EP0744459A1 - Multifunctional detergent raw material - Google Patents

Abstract

A raw material for a washing compsn. is obtd. by reacting (a) 2.5-19.6 wt.% of an ethylenically unsatd. sulphonic or carboxylic acid or anhydride with (b) 20-95 wt.% of a nonionic tenside of formula R2-O-(alkylene-O)n1-R2 and (c) 0-60% of a sugar deriv.. In the formula, R1 is a 8-22C alkyl or 8-18C alkenyl; R2 is H, 1-4C alkyl, at least 6C cycloaliphatic gp., or benzyl; alkylene is 2-4C; and n = 1-6.

Description

The present invention relates to a multifunctional detergent, the production of this raw material, its use in household detergents, and household detergents containing the detergent.

(a₁) 6 bis 12 Gew.%

Alkylbenzolsulfonat (LAS),

(a₂) 0 bis 7 Gew.-%

sek. Alkansulfonate,

(a₃) 3 bis 9 Gew.-%

nichtionogene Tenside,

(a₄) 0 bis 5 Gew.-%

kationische, zwitterionische und/oder amphotere Tenside,

(a₅) 0 bis 2 Gew.-%

Seife,

(a₆) 2 bis 6 Gew.%

Polymer, sowie

(b) 17 bis 46 Gew.%

Zeolith oder Na-tripolyphosphat,

(c) 2 bis 6 Gew.-%

Natriumsilikat oder gegebenenfalls mit kationischem Weichmacher imprägniertes Schichtsilikat,

(d) 0 bis 2 Gew.-%

Magnesiumsilikat,

(e) 0,8 bis 1,2 Gew.%

Carboxymethylcellulose (CMC),

(f) 0,2 bis 0,6 Gew.%

Phosphonat,

(g) 0 bis 25 Gew.%

Natriumsulfat,

(h) 5 bis 15 Gew.%

Natriumcarbonat,

(i) 15 bis 25 Gew.%

Natriumperborat-Tetrahydrat oder insbesondere -Monohydrat oder -Percarbonat

(k) 3 bis 5 Gew.%

Peroxidaktivator, wie z.B. TAED, NOBS, TAGU etc.

(l) 0,01 bis 0,5 Gew.%

Schauminhibitoren, und

(m) 0,01 bis 2 Gew.-%

Parfümöl, optische Aufheller, Farbstoffe

(n) 0 bis 2 Gew.-%

Enzyme,

(o) 0,5 bis 2 Gew.-%

Farbstofftransfer-Inhibitoren, wie z.B. Polyvinylpyrrolidon (Molekulargewicht 40,000)

(p) 5 bis 17 Gew.%

Natrium-Citrat und

ad 100 %

Wasser.

In addition to builders (zeolites / layered silicates), bleaching agents or bleaching systems (perborate / percarbonate plus TAED), optical brighteners and enzymes, surfactants of the alkylbenzenesulfonate (LAS) type, fatty alcohol sulfate, soaps and the like are used for the production of detergents for household laundry, such as washing powder Fatty alcohol ethoxylates used. Furthermore, polycarboxylates (polyacrylic acids) are used to improve the washing result and the Ca complexing capacity, and foam inhibitors (silicone / paraffin compounds) are used to reduce the foam. Such a powder detergent has, for example, the following composition:

(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 Na tripolyphosphate,

(c) 2 to 6% by weight

Sodium silicate or layered silicate impregnated with cationic plasticizer if necessary,

(d) 0 to 2% by weight

Magnesium silicate,

(e) 0.8 to 1.2% by weight

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 etc.

(l) 0.01 to 0.5% by weight

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.

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, if appropriate, sugar derivatives are washing raw materials which are capable of carrying out the components (a ₁ ) - (a ₆ ) specified in the above washing powder composition ) completely and to replace components (b), (e), (l) and (n) partially or completely.

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 60 Gew.% Zuckerderivaten
erhältlich ist.

