perhydrolases, Oxireduktasen and / or laccases. The amount of enzyme or of the enzymes is preferably 0.01 to 10 wt .-%, preferably 0.12 to about 3 wt .-%, based on the total washing or

Cleaning supplies. In liquid formulations, the enzymes are preferred as

Enzyme liquid formulation (s) used.

Preferred washing or cleaning agents according to the invention are characterized in that they contain at least one enzyme from the group of cellulases and / or proteases and / or amylases.

For the development of the washing performance, the washing or cleaning agents according to the invention preferably contain (a) surfactant (s), more preferably a mixture of several surfactants from different classes. The first surfactant used according to the invention is preferably at least one anionic surfactant. Suitable anionic surfactants in detergents or cleaners according to the invention are all anionic surface-active substances. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group,

 linear and branched fatty acids with 8 to 30 carbon atoms (soaps),

Ether carboxylic acids of the formula R-O- (CH 2 -CH 2 O) _x -CH 2 -COOH, in which R is a linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 16,

 Acylsarcosides having 8 to 24 carbon atoms in the acyl group,

 Acyltaurides having 8 to 24 carbon atoms in the acyl group,

 Acyl isethionates having 8 to 24 carbon atoms in the acyl group,

 Sulfosuccinic acid mono- and dialkyl esters having 8 to 24 C atoms in the alkyl group and sulfosuccinic acid monoalkylpolyoxyethyl esters having 8 to 24 C atoms in the alkyl group and 1 to 6 oxyethyl groups,

 linear alkanesulfonates having 8 to 24 C atoms,

 linear alpha-olefin sulfonates having 8 to 24 C atoms,

 Alpha-sulfofatty acid methyl esters of fatty acids having 8 to 30 carbon atoms,

Alkyl sulfates and alkyl polyglycol ether sulfates of the formula R-O (CH ₂ -CH ₂ O) _x -OSO ₃ H, in which R is a preferably linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 12,

 Mixtures of surface-active hydroxysulfonates,

sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers _T

 Sulfonates of unsaturated fatty acids having 8 to 24 carbon atoms and 1 to 6 double bonds,

 Esters of tartaric acid and citric acid with alcohols which are addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide onto fatty alcohols having 8 to 22 C atoms, alkyl and / or alkenyl ether phosphates of the formula (Tl),

O

R29 (OCH2CH2) _n - O - P - OR30 (T1)

OX in the R ^{29 is} preferably an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R ^{30 is} hydrogen, a radical (CH ₂ CH ₂ O) _n R ²⁹ or X, n is from 1 to 10 and X is hydrogen, an alkali or alkaline earth metal or NR ³ R ³² R ³³ R ³⁴ , where R ³ to R ^{34 are} independently of one another a C ¹ to C ₄ hydrocarbon radical, sulfated fatty acid alkylene glycol esters of the formula (TN)

R ³⁵ CO (AlkO) _n SO ₃ M (TN)

in the R ³⁵ CO- for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 C atoms, Alk for CH ₂ CH ₂ , CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ , n for numbers from 0.5 to 5 and M is a cation, as described in DE-OS 197 36 906.5,

 Monoglyceride sulfates and monoglyceride ether sulfates of the formula (TIN),

CH ₂ O (CH ₂ CH ₂ O) _x -COR36

 I

CHO (CH ₂ CH ₂ O) _y H (TIM)

 I

CH ₂ O (CH ₂ CH ₂ O) _z -SO ₃ X in the R ³⁶ CO for a linear or branched acyl radical having 6 to 22 carbon atoms, x, y and z in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and X is an alkali or alkaline earth metal. Typical examples of monoglyceride ether sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride,

 Coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride and their ethylene oxide adducts

 Sulfur trioxide or chlorosulfonic acid in the form of its sodium salts.

Monoglyceride sulfates of the formula (TIN) in which R ³⁶ CO is a linear acyl radical having 8 to 18 carbon atoms are preferably used.

Preferred anionic surfactants in detergents or cleaners according to the invention are

Alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and sulfosuccinic mono- and dialkyl esters having 8 to 18 carbon atoms in the alkyl group and

 Sulfosuccinic monoalkylpolyoxyethyl esters having 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups.

