EP0891411B1 - Washing power enhancer for detergents - Google Patents

Description

The invention relates to the use of amines and their reaction products and condensation products with acids as detergent boosters, and detergents containing them.

DE-A1-31 24 210 describes liquid detergents with additives for preventing dye transfer. The detergent contains nonionic or zwitterionic surfactants in combination with polyethylene, amines, polyamines, polyamine amides or polyacrylamides, which counteracts a dye transfer from colored textiles to white or light-colored textiles during washing together. The polyaminamides are accessible by condensation of polybasic acids such as dibasic, saturated, aliphatic C _3-8 acids and polyamines. The polymers are described as water-soluble, but are not identified more precisely.

In DE-A1-32 11 532 there are agents for washing and gentle on the color Bleaching textiles described. The detergents contain nonionic Surfactants, optionally with zwitterionic surfactants, bleaching compounds, and additives for protecting dyed textiles from color changes Are polyethyleneimines, polyamines, polyaminamides or polyacrylamides. This Compounds are described as water-soluble, but not in more detail specified.

DE-A-1 922 450 describes washing and cleaning agents which Graying inhibitors to prevent absorption of detached Contain dirt on the cleaned surfaces. As a graying inhibitor polyamides are used, which consist of polyethyleneimines with a medium Molecular weight from 300 to 6,000 and di- and tricarboxylic acids can be produced are. Also reaction products with diglycolic acid, thiodiglycolic acid, aminodiacetic acid and nitrilotriacetic acid are mentioned.

DE-A-2 165 900 describes detergents containing anti-graying additives. The reaction product of a polyethyleneimine with a molecular weight of 430 to 10,000 with C _8-18 alkyl glycidyl ethers is used as a graying inhibitor, which can also be reacted with ethylene oxide.

EP-A-0 411 436 describes the use of 2-hydroxy-3-aminopropionic acid derivatives as complexing agents, bleach stabilizers and builders described in detergents and cleaning agents. The propionic acid derivatives can include Have polyvinylamine residues or polyethyleneimine residues.

In P.F. Kikolski, Comun. Journ. Com. Esp. Deterg. 23 (1992) 332-333, is the use of rapeseed oil fatty amine as a detergency booster Removal of grease particle dirt described.

From WO 95/33035 detergent compositions are known which Contain oleoyl sarcosinate and a surfactant amine and especially for removal of greasy or oily soiling are effective. As Amines are preferably primary and tertiary amines. Also secondary amines with two long chain alkyl groups are disclosed.

WO 86/07603 relates to ether amines which differ from primary amines by ethoxylation derived, or amidoamines, which are characterized by one-sided amidation of alkylenediamines deduce. The primary ones derivatized with ethylene oxide or fatty acids and secondary amines are used to increase washing power.

DE-A-42 25 620 relates to reaction products from polybasic carboxylic acids and compounds containing amino groups and their use in Detergents and cleaning agents. In particular, Polyethyleneimines with Citric acid and similar acids implemented. They are called incrustation inhibitors used in detergents.

DE-A-27 00 640 relates to detergents suitable for cold washing. The textile detergent contain in addition to a surfactant a hydroxyalkylamine, the further May contain ethylene oxide attached. The connection calls especially in the cold wash liquor an effective increase in washing power.

AU-A-17 813 relates to particulate detergent compositions containing a Contain polyethyleneimine with a molecular weight of less than 1000. The polyethyleneimine is not described in detail. It is used as a polymeric chlorine scavenger used.

WO 97/32480, prior art according to Art. 54 (3) and Art. 158 EPC, relates to a Methods of killing or inhibiting microbial cells. In doing so Polyvinylamines, polyethyleneimines and derived polymers as antimicrobial Funds used. You can, for example, in detergent compositions be used.

An object of the present invention is to provide detergent boosters for Provide detergent.

Another job is to improve detergent boosters Dirt detachment, especially with soiling, which is a combination from fatty or oily and pigment or particulate constituents' included to provide.

Another task is to use detergents containing detergent boosters to provide.

Another job is to add detergent boosters for reduced phosphates or to provide phosphate-free detergents.

(a1) Aminen der allgemeinen Formel (I) RR'N-[-(CR^1'R^2')_x-NR^3'-]_a-[-(CR^4'R^5')_y-NR^6'-]_b-R"

wobei die Reste R, R' und R", R^1', R²', R^4' und R⁵' unabhängig voneinander Wasserstoffatome, lineare oder verzweigtkettige C_1-20-Alkyl-, -(Alkyl)carboxy-, -Alkyl-aminoreste, C_2-20-Alkenylreste oder C_6-20-Aryl-, -Aryloxy-, -Hydroxyaryl-, -Arylcarboxy- oder -Arylaminoreste sind,

die Reste R³' und R⁶' unabhängig voneinander Wasserstoffatome, lineare oder verzweigtkettige C_1-20-Alkylreste, C_6-20-Arylreste, oder Reste [(CR^7'R^8')_z-NR^9']_c-R¹⁰' sind,

wobei die Reste R^7', R^8', R^9' und R¹⁰' unabhängig voneinander wie vorstehend für R, R', R", R^1', R²', R^4', R⁵' definiert sind, x, y und z unabhängig voneinander einen Wert von 2, 3 oder 4 aufweisen und a, b und c unabhängig voneinander einen ganzzahligen Wert von 0 - 300 aufweisen, mit Ausnahme von Mono- und Diarninen, wobei Polyethylenimine durch Teilmodifizierung mit Benzolsäure hydrophobiert sein können,

(a2) Aminen der allgemeinen Formel (II) (R¹R¹)N-X-N(R¹R¹)

wobei die Reste R¹ Reste (R²R²)N-(CH₂)_n- sind,

die Reste R² Wasserstoffatome sind oder Reste (R³R³)N-(CH₂)_n-,

die Reste R³ Wasserstoffatome sind oder Reste (R⁴R⁴)N-(CH₂)_n-,

die Reste R⁴ Wasserstoffatome sind oder Reste (R⁵R⁵)N-(CH₂)_n-,

die Reste R⁵ Wasserstoffatome sind oder Reste (R⁶R⁶)N-(CH₂)_n-,

die Reste R⁶ Wasserstoffatome sind,

n einen Wert von 2, 3 oder 4 hat und der Rest X einer der Reste

-(CH₂)_n-, -(CH₂)₃-NR¹¹-(CH₂)₃-,
C_2-20-Alkylen,

der Rest Y ein Sauerstoffatom, ein Rest CR⁷R⁹C=O oder SO₂ ist,

n einen ganzzahligen Wert von 2 - 20 hat,

die Reste R⁷, R⁸, R⁹ und R¹⁰ unabhängig voneinander Wasserstoffatome oder C_1-6-Alkylreste sind

und der Rest R¹¹ ein C_1-20-Alkylrest, C_2-20-Dialkylamino-C_2-10-alkylrest, C_1-10-Alkoxy-C_2-10-alkylrest, C_2-20-Hydroxyalkylrest, C_7-20-Aralkylrest ist oder zwei Reste R¹¹ gemeinsam eine gegebenenfalls durch Stickstoff oder Sauerstoff unterbrochene Alkylenkette ergeben, wie Ethylenoxid, Propylenoxid, Butylenoxid und -CH₂-CH(CH₃)-O- oder Polyisobutylen mit 1 bis 100 iso-Butyleneinheiten,

(a3) Polymeren, die Wiederholungseinheiten entsprechend der nachstehenden Formel enthalten -[CH₂-CH(NH₂)]-, erhalten durch zumindest teilweise Verseifung von Oligo/Polyvinylformamiden sowie Copolymeren des Vinylformamids,
wobei 5 - 100% der Stickstoffatome in primären oder sekundären Aminogruppen vorliegen
sowie durch die Amine (a2) enthaltende Waschmittel.

These objects are achieved by the use of an amine with an average _pK a of 1 to 14 as detergency booster, preferably in textile detergents, in particular in color detergents, wherein the amine is selected from

(a1) amines of the general formula (I) RR'N - [- (CR ^{1 '} R ^2' ) _x -NR ^{3 '} -] _a - [- (CR ^4' R ^{5 '} ) _y -NR ^6' -] _b -R "

where the radicals R, R 'and R ", R ^1' , R ² ', R ^4' and R ⁵ 'independently of one another are hydrogen atoms, linear or branched chain C _1-20 -alkyl-, - (alkyl) carboxy-, -alkyl amino residues, C _2-20 alkenyl residues or C _6-20 aryl, aryloxy, hydroxyaryl, arylcarboxy or arylamino residues,

the radicals R ³ 'and R ⁶ ' independently of one another are hydrogen atoms, linear or branched-chain C _1-20 alkyl radicals, C _6-20 aryl radicals, or radicals [(CR ^{7 '} R ^8' ) _z -NR ^{9 '} ] _c -R ¹⁰ 'are

the radicals R ^{7 '} , R ^8' , R ^{9 '} and R ¹⁰ ' independently of one another as defined above for R, R ', R ", R ^1' , R ² ', R ^4' , R ⁵ ', x , y and z independently of one another have a value of 2, 3 or 4 and a, b and c independently of one another have an integer value of 0-300, with the exception of mono- and diarnines, where polyethyleneimines can be rendered hydrophobic by partial modification with benzene acid,