The present invention therefore relates to a washing raw material, characterized in that it is based on the total weight of the washing raw material from the reaction of
2.5 to 19.6% by weight of an ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride,
20 to 95% by weight of a nonionic surfactant of the formula

wherein

R ₁

C ₈ -C ₂₂ alkyl or C ₈ -C ₁₈ alkenyl;

R ₂

Hydrogen; C ₁ -C ₄ alkyl; a cycloaliphatic radical with at least 6 carbon atoms or benzyl;
"Alkylene" means an alkylene radical of 2 to 4 carbon atoms;

n ₁

a number from 1 to 60;
mean and
0 to 60% by weight sugar derivatives
is available.

Because of their low tendency to foam, especially when non-ionic surfactants of the formula (1) are used, low-ethoxylated fatty alcohol ethoxylates, such as C ₁₃ oxo alcohols with 4 to 6 ethylene oxide units, can be added to foam inhibitors (component ( I)) to be dispensed with.

The washing raw material according to the invention also has excellent anti-redeposition properties, so that in detergents containing this washing raw material, the 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.

As aliphatic saturated monoalcohols, natural alcohols, such as, for example, lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, and synthetic alcohols, such as, for example, 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethylnonyl alcohol Decanol, C ₉ -C ₁₁ oxo alcohol, tridecyl alcohol, isotridecyl alcohol or linear primary alcohols (alfoles) with 8 to 22 carbon atoms can be used. Some representatives of these alfoles 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, hexadecenyl alcohol or oleyl alcohol.

The alcohol residues can be present individually or in the form of mixtures of two or more components, e.g. Mixtures of alkyl and / or alkenyl groups which are derived from soy fatty acids, palm kernel fatty acids or tallow oils.

(Alkylene-O) chains are preferably divalent radicals of the formulas
- (CH ₂ -CH ₂ -O) -,

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

R ₃

C ₈ -C ₂₂ alkyl;

R ₄

Hydrogen or C ₁ -C ₄ alkyl;

Y ₁ , Y ₂ , Y ₃ and Y ₄ ,

independently of one another, hydrogen, methyl or ethyl;

n ₂

a number from 0 to 8; and

n ₃

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 nonionic surfactants correspond to the formula

wherein

R ₅

C ₉ -C ₁₄ alkyl;

R ₆

C ₁ -C ₄ alkyl;

Y ₅ , Y ₆ , Y ₇ and Y ₈ ,

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

n ₄ and n ₅ ,

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 formulas (1) to (3) can be used as mixtures. For example, non-end-capped fatty alcohol ethoxylates of the formula (1), ie compounds of the formula (1), in which

R ₁

C ₈ -C ₂₂ alkyl,

R ₂

Hydrogen and
the alkylene O chain the rest - (CH ₂ -CH ₂ -O) -
mean and end group-capped fatty alcohol ethoxylates of the formula (3).

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 moles of ethylene oxide, propylene oxide and / or butylene oxide or that To name reaction product of one mole of a C ₁₃ fatty alcohol with 6 moles of ethylene oxide and 1 mole of butylene oxide, it being possible for the addition products in each case to be end-capped with C ₁ -C ₄ -alkyl, preferably methyl or butyl.

The nonionic surfactants of the formula (1) are prepared 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 adduct 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), both monocarboxylic acids and dicarboxylic acids and their anhydrides as well as sulfonic acids, each of which is an ethylenically unsaturated aliphatic The rest and preferably have at most 7 carbon atoms can be used. Monocarboxylic acids having 3 to 5 carbon atoms, e.g. acrylic acid, methacrylic acid, α-haloacrylic acid, 2-hydroxyethylacrylic acid, α-cyanoacrylic acid, crotonic acid and vinyl acetic acid. Ethylenically unsaturated dicarboxylic acids are preferably fumaric acid, maleic acid or itaconic acid, furthermore mesaconic acid, citraconic acid, glutaconic acid and methylmalonic acid. Maleic anhydride should be mentioned in particular as the anhydride of these acids.

Examples of suitable monomeric sulfonic acids which are used for the reaction are vinylsulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid.

Monosaccharides, disaccharides, trisaccharides or oligosaccharides are suitable as sugar derivatives. In the context of the present invention, monosaccharide is understood to mean an aldopentose, aldohexose, aldotreose, ketopentose or ketohexose. The compounds mentioned can also be present as lactones, e.g. 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-Idose, D-Galactose, D-Talose, L-Fucose or L-Rhamnose; for a ketopentose D-ribulose or D-xylulose; for a tetrose D erythrosis or threosis; 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.

