EP1761622A1

EP1761622A1 - Method for producing granulated or powdery detergent compounds

Info

Publication number: EP1761622A1
Application number: EP05758640A
Authority: EP
Inventors: Kathrin Michl; Tanja Seebeck
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-06-25
Filing date: 2005-06-18
Publication date: 2007-03-14
Anticipated expiration: 2025-06-18
Also published as: CN1973025A; WO2006000357A1; ATE423836T1; CA2571706A1; DE102004031040A1; MXPA06014512A; DE502005006702D1; JP2008503623A; BRPI0512512A; EP1761622B1; CN1973025B; ES2320787T3; US20070238637A1; CA2571706C

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: 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 Mw 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

Process for the preparation of granular or pulverulent detergent compositions

description

The present invention relates to a process for the preparation of granular or powdered detergent compositions, comprising the preparation of a detergent base powder by drying an aqueous detergent slurries, and detergent compositions containing a by radical copolymerization of

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

(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 is} hydrogen or methyl; R ² - (CHz) _x -O-, -CH ₂ -NR ⁵ -, -CHz-O-CHz-CR ⁶ R ⁷ -CHr-O- or -CONH-; R ^{3 are} 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%; R ^{4 is} hydrogen, C ₁ -C ₄ -alkyl- ₁ -SO ₃ M or -PO ₃ M ₂ ; R ^{5 is} hydrogen or -CH ₂ -CR ¹ = CH ₂ ; R ^{6 is} -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 is} hydrogen or ethyl; M alkali metal or hydrogen; n 4 to 250; x 0 or 1,

(C) 0 to 50 mol% of a monoethylenically unsaturated dicarboxylic acid, an An¬ hydride and / or a salt thereof

and (D) 0 to 20 mol% of a further 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 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 done by slurrying in water , Various components, for example surfactants and the zeolites used as builders, give high-viscosity 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. Copolymers of acrylic acid and ethoxylated allyl ethers having an average molecular weight M _w of about 12,000 are used for this purpose in US Pat. Nos. 5,595,968, 5,618,782 and 5,733,861.

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

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

The object of the invention was to make possible the production of solid detergent compositions by employing viscosity-reducing polymers in an advantageous manner. In addition, the polymers used should have advantageous an¬ technical effect in the resulting detergents.

Accordingly, a process for the preparation of granular or pulverulent detergent compositions comprising the preparation of a detergent base powder by drying an aqueous detergent slurries was found, which characterized in that the slurry is added to a copolymer, which by radi¬ calische copolymerization of

in which the variables have the following meaning:

R ^{1 is} hydrogen or methyl; R ² - (CHz) _x -O-, -CH ₂ -NR ⁵ -, -CHz-O-CHz-CR ^ -CHr-O- or -CONH-; R ^{3 are the} same or different C ₂ -C ₄ -alkylene radicals which may be arranged blockwise or statically, the proportion of ethylene radicals being at least 50 mol%; R ^{4 is} hydrogen, C ₁ -C ₄ -alkyl, -SO ₃ M or -PO ₃ M ₂ ; R ^{5 is} hydrogen or -CH ₂ -CR ¹ = CH ₂ ; R ^{6 is} -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 is} hydrogen or ethyl; M alkali metal or hydrogen; n 4 to 250; x 0 or 1,

and

(D) 0 to 20 mol% of a further 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 ⁰ C). In addition, a process has been found for lowering the viscosity of detergent tablets, which is characterized in that the copolymers are added to the slurry.

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

Finally, the use of these copolymers was found as an additive in Waschmittelzu¬ compositions.

The copolymers used according to the invention contain as copolymerized monomer (A) a monoethylenically unsaturated monocarboxylic acid, preferably a CrCe monocarboxylic acid, and / or a water-soluble salt, in particular an alkali metal salt, such as potassium and, above all, 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 mol%, preferably from 70 to 95 mol%, of the monomer (A).