(a2) amines of the general formula (II) (R ¹ R ¹ ) NXN (R ¹ R ¹ )

where the R ¹ radicals are (R ² R ² ) N- (CH ₂ ) _n -,

the radicals R ^{2 are} hydrogen atoms or radicals (R ³ R ³ ) N- (CH ₂ ) _n -,

the radicals R ^{3 are} hydrogen atoms or radicals (R ⁴ R ⁴ ) N- (CH ₂ ) _n -,

the radicals R ^{4 are} hydrogen atoms or radicals (R ⁵ R ⁵ ) N- (CH ₂ ) _n -,

the radicals R ^{5 are} hydrogen atoms or radicals (R ⁶ R ⁶ ) N- (CH ₂ ) _n -,

the radicals R ^{6 are} hydrogen atoms,

n has a value of 2, 3 or 4 and the radical X is one of the radicals

- (CH ₂ ) _n -, - (CH ₂ ) ₃ -NR ¹¹ - (CH ₂ ) ₃ -,
C _2-20 alkylene,

the radical Y is an oxygen atom, a radical CR ⁷ R ⁹ C = O or SO ₂ ,

n has an integer value from 2 - 20,

the radicals R ⁷ , R ⁸ , R ⁹ and R ^{10 are} independently hydrogen atoms or C _1-6 alkyl radicals

and the radical R ^{11 is} a C _1-20 -alkyl radical, C _2-20 -dialkylamino-C _2-10 -alkyl radical, C _1-10 -alkoxy-C _2-10 -alkyl radical, C _2-20 -hydroxyalkyl radical, C _{7 -20} -aralkyl radical, or two radicals R ¹¹ together give a optionally interrupted by nitrogen or oxygen, alkylene such as ethylene oxide, propylene oxide, butylene oxide and -CH ₂ -CH (CH ₃₎ -O- or polyisobutylene having 1 to 100 iso-butylene,

(a3) Polymers containing repeating units according to the formula below - [CH ₂ -CH (NH ₂ )] -, obtained by at least partially saponifying oligo / polyvinylformamides and copolymers of vinylformamide,
where 5 - 100% of the nitrogen atoms are present in primary or secondary amino groups
and detergents containing amines (a2).

As described above, the use of certain polyethyleneimines, Polyamines and polyamides as graying inhibitors or agents against Color transfer known from the prior art.

In addition, modified with ethylene oxide and / or fatty acid residues have been determined Polyalkylene polyamines are used as detergent additives.

It has been found that certain amines and polyalkylene polyamines which are not modified with ethylene oxide and, if appropriate, fatty acid residues have a washing-strengthening effect. Addition of small amounts of unmodified or only partially modified amines or polyalkylene polyamines
Modern detergent and cleaning agent formulations significantly improve their washing power, particularly with regard to problematic soiling, which contain a combination of fatty or oily and pigment or particulate constituents. The amines according to the invention are used particularly advantageously in color textile detergents as detergency boosters. By using the amines according to the invention, the dirt detachability of the color detergents, which is more restricted than that of full detergents, can be significantly improved.

• Bessere Wirksamkeit bei gleicher Einsatzmenge,
• Verbesserung des Schmutzablösevermögens von Colortextilwaschmitteln,
• Verbesserung des Schmutzablösevermögens bei Öl/Partikel- bzw. Fett/ Partikel-Anschmutzungen auf baumwollhaltigen Geweben.

The amines according to the invention are particularly preferably used as detergency boosters in relation to oil / particle or fat / particle stains on cotton and cotton-containing blended fabrics. Compared to known detergent boosters, the detergent boosters according to the invention have the following advantages:

• Better effectiveness with the same amount used,
• Improvement of the dirt release ability of color textile detergents,
• Improvement of the dirt release ability with oil / particle or grease / particle soiling on cotton-containing fabrics.

Examples of such soiling are used motor oil, lipstick, Makeup, shoe polish, clay / oil mixture, etc.

Amines

According to the invention, the following amines as detergency booster, preferably in textile detergents Color used which have an average _pK a of 1 to 14, preferably 2 to 13, especially 5 to 12.5, having. The pK _s value means the value of the corresponding acid of the amine, ie the protonated amine, and is equal to 14-pK _{B of} the amine. The mean pK _s value is defined by half of the total acid consumption in the amine titration.

wobei die Reste R, R' und R", R¹', R²', R^4' und R⁵' unabhängig voneinander Wasserstoffatome, lineare oder verzweigtkettige C_1-20-Alkyl-, -(Alkyl)carboxy-, -Alkylaminoreste, C_2-20-Alkenylrest oder C_6-20-Aryl-, -Aryloxy-, -Hydroxyaryl-, -Arylcarboxy- oder -Arylamino- reste sind,

die Reste R³' und R⁶' unabhängig voneinander Wasserstoffatome, linear oder verzweigtkettige C_1-20-Alkylreste, C_6-20-Arylreste, oder Reste [(CR^7'R^8')_z-NR^9']_c-R^10' sind,

wobei die Reste R⁷', R^8', R⁹' und R¹⁰' unabhängig voneinander wie vorstehend für R, R', R", R^1', R²', R^4', R^5' definiert sind oder Carboxymethyl-, Carboxyethyl-, Phosphonomethyl- oder Carboxamidoethylreste sind,

x, y und z unabhängig voneinander einen Wert von 2, 3 oder 4 aufweisen und a, b und c unabhängig voneinander einen ganzzanligen Wert von 0-300 aufweisen, mit Ausnahme von Mono- und Diaminen, wobei Polyethylenimine durch Teilmodifizierung mit Benzoesäure hydrophobiert sein können.

According to one embodiment of the invention, the amine is selected from amines of the general formula (I) RR'N - [- (CR ^{1 '} R ^2' ) _x -NR ^{3 '} -] _a - [- (CR ^4' R ^{5 '} ) _y -NR ^6' -] _b -R "

where the radicals R, R 'and R ", R ¹ ', R ² ', R ^4' and R ⁵ 'independently of one another are hydrogen atoms, linear or branched chain C _1-20 alkyl, - (alkyl) carboxy, alkyl alcohol radicals Are C _2-20 alkenyl or C _6-20 aryl, aryloxy, hydroxyaryl, arylcarboxy or arylamino,

the radicals R ³ 'and R ⁶ ' independently of one another are hydrogen atoms, linear or branched-chain C _1-20 alkyl radicals, C _6-20 aryl radicals, or radicals [(CR ^{7 '} R ^8' ) _z -NR ^{9 '} ] _c -R ^{10 '} are

the radicals R ⁷ ', R ^8' , R ⁹ 'and R ¹⁰ ' independently of one another as defined above for R, R ', R ", R ^1' , R ² ', R ^4' , R ^{5 '} or carboxymethyl -, carboxyethyl, phosphonomethyl or carboxamidoethyl radicals,

x, y and z independently of one another have a value of 2, 3 or 4 and a, b and c independently of one another have an integer value of 0-300, with the exception of mono- and diamines, where polyethyleneimines can be rendered hydrophobic by partial modification with benzoic acid .

The above amines are 5 to 100%, in particular 10 to 95% of the nitrogen atoms in primary or secondary amino groups in front.

According to one embodiment of the invention, the above amines a number average molecular weight of 80 to 150,000, preferably 100 to 50,000, particularly preferably 110 to 10,000, in particular 129 to 5,000 on.

According to the invention it was found that the effectiveness of the amines as Detergent booster at lower molecular weights (up to about number average 2,500) is significantly better than that of amines or polyalkylene polyamines with higher molecular weights.

The amines used according to the invention should preferably have a molecular geometry which allows them to be in voids of textiles Penetrate fabrics while washing and displace dirt sitting there and thus detach.

The amine or polyalkylene polyamine according to general formula (I) can be a Block polymer or block copolymer, or according to one embodiment of the invention a polymer with randomly distributed blocks or an overall statistically distributed polymer.

Polymers which contain repeating units corresponding to the following formula can also be used according to the invention: - [CH ₂ -CH (NH ₂ )] -

These include in particular oligo / polyvinylformamides and copolymers of To understand vinylformamids, their formamide groups at least 5 - 100 mol%, converted into amino groups by saponification are. Oligo / polyvinylformamides whose Formamide groups to 20-100 mol%, in particular 40-100 mol%, by Saponification are converted into amino groups. The saponification can be both done in alkaline as well as in acidic medium.

According to one embodiment of the invention, these polymers have Number average molecular weight of 80 to 150,000, preferably 100 to 50,000, particularly preferably 110 to 10,000, in particular 129 to 5,000.

