EP1761622B1 - Method for producing granulated or powdery detergent compounds - Google Patents

Abstract

The present invention relates to a process for preparing granular or pulverulent detergent compositions, comprising the preparation of a detergent base powder by drying an aqueous detergent slurry, which comprises adding to the slurry a copolymer which is obtainable by free-radical copolymerization of (A) from 50 to 99.5 mol % of a monoethylenically unsaturated monocarboxylic acid and/or a salt thereof, (B) from 0.5 to 20 mol % of an alkoxylated monoethylenically unsaturated monomer I in which the variables are defined as follows: R<SUP>1 </SUP>is hydrogen or methyl; R<SUP>2 </SUP>is -(CH<SUB>2</SUB>)<SUB>x</SUB>-O-, -CH<SUB>2</SUB>-NR<SUP>5</SUP>-, -CH<SUB>2</SUB>-O-CH<SUB>2</SUB>-CR<SUP>6</SUP>R<SUP>7</SUP>-CH<SUB>2</SUB>-O- or -CONH-; R<SUP>3 </SUP>are each identical or different C<SUB>2</SUB>-C<SUB>4</SUB>-alkylene radicals which may be arranged blockwise or randomly, the proportion of ethylene radicals being at least 50 mol %; R<SUP>4 </SUP>is hydrogen, C<SUB>1</SUB>-C<SUB>4</SUB>-alkyl, -SO<SUB>3</SUB>M or -PO<SUB>3</SUB>M<SUB>2</SUB>; R<SUP>5 </SUP>is hydrogen or -CH<SUB>2</SUB>-CR<SUP>1</SUP>-CH<SUB>2</SUB>; R<SUP>6 </SUP>is -O-[R<SUP>3</SUP>-O]<SUB>n</SUB>-R<SUP>4</SUP>, where the -[R<SUP>3</SUP>-O]<SUB>n</SUB>- radicals may be different from the further -[R<SUP>3</SUP>-O]<SUB>n</SUB>- radicals present in formula I; R<SUP>7 </SUP>is hydrogen or ethyl; M is alkali metal or hydrogen; n is from 4 to 250; x is 0 or 1, (C) from 0 to 50 mol % of a monoethylenically unsaturated dicarboxyic acid, of an anhydride and/or of a salt thereof and (D) from 0 to 20 mol % of a further copolymerizable monoethylenically unsaturated monomer and has an average molecular weight M<SUB>w </SUB>of from 30 000 to 500 000 g/mol and a K value of from 40 to 150 (measured at pH 7 in 1% by weight aqueous solution at 25° C.).

Description

1. (A) 50 bis 99,5 mol-% einer monoethylenisch ungesättigten Monocarbonsäure und/oder eines Salzes davon,
2. (B) 0,5 bis 20 mol-% eines alkoxylierten monoethylenisch ungesättigten Monomers der Formel I
   
   in der die Variablen folgende Bedeutung haben:

   R¹

   Wasserstoff oder Methyl;

   R²

   -(CH₂)_xO-, -CH₂-NR⁵-, -CH₂-O-CH₂-CR⁶R⁷-CH₂-O- oder -CONH-;

   R³

   gleiche oder verschiedene C₂-C₄-Alkylenreste, die blockweise oder statis- tisch angeordnet sein können, wobei der Anteil an Ethylenresten mindes- tens 50 mol% beträgt;

   R⁴

   Wasserstoff, C₁-C₄-Alkyl, -SO₃M oder -PO₃M_2;

   R⁵

   Wasserstoff oder -CH₂-CR¹=CH₂;

   R⁸

   -O-[R³-O]_n-R⁴, wobei die Reste -[R³-O]_n- von den weiteren in Formel I enthaltenen Resten -[R³-O]_n- verschieden sein können;

   R⁷

   Wasserstoff oder Ethyl;

   M

   Alkalimetall oder Wasserstoff;

   n

   4 bis 250;

   x

   0 oder 1,

3. (C) 0 bis 50 mol-% einer monoethylenisch ungesättigten Dicarbonsäure, eines Anhydrids und/oder eines Salzes davon
   und
4. (D) 0 bis 20 mol-% eines weiteren copolymerisierbaren monoethylenisch ungesättigten Monomers

erhältliches Copolymer, das ein mittleres Molekulargewicht M_w von 30 000 bis 500 000 g/mol und einen K-Wert von 40 bis 150 (gemessen beim pH-Wert 7 in 1 gew.-%iger wäßriger Lösung bei 25°C) aufweist,
und die Verwendung dieses Copolymers als Zusatz in Waschmittelzusammensetzungen.The present invention relates to a process for the preparation of granular or powdered detergent compositions, which comprises the preparation of a detergent base powder by drying an aqueous detergent slurries, and detergent compositions containing by free-radical copolymerization of

1. (A) 50 to 99.5 mol% of a monoethylenically unsaturated monocarboxylic acid and / or a salt thereof,
2. (B) 0.5 to 20 mol% of an alkoxylated monoethylenically unsaturated monomer of the formula I.
   
   in which the variables have the following meaning:

   R ¹

   Hydrogen or methyl;

   R ²

   - (CH ₂ ) _x O-, -CH ₂ -NR ⁵ -, -CH ₂ -O-CH ₂ -CR ⁶ R ⁷ -CH ₂ -O- or -CONH-;

   R ³

   identical or different C ₂ -C ₄ -alkylene radicals which may be arranged blockwise or randomly, the proportion of ethylene radicals being at least 50 mol%;

   R ⁴

   Hydrogen, C ₁ -C ₄ -alkyl, -SO ₃ M or -PO ₃ M _2;

   R ⁵

   Hydrogen or -CH ₂ -CR ¹ = CH ₂ ;

   R ⁸

   -O- [R ³ -O] _n -R ⁴ , where the radicals - [R ³ -O] _n - may be different from the other radicals contained in formula I - [R ³ -O] _n -;

   R ⁷

   Hydrogen or ethyl;

   M

   Alkali metal or hydrogen;

   n

   4 to 250;

   x

   0 or 1,

3. (C) 0 to 50 mol% of a monoethylenically unsaturated dicarboxylic acid, an anhydride and / or a salt thereof
   and
4. (D) 0 to 20 mol% of another copolymerizable monoethylenically unsaturated monomer

copolymer which has an average molecular weight M _w of 30,000 to 500,000 g / mol and a K value of 40 to 150 (measured at pH 7 in 1% strength by weight aqueous solution at 25 ° C.),
and the use of this copolymer as an additive in detergent compositions.

In the preparation of powder detergents or base powders for further processing into solid detergents (for example extrusion with the addition of further components to granules), up to 30 liquid or solid components must be homogenized as intensively and uniformly as possible in partly very different amounts, which is achieved by slurrying in water. Here, various components, e.g. Surfactants and zeolites used as builders, highly viscous mixtures. Since highly concentrated slurries are desired for the subsequent spray drying, it is necessary to use auxiliaries which lower the viscosity of the slurries.

In the US-A-5 595 968 . 5,618,782 and 5,733,861 For this purpose, copolymers of acrylic acid and ethoxylated allyl ethers having an average molecular weight M _w of about 12,000 are used.

In the EP-A-778 340 describes the use of these copolymers as well as copolymers of acrylic acid and both propoxylated and ethoxylated allyl ethers as scale inhibitors in automatic dishwashing detergents.

Finally, according to the WO-A-91/09932 Copolymers based on unsaturated mono- and / or dicarboxylic acids with a hydrophilic backbone and hydrophobic side chains can also be used for this purpose. The side chains are linked to the skeleton via ester, ether or amide functions and may consist of polyalkylene oxides which either have a high proportion of C ₃ -C ₄ -alkylene oxides or are end-capped by long-chain alkyl radicals.

It is an object of the invention to advantageously enable the preparation of solid detergent compositions by the use of viscosity-reducing polymers. In addition, the polymers used should have advantageous performance effect in the resulting detergents.