Raffinose, panose or maltotriose may be mentioned as examples of trisaccharide.

Maltotetraose, maltohexaose and chitoheptaose may be mentioned as examples of oligosaccharide.

Particularly preferred sugar derivatives are enolizable saccharides, e.g. Fructose or palatinose. In addition, sugar acids, e.g. Gluconic acids (D-gluconic acid and its salts), glucaric acids (mucic acid), glucuronic acids (D-glucuronic acid, D-galacturonic acid) can be used according to the invention.

The individual components are preferably used in the following amounts for the reaction:
50 to 90% by weight of one or more nonionic surfactants,
5 to 13% by weight of an ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride,
0 to 30 wt .-% sugar derivatives, and
1 to 60, especially 1 to 20% water.

The raw material for washing according to the invention preferably corresponds to the reaction product of 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.

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

In particular, the ratio of nonionic surfactant or several nonionic tenides to ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride is 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.

Free radical-forming organic initiators are preferably used as catalysts. Suitable initiators for carrying out the radical polymerization are e.g. symmetrical aliphatic azo compounds such as azo-bis-isobutyronitrile, azo-bis-2-methylvaleronitrile, 1,1-azo-bis-1-cyclo-hexanitrile and 2,2-azo-bis-isobutyric acid alkyl ester; symmetrical diacyl peroxides, e.g. Acetyl, propionyl or butyryl peroxide, benzoyl peroxide, bromo, nitro, methyl or methoxy substituted benzoyl peroxides and lauroyl peroxide; symmetrical peroxydicarbonates, e.g. Diethyl, diisopropyl, dicyclohexyl and dibenzyl peroxidicarbonate; tert-butyl peroctoate, tert-butyl perbenzoate or tert-butylphenyl peracetate and peroxidicarbamates such as tert-butyl-N- (phenylperoxi) carbamate or tert-butyl-N- (2,3-dichloro- or -4-chlorophenyl- peroxi) carbamate. Other 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 generally used in amounts of 0.01 to 1% by weight, based on the starting products.

In a further production variant, the ethylenically unsaturated sulfonic acid or carboxylic acid is introduced in a high concentration in a first stage and then the fatty alcohol ethoxylate and optionally the sugar derivative are formulated.

After the reaction, the reaction product obtained is treated with an inorganic and / or organic base, such as e.g. Sodium hydroxide solution, potassium hydroxide solution, magnesium hydroxide, ethanolamine or triethanolamine to a pH of 3 to 10, preferably 4 to 5, partially neutralized. As bases one uses e.g. 1 to 8% by weight inorganic or organic bases, e.g. 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 to 100% by weight.

To improve the specific properties, such as flowability, foaming behavior, etc., further auxiliaries, such as hydrotroping agents, higher fatty alcohols, etc., can be incorporated after the reaction.

The washing raw material according to the invention has a good Ca dispersing capacity, i.e. additional amounts of polycarboxylates in the later detergent are no longer necessary. In addition, it is very stable to electrolytes and temperature. It has an excellent washing effect. The formation of macromicelles at elevated temperatures is eliminated by the polymerization.

The raw material for washing is therefore ideal for the production of household detergents, e.g. Powder or liquid detergents according to the usual methods. The use of the washing raw material according to the invention for the production of household detergents represents a further subject of the invention.

• (a) 5 bis 35 Gew.% eines Waschrohstoffes, erhältlich aus der Umsetzung aus einer ethylenisch ungesättigten Sulfonsäure oder Carbonsäure oder deren Anhydrid mit einem nichtionogenen Tensid der Formel
  
  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,
• (l) 0,01 bis 2 Gew.-% Zusatzstoffe und
  ad 100% Wasser
  ernthält.