The preparation of the amines or polyamines used according to the invention takes place according to known methods.

wobei die Reste R¹ Reste (R²R²)N-(CH₂)_n- sind,

die Reste R² Wasserstoffatome sind oder Reste (R³R³)N-(CH₂)_n-,

die Reste R³ Wasserstoffatome sind oder Reste (R⁴R⁴)N-(CH₂)_n-,

die Reste R⁴ Wasserstoffatome sind oder Reste (R⁵R⁵)N-(CH₂)_n-,

die Reste R⁵ Wasserstoffatome sind oder Reste (R⁶R⁶)N-(CH₂)_n-,

die Reste R⁶ Wasserstoffatome sind,

n einen Wert von 2, 3 oder 4 hat und

der Rest X einer der Reste

-(CH₂)_n-, -(CH₂)₃-NR¹¹-(CH₂)₃-,
C_2-20-Alkylen,

der Rest Y ein Sauerstoffatom, ein Rest CR⁷R⁹CßO oder SO₂ ist,

n einen ganzzahligen Wert von 2 - 20 hat,

die Reste R⁷, R⁸, R⁹ und R¹⁰ unabhängig voneinander Wasserstoffatome oder C_1-6-Alkylreste sind

und der Rest R¹¹ ein C_1-20-Alkylrest, C_2-20-Dialkylamino-C_2-10-alkylrest, C_{1- 10}-Alkoxy-C_2-10-alkylrest, C_2-20-Hydroxyalkylrest, C_3-12-Cycloalkylrest, C_4-20-Cycloalkyl-alkylrest, C_2-20-Alkenylrest, C_4-30-Dialkylaminoalkenylrest, C_3-30-Alkoxy-alkenylrest, C_3-20-Hydroxyalkenylrest, C_5-20-Cycloalkyl-alkenylrest, ein gegebenenfalls durch C_1-8-Alkylrest, C_2-8-Dialkylaminorest, C_1-8-Alkoxyrest, Hydroxylrest, C_3-8-Cycloalkylrest, C_4-12-Cycloalkyl-alkylrest, ein-bis fünffach substituierter Arylrest oder C_7-20-Aralkylrest ist oder zwei Reste R¹¹ gemeinsam eine gegebenenfalls durch Stickstoff oder Sauerstoff unterbrochene Alkylenkette ergeben, wie Ethylenoxid, Propylenoxid, Butylenoxid und -CH₂-CH(CH₃)-O- oder Polyisobutylen mit 1 bis 100 iso-Butyleneinheiten,

wobei 5 - 100% der Stickstoffatome in primären oder sekundären Aminogruppen vorliegen.

According to one embodiment of the invention, the amine is selected from amines of the general formula (II) (R ¹ R ¹ ) NXN (R ¹ R ¹ )

where the R ¹ radicals are (R ² R ² ) N- (CH ₂ ) _n -,

the radicals R ^{2 are} hydrogen atoms or radicals (R ³ R ³ ) N- (CH ₂ ) _n -,

the radicals R ^{3 are} hydrogen atoms or radicals (R ⁴ R ⁴ ) N- (CH ₂ ) _n -,

the radicals R ^{4 are} hydrogen atoms or radicals (R ⁵ R ⁵ ) N- (CH ₂ ) _n -,

the radicals R ^{5 are} hydrogen atoms or radicals (R ⁶ R ⁶ ) N- (CH ₂ ) _n -,

the radicals R ^{6 are} hydrogen atoms,

n has a value of 2, 3 or 4 and

the residue X is one of the residues

- (CH ₂ ) _n -, - (CH ₂ ) ₃ -NR ¹¹ - (CH ₂ ) ₃ -,
C _2-20 alkylene,

the radical Y is an oxygen atom, a radical CR ⁷ R ⁹ CßO or SO ₂ ,

n has an integer value from 2 - 20,

the radicals R ⁷ , R ⁸ , R ⁹ and R ^{10 are} independently hydrogen atoms or C _1-6 alkyl radicals

and the radical R ¹¹ is a C _1-20 alkyl, C _2-20 -dialkylamino-C _2-10 alkyl, C _1- C ₁₀ alkoxy-alkyl group _2-10, C _2-20 hydroxyalkyl, C _{3 -12-} cycloalkyl, C _4-20 -cycloalkyl-alkyl, C _2-20- alkenyl, C _4-30 -dialkylaminoalkenyl, C _3-30 -alkoxy-alkenyl, C _3-20 -hydroxyalkenyl, C _5-20 -cycloalkyl -alkenyl, optionally substituted by C _1-8 -alkyl, C _2-8 -dialkylamino, C _1-8 -alkoxy, hydroxyl, C _3-8 -cycloalkyl, C _4-12 -cycloalkyl-alkyl, mono- to pentasubstituted Aryl radical or C _7-20 aralkyl radical or two radicals R ¹¹ together form an alkylene chain which may be interrupted by nitrogen or oxygen, such as ethylene oxide, propylene oxide, butylene oxide and -CH ₂ -CH (CH ₃ ) -O- or polyisobutylene with 1 to 100 iso-butylene units,

where 5 - 100% of the nitrogen atoms are present in primary or secondary amino groups.

The amines according to general formula (II) are preferably prepared according to the method described in WO 96/15097.

They are preferably prepared from diamines of the general formula NH ₂ - (CH ₂ ) _n -NH ₂ , in which n has an integer value from 2 to 20. Examples of suitable such diamines are 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and 1,6-hexamethylenediamine. Primary tetraaminoalkylalkylenediamines are also preferably used, such as N, N, N ', N'-tetra-aminopropyl-1,2-ethylenediamine, N, N, N', N'-tetraaminopropyl-1,3-propylenediamine, N, N, N ', N'-tetraaminopropyl-1,4-butylene diamine and N, N, N', N'-tetraaminopropyl-1,6-hexamethylene diamine.

The radicals R ⁷ , R ⁸ , R ⁹ , R ^{10 of} the general formula II are C _1-6 alkyl radicals, preferably C _1-3 alkyl radicals, such as methyl, ethyl, n-propyl and iso-propyl radicals , particularly preferably methyl and ethyl radicals, in particular methyl radicals, or preferably hydrogen, the radicals R ⁷ and R ⁸ or R ⁹ and R ¹⁰ preferably being the same.

Examples of radicals R ¹¹ according to the invention are C _1-20 alkyl radicals, preferably C _1-12 alkyl radicals, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec .-Butyl-, tert-butyl-, n-pentyl-, iso-pentyl-, sec-pentyl-, neo-pentyl-, 1,2-dimethylpropyl-, n-hexyl-, iso-hexyl-, sec- Hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, n-nonyl, iso-nonyl, n-decyl, iso-decyl, n-undecyl, iso- Undecyl, n-dodecyl and iso-dodecyl radicals, particularly preferably C _1-4 alkyl radicals, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec. Butyl and tert-butyl residues, aryl residues, such as phenyl, 1-naphthyl and 2-naphthyl residues, preferably phenyl residues, C _7-20 aralkyl residues, preferably C _7-12 phenylalkyl residues, such as benzyl, 1-phenethyl , 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl radicals, particularly preferably benzyl, 1-phenethyl and 2 -Phenethyl radicals, C _7-20 -alkylaryl radicals, preferably C _7-12 -alk ylphenyl radicals, such as 2-methylphenyl, 2-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5- Dimethylphenyl, 2,3,4-trimethylphenyl, 2,3,4,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-tri-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2-i-propylphenyl, 3-n-propylphenyl and 4-n-propylphenyl radicals or polyisobutylene radicals with 1-100, preferably 1-70, particularly preferably 1-50 iso- Butylene units.

Preferred examples of amines (II) according to the invention, which are also known as dendrimers Amines, or their precursors, are N, N, N ', N'-tetra-aminopropylethylenediamine, hereinafter referred to as N6 amine, and the it can be produced by aminopropylation, according to the number of its N atoms designated dendrimeric amines such as N14, N30, N62 and N128 amine from BASF AG. These amines have an ethylenediamine backbone whose hydrogen atoms on the nitrogen are left by amino (n-propyl) are substituted. The terminal amino groups can in turn be substituted by corresponding aminopropyl groups (N14-amine), etc. Production processes for these amines are described in WO 96/15097, starting from ethylenediamine. Also preferred examples of this invention Amines are corresponding N-amines, as described in WO 93/14147 are described, starting from butylenediamine instead of as above described are made from ethylenediamine. Such amines are from the company DSM manufactured and distributed.

Preferred amines of the general formula (I) are also polyethyleneimines, such as Polyethyleniminhomopolymerisate with a degree of polymerization n of 5, 6, 10, 20, 35 and 100. These polyethyleneimine homopolymers can either be water-based or water-free or dewatered become. The synthesis of corresponding polyethyleneimines is in the examples described.

wobei die Reste R¹¹, R¹² und R¹³ unabhängig voneinander Wasserstoffatome, C_1-20-Alkylreste C_2-20-Alkenylreste oder C_6-20-Arylreste sind,

der Rest R¹⁴ ein Wasserstoffatom ist oder ein Rest -(CH₂)_o-[NH-(CH₂)_m-]_p-NH₂ oder ein Hydroxyalkyl- oder Alkoxyrest ist,

wobei x einen ganzzahligen Wert von 1-10 hat,

m einen ganzzahligen Wert von 2-4 hat,

o einen ganzzahligen Wert von 2-4 hat, und

p einen ganzzahligen Wert von 0-10 hat, mit Ausnahme von Diaminen.

The polyethyleneimines can also be partially modified, such as, for example, hydrophobized with benzoic acid according to one embodiment of the invention.
Amines of the general formula (I) preferred according to the invention are also polyamines of the formula below R ¹¹ R ¹² N - [- (CH ₂ ) _m -NR ¹³ ] _x -R ¹⁴

where the radicals R ¹¹ , R ¹² and R ^{13 are,} independently of one another, hydrogen atoms, C _1-20 alkyl radicals, C _2-20 alkenyl radicals or C _6-20 aryl radicals,

the radical R ^{14 is} a hydrogen atom or a radical - (CH ₂ ) _o - [NH- (CH ₂ ) _m -] _p -NH ₂ or a hydroxyalkyl or alkoxy radical,

where x is an integer from 1-10,

m has an integer value of 2-4,

o has an integer value of 2-4, and

p has an integer value of 0-10, with the exception of diamines.

wobei die Reste R und R' unabhängig voneinander C_1-20-Alkylreste, C_2-20-Alkenylreste oder C_6-20-Arylreste sind,

m den Wert 2,3 oder 4 hat, und

x einen ganzzahligen Wert von 1-10 hat, mit Ausnahme von Diaminen, H₂N-(CH₂)₄-NR¹⁵-(CH₂)₄-NH₂

wobei der Rest R¹⁵ ein Wasserstoffatom oder ein C_1-20-Alkylrest, C_2-20-Alkenylrest oder C_6-20-Arylrest ist, H₂N-[-(CH₂)_mNH]_x-(CH₂)_o-[NH-(CH₂)_m-]_p-NH₂

wobei m den Wert 2,3 oder 4 hat,

o den Wert 2,3 oder 4 hat,

x einen ganzzahligen Wert von 0-10 hat,

p einen ganzzahligen Wert von 0-10 hat, und

die Summe von x und p ≥1 ist.