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

R ¹

H ₂ C = C-R ² - | -R ³ -O ^ -R ⁴

in which the variables have the following meaning:

R ^{1 is} hydrogen or methyl, preferably hydrogen; R ² - (CH ₂ ) _X -O-, -CH _5n, NR ⁵ -, -CHR-O-CHz-CRV-CHz-O- or -CONH-, preferably - (CHz) _x -O-, - CH ₂ -NR ⁵ - or -CHz-O-CHz-CR ^ -CHz-O- and particularly preferably - (CH ₂ ) _X -O- or -CHr-O-CHr-CRW-CH ^ O-; R ^{3 are the} same 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 is} hydrogen, C ₁ -C ₄ -alkyl, -SO ₃ M or -PO ₃ M ₂ ; R ^{5 is} hydrogen or -CH ₂ -CR ¹ = CH ₂ ; R ^{6 is} -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 - and the preferences given for R ³ apply; R ^{7 is} hydrogen or ethyl; M alkali metal, preferably sodium or potassium, or hydrogen; n is 4 to 250, preferably 5 to 200 and particularly preferably 10 to 100; x O or l

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 contain in particular 5 to 20, especially 10 to 100 moles EO / mol.

The monomers (B) can be prepared by well-known standard methods of organic chemistry, for. Example by amidation and transamidation of ge suitable (meth) acrylic acids, by alkoxylation of allyl alcohol, glycerol monoallyl ether 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 from 1 to 15 mol%, preferably from 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, its anhydride and / or one of its water-soluble salts, in particular an alkali metal salt, such as potassium and, above all, 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.

Examples of suitable monomers (D) are:

Esters of monoethylenically unsaturated C ₃ -C 8 -carboxylic acids, in particular (meth) acrylic esters, such as methyl, ethyl, propyl, hydroxypropyl, n-butyl, isobutyl, 2-ethylhexyl, decyl, lauryl iso-bomyl, cetyl, palmityl and stearyl (meth) acrylate;

(Meth) acrylamides such as (meth) acrylamide, N- (C _r C ₁₂ alkyl) - and N, N-di (CrC 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 -, in particular C ₂ -C ₄ -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;

Vinyl aromatics, such as styrene and substituted styrenes, e.g. Alkylstyrenes, such as methylstyrene and Ethylstyroi.

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., according to H. Finkentscher, Cellulose-Chemie, Vol. 13, pp. 58-64 and 71-74 (1932)).

The copolymers used according to the invention can be obtained by the known radical polymerization processes. In addition to the polymerization in substance, in particular solution and emulsion polymerization should be mentioned, with the solution polymerization being 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 are initiators having a decomposition temperature in the range of 20 to 180 ⁰ C, in particular from 50 to 12O ⁰ C, be¬ preferred. Examples of suitable thermal initiators are inorganic peroxo compounds, such as peroxodisulfates (ammonium and preferably sodium peroxodisulfate), peroxosulfates, percarbonates and hydrogen peroxide; organic peroxo 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 from 0.1 to 1000 ppm, based on the sum of the monomers. For example, combinations of hydrogen peroxide and iron (II) salts are particularly advantageous, such as a combination of 0.5 to 30% by weight hydrogen peroxide and 0.1 to 500 ppm FeSO ₄ .7H 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.

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

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. If, for example, the preferred system peroxydisulphate / hydrogen sulphite is used, it is customary to use from 2 to 6% by weight, preferably from 3 to 5% by weight, of peroxodisulphate and generally from 5 to 30% by weight, preferably from 5 to 10 wt .-%, hydrogen sulfite, in each case based on the sum of the monomers einge¬ sets.

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.

If polymerization regulators are used, their amount used is generally from 0.1 to 15% by weight, preferably from 0.1 to 5% by weight and more preferably from 0.1 to 2.5% by weight, based on the sum of the monomers.

The polymerization temperature is generally from 30 to 200 ^° C., preferably from 50 to 150 ^° C., and more preferably from 80 to 130 ^° C.

The polymerization is preferably carried out under protective gas, such as nitrogen or argon, and can be carried out under atmospheric pressure, but it is preferably carried out in a closed system under the developing 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 according to the invention, the viscosity of aqueous detergent slurries, in particular of the slurries which are dried to produce granular or pulverulent detergent compositions, can be lowered effectively, so that even highly concentrated slurries can be handled without problems. Thus, the slurry concentrations may always be ≥ 50% by weight, preferably> 60% by weight and more 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 usually added to the slurries 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 amount, added.

They can either be added to the total mixture or incorporated in any desired amounts of individual detergent components, for example the surfactants or the builder premixes, whose solids contents can already be raised in this way. The copolymers used according to the invention are not only outstandingly suitable as process auxiliaries for detergent production because of their viscosity-lowering and stabilizing action, but are also notable for their advantageous performance properties during the washing process themselves. Thus, they act in solid and liquid detergent compositions both incrustation-inhibiting and graying-inhibiting.