Another object of the invention is a household detergent. It is characterized in that it

• (a) 5 to 35% by weight of a wash raw material, obtainable from the reaction from an ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride with a nonionic surfactant of the formula
  
  wherein

  R ₁

  C ₈ -C ₂₂ alkyl or C ₈ -C ₁₈ alkenyl;

  R ₂

  Hydrogen; C ₁ -C ₄ alkyl; a cycloaliphatic radical with at least 6 carbon atoms or benzyl;
  "Alkylene" means an alkylene radical of 2 to 4 carbon atoms;

  n ₁

  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 sheet silicate impregnated with cationic plasticizer if necessary,
• (d) 0.8 to 1.2% by weight carboxymethyl cellulose (CMC),
• (e) 0.2 to 0.6% by weight phosphonate,
• (f) 5 to 15% by weight sodium carbonate,
• (g) 15 to 25% by weight sodium perborate compounds
• (h) 3 to 5% by weight of peroxide activator,
• (i) 0.5 to 2% by weight of dye transfer inhibitors,
• (k) 5 to 17% by weight sodium citrate,
• (l) 0.01 to 2% by weight of additives and
  ad 100% water
  sustains.

Sodium perborate compounds (component (g)) include e.g. Sodium perborate tetrahydrate or in particular sodium perborate monohydrate or sodium perborate percarbonate.

Peroxide activators (component (h)) include e.g. TAED, NOBS or TAGU.

As additives (component (l)) come e.g. Perfume oil, optical brighteners or dyes.

• (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 furthermore 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 detergent raw material according to the invention simultaneously replaces the components LAS, nonionic surfactant, defoamer, complexing agent and fatty alcohol sulfate, the use of only one component facilitates the metering in the detergent composition and leads to a simplification of the detergent powder production process.

Through the use of various nonionic surfactants of the formula (1), (2) or (3) in the production of the detergent raw material according to the invention, a further variability of the properties of the detergent can be achieved. For example, the wetting capacity, the washing effect or the foaming behavior can be adjusted by using appropriate non-ionic surfactants. The complexing action and the washing action can be controlled via the amount of the ethylenically unsaturated sulfonic acids or carboxylic acids used. The sugar-acrylic acid polymers are known, highly biodegradable complexing agents and therefore also allow the calcium dispersing capacity to be adjusted.

The following examples serve to illustrate the invention.

A. Production of the washing raw materials according to the invention Example 1:

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 from 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 at the same time
195.6 g acrylic acid within 3 hours and
1.2 g potassium persulfate, dissolved in
29.0 g water deion.
metered in within 195 minutes.
After the catalyst solution has been metered in, the mixture is stirred for a further 30 minutes at 90 ° C. and then cooled to room temperature.
At an indoor temperature of 70 ° C
22.9 g sodium hydroxide solution (30%)
add and stir until a clear, homogeneous solution is obtained.

Example 2:

In a 1 liter reaction vessel with a heating jacket
80.8 g water deion.,
750.0 g adduct from 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 at the same time
125.0 g acrylic acid within 3 hours and
1.2 g potassium persulfate, dissolved in
29.0 g water deion.
metered in within 195 minutes.
After the catalyst solution has been metered in, the mixture is stirred for a further 30 minutes at 90 ° C. and then cooled to room temperature.
At an indoor temperature of 70 ° C
14.0 g sodium hydroxide solution (30%) was added
and stirred until a clear, homogeneous solution is obtained.

Example 3:

In a 1 liter reaction vessel with a heating jacket
80.8 g water deion.,
450.0 g adduct from one part of a C _9-11 fatty alcohol and 4 parts of EO and
300.0 g adduct from 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 at the same time
125.0 g of acrylic acid within 3 hours and
1.2 g potassium persulfate, dissolved in
29.0 g water deion.
metered in within 195 minutes.
After the catalyst solution has been metered in, the mixture is stirred for a further 30 minutes at 90 ° C. and then cooled to room temperature.
At an indoor temperature of 70 ° C
14.0 g sodium hydroxide solution (30%)
add and stir until a clear, homogeneous solution is obtained.

Example 4:

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 of adduct from one part of a C ₁₁ fatty alcohol and 5 parts of EO at 20-30 ° C. and heated to 90 ° C.
At an internal temperature of 90 ° C at the same time
125.0 g acrylic acid within 3 hours and
1.2 g potassium persulfate, dissolved in
29.0 g water deion.
metered in within 195 minutes.
After the catalyst solution has been metered in, the mixture is stirred for a further 30 minutes at 90 ° C. and then cooled to room temperature.
At an indoor temperature of 70 ° C
14.0 g sodium hydroxide solution (30%)
added and stirred until a clear, homogeneous solution is obtained.