The following amines of the general formula (I) are particularly preferred H ₂ N - [- (CH ₂ ) _m NH] _x -H where m is 2, 3 or 4 and x is an integer from 1-10, with the exception of diamines RR'N - [- (CH ₂ ) _m -NH] _x -H

where the radicals R and R 'are, independently of one another, C _1-20 alkyl radicals, C _2-20 alkenyl radicals or C _6-20 aryl radicals,

m has the value 2, 3 or 4, and

x has an integer value of 1-10, with the exception of diamines, H ₂ N- (CH ₂ ) ₄ -NR ¹⁵ - (CH ₂ ) ₄ -NH ₂

where the radical R ^{15 is} a hydrogen atom or a C _1-20 alkyl radical, C _2-20 alkenyl radical or C _6-20 aryl radical, H ₂ N - [- (CH ₂ ) _m NH] _x - (CH ₂ ) _o - [NH- (CH ₂ ) _m -] _p- NH ₂

where m has the value 2, 3 or 4,

o has the value 2, 3 or 4,

x has an integer value of 0-10,

p has an integer value of 0-10, and

is the sum of x and p ≥1.

Particularly preferred amines are N, N'-bisaminopropylalkylenediamines (m = 3, o = 4-20, x = p = 1) such as N, N'-bisaminopropyl-1,6-hexamethylene diamine or N, N'-bisaminopropyl-1, 8-octamethylenediamine.

Detergent formulations

It has been found that the addition of small amounts of the invention Amines, especially polyalkylene polyamines, to a modern color or Heavy duty detergent formulation clearly shows its dirt-removing properties improved. These compounds act as detergent boosters.

The invention also relates to detergents containing at least one surfactant and at least one amine (a2) of the general formula described above,
and any other usual ingredients.

According to the invention, these detergents can be used for cleaning textiles be used.

The usual constituents of the detergents according to the invention include Builders, surfactants, bleaches, enzymes and other ingredients like them are described below.

Builder

Suitable for combination with the (polyalkylene poly) amines according to the invention inorganic builders (A) are mainly crystalline or amorphous Alumosilicates with ion-exchanging properties such as zeolites in particular. Different types of zeolites are suitable, especially zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na partially exchanged for other cations such as Li, K, Ca, Mg or ammonium is. Suitable zeolites are described, for example, in EP-A 038591, EP-A 021491, EP-A 087035, US 4604224, GB-A 2013259, EP-A 522726, EP-A 384070 and WO 94/24251.

Suitable crystalline silicates (A) are, for example, disilicates or layered silicates, e.g. B. SKS-6 (manufacturer: Hoechst). The silicates can be in the form their alkali metal, alkaline earth metal or ammonium salts are used, preferably as Na, Li and Mg silicates.

Amorphous silicates such as sodium metasilicate, which is a polymer Has structure, or Britesil® H20 (manufacturer: Akzo) are also usable.

Suitable carbonate-based inorganic builder substances are carbonates and hydrogen carbonates. These can be in the form of their alkali metal, alkaline earth metal or ammonium salts can be used. Preferably Na, Li and Mg carbonates or bicarbonates, especially sodium carbonate and / or sodium bicarbonate used.

Common phosphates as inorganic builders are polyphosphates such as pentasodium triphosphate.

The components (A) mentioned can be used individually or in mixtures with one another be used. Of particular interest is inorganic Builder component is a mixture of aluminosilicate and carbonate, in particular from zeolites, especially zeolite A, and alkali metal carbonates, especially sodium carbonate, in a weight ratio of 98: 2 to 20:80, in particular from 85:15 to 40:60. In addition to this mixture, others can Components (A) are present.

In a preferred embodiment, the textile detergent formulation according to the invention contains 0.1 to 20% by weight, in particular 1 to 12% by weight organic cobuilders (B) in the form of low molecular weight, oligomeric or polymeric carboxylic acids, especially polycarboxylic acids, or Phosphonic acids or their salts, especially Na or K salts.

C₄- bis C₂₀-Di-, -Tri- und -Tetracarbonsäuren, wie Bernsteinsäure, Propantricarbonsäure, Butantetracarbonsäure, Cyclopentantetracarbonsäure und Alkyl- und Alkenylbernsteinsäuren mit C₂- bis C₁₆-Alkyl- bzw. -Alkenyl-Resten;

C₄- bis C₂₀-Hydroxycarbonsäuren, wie Äpfelsäure, Weinsäure, Gluconsäure, Glutarsäure, Citronensäure, Lactobionsäure und Saccharosemono-, -di- und - tricarbonsäure;

Aminopolycarbonsäuren, wie Nitrilotriessigsäure, β-Alanindiessigsäure, Ethylendiamintetraessigsäure, Serindiessigsäure, Isoserindiessigsäure, Methylglycindiessigsäure und Alkylethylendiamintriacetate;

Salze von Phosphonsäuren, wie Hydroxyethandiphosphonsäure.

Suitable low molecular weight carboxylic acids or phosphonic acids for (B) are, for example:

C ₄ - to C ₂₀ di-, tri- and tetracarboxylic acids, such as succinic acid, propane tricarboxylic acid, butane tetracarboxylic acid, cyclopentane tetracarboxylic acid and alkyl and alkenyl succinic acids with C ₂ to C ₁₆ alkyl or alkenyl radicals;

C ₄ to C ₂₀ hydroxycarboxylic acids, such as malic acid, tartaric acid, gluconic acid, glutaric acid, citric acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid;

Aminopolycarboxylic acids such as nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, methylglycinediacetic acid and alkylethylenediaminetriacetates;

Salts of phosphonic acids such as hydroxyethane diphosphonic acid.

Oligomaleinsäuren, wie sie beispielsweise in EP-A 451 508 und EP-A 396 303 beschrieben sind;

Co- und Terpolymere ungesättigter C₄-C₈-Dicarbonsäuren, wobei als Comonomere monoethylenisch ungesättigte Monomere

aus der Gruppe (i) in Mengen von bis zu 95 Gew.-%,

aus der Gruppe (ii) in Mengen von bis zu 60 Gew.-% und

aus der Gruppe (iii) in Mengen von bis zu 20 Gew.-%

einpolymerisiert sein können.Suitable oligomeric or polymeric carboxylic acids for (B) are, for example:

Oligomaleic acids as described, for example, in EP-A 451 508 and EP-A 396 303;

Copolymers and terpolymers of unsaturated C ₄ -C ₈ dicarboxylic acids, with monoethylenically unsaturated monomers as comonomers

from group (i) in amounts of up to 95% by weight,

from group (ii) in amounts of up to 60% by weight and

from group (iii) in amounts of up to 20% by weight

can be polymerized.

Examples of suitable unsaturated C ₄ -C ₈ dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleic acid is preferred.

Group (i) includes monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. From group (i), preference is given to using acrylic acid and methacrylic acid.

Group (ii) includes monoethylenically unsaturated C ₂ -C ₂₂ olefins, vinyl alkyl ethers with C ₁ -C ₈ alkyl groups, styrene, vinyl esters of C ₁ -C ₈ carboxylic acids, (meth) acrylamide and vinyl pyrrolidone. From group (ii), preference is given to using C ₂ -C ₆ olefins, vinyl alkyl ethers having C ₁ -C ₄ alkyl groups, vinyl acetate and vinyl propionate.

Group (iii) includes (meth) acrylic esters of C ₁ to C ₈ alcohols, (meth) acrylonitrile, (meth) acrylamides of C ₁ to C ₈ amines, N-vinylformamide and vinylimidazole.

If the polymers of group (ii) contain vinyl esters in copolymerized form, can also partially or completely to vinyl alcohol structural units are hydrolyzed. Suitable copolymers and terpolymers are, for example known from US 3 887 806 and DE-A 43 13 909.

Copolymere von Maleinsäure und Acrylsäure im Gewichtsverhältnis 100:90 bis 95:5, besonders bevorzugt solche im Gewichtsverhältnis 30:70 bis 90:10 mit Molmassen von 100.000 bis 150.000;

Terpolymere aus Maleinsäure, Acrylsäure und einem Vinylester einer C₁-C₃-Carbonsäure im Gewichtsverhältnis 10 (Maleinsäure) : 90 (Acrylsäure + Vinylester) bis 95 (Maleinsäure) : 10 (Acrylsäure + Vinylester), wobei das Gewichtsverhältnis von Acrylsäure zum Vinylester im Bereich von 30:70 bis 70:30 variieren kann;

Copolymere von Maleinsäure mit C₂-C₈-Olefinen im Molverhältnis 40:60 bis 80:20, wobei Copolymere von Maleinsäure mit Ethylen, Propylen oder Isobuten im Molverhältnis 50:50 besonders bevorzugt sind.

