EP0744459B1 - Multifunctional detergent raw material - Google Patents

Description

The present invention relates to a multifunctional laundry raw material, manufacture this raw material, its use in household detergents, as well as the washing raw material household detergents containing.

In addition to builders (zeolites / phyllosilicates), bleaches or bleach systems (perborate / percarbonate plus TAED), optical brighteners and enzymes, surfactants of the alkylbenzenesulfonate (LAS) type, fatty alcohol sulfate, soaps and Fatty alcohol ethoxylates are used. Furthermore, polycarboxylates (polyacrylic acids) and foam inhibitors (silicone / paraffin compounds) are used to improve the washing result and the Ca complexing ability. Such a powder detergent has the following composition, for example: (a ₁ ) 6 to 12% by weight Alkylbenzenesulfonate (LAS), (a ₂ ) 0 to 7% by weight sec. Alkanesulfonates, (a ₃ ) 3 to 9% by weight non-ionic surfactants, (a ₄ ) 0 to 5% by weight cationic, zwitterionic and / or amphoteric surfactants, (a ₅ ) 0 to 2% by weight Soap, (a ₆ ) 2 to 6% by weight Polymer, as well (b) 17 to 46% by weight Zeolite or sodium tripolyphosphate, (c) 2 to 6% by weight Sodium silicate or sheet silicate impregnated with a cationic plasticizer, (d) 0 to 2% by weight Magnesium silicate, (e) 0.8 to 1.2 wt.% Carboxymethyl cellulose (CMC), (f) 0.2 to 0.6% by weight Phosphonate, (G) 0 to 25% by weight Sodium sulfate, (H) 5 to 15% by weight Sodium, (i) 15 to 25% by weight Sodium perborate tetrahydrate or, in particular, monohydrate or percarbonate (k) 3 to 5% by weight Peroxide activator, such as TAED, NOBS, TAGU (l) 0.01 to 0.5 wt.% Foam inhibitors, and (m) 0.01 to 2% by weight Perfume oil, optical brighteners, dyes (n) 0 to 2% by weight Enzymes, (O) 0.5 to 2% by weight Dye transfer inhibitors, such as polyvinylpyrrolidone (molecular weight 40,000) (p) 5 to 17% by weight Sodium citrate and ad 100% Water.

EP-A-0,696,661 discloses multifunctional textile auxiliary compositions which one or more surfactants, a reaction product of one or more non-ionogenic Surfactants and an ethylenically unsaturated sulfonic acid or carboxylic acid or contains anhydride, a hydrotropic agent and other common ingredients. This document represents an earlier right under Article 54 (3) and (4) EPC.

EP-A-0,462,059 discloses low-foam, silicone-free, aqueous textile auxiliaries which are characterized in that they are a reaction product of a nonionic Surfactant with a compound having an acidic water-solubilizing group contain nonionic surfactant and optionally a hydrotropic agent.

Surprisingly, it has now been found that reaction products of an ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride and certain nonionic surfactants and optionally sugar derivatives are detergent raw materials which are capable of the components (a ₁ ) - (a ₆ ) completely and to replace components (b), (e), (l) and (n) in part or in full.

5 bis 13 Gew.% einer ethylenisch ungesättigten Sulfonsäure oder Carbonsäure oder deren Anhydrid,

50 bis 90 Gew.% eines nichtionogenen Tensides der Formel (1)   R₁-O-(Alkylen-O)_n1 -R₂ worin

R1

C₈-C₂₂-Alkyl oder C₈-C₁₈-Alkenyl;

R2

Wasserstoff; C₁-C₄-Alkyl; einen cycloaliphatischen Rest mit mindestens 6 C-Atomen oder Benzyl;

"Alkylen"

einen Alkylenrest von 2 bis 4 Kohlenstoffatomen;

n1

eine Zahl von 1 bis 60;

bedeuten, und

0 bis 30 Gew. % Zuckerderivaten und

mindestens 1 % Wasser

erhalten wird. The subject of the present invention is a laundry raw material, characterized in that it, based on the total weight of the laundry raw material, from the implementation of

5 to 13 % by weight of an ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride,

50 to 90 % by weight of a nonionic surfactant of the formula (1) R ₁ -O- (alkylene-O) _{n 1} -R ₂ wherein

R1

C ₈ -C ₂₂ alkyl or C ₈ -C ₁₈ alkenyl;

R2

Hydrogen; C ₁ -C ₄ alkyl; a cycloaliphatic radical with at least 6 carbon atoms or benzyl;

"Alkylene"

an alkylene group of 2 to 4 carbon atoms;

n1

a number from 1 to 60;

mean, and

0 to 30% by weight of sugar derivatives and

at least 1% water

is obtained.

Due to their low tendency to foam, especially when low-ethoxylated fatty alcohol ethoxylates are used as non-ionic surfactants of the formula (1), such as, for example, C ₁₃ -oxo alcohols with 4 to 6 ethylene oxide units, the addition of foam inhibitors customary in washing powder compositions (component ( I)) are waived.

The washing raw material according to the invention also has excellent anti-redeposition properties, so that in detergents that contain this washing raw material on the Addition of anti-redeposition agents such as carboxymethyl cellulose and / or polyacrylic acid, can be dispensed with (cf. Examples 21 to 23).

The substituents R ₁ and R ₂ in the formula (1) advantageously represent the hydrocarbon radical of an unsaturated or, preferably, saturated aliphatic monoalcohol having 8 to 22 carbon atoms. The hydrocarbon radical can be straight-chain or branched. R ₁ and R _{2 are} preferably an alkyl radical having 9 to 14 carbon atoms.