Preferred washing or cleaning agents according to the invention comprise at least one surfactant of the formula

R -O- (AO) _n -SO ₃ ^" X ⁺ .

In this formula, R is a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical. Preferred radicals R are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms prefers are. Particularly preferred radicals R are derived from C ₂ -C ₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or of C ₀ -C ₂₀ - oxo alcohols.

AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The index n stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8. X, stands for a monovalent cation or the nth part of an n-valent cation, preference is given to the alkali metal ions and below Na ⁺ or K ⁺ , with Na ^{+ being} extremely preferred. Other cations X + may be selected from NH ₄ ⁺ , V ₂ Zn ²⁺ , Mg ²⁺ , / Ca ²⁺ , / Mn ²⁺ , and theirs

Mixtures.

In summary, particularly preferred detergents or cleaners according to the invention comprise at least one anionic surfactant selected from fatty alcohol ether sulfates of the formula A-1

with k = 1 1 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na-Ci ₂ _i ₄

Fatty alcohol ether sulfates with 2 EO (k = 11 -13, n = 3 in formula A-1).

Preferred washing or cleaning agents according to the invention additionally comprise at least one surfactant of the formula

R ³ -A-SO ₃ ^" Y ⁺ .

In this formula, R ^{3 is} a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical and the grouping -A- for -O- or a chemical bond. In other words, sulfate (A = O) or sulfonate (A = chemical bond) surfactants can be described by the above formula. Depending on the choice of the group A, certain radicals R ^{3 are} preferred. In the sulfate surfactants (A = O), R ^{3 is} preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical. Preferred radicals R are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms are preferred. Particularly preferred radicals R are derived from C- ₂ - Ci ₈ fatty alcohols, such as coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or of Ci ₀ -C ₂₀ -oxo alcohols.

X, stands for a monovalent cation or the n-th part of an n-valent cation, preferred are the alkali metal ions and including Na ⁺ or K ⁺ , with Na ^{+ is} highly preferred. Other cations X + may be selected from NH ₄ ⁺ , V ₂ Zn ²⁺ , Mg ²⁺ , / Ca ²⁺ , / Mn ²⁺ , and mixtures thereof. Such particularly preferred surfactants are selected from fatty alcohol sulfates of the formula A-2

-S0 ₃ Na

H ₃ C ΪΓΟ ^'

 (A-2)

with k = 1 1 to 19. Very particularly preferred representatives are Na-C | ₂ -14 fatty alcohol sulfates (k = 11 -13 in formula A-2).

In the case of the sulfonate surfactants (A = chemical bond), which are preferred over the sulfate surfactants, R ^{3 is} preferably a linear or branched unsubstituted alkylaryl radical. Here, too, X is a monovalent cation or the nth part of an n-valent cation, the alkali metal ions being preferred, and Na ⁺ or K ⁺ being preferred, Na ^{+ being} extremely preferred. Other cations X + may be selected from NH ₄ ⁺ , V ₂ Zn ²⁺ , / Mg ²⁺ , / Ca ²⁺ , / Mn ²⁺ , and theirs

Mixtures.

Such highly preferred surfactants are selected from linear or branched

Alkylbenzenesulfonates of the formula A-3

in which R ^' and R ^" together contain from 9 to 19, preferably from 1 to 15, and in particular from 1 to 13, C atoms A particularly preferred representative can be described by the formula A-3a:

In addition to the anionic surfactant (s), the detergents or cleaners of the invention may contain nonionic surfactant (s). Such compounds are, for example, with a methyl or C ₂ -C ₆ - alkyl radical end-capped addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids with 8 bis 30 carbon atoms and with alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as those available under the trade names Dehydol ^® LS, LT Dehydol ^® types (Cognis),

Polyol fatty acid esters, such as the commercially available product ^® Hydagen HSP (Cognis) or Sovermol - types (Cognis), alkoxylated triglycerides,

alkoxylated fatty acid alkyl esters of the formula R ³⁷ CO- (OCH ₂ CHR ³⁸ ) _w OR ³⁹ , (TIV),

in the R ³⁷ CO for a linear or branched, saturated and / or unsaturated acyl radical

6 to 22 carbon atoms, R ^{38 is} hydrogen or methyl, R ^{39 is} linear or branched

Alkyl radicals having 1 to 4 carbon atoms and w is from 1 to 20,

 Amine oxides,

 hydroxy mixed,

 Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates,

 Sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters, addition products of ethylene oxide onto fatty acid alkanolamides and fatty amines,

 Fatty acid N-alkyl glucamides.