Pfropfpolymere ungesättigter Carbonsäuren auf niedermolekulare Kohlenhydrate oder hydrierte Kohlenhydrate, siehe US 5 227 446, DE-A 44 15 623 und DE-A 43 13 909, eignen sich ebenfalls als Komponente (B).

Suitable copolymers of dicarboxylic acids for component (B) are preferably:

Copolymers of maleic acid and acrylic acid in a weight ratio of 100:90 to 95: 5, particularly preferably those in a weight ratio of 30:70 to 90:10 with molecular weights of 100,000 to 150,000;

Terpolymers of maleic acid, acrylic acid and a vinyl ester of a C ₁ -C ₃ carboxylic acid in a weight ratio of 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 10 (acrylic acid + vinyl ester), the weight ratio of acrylic acid to vinyl ester in Range can vary from 30:70 to 70:30;

Copolymers of maleic acid with C ₂ -C ₈ olefins in a molar ratio of 40:60 to 80:20, copolymers of maleic acid with ethylene, propylene or isobutene in a molar ratio of 50:50 being particularly preferred.

Graft polymers of unsaturated carboxylic acids on low molecular weight carbohydrates or hydrogenated carbohydrates, see US Pat. No. 5,227,446, DE-A 44 15 623 and DE-A 43 13 909, are also suitable as component (B).

Suitable unsaturated carboxylic acids include maleic acid, Fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid and mixtures of acrylic acid and maleic acid, those in amounts of 40 to 95 wt .-%, based on the to be grafted Component to be grafted on.

For modification, up to 30% by weight, based on the additional grafting component, further monoethylenically unsaturated monomers are present in polymerized form. Suitable modifying monomers are those above mentioned monomers of groups (ii) and (iii).

Degraded polysaccharides, such as acidic or enzymatically degraded starches, inulins or cellulose, protein hydrolyzates and reduced (hydrogenated or hydrogenated aminated) degraded polysaccharides such as mannitol, sorbitol, aminosorbitol and N-alkylglucamine as well as polyalkylene glycols with molecular weights of up to M _{w are} suitable as a graft base = 5,000 such as polyethylene glycols, ethylene oxide / propylene oxide or ethylene oxide / butylene oxide or ethylene oxide / propylene oxide / butylene oxide block copolymers and alkoxylated mono- or polyvalent C ₁ to C ₂₂ alcohols, see US Pat. No. 5,756,456.

Grafted mined or mined from this group are preferred reduced starches and grafted polyethylene oxides are used, with 20 to 80% by weight of monomers, based on the graft component, in the graft polymerization be used. A graft is preferably used Mixture of maleic acid and acrylic acid in a weight ratio of 90:10 used until 10:90.

Polyglyoxylic acids suitable as component (B) are described, for example in EP-B 001 004, US 5 399 286, DE-A 41 06 355 and EP-A 0 656 914. The end groups of the polyglyoxylic acids can be different Have structures.

Suitable as component (B) and modified polyamidocarboxylic acids Polyamidocarboxylic acids are known for example from EP-A 454 126, EP-B 511 037, WO 94/01486 and EP-A 581 452.

Component (B) in particular also uses polyaspartic acids or cocondensates of aspartic acid with further amino acids, C ₄ -C ₂₅ mono- or dicarboxylic acids and / or C ₄ -C ₂₅ mono- or diamines. Polyaspartic acids modified with C ₆ -C ₂₂ mono- or dicarboxylic acids or modified with C ₆ -C ₂₂ mono- or diamines are particularly preferably used.

As component (B) suitable condensation products of citric acid Hydroxycarboxylic acids or polyhydroxy compounds are from WO 93/22362 and WO 92/16493 are known. Condensates containing such carboxyl groups usually have molecular weights of up to 10,000, preferably up to 5,000.

Also suitable as component (B) are ethylenediamine disuccinic acid, Oxydisuccinic acid, aminopolycarboxylates, aminopolyalkylene phosphonates and Polyglutamates.

In addition to component (B), oxidized starches can also be used as organic cobuilders can be used.

Surfactants

Suitable anionic surfactants (C) are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, such as C ₉ to C ₁₁ alcohol sulfates, C ₁₂ to C ₁₄ alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol .

Other suitable anionic surfactants are sulfated ethoxylated C ₈ to C ₂₂ alcohols (alkyl ether sulfates) or their soluble salts. Compounds of this type are prepared, for example, by first alkoxylating a C ₈ to C ₂₂ , preferably a C ₁₀ to C ₁₈ alcohol, such as a fatty alcohol, and then sulfating the alkoxylation product. Ethylene oxide is preferably used for the alkoxylation, 2 to 50, preferably 3 to 20, mol of ethylene oxide being used per mol of alcohol. However, the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide. Such alkoxylated C 8 to C ₂₂ alcohols, the ethylene oxide and propylene oxide or ethylene oxide and butylene oxide or ethylene oxide and propylene oxide and butylene oxide are suitable also included. The alkoxylated C 8 to C ₂₂ alcohols, the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in random distribution. Depending on the type of alkoxylation catalyst, alkyl ether sulfates with a broad or narrow alkylene oxide distribution can be obtained.

Further suitable anionic surfactants are alkanesulfonates, such as C ₈ - to C ₂₄ -, preferably C ₁₀ - to C ₁₈ -alkanesulfonates and soaps, such as the Na and K salts of C ₈ - to C ₂₄ -carboxylic acids.

Further suitable anionic surfactants are C ₉ to C ₂₀ linear alkylbenzenesulfonates (LAS) and alkyltoluenesulfonates.

Also suitable as anionic surfactants (C), C ₈ - to C ₂₄ olefin sulfonates and disulfonates, which may also be mixtures of alkene and hydroxyalkane sulfonates and disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerol, fatty acid glycerol, alkylphenol polyglycol ether sulfates, paraffin sulfonates having approx. 20 to approx. 50 carbon atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isethionates, acyl taurates, acyl methyl taurates, alkyl succinic acids, alkenyl succinic acids or their half esters or half amides, alkyl sulfosuccinic acids or their amides, mono- and diesters of sulfosuccinic acids , Acyl sarcosinates, sulfated alkyl polyglucosides, alkyl polyglycol carboxylates and hydroxyalkyl sarcosinates.

The anionic surfactants are preferably in the form of Added salts. Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium and ammonium salts, such as hydroxyethylammonium, Di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

Component (C) is preferably present in the textile detergent formulation according to the invention in an amount of 3 to 30% by weight, in particular 5 to 15% by weight. If C ₉ to C ₂₀ linear alkylbenzenesulfonates (LAS) are also used, these are usually used in an amount of up to 10% by weight, in particular up to 8% by weight. Only one class of anionic surfactants can be used alone, for example only fatty alcohol sulfates or only alkyl benzene sulfonates, but mixtures of different classes can also be used, such as a mixture of fatty alcohol sulfates and alkyl benzene sulfonates. Mixtures of different species can also be used within the individual classes of anionic surfactants.

Suitable nonionic surfactants (D), for example, alkoxylated C8 suitable to C ₂₂ -alcohols, such as fatty or oxo. The alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as surfactants. Here too, block polymers of ethylene oxide, propylene oxide and / or butylene oxide or addition products which contain the alkylene oxides mentioned in a statistical distribution are suitable. 2 to 50, preferably 3 to 20, mol of at least one alkylene oxide are used per mole of alcohol. Ethylene oxide is preferably used as the alkylene oxide. The alcohols preferably have 10 to 18 carbon atoms. Depending on the type of alkoxylation catalyst, alkoxylates with a broad or narrow alkylene oxide distribution can be obtained.

Another class of suitable nonionic surfactants are alkylphenol alkoxylates such as alkylphenol ethoxylates with C ₆ to C ₁₄ alkyl chains and 5 to 30 mol alkylene oxide units.

Another class of nonionic surfactants are alkyl polyglucosides or Hydroxyalkyl polyglucosides having 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain. These compounds usually contain 1 to 20, preferably 1.1 to 5 glucoside units.

Another class of nonionic surfactants are N-alkyl with C 6 to C ₂₂ alkyl chains. Such compounds are obtained, for example, by acylation of reducing aminated sugars with corresponding long-chain carboxylic acid derivatives.

Block copolymers are also suitable as nonionic surfactants (D) from ethylene oxide, propylene oxide and / or butylene oxide (Pluronic and Tetronic brands from BASF), polyhydroxy or polyalkoxy fatty acid derivatives such as Polyhydroxy fatty acid amides, N-alkoxy or N-aryloxy polyhydroxy fatty acid amides, Fatty acid amide ethoxylates, especially end group capped, as well Fatty acid alkanolamide alkoxylates.

Component (D) is preferably present in the textile detergent formulation according to the invention in an amount of 1 to 20% by weight, in particular 3 to 12% by weight. Only one class of nonionic surfactants can be used alone, in particular only alkoxylated C ₈ to C ₂₂ alcohols, but mixtures of different classes can also be used. Mixtures of different species can also be used within the individual classes of nonionic surfactants.

Since the balance between the types of surfactants mentioned is important for The detergent formulation according to the invention is effective anionic surfactants (C) and nonionic surfactants (D) preferably in Weight ratio of 95: 5 to 20:80, in particular from 70:30 to 50:50.

Cationic surfactants (E) may also be present in the detergents according to the invention.