Natural alcohols such as lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, as well as synthetic alcohols such as 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethylnonyl alcohol can be used as aliphatic saturated monoalcohols. Decanol, C ₉ -C ₁₁ -oxo alcohol, tridecyl alcohol, isotridecyl alcohol or linear primary alcohols (alfols) with 8 to 22 carbon atoms come into consideration. Some representatives of this Alfole are Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) or Alfol (16-18). ("Alfol" is a registered trademark).

Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol and hexadecenyl alcohol or oleyl alcohol.

The alcohol radicals can be used individually or in the form of mixtures of two or more Components are present, such as mixtures of alkyl and / or alkenyl groups, derived from soy fatty acids, palm kernel fatty acids or tallow oils.

(Alkylene-O) chains are preferably divalent radicals of the formulas

Examples of a cycloaliphatic radical are cycloheptyl, cyclooctyl or preferably Cyclohexyl.

in Betracht, worin

R3

C₈-C₂₂-Alkyl;

R4

Wasserstoff oder C₁-C₄-Alkyl;

Y1, Y2, Y3 und Y4,

unabhängig voneinander, Wasserstoff, Methyl oder Ethyl;

n2

eine Zahl von 0 bis 8; und

n3

eine Zahl von 2 bis 40;

bedeuten.Preferred nonionic surfactants are compounds of the formula

considering where

R3

C ₈ -C ₂₂ alkyl;

R4

Hydrogen or C ₁ -C ₄ alkyl;

Y1, Y2, Y3 and Y4,

independently of one another, hydrogen, methyl or ethyl;

n2

a number from 0 to 8; and

n3

a number from 2 to 40;

mean.

worin

R5

C₉-C₁₄-Alkyl;

R6

C₁-C₄-Alkyl;

Y5, Y6, Y7 und Y8,

unabhängig voneinander, Wasserstoff, Methyl oder Ethyl, wobei einer der Reste Y₅, Y₆ bzw. Y₇, Y₈ immer Wasserstoff ist; und

n4 und n5,

unabhängig voneinander, eine ganze Zahl von 4 bis 8;

bedeuten.Other important non-ionic surfactants correspond to the formula

wherein

R5

C ₉ -C ₁₄ alkyl;

R6

C ₁ -C ₄ alkyl;

Y5, Y6, Y7 and Y8,

independently of one another, hydrogen, methyl or ethyl, where one of the radicals Y ₅ , Y ₆ or Y ₇ , Y _{8 is} always hydrogen; and

n4 and n5,

independently of one another, an integer from 4 to 8;

mean.

R1

C₈-C₂₂-Alkyl,

R2

Wasserstoff und

die Alkylen-O-Kette den Rest -(CH₂-CH₂-O)-
bedeuten sowie endgruppenverschlossene Fettalkoholethoxylate der Formel (3) in Betracht.The nonionic surfactants of the formulas (1) to (3) can be used as mixtures. For example, surfactant mixtures that are not capped at end groups are fatty alcohol ethoxylates of the formula (1), ie compounds of the formula (1) in which

R1

C ₈ -C ₂₂ alkyl,

R2

Hydrogen and

the alkylene-O-chain the remainder - (CH ₂ -CH ₂ -O) -
and end-capped fatty alcohol ethoxylates of the formula (3) are also possible.

Examples of the nonionic surfactants of the formulas (1), (2) or (3) are reaction products of a C ₁₀ -C ₁₃ fatty alcohol, for example a C ₁₃ oxo alcohol with 3 to 10 mol of ethylene oxide, propylene oxide and / or butylene oxide or the Reaction product of one mole of a C ₁₃ fatty alcohol with 6 moles of ethylene oxide and 1 mole of butylene oxide may be mentioned, it being possible for the addition products to be end-group-capped with C ₁ -C ₄ -alkyl, preferably methyl or butyl.

The nonionic surfactants of the formula (1) are produced in a manner known per se, for example by reacting a fatty alcohol with alkylene oxides. The corresponding end-capped nonionic surfactants are prepared by subsequent reaction of the addition _{product formed with an alkyl halide R 2} -Hal, R ₄ -Hal or R ₆ -Hal, preferably with C ₁ -C ₄ -alkyl chloride.

As ethylenically unsaturated monomeric sulfonic acids or carboxylic acids or their anhydrides, which are suitable for reaction with the nonionic surfactants of the formulas (1) to (3) can be both monocarboxylic acids and dicarboxylic acids and their anhydrides as well as sulfonic acids, each an ethylenically unsaturated aliphatic radical and preferably have a maximum of 7 carbon atoms. Preferred are monocarboxylic acids with 3 to 5 carbon atoms, e.g. acrylic acid, methacrylic acid, α-haloacrylic acid, 2-hydroxyethyl acrylic acid, α-cyanoacrylic acid, crotonic acid and Vinyl acetic acid. Ethylenically unsaturated dicarboxylic acids are preferably the Fumaric acid, maleic acid or itaconic acid, also mesaconic acid, citraconic acid, Glutaconic acid and methylmalonic acid. As an anhydride of these acids is in particular Mention maleic anhydride.

The monomeric sulfonic acids used for the reaction include, for example Vinyl sulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid in question.