Solid detergent formulations according to the invention which comprise the copolymers used according to the invention advantageously have e.g. following composition:

(a) from 0.01 to 10% by weight of at least one copolymer according to the invention,

(b) 0.5 to 40% by weight of at least one nonionic, anionic and / or cationic surfactant,

(c) 0.5 to 80% by weight of an inorganic builder,

(d) 0 to 10% by weight of an organic cobuilder and

(E) 0 to 60 wt .-% of other conventional ingredients, such as setting agents, enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleach catalysts, color transfer inhibitors, other grayness inhibitors, soil release polyester, fiber and color protection additive, silicones , Dyes, bactericides, dissolution improvers and / or disintegrants,

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

Liquid detergent formulations according to the invention may e.g. be composed as follows:

(c) 0 to 20% by weight of an inorganic builder,

(d) 0 to 10% by weight of an organic cobuilder,

(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, catalysts, color transfer inhibitors, further grayness inhibitors, soil release polyesters, fiber and color protective additives, silicones, dyes, bactericides, organic solvents, solubilizers, hydrotropes, thickeners and / or alkanolamines and

(f) 0 to 99.45% by weight of water.

Suitable nonionic surfactants (b) are, in particular:

- Alkoxylated C ₈ -C ₂₂ -AlkOhOIe, such as fatty alcohol alkoxylates, Oxoalkoholalkoxylate 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.

- Alkylpolyglucoside containing C ₈ -C ₂₂ -, preferably C ₁₀ -C ₈ 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.

Suitable anionic surfactants are, for example:

Sulfates of men (fatty) alcohols having from 8 to 22, preferably 10 to 18, Kohlenstoffato¬, particularly CgCn alcohol sulfates, C ₂ C ₁₄ alcohol sulphates, C ₁₂ -C ₁₈ -Alkohol- sulfate, lauryl sulfate, cetyl sulfate, myristyl, palmityl, 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 characterized in that firstly a C ₈ -C ₂₂ -, preferably a pre-Ci ₀ -C ₈ alcohol, for example a fatty alcohol alkoxylated and the alkoxylation product is 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.

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

Il III in which the variables have the following meaning:

R ^{8 is} C ₁ -C 5 -alkyl or C ₂ -C ₂₅ -alkynyl I; R ^{9 is} C ₁ -C ₄ -alkyl or hydroxy-C ₁ -C ₄ -alkyl; R ^{10 is} C ₁ -C ₄ -alkyl, _{1 is} hydroxy-dC ₄ -alkyl or a radical R ^{8 is} - (CO) -X- (CH ₂ ) _P - (X: -O- or -NH-; p: 2 or 3 ), wherein at least one radical R ^{8 is} C ₇ -C ₂₂ -alkyl.

Suitable inorganic builders are, in particular:

Crystalline and amorphous aluminosilicates with ion-exchanging properties, especially 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 is partially soluble other cations such as Li, K, Ca, Mg or ammonium are 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, Erd¬ alkali 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.

As organic cobuilders are particularly suitable:

Low molecular weight carboxylic acids, such as citric acid, hydrophobically modified citric acid, eg. , 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, e.g. Nitrilotriacetic acid, .beta.-alanine diacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, ethylenediaminedisuccinic 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 1 -C 4 -olefins, for example isobutene or long-chain α-olefins, vinyl C 1 -C ₈ -alkyl ethers, vinyl acetate, vinyl propionate, ( Meth) acrylic esters of C ₁ - Cβ 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, homopolymers, copolymers 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, for. In WO-A-99/06524 and 99/04313; in Liquid Detergents, Editor: Kuo- Yann Lai, Surfactant Sei. Ser., Vol. 67, Marcel Decker, New York, 1997, p. 272-304, to find.