1. (A) 50 bis 99,5 mol-% einer monoethylenisch ungesättigten Monocarbonsäure und/oder eines Salzes davon,
2. (B) 0,5 bis 20 mol-% eines alkoxylierten monoethylenisch ungesättigten Monomers der Formel I
   
   in der die Variablen folgende Bedeutung haben:

   R¹

   Wasserstoff oder Methyl;

   R²

   -(CH₂)_x-O-, -CH₂-NR⁵-, -CH₂-O-CH₂-CR⁶R⁷-CH₂-O- oder -CONH-;

   R³

   gleiche oder verschiedene C₂-C₄-Alkylenreste, die blockweise oder statis- tisch angeordnet sein können, wobei der Anteil an Ethylenresten mindes- tens 50 mol-% beträgt;

   R⁴

   Wasserstoff, C₁-C₄-Alkyl, -SO₃M oder -PO₃M₂;

   R⁵

   Wasserstoff oder -CH₂-CR¹=CH₂;

   R⁶

   -O-[R³-O]_n-R⁴, wobei die Reste -[R³-O]_n- von den weiteren in Formel I enthaltenen Resten -[R³-O]_n- verschieden sein können;

   R⁷

   Wasserstoff oder Ethyl;

   M

   Alkalimetall oder Wasserstoff;

   n

   4 bis 250;

   x

   0 oder 1,

3. (C) 0 bis 50 mol% einer monoethylenisch ungesättigten Dicarbonsäure, eines Anhydrids und/oder eines Salzes davon
   und
4. (D) 0 bis 20 mol% eines weiteren copolymerisierbaren monoethylenisch ungesättigten Monomers

erhältlich ist und ein mittleres Molekulargewicht M_w von 30 000 bis 500 000 g/mol und einen K-Wert von 40 bis 150 (gemessen beim pH-Wert 7 in 1 gew.-%iger wäßriger Lösung bei 25°C) aufweist.Accordingly, there has been found a process for the preparation of granular or powder detergent compositions comprising the preparation of a detergent base powder by drying an aqueous detergent slurry which passes therethrough characterized in that the slurry is added to a copolymer by free-radical copolymerization of

1. (A) 50 to 99.5 mol% of a monoethylenically unsaturated monocarboxylic acid and / or a salt thereof,
2. (B) 0.5 to 20 mol% of an alkoxylated monoethylenically unsaturated monomer of the formula I.
   
   in which the variables have the following meaning:

   R ¹

   Hydrogen or methyl;

   R ²

   - (CH ₂ ) _x -O-, -CH ₂ -NR ⁵ -, -CH ₂ -O-CH ₂ -CR ⁶ R ⁷ -CH ₂ -O- or -CONH-;

   R ³

   identical or different C ₂ -C ₄ -alkylene radicals which may be arranged blockwise or randomly, the proportion of ethylene radicals being at least 50 mol%;

   R ⁴

   Hydrogen, C ₁ -C ₄ -alkyl, -SO ₃ M or -PO ₃ M ₂ ;

   R ⁵

   Hydrogen or -CH ₂ -CR ¹ = CH ₂ ;

   R ⁶

   -O- [R ³ -O] _n -R ⁴ , where the radicals - [R ³ -O] _n - may be different from the other radicals contained in formula I - [R ³ -O] _n -;

   R ⁷

   Hydrogen or ethyl;

   M

   Alkali metal or hydrogen;

   n

   4 to 250;

   x

   0 or 1,

3. (C) 0 to 50 mol% of a monoethylenically unsaturated dicarboxylic acid, an anhydride and / or a salt thereof
   and
4. (D) 0 to 20 mol% of another copolymerizable monoethylenically unsaturated monomer

is available and has an average molecular weight M _w of 30 000 to 500 000 g / mol and a K value of 40 to 150 (measured at pH 7 in 1 wt .-% aqueous solution at 25 ° C).

In addition, a process for reducing the viscosity of Waschmittellurries was found, which is characterized in that the slurry is added to these copolymers.

Furthermore, detergent slurries and detergent compositions containing these copolymers have been found.

Finally, the use of these copolymers has been found to be additive in detergent compositions.

The copolymers used according to the invention contain as copolymerized monomer (A) a monoethylenically unsaturated monocarboxylic acid, preferably a C ₃ -C ₆ -monocarboxylic acid, and / or a water-soluble salt, in particular an alkali metal salt, such as potassium and especially sodium salt, or ammonium salt, of this acid ,

Specific examples of suitable monomers (A) are: acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. Of course, mixtures of these acids can also be used.

Particularly preferred monomer (A) is acrylic acid.

The copolymers used according to the invention contain from 50 to 99.5 mol% of the monomer (A). If the copolymers are composed only of the monomers (A) and (B), the content of the monomer (A) is generally from 80 to 99.5 mol%, preferably from 90 to 98 mol%. Terpolymers of the monomers (A), (B) and (C) generally contain from 60 to 98 mole%, preferably 70 to 95 mole%, of the monomer (A).

in der die Variablen folgende Bedeutung haben:

R¹

Wasserstoff oder Methyl, vorzugsweise Wasserstoff;

R²

-(CH₂)_x-C)-, -CH₂-NR⁵-, -CH₂-O-CH₂-CR⁶R⁷-CH₂-O- oder -CONH-, bevor- zugt -(CH₂)_x-O-, -CH₂-NR⁵- oder -CH₂-O-CH₂-CR⁶R⁷-CH₂-O- und beson- ders bevorzugt -(CH₂)_x-O- oder -CH₂-O-CH₂-CR⁶R⁷-CH₂-O-;

R³

gleiche oder verschiedene C₂-C₄-Alkylenreste, die blockweise oder statistisch angeordnet sein können, wobei der Anteil an Ethylenresten mindestens 50 mol- %, bevorzugt mindestens 75 mol-% und besonders bevorzugt 100 mol-% beträgt;

R⁴

Wasserstoff, C₁-C₄-Alkyl, -SO₃M oder -PO₃M₂;

R⁵

Wasserstoff oder -CH₂-CR¹=CH₂;

R⁶

-O-[R³-O]_n-R⁴, wobei die Reste -[R³-O]_n- von den weiteren in Formel I enthal- tenen Resten -[R³-O]_n- verschieden sein können und die für R³ genannten Be- vorzugungen gelten;

R⁷

Wasserstoff oder Ethyl;

M

Alkalimetall, vorzugsweise Natrium oder Kalium, oder Wasserstoff;

n

4 bis 250, bevorzugt 5 bis 200 und besonders bevorzugt 10 bis 100;

x

0 oder 1.

As copolymerized monomer (B), the copolymers used according to the invention comprise an alkoxylated monoethylenically unsaturated monomer of the formula I.

in which the variables have the following meaning:

R ¹

Hydrogen or methyl, preferably hydrogen;

R ²

- (CH ₂ ) _x -C) -, -CH ₂ -NR ⁵ -, -CH ₂ -O-CH ₂ -CR ⁶ R ⁷ -CH ₂ -O- or -CONH-, preferably - (CH ₂ ) _x -O-, -CH ₂ -NR ⁵ - or -CH ₂ -O-CH ₂ -CR ⁶ R ⁷ -CH ₂ -O- and particularly preferably - (CH ₂ ) _x -O- or -CH ₂ -O-CH ₂ -CR ⁶ R ⁷ -CH ₂ -O-;

R ³

identical or different C ₂ -C ₄ -alkylene radicals which may be arranged in blocks or randomly, the proportion of ethylene radicals being at least 50 mol%, preferably at least 75 mol% and particularly preferably 100 mol%;

R ⁴

Hydrogen, C ₁ -C ₄ -alkyl, -SO ₃ M or -PO ₃ M ₂ ;

R ⁵

Hydrogen or -CH ₂ -CR ¹ = CH ₂ ;

R ⁶

-O- [R ³ -O] _n -R ⁴ , where the radicals - [R ³ -O] _n - of the other radicals contained in formula I - [R ³ -O] _n - may be different and the apply to R ³ preferences;

R ⁷

Hydrogen or ethyl;

M

Alkali metal, preferably sodium or potassium, or hydrogen;

n

4 to 250, preferably 5 to 200 and more preferably 10 to 100;

x

0 or 1.

Specific examples of particularly suitable monomers (B) are the alkoxylation products of the following unsaturated monomers: (meth) allyl alcohol, (meth) allylamines, diallylamines, glycerol monoallyl ethers, trimethylolpropane monoallyl ethers, vinyl ethers, vinylamides and vinylamines.

Of course, it is also possible to use mixtures of the monomers (B).

Particularly preferred are monomers (B) based on allyl alcohol, glycerol monoallyl ether, trimethylolpropane monoallyl ether and diallylamine.

Very particularly preferred monomer (B) are ethoxylated allyl alcohols which in particular contain from 5 to 20, especially from 10 to 100, mol of EO / mol.

The monomers (B) can be prepared by well-known standard methods of organic chemistry, e.g. Example by amidation and transamidation of suitable (meth) acrylic acids, by alkoxylation of allyl alcohol, Glycerinmonoallylether or Trimethylolpropanmonoallylether, by etherification of allyl halides with poly-C ₂ -C ₄ alkylene oxides and by vinylation of polyalkylene oxides with OH or NH end group with acetylene ,

If the copolymers used according to the invention have -SO ₃ M or -PO ₃ M ₂ end groups, these can be introduced by sulfation or phosphation of the monomers (B) or else the copolymers themselves, for example with chlorosulfonic acid or polyphosphoric acid.

The copolymers used according to the invention contain from 0.5 to 20 mol% of the monomer (B). If the copolymers are composed only of the monomers (A) and (B), the content of the monomer (B) is usually from 0.5 to 20 mol%, preferably at 1 to 10 mol%. Terpolymers of the monomers (A), (B) and (C) generally contain 1 to 15 mol%, preferably 1 to 10 mol%, of the monomer (B).

The copolymers used according to the invention may contain as copolymerized monomer (C) a monoethylenically unsaturated dicarboxylic acid, preferably a C ₄ -C ₈ -dicarboxylic acid. Of course, instead of the free acid and its anhydride and / or one of its water-soluble salts, in particular an alkali metal salt, such as potassium and especially sodium salt, or ammonium salt, are used.