Monosaccharides, disaccharides, trisaccharides or oligosaccharides are used as sugar derivatives into consideration. In the context of the present invention, a monosaccharide is understood an aldopentose, aldohexose, aldotreose, ketopentose or ketohexose. The mentioned Compounds can also be present as lactones, such as D (+) - gluconic acid-δ-lactone. Examples of an aldopentose are D-ribose, D-arabinose, D-xylose or D-lyose; for an aldohexose D-Allose, D-Altrose, D-Glucose, D-Mannose, D-Gulose, D-Ldose, D-Galactose, D-talose, L-fucose or L-rhamnose; for a ketopentose D-ribulose or D-xylulose; for a tetrose D-erythrose or threose; for a ketohexose D-psicose, D-fructose, D-sorbose or D-tagatose.

Examples of a disaccharide are trehalose, maltose, isomaltose, cellobiose, gentiobiose, Sucrose, lactose, chitobiose, N, N-diacetylchitobiose, palatinose or sucrose.

Examples of trisaccharides are raffinose, panose or maltotriose called.

Examples of oligosaccharides are maltotetraose, maltohexaose and chitoheptaose.

Particularly preferred sugar derivatives are enolizable saccharides, such as fructose or Palatinosis. In addition, sugar acids such as gluconic acids (D-gluconic acid and their salts), glucaric acids (mucic acid), glucuronic acids (D-glucuronic acid, D-galacturonic acid) can be used according to the invention.

The washing raw material according to the invention preferably corresponds to the reaction product from 5 to 13% by weight of acrylic acid or methacrylic acid and 50 to 90% by weight of the nonionic Surfactants of the formula (2) and 0 to 30% by weight of gluconic acid.

The washing raw material according to the invention is produced by reacting the nonionic surfactant of the formula (1) with an ethylenically unsaturated sulfonic acid or Carboxylic acid or its anhydride at temperatures of 30 to 100 ° C, preferably 80 to 95 ° C using a catalyst.

In particular, the ratio is nonionic surfactant or several nonionic surfactants to ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride, 8: 1 to 1: 1, in particular 6: 1 to 3: 1.

The reaction is advantageously carried out in an inert atmosphere, for example in the presence of nitrogen carried out.

Organic initiators which form free radicals are preferably used as catalysts used. Suitable initiators for carrying out the radical polymerization are e.g. symmetrical aliphatic azo compounds such as azo-bis-isobutyronitrile, azo-bis-2-methyl-valeronitrile, 1,1-azo-bis-1-cyclo-hexanitrile and 2,2-azo-bis-isobutyric acid alkyl ester; symmetrical diacyl peroxides, such as acetyl, propionyl or butyryl peroxide, Benzoyl peroxide, bromine, nitro, methyl or methoxy substituted benzoyl peroxides as well Lauroyl peroxide; symmetrical peroxydicarbonates, such as diethyl, diisopropyl, dicyclohexyl, and dibenzyl peroxydicarbonate; tert-butyl peroctoate, tert-butyl perbenzoate or tert-butylphenyl peracetate and peroxydicarbamates such as tert-butyl N- (phenylperoxy) carbamate or tert-butyl N- (2,3-dichloro- or -4-chlorophenyl peroxy) carbamate. More suitable Peroxides are: tert-butyl hydroperoxide, di-tert-butyl peroxide, cumene hydroperoxide, di-cumene peroxide and tert-butyl perpivalate. Another suitable compound is potassium persulfate, which is preferably used for the production of the washing raw material according to the invention.

The catalysts are usually in amounts of 0.01 to 1 wt .-%, based on the Starting products, used.

In a further production variant, the ethylenically unsaturated one is used in a first stage Sulphonic acid or carboxylic acid presented in high concentration and then the Fatty alcohol ethoxylate and optionally the sugar derivative formulated.

After the reaction, the reaction product obtained is with an inorganic and / or organic base, such as sodium hydroxide solution, potassium hydroxide solution, magnesium hydroxide, ethanolamine or triethanolamine to a pH of 3 to 10, preferably 4 to 5, partially neutralized. The bases used are, for example, 1 to 8% by weight inorganic or organic bases, such as sodium hydroxide, magnesium hydroxide, ethanolamine, triethanolamine, N, N, N, N-tetrakis (2-hydroxypropyl) ethylene amine or 1-amino-1-deoxysorbitol or mixtures thereof. Water is added up to 100% by weight.

To improve specific properties, such as flowability, foam behavior after the implementation, further auxiliaries, such as hydrotropic agents, higher fatty alcohols are incorporated.

The washing raw material according to the invention has a good Ca-dispersibility, i. E. additional amounts of polycarboxylates in the subsequent detergent are no longer necessary. It is also very stable to electrolytes and temperature. He owns an excellent Washing effect. The formation of macromicelles at elevated temperatures is caused by eliminates polymerization.

The laundry raw material is therefore ideally suited for the production of household detergents, such as powder or liquid detergents using the usual methods. The usage of the washing raw material according to the invention for the production of household detergents represents a further subject matter of the invention.