Suitable cationic surfactants are, for example, surface-active compounds containing ammonium groups, such as alkyldimethylammonium halides and compounds of the general formula R ¹⁸ R ¹⁹ R ²⁰ R ²¹ N ⁺ x ^- in which the radicals R ¹⁸ to R ^{21 represent} alkyl, aryl, alkylalkoxy, arylalkoxy, hydroxyalkyl (alkoxy), hydroxyaryl (alkoxy) groups and x is a suitable anion.

The detergents according to the invention can optionally also contain ampholytic surfactants (F), such as aliphatic derivatives of secondary or tertiary amines which contain an anionic group in one of the side chains, alkyldimethylamine oxides or alkyl or alkoxymethylamine oxides.

Components (E) and (F) can be present in amounts up to 25%, preferably from 3 up to 15% can be contained in the detergent formulation.

Bleach

In a further preferred embodiment, the invention contains Textile detergent formulation additionally 0.5 to 30 wt .-%, in particular 5 to 27 wt .-%, especially 10 to 23 wt .-% bleach (G). Examples are alkali perborates or alkali carbonate perhydrates, especially the sodium salts.

An example of a usable organic peracid is peracetic acid, which preferably in commercial textile washing or commercial Cleaning is used.

Bleach or textile detergent compositions which can be used advantageously contain C _1-12 -percarboxylic acids, C _8-16 -dipercarboxylic acids, imidopercaproic acids, or aryldipercaproic acids. Preferred examples of usable acids are peracetic acid, linear or branched octanoic, nonanoic, decanoic or dodecane monoperacids, decanoic and dodecanediperic acid, mono- and diperphthalic acids, isophthalic acids and terephthalic acids, phthalimidopercaproic acid and terephthaloyldipercaproic acid. Polymeric peracids can also be used, for example those which contain basic acrylic acid units in which a peroxy function is present. The percarboxylic acids can be used as free acids or as salts of the acids, preferably alkali or alkaline earth metal salts. These bleaching agents (G) are optionally used in combination with 0 to 15% by weight, preferably 0.1 to 15% by weight, in particular 0.5 to 8% by weight, of bleach activators (H). In the case of color detergents, the bleach (G) (if present) is generally used without a bleach activator (H), otherwise bleach activators (H) are usually present.

• polyacylierte Zucker, wie Pentaacetylglucose;
• Acyloxybenzolsulfonsäuren und deren Alkali- und Erdalkalimetallsalze, wie Natrium-p-isononanoyloxy-benzolsulfonat oder Natrium-p-benzoyloxy--benzolsulfonat;
• N,N-diacylierte und N,N,N',N'-tetraacylierte Amine, wie N,N,N',N'-Tetraacetyl-methylendiamin und -ethylendiamin (TAED), N,N-Diacetylanilin, N,N-Diacetyl-p-toluidin oder 1,3-diacylierte Hydantoine wie 1,3-Diacetyl-5,5-dimethylhydantoin;
• N-Alkyl-N-sulfonyl-carbonamide, wie N-Methyl-N-mesyl-acetamid oder N-Methyl-N-mesyl-benzamid;
• N-acylierte cyclische Hydrazide, acylierte Triazole oder Urazole, wie Monoacetyl-maleinsäurehydrazid;
• O,N,N-trisubstituierte Hydroxylamine, wie O-Benzoyl-N,N-succinylhydroxylamin, O-Acetyl-N,N-succinyl-hydroxylamin oder O,N,N-Triacetylhydroxylamin;
• N,N'-Diacyl-sulfurylamide, wie N,N'-Dimethyl-N,N'-diacetylsulfurylamid oder N,N'-Diethyl-N,N'-dipropionyl-sulfurylamid;
• Triacylcyanurate, wie Triacetylcyanurat oder Tribenzoylcyanurat;
• Carbonsäureanhydride, wie Benzoesäureanhydrid, m-Chlorbenzoesäureanhydrid oder Phthalsäureanhyrid;
• 1,3-Diacyl-4,5-diacyloxy-imidazoline, wie 1,3-Diacetyl-4,5-diacetoxyimidazolin;
• Tetraacetylglycoluril und Tetrapropionylglycoluril;
• diacylierte 2,5-Diketopiperazine, wie 1,4-Diacetyl-2,5-diketopiperazin;
• Acylierungsprodukte von Propylendiharnstoff und 2,2-Dimethylpropylendiharnstoff, wie Tetraacetylpropylendiharnstoff;
• α-Acyloxy-polyacyl-malonamide, wie α-Acetoxy-N,N'-diacetylmalon-amid;
• Diacyl-dioxohexahydro-1,3,5-triazine, wie 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin;
• Benz-(4H)1,3-oxazin-4-one mit Alkylresten, wie Methyl, oder aromatischen Resten z. B. Phenyl, in der 2-Position.

Suitable bleach activators (H) are:

• polyacylated sugars such as pentaacetyl glucose;
• Acyloxybenzenesulfonic acids and their alkali and alkaline earth metal salts, such as sodium p-isononanoyloxy-benzenesulfonate or sodium p-benzoyloxy-benzenesulfonate;
• N, N-diacylated and N, N, N ', N'-tetraacylated amines, such as N, N, N', N'-tetraacetyl-methylenediamine and -ethylenediamine (TAED), N, N-diacetylaniline, N, N- Diacetyl-p-toluidine or 1,3-diacylated hydantoins such as 1,3-diacetyl-5,5-dimethylhydantoin;
• N-alkyl-N-sulfonyl-carbonamides, such as N-methyl-N-mesyl-acetamide or N-methyl-N-mesyl-benzamide;
• N-acylated cyclic hydrazides, acylated triazoles or urazoles, such as monoacetyl-maleic acid hydrazide;
• O, N, N-trisubstituted hydroxylamines, such as O-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinyl-hydroxylamine or O, N, N-triacetylhydroxylamine;
• N, N'-diacylsulfurylamides, such as N, N'-dimethyl-N, N'-diacetylsulfurylamide or N, N'-diethyl-N, N'-dipropionylsulfurylamide;
• Triacyl cyanurates such as triacetyl cyanurate or tribenzoyl cyanurate;
• Carboxylic anhydrides such as benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride;
• 1,3-diacyl-4,5-diacyloxy-imidazolines such as 1,3-diacetyl-4,5-diacetoxyimidazoline;
• Tetraacetylglycoluril and tetrapropionylglycoluril;
• diacylated 2,5-diketopiperazines such as 1,4-diacetyl-2,5-diketopiperazine;
• Acylation products of propylene diurea and 2,2-dimethylpropylene diurea, such as tetraacetyl propylene diurea;
• α-acyloxy polyacyl malonamides such as α-acetoxy-N, N'-diacetylmalon amide;
• Diacyl-dioxohexahydro-1,3,5-triazines such as 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine;
• Benz- (4H) 1,3-oxazin-4-one with alkyl radicals, such as methyl, or aromatic radicals, for. B. phenyl, in the 2-position.

The described bleaching system consisting of bleaching agents and bleach activators can optionally also contain bleach catalysts. Suitable bleaching catalysts are, for example, quaternized imines and sulfonimines, for example in US 5 360 569 and EP-A 453 003. Particularly effective Bleaching catalysts are manganese complexes, which are described, for example, in WO 94/21777 are described. Such connections are in the case of their Use in detergent formulations at most in amounts up to 1.5 % By weight, in particular up to 0.5% by weight. Also usable Bleaching catalysts are those in the German patent application with the Title "Bleach booster for bleach and textile detergent compositions", Case number 196 25 908.8 amines described.

In addition to the bleaching system described, consisting of bleaching agents, bleach activators and optionally bleaching catalysts is for the textile detergent formulation according to the invention also the use of systems with enzymatic Peroxide release or from photoactivated bleaching systems possible.

Enzymes

In a further preferred embodiment, the invention contains Textile detergent formulation additionally 0.05 to 4 wt .-% enzymes (J). Enzymes preferably used in detergents are proteases, amylases, Lipases and cellulases. Quantities of the enzymes are preferred from 0.1 to 1.5% by weight, particularly preferably 0.2 to 1.0% by weight, of the added enzyme. Suitable proteases are, for example Savinase and Esperase (manufacturer: Novo Nordisk). A suitable lipase is for example Lipolase (manufacturer: Novo Nordisk). A suitable cellulase is for example Celluzym (manufacturer: Novo Nordisk). Use too of peroxidases to activate the bleaching system is possible. Man can be single enzymes or a combination of different enzymes deploy. If appropriate, the textile detergent formulation according to the invention still enzyme stabilizers, such as calcium propionate, sodium formate or boric acids or their salts, and / or antioxidants.