Specific examples of suitable monomers (C) are: maleic acid, fumaric acid, methylenemalonic acid, citraconic acid and itaconic acid. Of course, mixtures of these acids can also be used.

Particularly preferred monomer (C) is maleic acid.

When the monomer (C) is contained in the copolymers used in the invention, its content is usually 1 to 30 mol%, preferably 5 to 30 mol%.

The copolymers used according to the invention are preferably composed only of the monomers (A) and (B) or of the monomers (A), (B) and (C).

However, they may also contain another monoethylenically unsaturated monomer (D) other than the monomers (A) to (C) but copolymerizable with these monomers.

• Ester von monoethylenisch ungesättigten C₃-C₅-Carbonsäuren, insbesondere (Meth)Acrylsäureester, wie Methyl-, Ethyl-, Propyl-, Hydroxypropyl-, n-Butyl-, isoButyl-, 2-Ethylhexyl-, Decyl-, Lauryl-, iso-Bornyl-, Cetyl-, Palmityl- und Stearyl-(meth)acrylat;
• (Meth)Acrylamide, wie (Meth)Acrylamid, N-(C₁-C₁₂-Alkyl)- und N,N-Di(C₁-C₄-alkyl)-(meth)acrylamide, wie N-Methyl-, N,N-Dimethyl-, N-Ethyl-, N-Propyl-, N-tert.-Butyl-, N-tert.-Octyl- und N-Undecyl(meth)acrylamid;
• Vinylester von C₂-C₃₀-, insbesondere C₂-C₁₄-Carbonsäuren, wie Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinyl-2-ethylhexanoat und Vinyllaurat;
• N-Vinylamide und N-Vinyllactame, wie N-Vinylformamid, N-Vinyl-N-methylformamid, N-Vinylacetamid, N-Vinyl-N-methylacetamid, N-Vinylpyrrolidon, N-Vinylpiperidon und N-Vinylcaprolactam;
• Vinylsulfonsäure und Vinylphosphonsäure;
• Vinylaromaten, wie Styrol und substituierte Styrole, z.B. Alkylstyrole, wie Methylstyrol und Ethylstyrol.

Examples of suitable monomers (D) are:

• Esters of monoethylenically unsaturated C ₃ -C ₅ -carboxylic acids, in particular (meth) acrylic esters, such as methyl, ethyl, propyl, hydroxypropyl, n-butyl, isobutyl, 2-ethylhexyl, decyl, lauryl, iso-bornyl, cetyl, palmityl and stearyl (meth) acrylate;
• (Meth) acrylamides, such as (meth) acrylamide, N- (C ₁ -C ₁₂ -alkyl) - and N, N-di (C ₁ -C ₄ -alkyl) - (meth) acrylamides, such as N-methyl-, N, N-dimethyl, N-ethyl, N-propyl, N-tert-butyl, N-tert-octyl and N-undecyl (meth) acrylamide;
• Vinyl esters of C ₂ -C ₃₀ -, especially C ₂ -C _14, carboxylic acids, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate and vinyl laurate;
• N-vinylamides and N-vinyllactams such as N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinylpyrrolidone, N-vinylpiperidone and N-vinylcaprolactam;
• Vinylsulfonic acid and vinylphosphonic acid;
• Vinylaromatics, such as styrene and substituted styrenes, for example alkylstyrenes, such as methylstyrene and ethylstyrene.

If monomers (D) are present in the copolymers used according to the invention, their content is generally from 1 to 20 mol%, preferably from 1 to 10 mol%. If hydrophobic monomers are used as monomer (D), their content should be selected so that the copolymer retains its hydrophilic character as a whole.

The copolymers used according to the invention have an average molecular weight M _{w of} from 30,000 to 500,000 g / mol, preferably from 50,000 to 300,000 g / mol (determined by gel permeation chromatography at room temperature with aqueous eluent).

Their K values are accordingly from 40 to 150, preferably from 50 to 125 (measured at pH 7 in 1% strength by weight aqueous solution at 25 ° C.) H. Fikentscher, Cellulose Chemistry, Vol. 13, pp. 58-64 and 71-74 (1932 )).

The copolymers used according to the invention can be obtained by the known free-radical polymerization processes. In addition to the bulk polymerization, in particular solution and emulsion polymerization should be mentioned, with the solution polymerization is preferred.

The polymerization is preferably carried out in water as a solvent. However, it can also be carried out in alcoholic solvents, in particular in C ₁ -C ₄ -alcohols, such as methanol, ethanol and isopropanol, or in mixtures of these solvents with water.

Suitable polymerization initiators are both thermally and photochemically (photoinitiators) decomposing and thereby radical-forming compounds.

Among the thermally activatable polymerization initiators, preference is given to initiators having a decomposition temperature in the range from 20 to 180 ° C., in particular from 50 to 120 ° C. Examples of suitable thermal initiators are inorganic peroxo compounds, such as peroxodisulfates (ammonium and preferably sodium peroxodisulfate), peroxosulfates, percarbonates and hydrogen peroxide; organic peroxy compounds, such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, Didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toloyl) peroxide, succinyl peroxide, tert-butyl peracetate, tert-butyl permalate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perneodecanoate, tert-butyl perbenzoate tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2-ethyl-hexanoate and diisopropyl peroxydicarbamate; Azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) and azobis (2-amidopropane) dihydrochloride.

These initiators can be used in combination with reducing compounds as starter / regulator systems. Examples of such reducing compounds include phosphorus-containing compounds such as phosphorous acid, hypophosphites and phosphinates, and sulfur-containing compounds such as sodium hydrogen sulfite, sodium sulfite and sodium formaldehyde sulfoxilate.

In combination with the initiators or the redox initiator systems, it is additionally possible to use transition metal catalysts, for example salts of iron, cobalt, nickel, copper, vanadium and manganese. Suitable salts are, for example, iron (II) sulfate, cobalt (II) chloride, nickel (II) sulfate, copper (I) chloride. The reducing transition metal salt is usually used in an amount of 0.1 to 1000 ppm, based on the sum of the monomers. Particularly advantageous are, for example, combinations of hydrogen peroxide and iron (II) salts, such as a combination of 0.5 to 30 wt.% Hydrogen peroxide and 0.1 to 500 ppm FeSO ₄ x 7 H ₂ O, in each case based on the sum of the monomers.

Examples of suitable photoinitiators are benzophenone, acetophenone, benzoin ethers, Benzyldialkylketone and derivatives thereof.

Preferably, thermal initiators are used, with inorganic peroxo compounds, in particular hydrogen peroxide and especially sodium peroxodisulfate (sodium persulfate), being preferred.

The peroxo compounds are advantageously used in combination with sulfur-containing reducing agents, sodium hydrogen sulfite, as a redox initiator system. Using this starter / regulator system, copolymers are obtained which contain -SO ₃ ^- Na ⁺ and / or -SO ₄ ^- Na ⁺ as end groups.

Alternatively, phosphorus-containing starter / regulator systems may also be used, e.g. Hypophosphites / phosphinates.

The amounts of photoinitiator or starter / regulator system are to be matched to the particular monomers used. For example, when the preferred system peroxodisulfate / bisulfite is used, usually 2 to 6 wt%, preferably 3 to 5 wt%, peroxodisulfate and usually 5 to 30 wt%, preferably 5 to 10 wt .-%, hydrogen sulfite, in each case based on the sum of the monomers used.

If desired, polymerization regulators can also be used. Suitable compounds known to those skilled in the art, e.g. Sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid and dodecylmercaptan.

When polymerization regulators are used, their amount used is usually 0.1 to 15 wt .-%, preferably 0.1 to 5 wt .-% and particularly preferably 0.1 to 2.5 wt.%, Based on the sum of monomers.

The polymerization temperature is usually at 30 to 200 ° C, preferably at 50 to 150 ° C and particularly preferably at 80 to 130 ° C.

The polymerization is preferably carried out under protective gas, such as nitrogen or argon, and may be carried out under atmospheric pressure, but is preferably carried out in a closed system under the evolving autogenous pressure.

The copolymers used according to the invention are usually obtained in the form of a polymer solution which has a solids content of from 10 to 70% by weight, preferably from 25 to 60% by weight.

With the copolymers used in the invention, the viscosity of aqueous Waschmittelslurries, in particular of the slurries, which are dried to produce granular or powdered detergent compositions, effectively lower, so that even highly concentrated slurries can be handled easily. Thus, the slurry concentrations can always be ≥ 50% by weight, preferably ≥ 60% by weight and particularly preferably ≥ 65% by weight, based on the anhydrous detergent components.

The copolymers according to the invention additionally bring about stabilization and homogenization of the slurries and prevent separations.

They are added to the slurries usually in amounts of from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight and more preferably from 0.1 to 5% by weight, based on the total batch.

You can either added to the total mixture or in any subsets of individual detergent components, such as the surfactants or builder premixes, the solids contents can be raised in this way already be added.