(a) 5 bis 35 Gew.% eines Waschrohstoffes, erhältlich aus der Umsetzung aus 5 bis 13 Gew.% einer ethylenisch ungesättigten Sulfonsäure oder Carbonsäure oder deren Anhydrid mit 50 bis 90 Gew.% eines nichtionogenen Tensids der Formel (1)   R₁-O-(Alkylen-O)_n1 -R₂ worin

R1

C₈-C₂₂-Alkyl oder C₈-C₁₈-Alkenyl;

R2

Wasserstoff; C₁-C₄-Alkyl; einen cycloaliphatischen Rest mit mindestens 6 C-Atomen oder Benzyl;

"Alkylen"

einen Alkylenrest von 2 bis 4 Kohlenstoffatomen;

n1

eine Zahl von 1 bis 60;

bedeuten, und gegebenenfalls mit Zuckerderivaten,

(b) 7 bis 46 Gew.% Zeolith oder Na-tripolyphosphat,

(c) 2 bis 6 Gew.-% Natriumsilikat oder gegebenenfalls mit kationischem Weichmacher imprägniertes Schichtsilikat,

(d) 0,8 bis 1,2 Gew.% Carboxymethylcellulose (CMC),

(e) 0,2 bis 0,6 Gew.% Phosphonat,

(f) 5 bis 15 Gew.% Natriumcarbonat,

(g) 15 bis 25 Gew.% Natriumperboratverbindungen

(h) 3 bis 5 Gew.% Peroxidaktivator,

(i) 0,5 bis 2 Gew.-% Farbstofftransfer-Inhibitoren,

(k) 5 bis 17 Gew.% Natrium-Citrat,

(I) 0,01 bis 2 Gew.-% Zusatzstoffe und

ad 100% Wasser
ernthält. A household detergent represents a further subject matter of the invention. It is characterized in that it

(a) 5 to 35% by weight of a washing raw material, obtainable from the reaction of 5 to 13% by weight of an ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride with 50 to 90 % by weight of a nonionic surfactant of the formula (1) R ₁ -O- (alkylene-O) _{n 1} -R ₂ wherein

R1

C ₈ -C ₂₂ alkyl or C ₈ -C ₁₈ alkenyl;

R2

Hydrogen; C ₁ -C ₄ alkyl; a cycloaliphatic radical with at least 6 carbon atoms or benzyl;

"Alkylene"

an alkylene group of 2 to 4 carbon atoms;

n1

a number from 1 to 60;

mean, and optionally with sugar derivatives,

(b) 7 to 46% by weight of zeolite or sodium tripolyphosphate,

(c) 2 to 6% by weight of sodium silicate or, if appropriate, sheet silicate impregnated with a cationic plasticizer,

(d) 0.8 to 1.2% by weight of carboxymethyl cellulose (CMC),

(e) 0.2 to 0.6% by weight of phosphonate,

(f) 5 to 15% by weight sodium carbonate,

(g) 15 to 25 weight percent sodium perborate compounds

(h) 3 to 5% by weight peroxide activator,

(i) 0.5 to 2% by weight dye transfer inhibitors,

(k) 5 to 17% by weight sodium citrate,

(I) 0.01 to 2% by weight of additives and

ad 100% water
holds.

Sodium perborate compounds (component (g)) are, for example, sodium perborate tetrahydrate or in particular sodium perborate monohydrate or sodium perborate percarbonate into consideration.

TAED, NOBS or TAGU can be used as peroxide activators (component (h)) Consideration.

Additives (component (l)) are e.g. perfume oil, optical brighteners or Dyes into consideration.

(m) 0 bis 2 Gew.-% Magnesiumsilikat,

(n) 0 bis 25 Gew.% Natriumsulfat,

(o) 0 bis 0,5 Gew.% Schauminhibitoren und

(p) 0 bis 2 Gew.-% Enzyme

enthalten.The detergent according to the invention can also be used as optional components

(m) 0 to 2% by weight magnesium silicate,

(n) 0 to 25% by weight sodium sulfate,

(o) 0 to 0.5% by weight foam inhibitors and

(p) 0 to 2% by weight of enzymes

contain.

Since the washing raw material according to the invention also contains the components LAS, non-ionic Replacing surfactants, defoamers, complexing agents and fatty alcohol sulfate makes this easier Use of only one component, the dosage in the detergent composition and leads to a simplification of the washing powder manufacturing process.

Through the use of various non-ionic surfactants of the formula (1), (2) or (3) the production of the inventive washing raw material can be a further variability of the Detergent can be achieved in terms of its properties. For example, the network capacity, the washing effect or the foam behavior through the use of appropriate non-ionic surfactants can be adjusted. The complexing effect and the washing effect are about the amount of ethylenically unsaturated sulfonic acids used or Carboxylic acids controllable. The sugar-acrylic acid polymers are well-known, very biologically easily degradable complexing agents and therefore also allow the calcium dispersing power to be adjusted.

The following examples serve to illustrate the invention.

A. Production of the laundry raw materials according to the invention Example 1: (not according to the invention)

Be in a 1 liter reaction vessel with a heating jacket 555.7 g Water deion. 119.9 g Adduct of one part of a C ₁₃ oxo alcohol and 9 parts of EO and 75.70 g Adduct of one part of a C ₁₃ oxo alcohol and 10 parts of EO Submitted at 20-30 ° C and heated to 90 ° C.

At an internal temperature of 90 ° C, simultaneously 195.6 g Acrylic acid within 3 hours and 1.2 g Potassium persulfate dissolved in 29.0 g Water deion. added within 195 minutes.

After the end of the metering in of the catalyst solution, the mixture is kept at 90.degree. C. for a further 30 minutes stirred and then cooled to room temperature.

At an internal temperature of 70 ° C 22.9 g Caustic soda (30%) add and stir until a clear, homogeneous solution is obtained.

Example 2:

Be in a 1 liter reaction vessel with a heating jacket 80.8 g Water deion., 750.0 g Adduct of one part of a C _9-11 fatty alcohol and 4 parts of EO Submitted at 20-30 ° C and heated to 90 ° C.

At an internal temperature of 90 ° C, simultaneously 125.0 g Acrylic acid within 3 hours and 1.2 g Potassium persulfate dissolved in 29.0 g Water deion. added within 195 minutes.