Other ingredients

• Vergrauungsinhibitoren und Soil-Release-Polymere
• Geeignete Soil-Release-Polymere und/oder Vergrauungsinhibitoren für Waschmittel sind beispielsweise:
• Polyester aus Polyethylenoxiden mit Ethylenglycol und/oder Propylenglycol und aromatischen Dicarbonsäuren oder aromatischen und aliphatischen Dicarbonsäuren;
• Polyester aus einseitig endgruppenverschlossenen Polyethylenoxiden mit zwei-und/oder mehrwertigen Alkoholen und Dicarbonsäure.
• Derartige Polyester sind bekannt, beispielsweise aus US 3,557,039, GB-A 1 154 730, EP-A-185 427, EP-A-241 984, EP-A-241 985, EP-A-272 033 und US 5,142,020.
• Weitere geeignete Soil-Release-Polymere sind amphiphile Pfropf- oder Copolymere von Vinyl-und/oder Acrylestern auf Polyalkylenoxide (vgl. US 4,746,456, US 4,846,995, DE-A-37 11 299, US 4,904,408, US 4,846,994 und US 4,849,126) oder modifizierte Cellulosen wie Methylcellulose, Hydroxypropylcellulose oder Carboxymethylcellulose.
• Farbübertragungsinhibitoren, beispielsweise Homo- und Copolymerisate des Vinylpyrrolidons, des Vinylimidazols, des Vinyloxazolidons oder des 4-Vinylpyridin-N-oxids mit Molmassen von 15.000 bis 100.000 sowie vernetzte feinteilige Polymere auf Basis dieser Monomere;
• nichttensidartige Schaumdämpfer oder Schauminhibitoren, beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure;
• Komplexbildner (auch in der Funktion von organischen Cobuildern);
• optische Aufheller;
• Polyethylenglykole;
• Parfüme oder Duftstoffe;
• Füllstoffe;
• anorganische Stellmittel, wie Natriumsulfat;
• Konfektionierhilfsmittel;
• Löslichkeitsverbesserer;
• Trübungs- und Perlglanzmittel;
• Farbstoffe;
• Korrosionsinhibitoren;
• Peroxidstabilisatoren;
• Elektrolyte.

In addition to the main components (A) to (J) mentioned, the textile detergent formulation according to the invention can also contain the following further customary additives in the amounts customary for this:

• Graying inhibitors and soil release polymers
• Suitable soil release polymers and / or graying inhibitors for detergents are, for example:
• Polyesters of polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids;
• Polyester made of polyethylene oxides end capped on one side with di- and / or polyhydric alcohols and dicarboxylic acid.
• Such polyesters are known, for example from US 3,557,039, GB-A 1 154 730, EP-A-185 427, EP-A-241 984, EP-A-241 985, EP-A-272 033 and US 5,142,020.
• Other suitable soil release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides (cf. US Pat. No. 4,746,456, US Pat. No. 4,846,995, DE-A-37 11 299, US Pat. No. 4,904,408, US Pat. No. 4,846,994 and US Pat. No. 4,849,126) or modified Celluloses such as methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.
• Color transfer inhibitors, for example homopolymers and copolymers of vinylpyrrolidone, vinylimidazole, vinyloxazolidone or 4-vinylpyridine-N-oxide with molecular weights from 15,000 to 100,000, and crosslinked, finely divided polymers based on these monomers;
• non-surfactant-like foam dampers or foam inhibitors, for example organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica;
• Complexing agents (also in the function of organic cobuilders);
• optical brighteners;
• Polyethylene glycols;
• Perfumes or fragrances;
• Fillers;
• inorganic leveling agents, such as sodium sulfate;
• Assembly aids;
• Solubility enhancer;
• Opacifiers and pearlescent agents;
• Dyes;
• Corrosion inhibitors;
• Peroxide stabilizers;
• Electrolytes.

The detergent formulation according to the invention is solid, that is to say usually lies in powder or granule form or in extrudate or tablet form in front.

The powder or granular detergents according to the invention can up to contain 60% by weight of inorganic fillers. Usually this is done Sodium sulfate used. The detergents according to the invention are preferably but low in adjusting agents and contain only up to 20% by weight, especially preferably only up to 8% by weight of adjusting agents, especially in the case of compact or ultra compact detergents. The solid detergents according to the invention can have different bulk densities in the range of 300 to 1,300 g / l, in particular from 550 to 1,200 g / l. Modern compact detergents usually have high bulk densities and show a granular structure. For the desired compression of the detergent, the in the Technique usual processes are used.

The detergent formulation according to the invention is made by customary methods manufactured and possibly assembled.

The following are typical compositions for compact heavy duty laundry detergents and color detergent (the percentages refer to in the following and in the examples on the weight; the information in Parentheses in compositions (a) and (b) are preferred ranges):

(a) Composition of compact heavy duty detergent (powder or granular)

1-60% (8-30%)

at least one anionic (C) and one nonionic Surfactants (D)

5-50% (10-45%)

at least one inorganic builder (A)

0.1-20% (0.5-15%)

at least one organic cobuilder (B)

5-30% (10-25%)

an inorganic bleaching agent (G)

0.1-15% (1-8%)

a bleach activator (G)

0-1% (maximum 0.5%)

a bleaching catalyst

0.05-5% (0.2-2.5%)

a color transfer inhibitor

0.3-1.5%

of a soil release polymer

0.1-4% (0.2-2%)

Enzyme or enzyme mixture (H)

Other common additives:
Sodium sulfate, complexing agents, phosphonates, optical brighteners, perfume oils, foam suppressants, graying inhibitors, bleach stabilizers

The total amount of ingredients is 100% by weight.

(b) Color detergent composition (powder or granular)

3 - 50% (8 - 30%)

at least one anionic (C) and one nonionic Surfactants (D)

10 - 60% (20 - 55%)

at least one inorganic builder (A)

0 - 15% (0 - 5%)

an inorganic bleaching agent (G)

0.05-5% (0.2-2.5%)

a color transfer inhibitor

0.1-20% (1-8%)

at least one organic cobuilder (B)

0.2-2%

Enzyme or enzyme mixture (J)

0.2-1.5%

Soil release polymer

Other common additives:
Sodium sulfate, complexing agents, phosphonates, optical brighteners, perfume oils, foam suppressants, graying inhibitors, bleach stabilizers.
The total amount of ingredients is 100% by weight.

The amines according to the invention are in detergents according to the invention in amounts of 0.1 to 5% by weight, preferably 0.2 to 4% by weight, in particular 0.5 to 2.5% by weight contain. In compact heavy duty detergents (powder or granular) the amounts 0.1 to 5% by weight (0.2 to 4.5% by weight), preferably 0.4 to 3% by weight (0.5 to 2.5% by weight).

The invention is illustrated by the examples below.

EXAMPLES Example 1: N, N, N ', N'-tetraaminopropyl-1,2-ethylenediamine (N6-amine)

Preparation of N, N, N ', N'-tetracyanoethyl-1,2-ethylenediamine:
443 g (8.35 mol) of acrylonitrile are added to a solution of 100 g (1.67 mol) of 1,2-ethylenediamine in 1176 ml of water within 90 minutes. The temperature must not exceed 40 ° C. After the addition of the acrylonitrile has ended, the mixture is stirred for a further hour at 40 ° C. and two further hours at 80 ° C. Excess acrylonitrile is then distilled off and then the water is largely distilled off by applying a water jet or an oil pump vacuum. The tetracyanoethylated ethylenediamine is recrystallized from methanol and suction filtered. The yield is 478 g (1.58 mol).

Preparation of N, N, N ', N'-tetraaminopropyl-1,2-ethylenediamine (N6-amine):
400 ml / h of a mixture of 20% by weight of N, N, N ', N'-tetracyanoethyl-1,2-ethylenediamine and 80% by weight of N-methylpyrrolidone and 3,500 ml / h of ammonia are passed in at 130 ° C. and 200 bar hydrogen pressure in a 5 1 fixed bed reactor over 4 1 of a fixed bed catalyst with the composition 90% by weight CoO, 5% by weight MnO, 5% by weight P ₂ O ₅ . After removal of the N-methylpyrrolidone in vacuo and fractional distillation (bp .: 218 ° C. at 6 mbar), N, N, N ', N'-tetraaaminopropyl-1,2-ethylenediamine (N6-amine) is obtained in 95%. yield. The product was checked for uniformity and completeness of the reaction by means of ¹³ C and ¹ H NMR and mass spectroscopy.

Example 2 (comparison): reaction product N6-amine / succinic acid 1: 1

3.7 g (0.0125 mol) N6-amine (from example 1) and 1.5 g (0.0125 mol) Succinic acid is dissolved in 10.4 g of dioxane at 140 ° C bath temperature for 2 hours cooked under reflux. For azeotropic removal of the water of reaction the dioxane is distilled off. Then the azeotropic removal of the Water of reaction continued by adding 13 g of dioxane four times and also be distilled off. After the last distillation deionized water and the remaining dioxane by means of a Steam distillation removed. The resulting solution has a solids content from 5.2%.

Example 3 (comparison): reaction product N6-amine and Sokalan® DCS 1: 1

The preparation is carried out analogously to Example 2 using 3.7 g (0.0125 mol) N6-amine, 1.7 g Sokalan® DCS (corresponding to an average of 0.0125 mol of a mixture of succinic acid, glutaric acid and adipic acid). As Solvents were used 13 g of dioxane. You get a solution with a solids content of 7.3%.

Example 4: Polyethyleneimine

The polyethyleneimine was made from ethyleneimine with EDA / H ₂ SO ₄ catalyst. 80 g (1.33 mol) of ethylenediamine and 65.3 g (0.67 mol) of concentrated H ₂ SO ₄ and 260 g of demineralized water were initially introduced as the catalyst solution. A 60% ethyleneimine solution composed of 344 g (8 mol) of ethyleneimine and 229 g of ice was added dropwise at 90.degree. The mixture is stirred at 90 ° C. until the test for alkylating substances according to Preussmann is negative. The Preussmann test was carried out according to J. Epstein et al, Analyt. Chem. 27 (1955) 1435 and R. Preussmann et al, drug research. 19 (1969) 1059.