With particular preference, the washing or cleaning agent according to the invention contains at least one nonionic surfactant from the group of fatty alcohol ethoxylates, since these surfactants give high-performance detergents even at low washing temperatures and have excellent low-temperature stability in the case of liquid preparations.

Accordingly, preferred detergents or cleaners according to the invention additionally comprise at least one nonionic surfactant of the formula

R ² -O- (AO) _m -H,

in the

R ^{2 is} a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical,

 AO for an ethylene oxide (EO) or propylene oxide (PO) grouping,

 m stands for integers from 1 to 50.

In the abovementioned formula, R ^{2 is} a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ² are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms Atoms are preferred. Particularly preferred radicals R ² are derived from C ₂ -C ₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C ₀ -C ₂ o-oxo alcohols. AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The subscript m is an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, m is the numbers 2, 3, 4, 5, 6, 7 or 8.

In summary, particularly preferred surfactants are selected from fatty alcohol ethoxylates of the formula C-1

with k = 1 1 to 19, m = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are C _12-18 fatty alcohols with 7 EO (k = 1 1 -17, m = 7 in formula C-1).

Summarizing the above statements, washing or cleaning agents according to the invention are preferred which

i) at least one anionic surfactant of the formula R -O- (AO) _n -SO ₃ ^" X ⁺ ,

ii) at least one anionic surfactant of the formula R ³ -A-S0 ₃ ^" Y ⁺

iii) at least one nonionic surfactant of the formula R ² -O- (AO) _m -H,

contain, in which

R ¹ , R ² , R ³ independently of one another represent a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical,

 AO for an ethylene oxide (EO) or propylene oxide (PO) grouping,

 n, m for integers from 1 to 50,

 A is -O- or a chemical bond,

 X, Y independently of one another represent a monovalent cation or the nth part of an n-valent cation.

The surfactants i) and ii) have been described above as preferred surfactants a) of the formulas (A-2) and (A-3), the surfactant iii) as the preferred surfactant having the formula (C-1).

Preferred detergents or cleaners according to the invention comprise fatty alcohol ether sulfate (s), fatty alcohol ethoxylate (s) and alkyl benzene sulfonate (s). Most preferably, these are used within even narrower ranges.

Preferred detergents or cleaners contain 2 to 25% by weight, preferably 2.5 to 20% by weight, more preferably 3 to 17.5% by weight and in particular 5 to 12, based on the total amount of the detergent or cleaning agent 5% by weight of fatty alcohol ether sulfate (e). Further preferred washing or cleaning agents contain, based on the total amount of the washing or cleaning agent, 2.5 to 20 wt .-%, preferably 3 to 18 wt .-%, more preferably 3.5 to 17 wt .-%, even more preferably 4 to 15 wt .-% and in particular 5 to 10 wt .-% of surfactants from the group comprising C ₉ _i ₃ -alkylbenzenesulfonates, olefin sulfonates, Ci2-i8-alkanesulfonates ester sulfonates, alk (en) ylsulfate, and mixtures thereof.

Further preferred detergents or cleaning agents contain 1 to 15% by weight, preferably 2 to 14% by weight, more preferably 2.5 to 13% by weight, even more preferably 3 to 15, based on the total amount of the detergent or cleaning agent 10 wt .-% and in particular 3.5 to 6 wt .-%

Fatty alcohol ethoxylate (e).

Particularly preferred detergents or cleaners contain nonionic surfactants in specific amounts. Extremely preferred detergents or cleaners according to the invention are characterized in that the total amount of nonionic surfactants, based on the weight of the washing or cleaning agent, is 1 to 20% by weight, preferably 2 to 15% by weight, more preferably 2.5 to 12 , 5 wt .-%, even more preferably 3 to 11 wt .-% and in particular 4 to 10 wt .-% is.

It has proved to be advantageous for the cold washing performance if the detergents or cleaners according to the invention additionally contain soap (s). Preferred washing or cleaning agents according to the invention are characterized in that they contain, based on their weight, 0.5 to 15% by weight, preferably 1 to 12.5% by weight, more preferably 1 to 5 to 10% by weight. %, more preferably 2 to 7.5 wt .-% and in particular 2.5 to 6 wt .-% soap (s) included.