After the end of the metering in of the catalyst solution, the mixture is stirred at 90 ° C. for a further 30 minutes and then cooled to room temperature.

At an internal temperature of 70 ° C 14.0 g Sodium hydroxide solution (30%) was added and stirred until a clear, homogeneous solution is obtained.

Example 3:

Be in a 1 liter reaction vessel with a heating jacket 80.8 g Water deion., 450.0 g Adduct of one part of a C _9-11 fatty alcohol and 4 parts of EO and 300.0 g Adduct of one part of a decyl alcohol and 3 parts of EO Submitted at 20-30 ° C and heated to 90 ° C.

At an internal temperature of 90 ° C, simultaneously 125.0 g Acrylic acid within 3 hours and 1.2 g Potassium persulfate dissolved in 29.0 g Water deion. added within 195 minutes.

After the end of the metering in of the catalyst solution, the mixture is stirred at 90 ° C. for a further 30 minutes and then cooled to room temperature.

At an internal temperature of 70 ° C 14.0 g Caustic soda (30%) add and stir until a clear, homogeneous solution is obtained.

Example 4:

Be in a 1 liter reaction vessel with a heating jacket 80.8 g Water deion., 520.0 g Adduct of one part of a C ₁₁ fatty alcohol and 3 parts of EO and 239.0 g Adduct of one part of a C ₁₁ fatty alcohol and 5 parts of EO Submitted at 20-30 ° C and heated to 90 ° C.

At an internal temperature of 90 ° C, simultaneously 125.0 g Acrylic acid within 3 hours and 1.2 g Potassium persulfate dissolved in 29.0 g Water deion. added within 195 minutes.

After the end of the metering in of the catalyst solution, the mixture is stirred at 90 ° C. for a further 30 minutes and then cooled to room temperature.

At an internal temperature of 70 ° C 14.0 g Caustic soda (30%) added and stirred until a clear, homogeneous solution is formed.

Example 5: (not according to the invention)

Be in a 1 liter reaction vessel with a heating jacket 157.5 g Water deion., 208.0 g Adduct of one part of a C ₁₃ oxo alcohol and 3 parts of EO, 208.0 g Adduct of one part of a C ₁₃ oxo alcohol and 10 parts of EO and 208.0 g Adduct of one part of a decyl alcohol and 6 parts of EO / 4 parts of PO Submitted at 20-30 ° C and heated to 90 ° C.

At an internal temperature of 90 ° C, simultaneously 187.0 g Acrylic acid within 3 hours and 1.5 g Potassium persulfate dissolved in 30.0 g Water deion. added within 195 minutes.

After the end of the metering in of the catalyst solution, the mixture is stirred at 90 ° C. for a further 30 minutes and then cooled to room temperature.

Example 6:

Be in a 1 liter reaction vessel with a heating jacket 94.8 g Water deion., 375.0 g Adduct of one part of a C ₁₁ fatty alcohol and 3 parts of EO and 375.0 g Adduct of one part of a C ₁₁ fatty alcohol and 5 parts of EO Submitted at 20-30 ° C and heated to 90 ° C.

At an internal temperature of 90 ° C, simultaneously 125.0 g Acrylic acid within 3 hours and 1.2 g Potassium persulfate dissolved in 29.0 g Water deion. added within 195 minutes.

After the end of the metering in of the catalyst solution, the mixture is stirred at 90 ° C. for a further 30 minutes and then cooled to room temperature.

Example 7: (not according to the invention)

Be in a 1 liter reaction vessel with a heating jacket 154.0 g Water deion., 375.0 g Adduct of one part of a C ₁₃ oxo alcohol and 6 parts of EO, 156.0 g Adduct of one part of a decyl alcohol and 6 parts of EO / 4PO and 78.0 g Sodium gluconate Submitted at 20-30 ° C and heated to 90 ° C.

At an internal temperature of 90 ° C, simultaneously 195.0 g Acrylic acid within 3 hours and 2.0 g Potassium persulfate dissolved in 40.0 g Water deion. added within 195 minutes.

After the end of the metering in of the catalyst solution, stirring is continued at 90 ° C. for a further 30 minutes and then cooled to room temperature.

Example 8: (not according to the invention)

Be in a 1 liter reaction vessel with a heating jacket 66.0 g Water deion., 375.0 g Adduct of one part of a C ₁₃ oxo alcohol and 6 parts of EO, 156.0 g Decyl alcohol 6EO / 4PO and 78.0 g Sodium gluconate Submitted at 20-30 ° C and heated to 90 ° C.

At an internal temperature of 90 ° C, simultaneously 195.0 g Acrylic acid within 3 hours and 4.8 g Potassium persulfate dissolved in 125.0 g Water deion. added within 195 minutes.

After the catalyst solution has been metered in, the mixture is subsequently stirred at 90 ° C. for a further 30 minutes and then cooled to room temperature.

Example 9: (not according to the invention)

Be in a 1 liter reaction vessel with a heating jacket 193.8 g Water deion., 375.0 g Adduct of one part of a C ₁₃ oxo alcohol and 6 parts of EO, 156.0 g Adduct of one part of a decyl alcohol and 6 parts of EO / 4PO and 50.0 g D-gluconic acid lactone Submitted at 20-30 ° C and heated to 90 ° C.

At an internal temperature of 90 ° C, simultaneously 195.0 g Acrylic acid within 3 hours and 1.2 g Potassium persulfate dissolved in 29.0 g Water deion. added within 195 minutes.

After the end of the metering in of the catalyst solution, the mixture is stirred at 90 ° C. for a further 30 minutes and then cooled to room temperature.