Example 5: Polyethyleneimine

6.0 g (0.1 mol) of ethylenediamine, 2.2 g (0.05 mol) of CO ₂ and 17 g of demineralized water were introduced into the catalyst solution. At 90 ° C., 60% ethyleneimine solution consisting of 43 g (1 mol) ethyleneimine and 29 g ice was added dropwise to the mixture. The mixture is stirred at 90 ° C. until the test for alkylating substances according to Preussmann is negative.

Example 6: Polyethyleneimine

3.0 g (0.05 mol) of ethylenediamine and 1.1 g (0.025 mol) of CO ₂ and 17 g of demineralized water were initially introduced as the catalyst solution. At 90 ° C., 60% ethyleneimine solution consisting of 43 g (1 mol) of ethyleneimine and 29 g of ice was added dropwise to the mixture. The mixture is stirred at 90 ° C. until the test for alkylating substances according to Preussmann is negative.

Example 7: Amidation of polyethyleneimine with benzoic acid 20: 1

1290 g of polyethyleneimine according to Example 5 were placed under nitrogen. At 140 ° C 183.18 g of benzoic acid (1.5 mol) were added in portions. The mixture is then stirred at 180 ° C until the acid number is less than 5% of the application value.

Example 8 (comparison): Condensation of polyethyleneimine anhydrous with Sokalan DCS®

645 g of polyethyleneimine according to Example 5 were placed under nitrogen. 68.6 g (0.5 mol) of Sokalan DCS® were metered in at 140 ° C. in portions. The mixture is then stirred at 180 ° C for 26 hours.

Washing attempts

The washing-strengthening effect of the amines according to the invention (primary washing power) was underwashed in a Launder-O-Meter standardized conditions. The following detergent formulations were used A and B used, their composition in table 1 is specified. The use of detergent formulations C - M is also possible according to the invention.

The detergent formulations A and B were initially without the invention Detergent booster examined and then with the invention Detergent boosters from Examples 1 to 8 in concentrations of 1 or 2% by weight, based on the total amount of detergent, examined.

With the additive / non-additive detergent formulations A and B were cotton BW221, polyester PES850, mixed fabric as test fabric Cotton / polyester MG 768 among those listed below Pre-washed washing conditions. Then they were dried and 0.2 g dirty used engine oil. The soiled test fabrics was allowed to age for 14 hours. Then the test fabrics again with the additive / non-additive detergent formulations A and B washed and the primary washability determined.

For this purpose, the reflectance values of the soiled test fabric before the Wash (R before) and after wash (R after) determined using a Datacolor photometers (Elrepho 2000).

Washing conditions:

device Launder-O-Meter from Atlas, Chicago Wash liquor 250 ml Washing time 30 min at 60 ° C Detergent dosage 6 g / l Water hardness 3 mmol; Ca: Mg 4: 1 Fleet ratio 1: 12.5 Test fabric BW221, PES850, MG 768

Washing result

The remission values of the Test industry before soiling (R zero), the soiled test fabric determined before washing (R before) and after washing (R after). Then the ratio of R to / R zero was determined to be 100 multiplied. The higher the percentage obtained, the better the stain removed. With a complete stain removal results R to / R zero x 100 = 100%.

Furthermore, the difference in stain removal between the Detergent formulation without and with a detergent booster according to the invention certainly. To do this, the difference between R after and R before, i.e. delta R = R after minus R before, determined for the detergent formulation without a detergent booster according to the invention as delta R without and with the inventive detergency booster as delta R with.

The higher the difference delta (delta R) = delta R with minus delta R without is, the greater the washing-strengthening effect of the added Detergent booster according to the invention.

In addition to the detergency boosters according to the invention according to Examples 1 and 4 to 7 were in two comparative examples I and II (I = reaction product of N-coconut fat-1,3-diaminopropane with 4 mol EO (ethylene oxide), II = Reaction product of N-tallow fat-1,3-diaminopropane with 4.5 mol EO) used, as described in EP-A-042 187.

From Tables 2 and 3 it can be seen that the inventive Detergent booster of Examples 1 and 4 to 7 the primary washing power of Detergent formulations A and B, especially on cotton fabrics improve significantly.

These compounds are also effective in other modern compact detergent formulations, as listed in Table 1, on other types of soiling, such as lipstick or make-up, or on other test fabrics, such as polyester fabrics or polyester-containing blended fabrics.

Claims (3)

1. The use of an amine with an average pK_A of from 1 to 14 as detergency booster, preferably in textile detergents, in particular in color detergents, wherein the amine is selected from

   (a1) amines of the general formula (I) RR'N- [-(CR¹'R²)_x-NR³'-]_a-[-(CR^4'R^5')_y-NR^6'-]_b-R"

   where the radicals R, R' and R", R¹, R²', R^4' and R⁵' are, independently of one another, hydrogen atoms, linear or branched-chain C_1-20-alkyl, -(alkyl)carboxy or alkylamino radicals, C_2-20-alkenyl radicals or C_6-20-aryl, -aryloxy, -hydroxyaryl, -arylcarboxy or -arylamino radicals, while the radicals R³ and R⁶ are, independently of one another, hydrogen atoms, linear or branched-chain C_1-20-alkyl radicals, C_6-20-aryl radicals or radicals [(CR^7'R^8')_z-NR^9']_c-R^10',

   where the radicals R^7', R^8', R^9' and R¹⁰' are, independently of one another, defined as above for R, R', R", R^1', R^2', R^4' and R^5',

   x, y and z have, independently of one another, a value of 2, 3 or 4, and a, b and c have, independently of one another, an integral value of 0 - 300, with the exception of mono- and diamines, where polyethyleneimines may be rendered hydrophobic by partial modification with benzoic acid,

   (a2) amines of the general formula (II) (R¹R¹)N-X-N(R¹R¹)

   where the radicals R¹ are (R²R²)N-(CH₂)_n-radicals,

   the radicals R² are hydrogen atoms or (R³R³)N-(CH₂)_n- radicals,

   the radicals R³ are hydrogen atoms or (R⁴R⁴)N-(CH₂)_n- radicals,

   the radicals R⁴ are hydrogen atoms or (R⁵R⁵)N-(CH₂)_n- radicals,

   the radicals R⁵ are hydrogen atoms or (R⁶R⁶)N-(CH₂)_n- radicals,

   the radicals R⁶ are hydrogen atoms,

   n has a value of 2, 3 or 4, and

   the radical X is one of the radicals

   

   

   ―(CH₂)_n- , -(CH₂)₃-NR¹¹-(CH₂)₃-,
   C_2-20-alkylene,

   the radical Y is an oxygen atom, a CR⁷R⁹C=O radical or SO₂,

   n has an integral value of 2 - 20,

   the radicals R⁷, R⁸, R⁹ and R¹⁰ are, independently of one another, hydrogen atoms or C_1-6-alkyl radicals,

   and the radical R¹¹ is C_1-20-alkyl, C_2-20-dialkylamino-C_2-10-alkyl, C_1-10-alkoxy-C_2-10-alkyl, C_2-20-hydroxyalkyl or C₇-₂₀-aralkyl radical, or two radicals R¹¹ together afford an alkylene chain which is uninterrupted or interrupted by nitrogen or oxygen, such as ethylene oxide, propylene oxide, butylene oxide and -CH₂-CH(CH₃)-O- or polyisobutylene with from 1 to 100 isobutylene units,

   (a3) polymers which comprise repeating units corresponding to the following formula -[CH₂-CH(NH₂)]-,

   obtained by at least partial hydrolysis of oligo/polyvinylformamides and copolymers of vinylformamide,

   where 5 - 100% of the nitrogen atoms are present in primary or secondary amino groups.
2. A detergent formulation comprising at least one surfactant and at least one amine selected from
   (a2) amines of the general formula (II) (R¹R¹)N-X-N(R¹R¹)

   where the radicals R¹ are (R²R²)N-(CH₂)_n-radicals,

   the radicals R² are hydrogen atoms or (R³R³)N-(CH₂)_n- radicals,

   the radicals R³ are hydrogen atoms or (R⁴R⁴)N-(CH₂)_n- radicals,

   the radicals R⁴ are hydrogen atoms or (R⁵R⁵)N-(CH₂)_n- radicals,

   the radicals R⁵ are hydrogen atoms or (R⁶R⁶)N-(CH₂)_n- radicals,

   the radicals R⁶ are hydrogen atoms,

   n has a value of 2, 3 or 4, and

   the radical X is one of the radicals

   

   

   -(CH₂)_n-, -(CH₂)₃-NR¹¹-(CH₂)₃-,
   C_2-20-alkylene,

   the radical Y is an oxygen atom, a CR⁷R⁹C=O radical or SO₂, n has an integral value of 2 - 20,

   the radicals R⁷, R⁸, R⁹ and R¹⁰ are, independently of one another, hydrogen atoms or C_1-6-alkyl radicals,

   and the radical R¹¹ is C_1-20-alkyl, C_2-20-dialkylamino-C_2-10-alkyl, C_1-10-alkoxy-C_2-10-alkyl, C_2-20-hydroxyalkyl or C_7-20-aralkyl radical, or two radicals R¹¹ together afford an alkylene chain which is uninterrupted or interrupted by nitrogen or oxygen, such as ethylene oxide, propylene oxide, butylene oxide and -CH₂-CH(CH₃)-O- or polyisobutylene from with 1 to 100 isobutylene units.
3. The use of a detergent formulation as claimed in claim 2 for cleaning textiles.