In addition, the washing or cleaning agent according to the invention may contain other ingredients that the performance and / or aesthetic properties of the washing or

Cleaner further improve. In the context of the present invention, the washing or cleaning agent preferably additionally contains one or more substances from the group of builders, bleaches, electrolytes, nonaqueous solvents, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotropes, foam inhibitors, silicone oils, antiredeposition agents, Grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives,

Corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, plasticizing components and UV absorbers.

As builders, which may be contained in the washing or cleaning agent, in particular silicates, aluminum silicates (especially zeolites), carbonates, salts of organic di- and

To name polycarboxylic acids and mixtures of these substances. Organic builders which may be present in the washing or cleaning agent are, for example, the usable in the form of their sodium salts polycarboxylic acids, wherein

Polycarboxylic acids are understood as meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

As builders further polymeric polycarboxylates are suitable. These are, for example, the

Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 600 to 750,000 g / mol.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of from 1, 000 to 15, 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1 000 to 10 000 g / mol, and particularly preferably from 1 000 to 5 000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. To improve the water solubility, the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

Soluble builders, such as, for example, citric acid, or acrylic polymers having a molar mass of from 1,000 to 5,000 g / mol are preferably used in liquid detergents or cleaners.

Preferred detergents or cleaners are liquid and preferably contain water as the main solvent. It is preferred that the washing or cleaning agent more than 5% by weight, preferably more than 15 wt .-% and particularly preferably more than 25 wt .-%, each based on the total amount of detergent or cleaning agent, water contains.

 Particularly preferred liquid detergents or cleaners according to the invention contain, based on their weight, 5 to 90% by weight, preferably 10 to 85% by weight, particularly preferably 25 to 75% by weight and in particular 35 to 65% by weight. Water.

In addition, nonaqueous solvents can be added to the washing or cleaning agent. Suitable non-aqueous solvents include mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the specified concentration range.

The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, Hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether,

Ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether,

Propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether,

Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures of these solvents. However, it is preferred that the washing or cleaning agent contains an alcohol, in particular ethanol and / or glycerol, in amounts of between 0.5 and 5 wt .-%, based on the total washing or cleaning agent.

In addition to these constituents, a liquid washing or cleaning agent may contain dispersed particles whose diameter along their greatest spatial extent is preferably 1 to 2000 μm.

For the purposes of the present invention, particles may be capsules, abrasives as well as powders, granules or compounds of compounds which are insoluble in the washing or cleaning agent, with capsules being preferred.

The term "capsule" on the one hand understood aggregates with a core-shell structure and on the other hand aggregates with a matrix. Core-shell capsules contain at least one solid or liquid core which is enclosed by at least one continuous shell, in particular a shell of polymer (s).

Inside the capsules, sensitive, chemically or physically incompatible as well as volatile components (= active ingredients) of the liquid washing or cleaning agent can be enclosed stable in storage and transport. In the capsules, for example, optical brighteners, surfactants, complexing agents, bleaching agents, bleach activators, dyes and fragrances, antioxidants, builders, enzymes, enzyme stabilizers, antimicrobial agents, grayness inhibitors,

Anti redeposition agents, pH adjusters, electrolytes, detergency boosters, vitamins, proteins,

Foam inhibitors and UV absorbers are located. The fillings of the capsules may be solids or liquids in the form of solutions or emulsions or suspensions.

The capsules may have any shape in the production-related framework, but they are preferably approximately spherical. Their diameter along their largest spatial

Expansion can be between 1 μητι and 2000 [depending on the components contained in their interior and the application. Alternatively, it is also possible to use particles which have no core-shell structure but in which the active substance is distributed in a matrix of a matrix-forming material. Such particles are also referred to as "matrix particles".

The matrix formation in these materials takes place for example via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions and is well known in the art as well as the production of particles with these matrix-forming materials. An exemplary matrix-forming material is alginate. For the production of alginate-based speckles is an aqueous alginate solution, which also includes the active ingredient or the

containing active ingredients, dripped and then cured in a Ca ²⁺ -ions or Al ³⁺ ions-containing precipitation bath. Alternatively, other, matrix-forming materials can be used instead of alginate.