Example 10:

Be in a 1 liter reaction vessel with a heating jacket 417.00 g Adduct of one part of a C ₁₁ oxo alcohol and 3 parts of EO, 417.00 g Adduct of one part of a C ₁₁ oxo alcohol and 5 parts of EO and 10.00 g Adduct of one part of a C ₁₃ oxo alcohol and 10 parts of EO Submitted at 20-30 ° C and heated to 90 ° C.

At an internal temperature of 90 ° C, simultaneously 105.0 g Acrylic acid within 3 hours and 2.0 g Potassium persulfate dissolved in 49.0 g Water deion. added within 195 minutes.

After the end of the metering in of the catalyst solution, the mixture is stirred at 90 ° C. for a further 30 minutes and then cooled to room temperature.

Example 11: (not according to the invention)

Be in a 1 liter reaction vessel with a heating jacket 343.0 g Water deion., 76.0 g Adduct of one part of a C ₁₃ oxo alcohol and 9 parts of EO, 48.0 g Adduct of one part of a C ₁₃ oxo alcohol and 10 parts of EO and 368.0 g Adduct of one part of a C ₁₀ fatty alcohol and 6 parts of EO / 1 BuO methyl ether Submitted at 20-30 ° C and heated to 90 ° C

At an internal temperature of 90 ° C, simultaneously 124.0 g Acrylic acid within 3 hours and 1.0 g Potassium persulfate dissolved in 25.0 g Water deion. added within 195 minutes.

After the end of the metering in of the catalyst solution, the mixture is stirred at 90 ° C. for a further 30 minutes and then cooled to room temperature.

At an internal temperature of approx. 70 ° C 15.0 g Caustic soda (30%) added and cooled further.

The reaction products prepared in Examples 1 to 11 can be mixed with sodium hydroxide solution, Potash lye, org. Amines (ethanolamine, triethanolamine), magnesium hydroxide etc. neutralized will. The pH value can be set between 3.0 and 10.0.

The water contained in the reaction product is removed, if necessary, preferably in a falling film evaporator.

Manufacture of powder detergent Example 12:

• Zeolith,
• Natriumcarbonat,
• Natriumsilikat,
• Phosphonat und
• Natriumsulfat.

A powder detergent is produced by spray-drying an aqueous slurry that contains the following ingredients:

• Zeolite,
• Sodium,
• Sodium silicate,
• Phosphonate and
• Sodium sulfate.

• Natriumtetraborat-Tetrahydrat bzw. vorzugsweise -Monohydrat oder -Percarbonat,
• TAED und
• andere Beimischungen wie optische Aufheller

zugemischt. Anschliessend wird der aus den Beispielen 1 bis 11 erhältliche Waschrohstoff aufgesprüht, sodass die Endformulierung 5 bis 35 Gew.-% des aktiven Waschrohstoffes enthält. Schliesslich wird gegebenenfalls Parfümöl aufgesprüht.These spray granules are then placed in a fluidized bed or ploughshare mixer

• Sodium tetraborate tetrahydrate or preferably monohydrate or percarbonate,
• TAED and
• other admixtures such as optical brighteners

mixed in. The washing raw material obtainable from Examples 1 to 11 is then sprayed on, so that the final formulation contains 5 to 35% by weight of the active washing raw material. Finally, perfume oil is sprayed on if necessary.

Example 13:

The procedure described in Example 12 is followed, but a portion of the Washing raw material obtainable from Examples 1 to 11 is admixed with the spray slurry. The final formulation contains 5 to 35% by weight of the active detergent raw material.

Example 14:

The procedure is as described in Example 12, but the entire amount is of the detergent raw material obtainable from Examples 1 to 11 is added to the spray slurry. The powder detergent contains 5 to 35% by weight of the active detergent raw material.

Example 15:

The ingredients mentioned in Example 12 are directly in the fluidized bed or Ploughshare mixers granulated or mixed and low-water or water-free washing raw materials from Examples 1 to 11 sprayed on. The content of active detergent raw material is 5 to 35 wt%.

Example 16:

All of the solid components of the spray slurry mentioned in Example 12 are used a mixing and grinding process, e.g. in a Pfugshar mixer and / or a fluidized bed unit subjected. The resulting powder material is mixed with the detergent raw material, as well as sprayed with perfume oil, so that compact granules with a high bulk density are obtained will. Finally, perborate / tetra- or preferably monohydrate or percarbonate, as well as an activator such as TAED, NOBS and, if necessary, a protective silicate mixed in. It will be a sturdy, non-sticky one Compact detergent received.

Example 17:

The washing raw material obtainable from Examples 1 to 11 is mixed with water diluted so that the final formulation contains 50 to 58% by weight of active detergent raw material and has a viscosity favorable to the end user. The solution will be silicate for setting a pH value between 7.5 and 11, as well as perfume oil, optical brighteners and optionally mixed in dyes. An "opacifier" can also be added. Very effective, liquid heavy-duty detergents are obtained.