The copolymers used according to the invention are outstandingly suitable not only for their viscosity-lowering and stabilizing action as process auxiliaries for detergent production, but are also distinguished by their unforeseeable advantageous application properties during the washing process itself. Thus, they act in solid and liquid detergent compositions, both incrustation-inhibiting and graying-inhibiting.

1. (a) 0,01 bis 10 Gew.-% mindestens eines erfindungsgemäßen Copolymers,
2. (b) 0,5 bis 40 Gew.-% mindestens eines nichtionischen, anionischen und/oder kationischen Tensids,
3. (c) 0,5 bis 80 Gew.-% eines anorganischen Builders,
4. (d) 0 bis 10 Gew.-% eines organischen Cobuilders und
5. (e) 0 bis 60 Gew.-% anderer üblicher Inhaltsstoffe, wie Stellmittel, Enzyme, Parfum, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, Farbübertragungsinhibitoren, weitere Vergrauungsinhibitoren, Soil-Release-Polyester, Faser- und Farbschutzadditve, Silicone, Farbstoffe, Bakterizide, Auflösungsverbesserer und/oder Sprengmittel,

wobei die Summe der Komponenten (a) bis (e) 100 Gew.-% ergibt.Solid detergent formulations according to the invention which contain the copolymers used according to the invention advantageously have, for example, the following composition:

1. (a) from 0.01 to 10% by weight of at least one copolymer according to the invention,
2. (b) 0.5 to 40% by weight of at least one nonionic, anionic and / or cationic surfactant,
3. (c) 0.5 to 80% by weight of an inorganic builder,
4. (d) 0 to 10% by weight of an organic cobuilder and
5. (e) 0 to 60% by weight of other conventional ingredients, such as sizing agents, enzymes, perfume, chelating agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, dye transfer inhibiting agents, other grayness inhibitors, soil release polyesters, fiber and color protective additives, silicones, dyes , Bactericides, dissolution improvers and / or disintegrants,

wherein the sum of components (a) to (e) gives 100 wt .-%.

1. (a) 0,01 bis 10 Gew.-% mindestens eines erfindungsgemäßen Copolymers,
2. (b) 0,5 bis 40 Gew.-% mindestens eines nichtionischen, anionischen und/oder kationischen Tensids,
3. (c) 0 bis 20 Gew.-% eines anorganischen Builders,
4. (d) 0 bis 10 Gew.-% eines organischen Cobuilders,
5. (e) 0 bis 60 Gew.-% anderer üblicher Inhaltsstoffe, wie Soda, Enzyme, Parfum, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, Farbübertragungsinhibitoren, weitere Vergrauungsinhibitoren, Soil-Release-Polyester, Faser- und Farbschutzadditve, Silicone, Farbstoffe, Bakterizide, organische Lösungsmittel, Löslichkeitsvermittler, Hydrotrope, Verdicker und/oder Alkanolamine und
6. (f) 0 bis 99,45 Gew.-% Wasser.

Liquid detergent formulations according to the invention can be composed, for example, as follows:

1. (a) from 0.01 to 10% by weight of at least one copolymer according to the invention,
2. (b) 0.5 to 40% by weight of at least one nonionic, anionic and / or cationic surfactant,
3. (c) 0 to 20% by weight of an inorganic builder,
4. (d) 0 to 10% by weight of an organic cobuilder,
5. (e) from 0% to 60% by weight of other common ingredients such as soda, enzymes, perfume, chelating agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, Color transfer inhibitors, other grayness inhibitors, soil release polyester, fiber and color protection additive, silicones, dyes, bactericides, organic solvents, solubilizers, hydrotropes, thickeners and / or alkanolamines and
6. (f) 0 to 99.45% by weight of water.

• Alkoxylierte C₈-C₂₂-Alkohole, wie Fettalkoholalkoxylate, Oxoalkoholalkoxylate und Guerbet-alkoholethoxylate: Die Alkoxylierung kann mit Ethylenoxid, Propylenoxid und/oder Butylenoxid erfolgen. Es können Blockcopolymerisate oder statistische Copolymere vorliegen. Pro mol Alkohol enthalten sie üblicherweise 2 bis 50 mol, vorzugsweise 3 bis 20 mol, mindestens eines Alkylenoxids. Bevorzugtes Alkylenoxid ist Ethylenoxid. Die Alkohole haben vorzugsweise 10 bis 18 Kohlenstoffatome.
• Alkylphenolalkoxylate, insbesondere Alkylphenolethoxylate, die C₆-C₁₄-Alkylketten und 5 bis 30 mol Alkylenoxid/mol enthalten.
• Alkylpolyglucoside, die C₈-C₂₂-, vorzugsweise C₁₀-C₁₈-Alkylketten und in der Regel 1 bis 20, vorzugsweise 1,1 bis 5, Glucosideinheiten enthalten.
• N-Alkylglucamide, Fettsäureamidalkoxylate, Fettsäurealkanolamidalkoxylate sowie Blockcopolymere aus Ethylenoxid, Propylenoxid und/oder Butylenoxid.

Suitable nonionic surfactants (b) are, in particular:

• Alkoxylated C ₈ -C ₂₂ -alcohols, such as fatty alcohol alkoxylates, oxo alcohol alkoxylates and Guerbet alcohol ethoxylates: The alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide. There may be block copolymers or random copolymers. They usually contain from 2 to 50 mol, preferably from 3 to 20 mol, of at least one alkylene oxide per mole of alcohol. Preferred alkylene oxide is ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms.
• Alkylphenolalkoxylate, especially alkylphenol ethoxylates containing C ₆ -C ₁₄ alkyl chains and 5 to 30 moles of alkylene oxide / mol.
• Alkylpolyglucosides containing C ₈ -C ₂₂ -, preferably C ₁₀ -C ₁₈ -alkyl chains and usually 1 to 20, preferably 1.1 to 5, glucoside units.
• N-alkylglucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates and block copolymers of ethylene oxide, propylene oxide and / or butylene oxide.

• Sulfate von (Fett)alkoholen mit 8 bis 22, vorzugsweise 10 bis 18, Kohlenstoffatomen, insbesondere C₉C₁₁-Alkoholsulfate, C₁₂C₁₄-Alkoholsulfate, C₁₂-C₁₈-Alkohol-sulfate, Laurylsulfat, Cetylsulfat, Myristylsulfat, Palmitylsulfat, Stearylsulfat und Talgfettalkoholsulfat.
• Sulfatierte alkoxylierte C₈-C₂₂-Alkohole (Alkylethersulfate): Verbindungen dieser Art werden beispielsweise dadurch hergestellt, daß man zunächst einen C₈-C₂₂-, vorzugsweise einen C₁₀-C₁₈-Alkohol, z.B. einen Fettalkohol, alkoxyliert und das Alkoxylierungsprodukt anschließend sulfatiert. Für die Alkoxylierung verwendet man vorzugsweise Ethylenoxid.
• Lineare C₈-C₂₀-Alkylbenzolsulfonate (LAS), vorzugsweise lineare C₉-C₁₃-Alkylbenzolsulfonate und -Alkyltoluolsulfonate.
• Alkansulfonate, insbesondere C₈-C₂₄-, vorzugsweise C₁₀-C₁₈-Alkansulfonate.
• Seifen, wie die Na- und K-Salze von C₈-C₂₄-Carbonsäuren.

Suitable anionic surfactants are, for example:

• Sulfates of (fatty) alcohols having 8 to 22, preferably 10 to 18, carbon atoms, in particular C ₉ C ₁₁ -alcohol sulfates, C ₁₂ C ₁₄ -alcohol sulfates, C ₁₂ -C ₁₈ -alcohol sulfate, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmitylsulfate , Stearyl sulfate and tallow fatty alcohol sulfate.
• Sulfated alkoxylated C ₈ -C ₂₂ -alcohols (alkyl ether sulfates): compounds of this type are prepared, for example, by first alkoxylating a C ₈ -C ₂₂ -alcohol, preferably a C ₁₀ -C ₁₈ -alcohol, for example a fatty alcohol, and the alkoxylation product subsequently sulfated. For the alkoxylation is preferably used ethylene oxide.
• Linear C ₈ -C ₂₀ -alkylbenzenesulfonates (LAS), preferably linear C ₉ -C ₁₃ -alkylbenzenesulfonates and -alkyltoluenesulfonates.
• Alkanesulfonates, in particular C ₈ -C ₂₄ -, preferably C ₁₀ -C ₁₈ -alkanesulfonates.
• Soaps, such as the Na and K salts of C ₈ -C ₂₄ carboxylic acids.