The capsules can be stably dispersed in the liquid detergents or cleaners. Stable means that the detergents or cleaning agents are stable at room temperature for a period of at least 4 weeks, and preferably for at least 6 weeks, without the particles in the medium creaming or sedimenting.

The release of the active ingredients from the capsules is usually carried out by destruction of the shell or the matrix due to mechanical, thermal, chemical or enzymatic action.

In a preferred embodiment, the liquid detergents or cleaners contain capsules in which one or more fragrances are contained.

Alternatively, the particles may comprise abrasives such as plastic or calcium carbonate beads as well as powders, granules or compounds of compounds insoluble in the detergent or cleaning agent.

In a preferred embodiment of the invention, the liquid washing or contain

Detergent identical or different particles in amounts of 0.05 to 10 wt .-%, in particular 0.1 to 8 wt .-% and most preferably 0.2 to 5 wt .-%.

A further subject of the present invention relates to the use of compounds of the formula (I)

 in the

R, R ² and R ³ independently of one another are -H, -CH ₃ , -CH ₂ -CH ₃ , - (CH ₂ ) ₂ -CH ₃ , -CH- (CH ₃ ) ₂ or - (CH ₂ ) _n - CH ₃ with n = 3, 4, 5, 6, 7, 8, 9, 10 or 11;

 X represents a hydrogen atom, a monovalent cation or the n-th part of an n-valent cation,

 Improvement of stain removal.

A further subject of the present invention relates to the use of compounds of the formula (I)

 in the

R ¹ , R ² and R ^{3 are} independently -H, -CH ₃ , -CH ₂ -CH ₃ , - (CH ₂ ) ₂ -CH ₃ , -CH- (CH ₃ ) ₂ or - (CH ₂ ) _n -CH ₃ with n = 3, 4, 5, 6, 7, 8, 9, 10 or 11;

 X represents a hydrogen atom, a monovalent cation or the n-th part of an n-valent cation,

 Improvement of the removal of enzymatic soiling.

With respect to preferred embodiments of the uses according to the invention mutatis mutandis applies to the surfactant systems according to the invention and liquid washing or

Detergents said. Examples:

Example 1 Caicium binding capacity

The calcium binding capacity of the complexing agents used according to the invention was tested by adding 5 ml of a solution (1 g / l) of the complexing agent used according to the invention to 250 ml of water having a pH of 8.5 or 10 and 30 ° dH at 25 ° C. and Value was re-adjusted to 8.5 or 10 if necessary. Then, after 5 minutes using a calcium-sensitive electrode, the residual hardness of the solutions was determined.

Table 1: Residual hardness

 DHEG N- (1,2-dicarboxy-2-hydroxyethyl) glycine, Na salt

DHES: N- (1,2-dicarboxy-2-hydroxyethyl) sarcosine, Na salt

DHEA: N- (1,2-dicarboxy-2-hydroxyethyl) alanine, Na salt

IDS: iminodisuccinic acid, Na salt

 HIDS: N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid, Na salt

The results show that the calcium binding capacity of IDS is worse than that

Caicium binding capacity of the compounds used according to the invention (DHEG, DHES and DHEA). All the compounds used according to the invention achieve the Caiciumbindeabmögen of HIDS or exceed it even significantly.

Example 2: detergent formulations

Table 2 shows the liquid detergent A according to the invention in comparison with a commercial liquid detergent B without essential to the invention complexing agent: Table 2 (all data in% by weight):

 For the washing tests, household washing machines (Miele W 1514) were loaded with 3.5 kg accompanying laundry as well as soiled cloth rags. In addition, 80g / 75ml of the to be tested

 Detergent added and washed at 40 ° C. Detergent B from Table 2 was used as a reference and compared with the detergent A according to the invention, which contained 1.5% of the complexing agent used according to the invention. After hanging drying and mangling of the cloth rags their whiteness was determined spectrophotometrically (Minolta CR400-1).