Application examples Examples 18 to 20:

• 100 ml deionisiertes Wasser, mit NaOH auf pH 8,5, resp. 10,5 eingestellt, sowie
• die zu prüfenden Waschrohstoffe in folgenden Konzentrationen (bezogen auf den Aktivsubstanzgehalt):
• Waschbad A: keine Aktivsubstanz
• Waschbad B: 0,5 g/l
• Waschbad C: 1 g/l
• Waschbad D: 2 g/l
• Waschbad E: 4 g/l

5g-Stücke des EMPA-Standard-Testgewebes Nr. 101 (Baumwolle mit Olivenöl/Russ-Standardanschwärzung) werden je zu 100 ml Waschbad gegeben und bei 60°C während 20 Minuten gewaschen, dann 30 Sekunden mit deionisiertem Wasser gespült, geschleudert und bei 160°C gebügelt.5 washing baths (AE) are prepared, each containing

• 100 ml of deionized water, with NaOH to pH 8.5, respectively. 10.5 set, as well
• the detergent raw materials to be tested in the following concentrations (based on the active substance content):
• Wash bath A: no active substance
• Wash bath B: 0.5 g / l
• Wash bath C: 1 g / l
• Wash bath D: 2 g / l
• Wash bath E: 4 g / l

5g pieces of the EMPA standard test fabric No. 101 (cotton with olive oil / soot standard blackening) are added to 100 ml washing bath and washed at 60 ° C for 20 minutes, then rinsed for 30 seconds with deionized water, spun and at 160 Ironed at ° C.

The lightness Y of the samples is measured spectrophotometrically before and after washing, respectively measured. The difference ΔY before and after washing is a measure of the distance of dirt.

The washing results are shown in Tables 1a and 1b. Measured ΔY values
pH = 8.5 Washing bath A
no active substance Wash bath B
0.5 g / l Washing bath C
1 g / l Washing bath D
2 g / l Washing bath E
4 g / l Example 18:
Washing raw material from example 5 3 10.5 19th 21st 30th Example 19:
Washing raw material from Example 6 3 9 13th 27 28 Example 20:
Washing raw material from Example 7 3 10 12th 25th 29 Measured ΔY values
pH = 10.5 Washing bath A
no active substance Wash bath B
0.5 g / l Washing bath C
1 g / l Washing bath D
2 g / l Washing bath E
4 g / l Example 18:
Washing raw material from example 5 4.5 15th 20th 27 27 Example 19:
Washing raw material from Example 6 4.5 18th 25.5 28.5 29 Example 20:
Washing raw material from Example 7 4.5 25th 28 27 29

The results from Tables 1a and 1b show that with the inventive Very good washing results can be achieved.

Examples 21 to 23:

As a rule, detergents contain so-called "anti-redeposition agents", mostly carboxymethyl cellulose (CMC) and / or polyacrylic acid, including sodium triphosphates has such a dirt-carrying effect.

The anti-redeposition properties are tested as follows:
5 g of bleached cotton test fabric are washed in 100 ml of deionized water with a pH of 10.5 (adjusted with NaOH) for 20 minutes at 60 ° C., 40 mg of defined types of soot being added to the washing bath. It is then rinsed briefly with tap water and dried at 60.degree.

0.5 g / l each of the active detergent raw materials from Examples 5, 6 and 7 are tested. Each experiment is carried out twice, with 8 different locations on the piece of textile the lightness value Y measured spectrophotometrically, as well as the average value (= ⊘) of the 16 measured values and the standard deviation (= σ) can be calculated. When untreated Cotton material is Y = 93.0 (σ = 0.1). The decrease in brightness is a measure of the "Deposition". The more effective the anti-redeposition effect of a system, the less is this decrease, i.e. the higher the Y-number.

a) ® Cabot SRF N762 der Firma Cabot (lodadsorption 30 mg/g; DBP-Absorption = 65 ml/100 g; Siebrückstand = 325 mesh = 500 ppm, Schüttdichte = 505 g/dm³).

b) ® Carax N 765 der Firma Degussa (lodadsorption = 34 mg/g; DBP-Absorption = 122 ml/100 g; Siebrückstand 325 mesh = 500 ppm, Schüttdichte = 375 g/dm³.

The tests are carried out with the following types of soot:

a) ® Cabot SRF N762 from Cabot (iodine adsorption 30 mg / g; DBP absorption = 65 ml / 100 g; sieve residue = 325 mesh = 500 ppm, bulk density = 505 g / dm ³ ).

b) ® Carax N 765 from Degussa (iodine adsorption = 34 mg / g; DBP absorption = 122 ml / 100 g; sieve residue 325 mesh = 500 ppm, bulk density = 375 g / dm ³ .

The washing results are shown in Table 2. Y values after one wash ®Cabot SRF N762 ®Carax N765 ⊘ σ ⊘ σ Example 21:
Washing raw material from example 5 73.2 1.8 64.2 1.6 Example 22:
Washing raw material from Example 6 70.8 2.4 68.7 2.2 Example 23:
Washing raw material from example 7 70.6 1.0 63.8 2.0

The results show that the laundry raw materials according to the invention have very good redeposition properties and replace the otherwise customary redeposition means can.

Examples 24 to 26:

Surfactant solutions a) to c) are prepared, each containing 2.0 g / l des contain from Examples 5, 6 and 7 available washing raw material. Total will be so 9 solutions made.

a) mit deionisiertem Wasser,

b) mit deionisiertem Wasser und Zugabe von 5 g Olivenöl auf 50 ml Lösung,

c) Einstellung der Wasserhärte auf 15°dH durch Zugabe der entsprechenden Menge von CaCl₂-und MgSO₄-Lösungen gemäss DIN 53905

The surfactant solutions a) to c) are prepared as follows:

a) with deionized water,

b) with deionized water and adding 5 g of olive oil to 50 ml of solution,

c) Adjusting the water hardness to 15 ° dH by adding the appropriate amount of CaCl ₂ and MgSO ₄ solutions in accordance with DIN 53905

In a cylindrical glass with a diameter of 4 cm and a height of 40 cm, 50 ml of the surfactant solution was poured in and the glass was closed with a plug. After that, will the glass 10x by hand upside down and then back again. The foam height is immediately then measured at intervals of 30 seconds to 10 minutes.