Examples

I) Preparation of copolymers according to the invention

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 metering device, 251.8 g of distilled water and 3.40 g of 50% strength by weight phosphorous acid were heated to an internal temperature of 95 ^° C. with introduction of nitrogen and stirring. Then 595.9 g of acrylic acid (97.7 mol%) were continuously added in four separate feeds in 4 hours, 303.0 g of a 50% strength by weight aqueous solution of monomer (B1) (2, 3 mol%), in 4 h 74.4 g of a 40 wt .-% aqueous sodium bisulfite solution and in 4.25 h, a mixture of 18.2 g of sodium persulfate and 242.5 g of distilled water was added. After stirring for one hour at 95 ⁰ C and cooling to 5O ⁰ C was treated with 50% strength by weight sodium hydroxide solution in 1, 5, a pH of 6.7 h set. Then, under Einhal¬ tung a temperature of 50 to 6O ⁰ C 3.36 g of a 50 wt .-% aqueous Wasser¬ peroxide solution in 30 minutes added. After stirring for a further 30 minutes at this temperature, it 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

135.1 g of distilled water and 2.27 g of 50% strength by weight phosphorous acid were heated to an internal temperature of 95 ° C. in a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering device while supplying nitrogen and stirring. Then in 4 separate feeds, 368.8 g of acrylic acid (97.0 mol%) were continuously added in four separate feeds, 150.0 g of a 50% strength by weight 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 5O ⁰ C was adjusted with 50 wt% sodium hydroxide solution in 1.5 h, a pH of 6.9. Then, under Einhal¬ tung a temperature of 50 to 60 ⁰ C. 2.14 g of a 50 wt .-% aqueous Wasser¬ peroxide solution in 30 min and stirred metered nach¬ 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% strength by weight phosphorous acid were heated to an internal temperature of 95 ° C. with introduction of nitrogen and stirring. 417.1 g of acrylic acid (97.0 mol%) were then continuously added in four separate feeds in 4 hours, 282.8 g of a 50% strength by weight aqueous solution of monomer (B6) in 4 hours (3, 0 mol%), in 4 h 69.8 g of a 40 wt .-% aqueous sodium bisulfite solution and in 4.25 h, a mixture of 13.6 g of sodium persulfate and 242.5 g of distilled water was added. After one hour of stirring at 95 ° C and cooling to 50 ⁰ C was adjusted with 50 wt% sodium hydroxide solution in 1.5 h, a pH of 6.8. Then, under Einhal¬ tung a temperature of 50 to 6O ⁰ C 2.42 g of a 50 wt .-% aqueous Wasser¬ peroxide solution in 30 minutes added. Finally, the mixture was stirred for 30 minutes 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 device were 242.3 g of distilled water and 3.40 g of 50 wt .-% phosphorous Acid under nitrogen and stirring to 95 ⁰ C internal temperature. Then 595.9 g of acrylic acid (97.7 mol%) were continuously added in four separate feeds 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 wt .-% aqueous sodium bisulfite solution and in 4.25 h, a mixture of 18.2 g of sodium persulfate and 242.5 g of distilled water was added. After stirring for one hour at 95 ⁰ C and cooling to 50 ⁰ C was adjusted with 50 wt% sodium hydroxide solution in 1.5 h, a pH of 6.7. Then, under Einhal¬ tung a temperature of 50 to 60 ⁰ C. 3.36 g of a 50 wt .-% aqueous Wasser¬ peroxide solution in 30 minutes added. After stirring for a further 30 minutes at this temperature, it 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 initially charged in a pressure reactor with stirrer, nitrogen feed, 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, 278.1 g of acrylic acid (89.6 mol%) were continuously added over 4 h, 202.0 g of a 50% strength by weight 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 25 ° C).

Example 6

161.5 g of distilled water and 69.5 g of maleic anhydride (15.0 mol%) were heated to an internal temperature of 98.degree. C. in a pressure reactor with stirrer, nitrogen feed, reflux condenser and metering device while feeding with nitrogen and stirring. Then, in four separate feeds, 278.1 g of acrylic acid (82.0 mol%) were continuously added in four separate feeds, 202.0 g of a 50% strength by weight 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 stirring for one hour at 98 ° C and cooling to 50 ⁰ 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% strength by weight aqueous water peroxide solution added in 30 min. After stirring for a further 30 minutes at this temperature, 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 under nitrogen to 99 ° C internal temperature. 484.0 g of acrylic acid (82.5 mol%) were then continuously added in three separate feeds over 4 hours, and 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 25 ⁰ C) received.