The anionic surfactants are preferably added to the detergent in the form of salts. Suitable salts are e.g. Alkali metal salts such as sodium, potassium and lithium salts, and ammonium salts such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

• C₇-C₂₅-Alkylamine;
• N,N-Dimethyl-N-(hydroxy-C₇-C₂₅-alkyl)ammoniumsalze;
• mit Alkylierungsmitteln quaternisierte Mono- und Di-(C₇-C₂₅-alkyl)dimethylammoniumverbindungen;
• Esterquats, insbesondere quaternäre veresterte Mono-, Di- und Trialkanolamine, die mit C₈-C₂₂-Carbonsäuren verestert sind;
• Imidazolinquats, insbesondere 1-Alkylimidazoliniumsalze der Formeln II oder III
  
  in denen die Variablen folgende Bedeutung haben:

  R⁸

  C₁-C₂₅-Alkyl oder C₂-C₂₅-Alkenyl;

  R⁹

  C₁-C₄-Alkyl oder Hydroxy-C₁-C₄-alkyl;

  R¹⁰

  C₁-C₄-Alkyl, Hydroxy-C₁-C₄-alkyl oder ein Rest R⁸-(CO)-X-(CH₂)_p (X: -O- oder -NH-; p: 2 oder 3),

wobei mindestens ein Rest R⁸ C₇-C₂₂-Alkyl ist.Particularly suitable cationic surfactants are:

• C ₇ -C ₂₅ -alkylamines;
• N, N-dimethyl-N- (hydroxy-C ₇ -C ₂₅ -alkyl) ammonium salts;
• mono- and di (C ₇ -C ₂₅ -alkyl) dimethylammonium compounds quaternized with alkylating agents;
• Esterquats, in particular quaternary esterified mono-, di- and trialkanolamines esterified with C ₈ -C ₂₂ -carboxylic acids;
• Imidazolinquats, in particular 1-Alkylimidazoliniumsalze of the formulas II or III
  
  in which the variables have the following meaning:

  R ⁸

  C ₁ -C ₂₅ alkyl or C ₂ -C ₂₅ alkenyl;

  R ⁹

  C ₁ -C ₄ -alkyl or hydroxy-C ₁ -C ₄ -alkyl;

  R ¹⁰

  C ₁ -C ₄ -alkyl, hydroxy-C ₁ -C ₄ -alkyl or a radical R ⁸ - (CO) -X- (CH ₂ ) _p (X: -O- or -NH-; p: 2 or 3 )

wherein at least one R ^{8 is} C ₇ -C ₂₂ alkyl.

• Kristalline und amorphe Alumosilikate mit ionenaustauschenden Eigenschaften, wie vor allem Zeolithe: Verschiedene Typen von Zeolithen sind geeignet, insbesondere die Zeolithe A, X, B, P, MAP und HS in ihrer Na-Form oder in Formen, in denen Na teilweise gegen andere Kationen wie Li, K, Ca, Mg oder Ammonium ausgetauscht ist.
• Kristalline Silikate, wie insbesondere Disilikate und Schichtsilikate, z.B. δ- und β-Na₂Si₂O₅. Die Silikate können in Form ihrer Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze eingesetzt werden, bevorzugt sind die Na-, Li- und Mg-Silicate.
• Amorphe Silikate, wie Natriummetasilikat und amorphes Disilikat.
• Carbonate und Hydrogencarbonate: Diese können in Form ihrer Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze eingesetzt werden. Bevorzugt sind Na-,Li- und Mg-Carbonate und -Hydrogencarbonate, insbesondere Natriumcarbonat und/oder Natriumhydrogencarbonat.
• Polyphosphate, wie Pentanatriumtriphosphat.

Suitable inorganic builders are, in particular:

• Crystalline and amorphous aluminosilicates with ion-exchanging properties, in particular zeolites: Various types of zeolites are suitable, in particular the zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na partially opposes other cations as Li, K, Ca, Mg or ammonium is exchanged.
• Crystalline silicates, in particular disilicates and sheet silicates, for example δ- and β-Na ₂ Si ₂ O ₅ . The silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preference being given to the Na, Li and Mg silicates.
• Amorphous silicates such as sodium metasilicate and amorphous disilicate.
• Carbonates and bicarbonates: These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preference is given to Na, Li and Mg carbonates and hydrogen carbonates, in particular sodium carbonate and / or sodium bicarbonate.
• Polyphosphates, such as pentasodium triphosphate.

• Niedermolekulare Carbonsäuren, wie Citronensäure, hydrophob modifizierte Citronensäure, z. B. Agaricinsäure, Äpfelsäure, Weinsäure, Gluconsäure, Glutarsäure, Bernsteinsäure, Imidodibernsteinsäure, Oxydibernsteinsäure, Propantricarbonsäure, Butantetracarbonsäure, Cyclopentantetracarbonsäure, Alkyl- und Alkenylbernsteinsäuren und Aminopolycarbonsäuren, z.B. Nitrilotriessigsäure, β-Alanindiessigsäure, Ethylendiamintetraessigsäure, Serindiessigsäure, Isoserindiessigsäure, N-(2-Hydroxyethyl)iminodiessigsäure, Ethylendiamindibernsteinsäure und Methyl- und Ethylglycindiessigsäure.
• Oligomere und polymere Carbonsäuren, wie Homopolymere von Acrylsäure und Asparaginsäure, Oligomaleinsäuren, Copolymere der Maleinsäure mit Acrylsäure, Methacrylsäure oder C₂-C₂₂-Olefinen, z.B. Isobuten oder langkettigen α-Olefinen, Vinyl-C₁-C₈-alkylether, Vinylacetat, Vinylpropionat, (Meth)Acrylsäureester von C₁-C₈-Alkoholen und Styrol. Bevorzugt sind die Homopolymere der Acrylsäure und Copolymere von Acrylsäure mit Maleinsäure. Die oligomeren und polymeren Carbonsäuren werden in Säureform oder als Natriumsalz eingesetzt.

As organic cobuilders are particularly suitable:

• Low molecular weight carboxylic acids such as citric acid, hydrophobically modified citric acid, e.g. , Agaricic acid, malic acid, tartaric acid, gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid, oxydisuccinic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, alkyl- and alkenylsuccinic acids and aminopolycarboxylic acids, eg nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, N- (2-hydroxyethyl ) iminodiacetic acid, ethylenediamine disuccinic acid and methyl and ethylglycinediacetic acid.
• Oligomeric and polymeric carboxylic acids, such as homopolymers of acrylic acid and aspartic acid, oligomaleic acids, copolymers of maleic acid with acrylic acid, methacrylic acid or C ₂ -C ₂₂ -olefins, for example isobutene or long-chain α-olefins, vinyl-C ₁ -C ₈ -alkyl ethers, vinyl acetate, Vinyl propionate, (meth) acrylic acid esters of C ₁ -C ₈ -alcohols and styrene. Preferred are the homopolymers of acrylic acid and copolymers of acrylic acid with maleic acid. The oligomeric and polymeric carboxylic acids are used in acid form or as the sodium salt.

Suitable bleaching agents are, for example, adducts of hydrogen peroxide with inorganic salts, such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium carbonate perhydrate, and percarboxylic acids, such as phthalimidopercaproic acid.

Suitable bleach activators are e.g. N, N, N ', N'-tetraacetylethylenediamine (TAED), sodium p-nonanoyloxybenzenesulfonate and N-methylmorpholinium acetonitrile methylsulfate.

Enzymes preferably used in detergents are proteases, lipases, amylases, cellulases, oxidases and peroxidases.

Suitable color transfer inhibitors are, for example, homo-, co- and graft polymers of 1-vinylpyrrolidone, 1-vinylimidazole or 4-vinylpyridine-N-oxide. Homo- and copolymers of 4-vinylpyridine reacted with chloroacetic acid are also suitable as color transfer inhibitors.

Detergent ingredients are otherwise well known. Detailed descriptions are z. Tie WO-A-99/06524 and 99/04313 ; in Liquid Detergents, Editor: Kuo-Yann Lai, Surfactant Sci. Ser., Vol. 67, Marcel Decker, New York, 1997, p. 272-304 , to find.

Examples I) Preparation of copolymers according to the invention

• Monomer (B1): ethoxylierter Allylalkohol (16,6 mol EO/mol)
• Monomer (B2): sulfatierter ethoxylierter Glycerinmonoallylether (20 mol EO/mol)
• Monomer (B3): phosphatierter ethoxylierter Glycerinmonoallylether (20 mol EO/mol)
• Monomer (B4): ethoxylierter Glycerinmonoallylether (20 mol EO/mol)
• Monomer (B5): ethoxylierter Trimethylolpropanmonoallylether (15 mol EO/mol)
• Monomer (B6): ethoxylierter Allylalkohol (10 mol EO/mol)

The following monomers were used as monomer (B) in the form of solutions in distilled water to prepare the following copolymers:

• Monomer (B1): ethoxylated allyl alcohol (16.6 mol EO / mol)
• Monomer (B2): sulfated ethoxylated glycerol monoallyl ether (20 mol EO / mol)
• Monomer (B3): phosphated ethoxylated glycerol monoallyl ether (20 mol EO / mol)
• Monomer (B4): ethoxylated glycerol monoallyl ether (20 mol EO / mol)
• Monomer (B5): ethoxylated trimethylolpropane monoallyl ether (15 mol EO / mol)
• Monomer (B6): ethoxylated allyl alcohol (10 mol EO / mol)

example 1

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and dosing were 251.8 g of distilled water and 3.40 g of 50 wt.% Phosphorous acid under nitrogen and stirring to 95 ° C internal temperature. Then, in four separate feeds, 595.9 g of acrylic acid (97.7 mol%) were continuously added in 4 hours, 303.0 g of a 50% strength by weight aqueous solution of monomer (B1) (2.3 mol 74.4 g of a 40% strength by weight aqueous sodium hydrogen sulfite solution and 4.25 h of a mixture of 18.2 g of sodium persulfate and 242.5 g of distilled water were added in 4 hours. After stirring for one hour at 95 ° C and cooling to 50 ° C was adjusted with 50 wt .-% sodium hydroxide solution in 1.5 h, a pH of 6.7. Then, while maintaining a temperature of 50 to 60 ° C 3.36 g of a 50 wt .-% aqueous hydrogen peroxide solution in 30 min were added. After stirring for 30 minutes at this temperature was diluted with 100 g of distilled water.