The results are shown in Table 3. Test of foam heights Surfactant solution a) Surfactant solution b) Surfactant solution c) immediately after 10' immediately after 10' immediately after 10' Example 24:
Washing raw material from example 5 13th 10 18th 10 18th 10 Example 25:
Washing raw material from Example 6 15th 10 42 30th 17th 10 Example 26:
Washing raw material from example 7 38 31 22nd 17th 20th 13th

The results show that the laundry raw materials according to the invention even under load the detergent manufacturers want it with oil or water hardness Have foam behavior, i.e. that some foam is formed at the beginning of the washing process which remains on the one hand during the entire washing process, but on the other hand, is not pronounced in order to prevent overflow from the washing machine.

Claims (14)

1. A detergent base which is obtained, based on the total weight of the detergent base, from the reaction of
   5 to 13 % by weight of an ethylenically unsaturated sulfonic acid or carboxylic acid or anhydride thereof, 50 to 90 % by weight of a nonionic surfactant of the formula (1)   R₁-O-(alkylene-O)_n1 -R₂ in which

   R₁ is C₈-C₂₂alkyl or C₈-C₁₈alkenyl;

   R₂ is hydrogen; C₁-C₄alkyl; a cycloaliphatic radical having at least 6 C atoms or benzyl;

   "alkylene" is an alkylene radical having 2 to 4 carbon atoms;

   n₁ is a number from 1 to 60; and

   0 to 30 % by weight of sugar derivatives, and

   at least 1 % of water.
2. A detergent base according to claim 1, wherein the (alkylene-O) chains in formula (1) are divalent radicals of the formulae

   
3. A detergent base according to claim 1, wherein the nonionic surfactant has the formula

   

   in which

   R₃ is C₈-C₂₂ alkyl;

   R₄ is hydrogen or C₁-C₄alkyl;

   Y₁, Y₂, Y₃ and Y₄, independently of one another, are hydrogen, methyl or ethyl;

   n₂ is a number from 0 to 8; and

   n₃ is a number from 2 to 40.
4. A detergent base according to any one of claims 1 to 3, wherein the nonionic surfactant has the formula

   

   in which

   R₅ is C₉-C₁₄alkyl;

   R₆ is C₁-C₄alkyl;

   Y₅, Y₆, Y₇ and Y₈, independently of one another, are hydrogen, methyl or ethyl, where one of the radicals Y₅, Y₆ or Y₇, Y₈ is always hydrogen; and

   n₄ and n₅, independently of one another, are an integer from 4 to 8.
5. A detergent base according to any one of claims 1 to 4, wherein a monocarboxylic acid having 3 to 5 carbon atoms is used as the ethylenically unsaturated carboxylic acid.
6. A detergent base according to claim 5, wherein methacrylic acid or acrylic acid is used as the monocarboxylic acid.
7. A detergent base according to any one of claims 1 to 6, wherein an enolizable saccharide or sugar acid is used as the sugar derivative.
8. A detergent base according to claim 7, wherein gluconic acid is used as the sugar derivative.
9. A detergent base according to any one of claims 1 to 8, which is obtainable from 5 to 13 % by weight of acrylic acid or methacrylic acid and 50 to 90 % by weight of the nonionic surfactant of the formula (2) and 0 to 30 % by weight of gluconic acid.
10. A detergent base according to any one of claims 1 to 9, wherein the reaction is carried out in the presence of a catalyst and at a temperature of 30 to 100°C.
11. A detergent base according to claim 10, wherein potassium persulfate is used as the catalyst.
12. The use of a detergent base according to any one of claims 1 to 11 for the preparation of a household laundry detergent.
13. A household laundry detergent comprising

    (a) from 5 to 35 % by weight of a detergent base obtainable from the reaction of 5 to 13 % by weight of an ethylenically unsaturated sulfonic acid or carboxylic acid or anhydride thereof with 50 to 90 % by weight of a nonionic surfactant of the formula (1)   R₁-O-(alkylene-O)_n1 -R₂ in which

    R₁ is C₈-C₂₂alkyl or C₈-C₁₈alkenyl;

    R₂ is hydrogen; C₁-C₄alkyl; a cycloaliphatic radical having at least 6 C atoms or benzyl;

    "alkylene" is an alkylene radical having 2 to 4 carbon atoms;

    n₁ is a number from 1 to 60

    and if appropriate with sugar derivatives,

    (b) from 7 to 46 % by weight of zeolite or Na tripolyphosphate,

    (c) from 2 to 6 % by weight of sodium silicate or of phyllosilicate impregnated if desired with cationic softener,

    (d) from 0.8 to 1.2 % by weight of carboxymethylcellulose (CMC),

    (e) from 0.2 to 0.6 % by weight of phosphonate,

    (f) from 5 to 15 % by weight of sodium carbonate,

    (g) from 15 to 25 % by weight of sodium perborate compounds,

    (h) from 3 to 5 % by weight of peroxide activator,

    (i) from 0.5 to 2 % by weight of dye transfer inhibitors,

    (k) from 5 to 17 % by weight of sodium citrate,

    (l) from 0.01 to 2 % by weight of additives, and

    water to 100 %.
14. A household laundry detergent according to claim 13, further comprising

    (n) from 0 to 2 % by weight of magnesium silicate,

    (o) from 0 to 25 % by weight of sodium sulfate, and

    (p) from 0 to 0.5 % by weight of foam inhibitors.