The values given (Table 3) are mean values of 6 determinations. The soiled textiles were bought. Shown are the differences of the remission values to the standard detergent B and the errors in the 6-fold determination (LSD). The addition of the complexing agents leads to improvements in the washability of various stains, in particular on enzymatic but also on greasy and bleach-sensitive stains. Table 3:

Soiling difference A vs B LSD

Dust / skin fat 1, 4 1, 3

Lipstick, red 2.2 1, 6

Corn starch, colored 0.9 0.6

Full egg with pigment 3.1 2.8

Tea 0,6 0,5

Coffee 0,5

Blood 3.7 2.3

Cocoa / soot 3.3 1, 5

Chocolate cream 2.1 0.9

Claims

Patent claims:

1. Detergent or cleaning agent containing at least one compound of the formula (I)

in the

R ¹ , R ² and R ³ independently represent -H, -CH ₃ , -CH ₂ -CH ₃ , -(CH ₂ ) ₂ -CH ₃ , -CH-(CH ₃ ) ₂ or -(CH ₂ ) _n -CH ₃ with n = 3, 4, 5, 6, 7, 8, 9, 10 or 11;

X represents a hydrogen atom, a monovalent cation or the nth part of an n-valent cation.

2. Washing or cleaning agent according to claim 1, characterized in that the compound of formula (I) in an amount of 0.1 to 5% by weight, preferably from 0.2 to 3% by weight, more preferably of 0.3 to 2.5% by weight, even more preferably from 0.4 to 2% by weight and in particular from 0.5 to 1.5% by weight, in each case based on the weight of the detergent or cleaning agent is included.

3. Washing or cleaning agent according to one of claims 1 or 2, characterized in that it - based on its weight - 0.1 to 5% by weight, preferably from 0.2 to 3% by weight, more preferably from 0.3 to 2.5% by weight, even more preferably from 0.4 to 2% by weight and in particular from 0.5 to 1.5% by weight of a compound of the formula (la).

in which X represents a hydrogen atom, a monovalent cation or the nth part of an n-valent cation.

4. Washing or cleaning agent according to one of claims 1 to 3, characterized in that it - based on its weight - 0.1 to 5% by weight, preferably from 0.2 to 3% by weight, further preferably from 0.3 to 2.5% by weight, even more preferably from 0.4 to 2% by weight and in particular from 0.5 to 1.5% by weight of a compound of the formula (Ib).

in which X represents a hydrogen atom, a monovalent cation or the nth part of an n-valent cation.

5. Washing or cleaning agent according to one of claims 1 to 4, characterized in that it - based on its weight - 0.1 to 5% by weight, preferably from 0.2 to 3% by weight, more preferably from 0.3 to 2.5% by weight, even more preferably from 0.4 to 2% by weight and in particular from 0.5 to 1.5% by weight of a compound of the formula (Ic).

in which X represents a hydrogen atom, a monovalent cation or the nth part of an n-valent cation.

6. Washing or cleaning agent according to one of claims 1 to 5, characterized in that it - based on its weight - 0.1 to 5% by weight, preferably from 0.2 to 3% by weight, more preferably from 0.3 to 2.5% by weight, even more preferably from 0.4 to 2% by weight and in particular from 0.5 to 1.5% by weight of a compound of the formula (Id).

in which X represents a monovalent cation or the nth part of an n-valent cation. Detergent or cleaning agent according to one of claims 1 to 6, characterized in that X ⁺ in the formulas (I), (la), (Ib), (Ic), (Id) represents Na ⁺ .

Detergent or cleaning agent according to one of claims 1 to 7, characterized in that it contains at least one enzyme from the group of cellulases and/or proteases and/or amylases.

Use of compounds of formula (I)

in the

R ¹ , R ² and R ³ independently represent -H, -CH ₃ , -CH ₂ -CH ₃ , -(CH ₂ ) ₂ -CH ₃ , -CH-(CH ₃ ) ₂ or -(CH ₂ ) _n -CH ₃ with n = 3, 4, 5, 6,

7,

8th,

9, 10 or 11 stand;

X represents a hydrogen atom, a monovalent cation or the nth part of an n-valent cation,

to improve stain removal.

10. Use of compounds of formula (I)

in the

R ¹ , R ² and R ³ independently represent -H, -CH ₃ , -CH ₂ -CH ₃ , -(CH ₂ ) ₂ -CH ₃ , -CH-(CH ₃ ) ₂ or -(CH ₂ ) _n -CH ₃ with n = 3, 4, 5, 6, 7, 8, 9, 10 or 11;

X represents a hydrogen atom, a monovalent cation or the nth part of an n-valent cation,

to improve the removal of enzymatic soiling.