Example 5:

In a 1 liter reaction vessel with a heating jacket
157.5 g water deion.,
208.0 g adduct from one part of a C ₁₃ oxo alcohol and 3 parts of EO,
208.0 g adduct from one part of a C ₁₃ oxo alcohol and 10 parts of EO and
208.0 g of adduct from one part of a decyl alcohol and 6 parts of EO / 4 parts of PO are introduced at 20-30 ° C. and heated to 90 ° C.
At an internal temperature of 90 ° C at the same time
187.0 g of acrylic acid within 3 hours and
1.5 g potassium persulfate, dissolved in
30.0 g water deion.
metered in within 195 minutes.
After the catalyst solution has been metered in, the mixture is stirred for a further 30 minutes at 90 ° C. and then cooled to room temperature.

Example 6:

In a 1 liter reaction vessel with a heating jacket
94.8 g water deion.,
375.0 g of adduct from one part of a C ₁₁ fatty alcohol and 3 parts of EO and
375.0 g of adduct from one part of a C ₁₁ fatty alcohol and 5 parts of EO at 20-30 ° C. and heated to 90 ° C.
At an internal temperature of 90 ° C at the same time
125.0 g of acrylic acid within 3 hours and
1.2 g potassium persulfate, dissolved in
29.0 g water deion.
metered in within 195 minutes.
After the catalyst solution has been metered in, the mixture is stirred for a further 30 minutes at 90 ° C. and then cooled to room temperature.

Example 7:

In a 1 liter reaction vessel with a heating jacket
154.0 g water deion.,
375.0 g of adduct from 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 at the same time
195.0 g of acrylic acid within 3 hours and
2.0 g potassium persulfate, dissolved in
40.0 g water deion.
metered in within 195 minutes.
After the catalyst solution has been metered in, the mixture is stirred for a further 30 minutes at 90 ° C. and then cooled to room temperature.

Example 8:

In a 1 liter reaction vessel with a heating jacket
66.0 g water deion.,
375.0 g of adduct from 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 at the same time
195.0 g of acrylic acid within 3 hours and
4.8 g potassium persulfate, dissolved in
125.0 g water deion.
metered in within 195 minutes.
After the catalyst solution has been metered in, the mixture is stirred for a further 30 minutes at 90 ° C. and then cooled to room temperature.

Example 9:

In a 1 liter reaction vessel with a heating jacket
193.8 g water deion.,
375.0 g of adduct from 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 at the same time
195.0 g of acrylic acid within 3 hours and
1.2 g potassium persulfate, dissolved in
29.0 g water deion.
metered in within 195 minutes.
After the catalyst solution has been metered in, the mixture is stirred for a further 30 minutes at 90 ° C. and then cooled to room temperature.

Example 10:

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 of adduct from one part of a C ₁₃ oxo alcohol and 10 parts of EO at 20-30 ° C. and heated to 90 ° C.
At an internal temperature of 90 ° C at the same time
105.0 g acrylic acid within 3 hours and
2.0 g potassium persulfate, dissolved in
49.0 g water deion.
metered in within 195 minutes.
After the catalyst solution has been metered in, the mixture is stirred for a further 30 minutes at 90 ° C. and then cooled to room temperature.

Example 11:

In a 1 liter reaction vessel with a heating jacket
343.0 g water deion.,
76.0 g adduct from 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 from one part of a C ₁₀ fatty alcohol and 6 parts of EO / 1BuO methyl ether
submitted at 20 - 30 ° C and heated to 90 ° C
At an internal temperature of 90 ° C at the same time
124.0 g of acrylic acid within 3 hours and
1.0 g potassium persulfate, dissolved in
25.0 g water deion.
metered in within 195 minutes.
After the catalyst solution has been metered in, the mixture is stirred for a further 30 minutes at 90 ° C. and then cooled to room temperature.
At an internal temperature of approx. 70 ° C
15.0 g sodium hydroxide solution (30%)
added and cooled further.

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

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

Production of a powder detergent Example 12:

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

A powder detergent is made by spray drying an aqueous slurry containing the following ingredients:

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

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

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.This spray granulate is then placed in a fluid bed or ploughshare mixer

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

added. The wash 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 wash raw material. Finally, perfume oil is sprayed on if necessary.