A polymer solution having a solids content of 46.2% by weight and a K value of 66.5 (measured at pH 7 in 1% strength by weight aqueous solution at 25 ° C.) was obtained.

Example 2

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering device 135.1 g of distilled water and 2.27 g of 50 wt .-% phosphorous acid were heated with nitrogen and stirring to 95 ° C internal temperature. Then in four separate feeds in 4 h 368.8 g of acrylic acid (97.0 mol%), in 4 h 150.0 g of a 50 wt .-% aqueous solution of monomer (B1) (3.0 mol %), in 4 h 74.1 g of a 40 wt .-% aqueous sodium bisulfite solution and in 4.25 h, a mixture of 12.1 g of sodium persulfate and 160.1 g of distilled water was added. After stirring for one hour at 95 ° C and cooling to 50 ° C was adjusted with 50 wt .-% sodium hydroxide solution in 1.5 h, a pH of 6.9. Then, while maintaining a temperature of 50 to 60 ° C 2.14 g of a 50 wt .-% aqueous solution of hydrogen peroxide added in 30 min and stirred for a further 30 min at this temperature.

There was obtained a polymer solution having a solids content of 47.8 wt .-% and a K value of 45.9 (measured at pH 7 in 1 wt .-% aqueous solution at 25 ° C).

Example 3

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering device 536.4 g of distilled water and 2.57 g of 50 wt .-% phosphoric acid were heated under nitrogen and stirring to 95 ° C internal temperature. Then 417.1 g of acrylic acid (97.0 mol%) were continuously added in four separate feeds in 4 hours, 282.8 g of a 50% strength by weight aqueous solution of monomer (B6) (3.0 mol 69.8 g of a 40% strength by weight aqueous sodium hydrogen sulfite solution and 4.25 h of a mixture of 13.6 g of sodium persulfate and 242.5 g of distilled water were added in 4 hours. After one hour of stirring at 95 ° C and cooling to 50 ° C was adjusted with 50 wt .-% sodium hydroxide solution in 1.5 h, a pH of 6.8. Then, while maintaining a temperature of 50 to 60 ° C 2.42 g of a 50 wt .-% aqueous hydrogen peroxide solution in 30 min were added. Finally, stirring was continued for 30 min at this temperature.

A polymer solution having a solids content of 39.6% by weight and a K value of 52.9 (measured at pH 7 in 1% strength by weight aqueous solution at 25.degree. C.) was obtained.

Example 4

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering were 242.3 g of distilled water and 3.40 g of 50 wt .-% phosphoric Acid under nitrogen and stirring to 95 ° C internal temperature. Then, in four separate feeds, 595.9 g of acrylic acid (97.7 mol%) were continuously added in 4 hours, 303.0 g of a 50% strength by weight aqueous solution of monomer (B1) (2.3 mol In 4 h, 65.4 g of a 40% strength by weight aqueous sodium hydrogen sulfite solution and in 4.25 h a mixture of 18.2 g of sodium persulfate and 242.5 g of distilled water were added. After stirring for one hour at 95 ° C and cooling to 50 ° C was adjusted with 50 wt .-% sodium hydroxide solution in 1.5 h, a pH of 6.7. Then, while maintaining a temperature of 50 to 60 ° C 3.36 g of a 50 wt .-% aqueous hydrogen peroxide solution in 30 min were added. After stirring for 30 minutes at this temperature was diluted with 150 g of distilled water.

A polymer solution having a solids content of 43.7% by weight and a K value of 65.9 (measured at pH 7 in 1% strength by weight aqueous solution at 25.degree. C.) was obtained.

Example 5

161.5 g of distilled water, 4.07 mg of FeSO ₄ × 7 H ₂ O and 31.0 g of maleic anhydride (7.4 mol%) were placed in a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering device. With simultaneous addition of 43.0 g of a 50 wt .-% sodium hydroxide solution was heated under nitrogen to 99 ° C internal temperature. Then in three separate feeds in 4 h 278.1 g of acrylic acid (89.6 mol%), in 4 h 202.0 g of a 50 wt .-% aqueous solution of monomer (B1) (3.0 mol -%) and added in 4.25 h 82.0 g of a 30 wt .-% aqueous hydrogen peroxide solution. Finally, the mixture was stirred at 99 ° C for 1 h.

It was a polymer solution having a solids content of 44.4 wt.%, A pH of 3.4 and a K value of 67.9 (measured at pH 7 in 1 wt .-% aqueous solution at 25 ° C).

Example 6

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering device 161.5 g of distilled water and 69.5 g of maleic anhydride (15.0 mol%) were heated under nitrogen and stirring to 98 ° C internal temperature. Then in four separate feeds in 4 h 278.1 g of acrylic acid (82.0 mol%), in 4 h 202.0 g of a 50 wt .-% aqueous solution of monomer (B1) (3.0 mol -%), in 4 h 44.8 g of a 40 wt .-% aqueous sodium bisulfite solution and in 4.25 h, a mixture of 10.9 g of sodium persulfate and 161.7 g of distilled water was added. After one hour of stirring at 98 ° C and cooling to 50 ° C was adjusted with 50 wt .-% sodium hydroxide solution in 1.5 h, a pH of 6.7. Then, while maintaining a temperature of 50 to 60 ° C 2.24 g of a 50 wt .-% aqueous hydrogen peroxide solution added in 30 min. After stirring at this temperature for 30 minutes, 600 g of distilled water were added.

There was obtained a polymer solution having a solids content of 28.8 wt .-% and a K value of 50.3 (measured at pH 7 in 1 wt .-% aqueous solution at 25 ° C).

Example 7

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering device, 242.3 g of distilled water, 7.51 mg of FeSO ₄ × 7 H ₂ O and 121.0 g of maleic anhydride (15.0 mol%) were initially charged. With simultaneous addition of 168.0 g of a 50 wt.% Sodium hydroxide solution was heated to 99 ° C internal temperature with nitrogen. 484.0 g of acrylic acid (82.5 mol%) were then continuously added in three separate feeds in 4 hours, 303.0 g of a 50% strength by weight aqueous solution of monomer (B1) (2.5 mol -%) and added in 4.25 h 126.0 g of a 30 wt .-% aqueous hydrogen peroxide solution. After stirring at this temperature for 30 minutes, 450 g of distilled water were added.

It was a polymer solution having a solids content of 39.0 wt.%, A pH of 3.6 and a K value of 86.3 (measured at pH 7 in 1 wt .-% aqueous solution at 25 ° C).

Example 8

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering device, 161.5 g of distilled water were heated to 95 ° C. internal temperature with the introduction of nitrogen and stirring. Then, in four separate feeds, 399.0 g of acrylic acid (97.7 mol%) were continuously added in 4 hours, 202.0 g of a 50% strength by weight aqueous solution of monomer (B1) (2.3 mol. %), in 4 h 56.0 g of a 40 wt .-% aqueous sodium bisulfite solution and in 4.25 h, a mixture of 12.2 g of sodium persulfate and 161.7 g of distilled water was added. After stirring for one hour at 95 ° C, addition of 200.0 g of distilled water and cooling to 50 ° C, a pH of 6.6 was set at 50 g.% Sodium hydroxide solution in 1.5 h at this temperature.

A polymer solution having a solids content of 42.1% by weight and a K value of 63.5 (measured at pH 7 in 1% strength by weight aqueous solution at 25.degree. C.) was obtained.

Example 9

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and dosing were 161.5 g of distilled water, 202.0 g of a 50 wt.% Aqueous solution of monomer (B1) (2.3 mol%) and 2.27 g 50th wt .-% phosphoric acid under nitrogen and stirring to 95 ° C internal temperature. 397.3 g of acrylic acid (97.7 mol%) were then continuously added in three separate feeds in 4 hours, 43.6 g of a 40% strength by weight aqueous sodium hydrogen sulfite solution in 4 hours and a mixture of 12 in 4.25 hours , 2 g sodium persulfate and 161.7 g distilled water. After stirring for one hour at 95 ° C, addition of 200.0 g of distilled water and cooling to 50 ° C was set at this temperature with 50 wt .-% sodium hydroxide solution in 1.5 h, a pH of 6.6.

There was obtained a polymer solution having a solids content of 40.2 wt .-% and a K value of 74.6 (measured at pH 7 in 1 wt .-% aqueous solution at 25 ° C).

Example 10

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering were 161.5 g of distilled water and 202.0 g of a 50 wt .-% aqueous solution of monomer (B1) (2.3 mol%) under nitrogen and stirring 95 ° C internal temperature heated. Then in three separate feeds in 397.3 g of acrylic acid (97.7 mol%) in 4 h, in 4 h 31.5 g of a 40 wt.% Aqueous solution of sodium bisulfite and in 4.25 h a mixture of 12, 2 g of sodium persulfate and 161.7 g of distilled water were added. After stirring for one hour at 95 ° C, addition of 200.0 g of distilled water and cooling to 50 ° C, a pH of 6.7 was set with 50 wt.% Sodium hydroxide solution in 1.5 h at this temperature.

A polymer solution having a solids content of 35.7% by weight and a K value of 88.2 (measured at pH 7 in 1% strength by weight aqueous solution at 25 ° C.) was obtained.

Example 11

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering device, 500.0 g of distilled water and 4.88 mg of FeSO ₄ × 7 H ₂ O, 101.0 g of a 50% strength by weight aqueous solution of monomer (B1) ( 2.3 mol) under nitrogen and stirring to 100 ° C internal temperature. 397.3 g of acrylic acid (97.7 mol%) and in 4.5 h 149.4 g of a 50% strength by weight aqueous hydrogen peroxide solution were then added continuously in two separate feeds in the course of 4 hours. After one hour Stirring at 100 ° C and cooling to 50 ° C was adjusted at this temperature with 50 wt.% Sodium hydroxide in 1.5 h, a pH of 6.6.

There was obtained a polymer solution having a solids content of 22.6 wt .-% and a K value of 124.0 (measured at pH 7 in 1 wt .-% aqueous solution at 25 ° C).

Example 12

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and dosing were 161.5 g of distilled water, 202.0 g of a 50 wt.% Aqueous solution of monomer (B1) (2.3 mol%) and 2.27 g 50th wt .-% phosphoric acid under nitrogen and stirring to 95 ° C internal temperature. Then 399.0 g of acrylic acid (97.7 mol%) were added continuously in three separate feeds in 4 hours, a mixture of 10.0 g of sodium hypophosphite and 40.0 g of distilled water in 4 h and a mixture in 4.25 h from 12.2 g of sodium persulfate and 161.7 g of distilled water. After stirring for one hour at 95 ° C, addition of 200.0 g of distilled water and cooling to 50 ° C, a pH of 6.9 was set at this temperature with 50 wt .-% sodium hydroxide solution in 1.5 h.

There was obtained a polymer solution having a solids content of 30.8 wt .-% and a K value of 95.1 (measured at pH 7 in 1 wt .-% aqueous solution at 25 ° C).

Example 13

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering were 161.5 g of distilled water, 202.0 g of a 50 wt .-% aqueous solution of monomer (B1) (2.5 mol%) and 20.0 g Maleic anhydride (2.5 mol%) under nitrogen and stirring to 95 ° C internal temperature. 379.0 g of acrylic acid (82.5 mol%) were then continuously added in three separate feeds in 4 hours, 44.0 g of a 40% strength by weight aqueous sodium hydrogen sulfite solution in 4 hours and a mixture of 12 in 4.25 hours , 2 g sodium persulfate and 161.7 g distilled water. After stirring for one hour at 95 ° C, addition of 200.0 g of distilled water and cooling to 50 ° C was set at this temperature with 50 wt .-% sodium hydroxide solution in 1.5 h, a pH of 6.6.

There was obtained a polymer solution having a solids content of 28.3 wt .-% and a K value of 101.8 (measured at pH 7 in 1 wt .-% aqueous solution at 25 ° C).

Example 14

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering device, 161.5 g of distilled water and 31.0 g of maleic anhydride (7.4 mol%) were heated to an internal temperature of 98 ° C. under nitrogen and with stirring. Then in four separate feeds in 4 h 278.1 g of acrylic acid (89.6 mol%), in 4 h 202.0 g of a 50 wt .-% aqueous solution of monomer (B1) (3.0 mol %), in 4 hours 30.0 g of a 40 wt .-% aqueous sodium bisulfite solution and in 4.5 h, a mixture of 10.0 g of sodium persulfate and 161.6 g of water was added. After stirring for one hour at 98 ° C and cooling to 50 ° C was adjusted at this temperature with 50 wt .-% sodium hydroxide solution in 1.5 h, a pH of 6.8. Then, while maintaining a temperature of 50 to 60 ° C., 2.24 g of a 50% strength by weight aqueous hydrogen peroxide solution were added in 30 minutes. Finally, stirring was continued for 30 min at this temperature.

There was obtained a polymer solution having a solids content of 37.4 wt .-%, and a K value of 72.9 (measured at pH 7 in 1 wt .-% aqueous solution at 25 ° C).

Example 15

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering device, 161.5 g of distilled water, 4.07 mg of FeSO ₄ .7H ₂ O and 31.0 g of maleic anhydride (7.4 mol.%) Were added to the reactor under nitrogen and stirring ° C internal temperature heated. Then in three separate feeds in 4 h 278.1 g of acrylic acid (89.6 mol%), in 4 h 202.0 g of a 50 wt .-% aqueous solution of monomer (B1) (3.0 mol %) and in 4.25 h a mixture of 41.0 g of a 30 wt .-% aqueous solution of hydrogen peroxide and 161.6 g of water was added. After stirring for one hour at 98 ° C, 200.0 g of distilled water were added.

It was a polymer solution having a solids content of 37.6 wt.%, A pH of 1.8 and a K value of 108.8 (measured at pH 7 in 1 wt .-% aqueous solution at 25 ° C).

Example 16

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering device 95.0 g of distilled water were heated with nitrogen and stirring to 99 ° C internal temperature. Then in four separate feeds, 144.93 g of acrylic acid (97.8 mol%) were continuously added in 4 h, in 4 h a mixture of 55.1 g of the monomer (B2) (2.2 mol%) and 30, 0 g of distilled water, in 4 h, a mixture of 16.4 g of a 40 wt .-% aqueous sodium bisulfite solution and 15.16 g of distilled water and a mixture of 5.74 g of sodium persulfate and 50.0 g of distilled water was added in 5 hours. After one hour of stirring at 99 ° C and cooling to 50 ° C was adjusted at this temperature with 50 wt .-% sodium hydroxide solution, a pH of 6.7. Finally, another 100.0 g of distilled water was added.

A polymer solution having a solids content of 41.1% by weight and a K value of 60.4 (measured at pH 7 in 1% strength by weight aqueous solution at 25.degree. C.) was obtained.

Example 17

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering were 95.0 g of distilled water and 1.10 g of 50 wt.% Phosphorous acid under nitrogen and stirring to 99 ° C internal temperature heated. Then 146.39 g of acrylic acid (97.8 mol%) were continuously added in four separate feeds in 4 h, in 4 h a mixture of 53.61 g of the monomer (B3) (2.2 mol%) and 30, 0 g of distilled water, in 4 h 49.5 g of a 40 wt .-% aqueous sodium bisulfite solution and in 5 h, a mixture of 5.74 g of sodium persulfate and 45.3 g of distilled water was added. After about 2.5 h, 100.0 g of distilled water were added. After completion of Natriumpersulfatzulauf 1 h at 99 ° C was stirred. After cooling to 50 ° C, a pH of 6.5 was set at this temperature with 50 wt .-% sodium hydroxide solution.

A polymer solution having a solids content of 40.8% by weight and a K value of 69.6 (measured at pH 7 in 1% strength by weight aqueous solution at 25 ° C.) was obtained.

Example 18

In a pressure reactor equipped with stirrer, nitrogen inlet, reflux condenser and metering device, 240.0 g of distilled water and 120.0 g of monomer (B4) (2.3 mol%) were heated to 95 ° C internal temperature with nitrogen and stirring. Then in three separate feeds in 4 h 380.0 g of acrylic acid (97.8 mol%), in 4 h, a mixture of 22.0 g of sodium bisulfite and 100.0 g of distilled water and in 4.25 h a mixture from 12.2 g of sodium persulfate and 160.0 g of distilled water. After stirring for one hour at 95 ° C and cooling to 60 ° C, a pH of 6.4 was set at this temperature with 50 wt .-% sodium hydroxide solution. Finally, another 100.0 g of distilled water was added.

There was obtained a polymer solution having a solids content of 47.3 wt .-% and a K value of 61.7 (measured at pH 7 in 1 wt .-% aqueous solution at 25 ° C).