EXAMPLE 13 The procedure is as described in Example 12, but a subset of the wash raw material obtainable from Examples 1 to 11 is mixed into the spray slurry. The final formulation contains 5 to 35% by weight of the active wash raw material.

Example 14: The procedure is as described in Example 12, but the entire amount of the wash raw material obtainable from Examples 1 to 11 is mixed into the spray slurry. The powder detergent contains 5 to 35% by weight of the active detergent.

Example 15: The ingredients mentioned in Example 12 are granulated or mixed directly in the fluidized bed or ploughshare mixer and low-water or water-free washing raw materials from Examples 1 to 11 are sprayed on. The active wash raw material content is 5 to 35% by weight.

Example 16: All solid components of the spray slurry mentioned in Example 12 are subjected to a mixing and grinding process, for example in a ploughshare mixer and / or a fluidized bed unit. The resulting powder material is sprayed with the wash raw material and with perfume oil, so that compact granules with a high bulk density are obtained. Finally, perborate / tetra or preferably monohydrate or percarbonate, and an activator such as TAED, NOBS and optionally a protective silicate are mixed in the fluidized bed or ploughshare mixer. A stable, non-sticky, compact detergent is obtained.

Example 17: The wash raw material obtainable from Examples 1 to 11 is diluted with water, so that the final formulation contains 50 to 58% by weight of active wash raw material and has a viscosity which is favorable for the end user. Silicate is added to the solution to adjust a pH between 7.5 and 11, and perfume oil, optical brighteners and, if appropriate, dyes. An "opazifier" can also be added. Very effective, liquid heavy-duty detergents are obtained.

Application examples

• 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. Examples 18 to 20: 5 washing baths (AE) are prepared, each containing

• 100 ml deionized water, with NaOH to pH 8.5, respectively. 10.5 set, as well
• the washing 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

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

The brightness Y of the samples is measured spectrophotometrically before and after washing. The difference ΔY before and after washing is a measure of the removal of dirt.

The washing results are shown in Tables 1a and 1b.

The results from Tables 1a and 1b show that very good washing results are achieved with the washing raw materials according to the invention.

Examples 21 to 23: As a rule, detergents contain so-called “anti-redeposition agents”, mostly carboxymethyl cellulose (CMC) and / or polyacrylic acid, Na triphosphates also having 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., whereby 40 mg of defined soot types are added to the wash bath. Then it is rinsed briefly with tap water and dried at 60 ° C.

0.5 g / l of the active wash raw materials from Examples 5, 6 and 7 are tested in each case. Each test is carried out twice, with the brightness value Y being measured spectrophotometrically at 8 different points on the textile piece, the average value (= ⌀) of the 16 measured values and the standard deviation (= σ) being calculated. For the untreated cotton material, 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 this decrease, i.e. the higher the Y number.

• a) ®Cabot SRF N762 der Firma Cabot (Iodadsorption 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 (Iodadsorption = 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. 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 washing raw materials according to the invention have very good redeposition properties and can replace the otherwise commercially available redeposition agents.

Examples 24 to 26: Surfactant solutions a) to c) are prepared, each containing 2.0 g / l of the wash raw material obtainable from Examples 5, 6 and 7. In total, 9 solutions are produced.

• 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) Setting the water hardness to 15 ° dH by adding the appropriate amount of
• CaCl ₂ and MgSO ₄ solutions according to DIN 53905

50 ml of the surfactant solution are poured into a cylindrical glass 4 cm in diameter and 40 cm high at room temperature and the glass is closed with a plug. Then the glass is turned upside down 10 times by hand and back again. The foam height is measured immediately, then at intervals of 30 seconds to 10 minutes.

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

The results show that the washing raw materials according to the invention have the foaming behavior desired by the detergent manufacturers even when exposed to oil or water hardness, i.e. that at the beginning of the washing process some foam is formed which remains on the one hand during the entire washing process but on the other hand is not pronounced in order to prevent it from overflowing out of the washing machine.