Example 19

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering device 120.0 g of distilled water and 1.35 g of 50 wt .-% phosphorous acid were heated with nitrogen and stirring to 95 ° C internal temperature. Then in four separate feeds in 4 h 198.3 g (97.8 mol%) of acrylic acid, in 4 h a mixture of 51.7 g of the monomer (B5) (2.2 mol%) and 30, 0 g of distilled water, in 4 h, a mixture of 8.2 g of sodium bisulfite and 50.0 g of distilled water and 4.25 h, a mixture of 6.1 g of sodium persulfate and 50.0 g of distilled water was added. After stirring for one hour at 95 ° C and cooling to 60 ° C was adjusted to a pH of 6.5 with 50 wt .-% sodium hydroxide solution.

A polymer solution having a solids content of 46.0% by weight and a K value of 60.0 (measured at pH 7 in 1% strength by weight aqueous solution at 25 ° C.) was obtained.

Comparative Example C1

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering device 150.0 g of distilled water and 2.17 g of 85 wt .-% phosphoric acid were heated with nitrogen and stirring to 95 ° C internal temperature. Then, in four separate feeds, 375.4 g of acrylic acid (99.2 mol%) were continuously added in 4 hours, 63.6 g of a 50% strength by weight solution of monomer (B1) (0.8 mol %), in 4 h 66.2 g of a 40 wt .-% aqueous sodium bisulfite solution and in 4.25 h, a mixture of 11.50 g of sodium persulfate and 152.2 g of distilled water was added. After one hour of stirring at 95 ° C and cooling to 50 ° C was adjusted with 50 wt.% Sodium hydroxide in 1.5 h, a pH of 6.7. Then, while maintaining a temperature of 50 to 60 ° C 2.12 g of a 50 wt .-% aqueous hydrogen peroxide solution in 30 min were added. Finally, stirring was continued for 30 min at this temperature.

There was obtained a polymer solution having a solids content of 47.3 wt .-% and a K value of 34.3 (measured at pH 7 in 1 wt .-% aqueous solution at 25 ° C).

II) Testing of copolymers according to the invention IIa) Testing of the viscosity-lowering effect in detergent slurries

Three different detergent slurries were prepared with stirring in a 500 ml heatable double-walled stainless steel vessel. For this purpose, the liquid components were first heated to 50 ° C. with stirring for 10 minutes. The stirrer used had via a torque pickup. The previously mixed solid components were then uniformly metered in over 4 minutes, with the slurry being further stirred at 150 rpm. After completion of the addition, the slurry was stirred at a constant speed while determining the torque.

The torque reflects the force needed to stir the slurry at a constant speed of rotation. The lower the torque, the lower the viscosity of the detergent slurry.

Table 1 lists the compositions of the detergent slurries. The amounts mentioned here refer to feedstocks in anhydrous form, i. without water or water of crystallization contained in the total water content.

Table 2 to 4 summarize the torques obtained after each 30 minutes. For comparison, the results obtained without added polymer and also using the copolymer of Comparative Example 1 are included. The result nb means that the viscosity of the slurries was very high and the torque was no longer determinable. Table 1: Composition of the washing agent slurries feedstock Slurry 1 [% by weight] Slurry 2 [% by weight] Slurry 3 [% by weight] Dodecylbenzenesulfonate, Na salt 13.9 17.2 8.1 C _13/15 -oxo alcohol x 7 EO 7.5 6.2 5.4 Soap - - 1.6 Zeolite A 21.4 - - soda 16.0 7.8 17.9 sodium - - 17.9 metasilicate 10.7 - 8.1 sodium disilicate - - 3.6 sodium tripolyphosphate - 15.6 - sodium citrate - - 9.0 sodium sulphate - 27.3 - copolymer 1.1 1.8 0.9 Total water content 29.4 24.1 27.5 Total solids content 70.6 75.9 72.5 Copolymer from Ex. Torque [Ncm] after 30 min - Slurry 1 1 12 2 10 3 10 4 15 5 15 6 10 7 15 8th 16 9 19 10 15 11 14 12 24 13 17 14 20 15 15 16 12 17 15 18 12 19 15 - nb V1 nb Copolymer from Ex. Torque [Ncm] after 30 min - Slurry 2 1 45 2 30 4 45 8th 40 9 35 10 40 11 36 12 30 13 40 - nb V1 nb Copolymer from Ex. Torque [Ncm] after 30 min - Slurry 3 4 20 - nb

The results obtained demonstrate the viscosity-lowering effect of the copolymers according to the invention on detergent slurries, which at the same time also permits the production of detergent concentrates of higher concentration. Thus, in the case of the composition Slurry 1 without the addition of a copolymer according to the invention only a total solids content of 68 wt .-% (compared to 73.5 wt .-% with the addition of 1 wt .-% of the copolymer of Example 4) can be achieved.

IIb) Examination of the incrustation-inhibiting effect in detergents

To determine the incrustation-inhibiting effect, the inorganic tissue deposits (incrustation) were determined in the form of the ash content.

For this purpose, a cotton test fabric was washed with the detergent formulation described in Table 5 under the wash conditions indicated in Table 6. After washing 15 times, the ash content of the test fabric was determined by ashing at 700 ° C.

The results obtained are summarized in Table 7. Without addition of polymer, an ash content of 6.56 wt .-% was determined. Table 5: Detergent composition ingredients [Wt .-%] linear alkyl benzene sulphonate (50%) 6.0 C ₁₂ fatty alcohol sulfate x 2 EO 2.0 C ₁₃ C ₁₅ oxo alcohol x 7 EO 7.0 Soap 1.0 Zeolite A 36.0 sodium 12.0 Sodium metasilicate x 5 H ₂ O 3.5 sodium perborate 15.0 tetraacetylethylenediamine 3.5 sodium sulphate 3.0 carboxymethylcellulose 1.5 water on 100 device Launder-o-meter of the company Atlas, Chicago, USA wash liquor 250 ml washing time 30 min at 60 ° C detergent dosage 4.5 g / l water hardness 4 mmol / l Ca: Mg: HCO ₃ 4: 1: 8 liquor ratio 1: 12.5 wash cycles 15 copolymer addition 5% by weight Test fabric 10.0 g cotton test fabric (BW 283, Fa. Reichenbach) Copolymer from Ex. Ash content [% by weight] 2 5.41 7 4.70 8th 4.06 15 3.91 16 3.72

Claims (10)

1. A process for preparing granular or pulverulent detergent compositions, comprising the preparation of a detergent base powder by drying an aqueous detergent slurry, which comprises adding to the slurry a copolymer which is obtainable by free-radical copolymerization of

   (A) from 50 to 99.5 mol% of a monoethylenically unsaturated monocarboxylic acid and/or a salt thereof,

   (B) from 0.5 to 20 mol% of an alkoxylated monoethylenically unsaturated monomer of the formula I

   

   in which the variables are defined as follows:

   R¹ is hydrogen or methyl;

   R² is -(CH₂)_x-O-, -CH₂-NR⁵-, -CH₂-O-CH₂-CR⁶R⁷- CH₂-O- or -CONH-;

   R³ are each identical or different C₂-C₄- alkylene radicals which may be arranged blockwise or randomly, the proportion of ethylene radicals being at least 50 mol%;

   R⁴ is hydrogen, C₁-C₄-alkyl , -SO₃M or -PO₃M₂ ;

   R⁵ is hydrogen or -CH₂-CR¹=CH₂;

   R⁶ is -O-[R³-O]_n-R⁴, where the -[R³-O]_n- radicals may be different from the further -[R³-O]_n- radicals present in formula I;

   R⁷ is hydrogen or ethyl;

   M is alkali metal or hydrogen;

   n is from 4 to 250;

   x is 0 or 1,

   (C) from 0 to 50 mol% of a monoethylenically unsaturated dicarboxyic acid, of an anhydride and/or of a salt thereof
   and

   (D) from 0 to 20 mol% of a further copolymerizable monoethylenically unsaturated monomer

   and has an average molecular weight M_w of from 30 000 to 500 000 g/mol and a K value of from 40 to 150 (measured at pH 7 in 1% by weight aqueous solution at 25°C).
2. The process according to claim 1, wherein a copolymer is used which is obtainable by free-radical copolymerization of from 80 to 99.5 mol% of the monomers (A) and from 0.5 to 20 mol% of the monomers (B) .
3. The process according to claim 1, wherein a copolymer is used which is obtainable by free-radical copolymerization of from 60 to 98 mol% of the monomers (A), from 1 to 15 mol% of the monomers (B) and from 1 to 30 mol% of the monomers (C).
4. The process according to claims 1 to 3, wherein a copolymer based on acrylic acid is used as monomer (A).
5. The process according to claims 1 to 4, wherein a copolymer based on ethoxylated allyl ethers having from 10 to 100 mol of ethylene oxide/mol is used as monomer (B).
6. The process according to claims 1 or 3 to 5, wherein a copolymer based on maleic acid is used as monomer (C).
7. A process for reducing the viscosity of aqueous detergent slurries, which comprises adding to the slurry a copolymer according to claims 1 to 6.
8. A detergent slurry comprising a copolymer according to claims 1 to 6.
9. A detergent composition comprising a copolymer according to claims 1 to 6.
10. The use of copolymers according to claims 1 to 6 as an additive in detergent compositions.