Claims (15)

Washing raw material, characterized in that it, based on the total weight of the washing raw material, from the implementation of
2.5 to 19.6% by weight of an ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride,
20 to 95% by weight of a nonionic surfactant of the formula

wherein R _{1 is} C ₈ -C ₂₂ alkyl or C ₈ -C ₁₈ alkenyl; R _{2 is} hydrogen; C ₁ -C ₄ alkyl; a cycloaliphatic radical with at least 6 carbon atoms or benzyl;
"Alkylene" means an alkylene radical of 2 to 4 carbon atoms; n _{1 is} a number from 1 to 60;
mean and
0 to 60% by weight sugar derivatives
is available. Washing raw material according to claim 1, characterized in that the (alkylene-O) chains in formula (1) divalent radicals of the formulas
- (CH ₂ -CH ₂ -O) -,

are. Washing raw material according to claim 1, characterized in that the nonionic surfactants of the formula

correspond to what R _{3 is} C ₈ -C ₂₂ alkyl; R _{4 is} hydrogen or C ₁ -C ₄ alkyl; Y ₁ , Y ₂ , Y ₃ and Y ₄ , independently of one another, are hydrogen, methyl or ethyl; n _{2 is} a number from 0 to 8; and n _{3 is} a number from 2 to 40;
mean. Washing raw material according to one of claims 1 to 3, characterized in that the nonionic surfactants of the formula

correspond to what R _{5 is} C ₉ -C ₁₄ alkyl; R ₆ C ₁ -C ₄ alkyl; Y ₅ , Y ₆ , Y ₇ and Y ₈ , independently of one another, are hydrogen, methyl or ethyl, where one of the radicals Y ₅ , Y ₆ or Y ₇ , Y _{8 is} always hydrogen; and n ₄ and n ₅ , independently of one another, are an integer from 4 to 8;
mean. Washing raw material according to one of claims 1 to 4, characterized in that monocarboxylic acids having 3 to 5 carbon atoms are used as ethylenically unsaturated carboxylic acids. Washing raw material according to claim 5, characterized in that methacrylic acid or acrylic acid is used as monocarboxylic acids. Washing raw material according to one of claims 1 to 6, characterized in that enolizable saccharides or sugar acids are used as sugar derivatives. Washing raw material according to claim 7, characterized in that gluconic acid is used as the sugar derivative. Washing raw material according to one of claims 1 to 8, characterized in that it consists of
50 to 90% by weight of one or more nonionic surfactants,
5 to 13% by weight of an ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride,
0 to 30% by weight of sugar derivatives, and
1 to 60, especially 1 to 20% water.
is available. Washing raw material according to one of claims 1 to 9, characterized in that it can be obtained 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 is. Washing raw material according to one of claims 1 to 10, characterized in that the reaction is carried out in the presence of a catalyst and at temperatures of 30 to 100 ° C. Washing raw material according to claim 11, characterized in that potassium persulfate is used as catalyst. Use of the washing raw material according to one of claims 1 to 12 for the production of a household detergent. Household detergents containing (a) 5 to 35% by weight of a wash raw material, obtainable from the reaction from an ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride with a nonionic surfactant of the formula

wherein R _{1 is} C ₈ -C ₂₂ alkyl or C ₈ -C ₁₈ alkenyl; R _{2 is} hydrogen; C ₁ -C ₄ alkyl; a cycloaliphatic radical with at least 6 carbon atoms or benzyl;
"Alkylene" means an alkylene radical of 2 to 4 carbon atoms; n _{1 is} 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 sheet silicate impregnated with cationic plasticizer if necessary, (d) 0.8 to 1.2% by weight carboxymethyl cellulose (CMC), (e) 0.2 to 0.6% by weight phosphonate, (f) 5 to 15% by weight sodium carbonate, (g) 15 to 25% by weight sodium perborate compounds (h) 3 to 5% by weight of peroxide activator, (i) 0.5 to 2% by weight of dye transfer inhibitors, (k) 5 to 17% by weight sodium citrate, (l) 0.01 to 2% by weight of additives and
ad 100% water. Household detergent according to claim 14, characterized in that it is additionally (n) 0 to 2% by weight magnesium silicate, (o) 0 to 25% by weight sodium sulfate and (p) 0 to 0.5% by weight foam inhibitors
contains.