Example 8

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and Dosiervor¬ direction 161.5 g of distilled water were heated with nitrogen and stirring to 95 ° C internal temperature. Then in four separate feeds in 399.0 g of acrylic acid (97.7 mol%) in 4 h, 202.0 g of a 50 wt .-% 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 one hour of stirring at 95 ⁰ C, addition of 200.0 g of distilled water and cooling to 50 ⁰ C was at this temperature with 50 wt .-% sodium hydroxide solution in 1.5 h, a pH of 6.6 set ,

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 feed, reflux condenser and metering device, 161.5 g of distilled water, 202.0 g of a 50% strength by weight aqueous solution of monomer (B1) (2.3 mol%) and 2, 27 g of 50 wt .-% phosphoric acid under nitrogen and stirring to 95 ⁰ C internal temperature. Then, in three separate feeds, 397.3 g of acrylic acid (97.7 mol%) were continuously added in three hours, 43.6 g of a 40% strength by weight aqueous sodium hydrogen sulfite solution 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 ⁰ C was adjusted 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

161.5 g of distilled water and 202.0 g of a 50% strength by weight aqueous solution of monomer (B1) (2.3 mol%) were placed in a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering device Nitrogen feed and stirring heated to 95 ° C internal temperature. 397.3 g of acrylic acid (97.7 mol%) were then continuously added in three separate feeds over 4 hours, 31.5 g of a 40% strength by weight aqueous sodium hydrogen sulfite solution in 4 hours and a mixture in 4.25 hours 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 ⁰ C was set at this temperature with 50 wt .-% sodium hydroxide solution in 1.5 h, a pH of 6.7.

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

Example 11

500.0 g of distilled water and 4.88 mg of FeSO ₄ .7H ₂ O, 101.0 g of a 50% strength by weight aqueous solution of monomer were used in a pressure reactor with stirrer, nitrogen feed, reflux condenser and metering device (B1) (2.3 mol) under Stickstoffzu¬ drove and stirring at 100 ⁰ 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 ⁰ C and cooling to 5O ⁰ C was adjusted 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 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 metering device, 161.5 g of distilled water, 202.0 g of a 50% strength by weight aqueous solution of monomer (B1) (2.3 mol%) and 2, 27 g of 50 wt .-% phosphoric acid under nitrogen and stirring to 95 ⁰ C internal temperature. Then, in three separate feeds, 399.0 g of acrylic acid (97.7 mol%) were added continuously in 4 h, in 4 h a mixture of 10.0 g of sodium hypophosphite and 40.0 g of distilled water and in 4.25 h a mixture of 12.2 g of sodium persulfate and 161, 7 g of distilled water given zu¬. After stirring for one hour at 95 ⁰ C, addition of 200.0 g of distilled water and cooling to 5O ⁰ C was at this temperature with 50 wt .-% sodium hydroxide solution in 1.5 h, a pH of 6.9 set ,

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 feed, reflux condenser and metering device, 161.5 g of distilled water, 202.0 g of a 50% strength by weight aqueous solution of monomer (B1) (2.5 mol%) and 20, 0 g of maleic anhydride (2.5 mol%) under nitrogen and stirring to 95 ° C internal temperature. Then, in three separate feeds, 379.0 g of acrylic acid (82.5 mol%) were added continuously in 4 hours, 44.0 g of a 40% strength by weight aqueous sodium hydrogen sulfite solution in 4 hours and a mixture in 4.25 hours from 12.2 g of sodium persulfate and 161, 7 g of distilled water. After stirring for one hour at 95 ⁰ C, addition of 200.0 g of distilled water and cooling to 50 ⁰ C was adjusted at this temperature with 50 wt .-% sodium hydroxide solution in 1.5 h, a pH of 6.6.

A polymer solution having a solids content of 28.3% by weight and a K value of 101.8 (measured at pH 7 in 1% strength by weight aqueous solution at 25.degree. C.) was obtained. Example 14

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and dosing device 161, 5 g of distilled water and 31 0 g of maleic anhydride (7.4 mol%) were heated under nitrogen and with stirring to 98 ⁰ C internal temperature. 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 h 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 einstün- DIGEM stirring at 98 ⁰ C and cooling to 50 ⁰ C was added at this temperature with a 50 wt .-% sodium hydroxide solution in 1.5 h, a pH value of 6.8 adjusted. Then, while maintaining a temperature of 50 to 6O ⁰ C were 2.24 g of a 50 wt% aqueous hydrogen peroxide solution in 30 metered .- min. 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

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.%) Under nitrogen were used in a pressure reactor with stirrer, nitrogen feed, reflux condenser and metering device and stirring at 98 ⁰ 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.degree. 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 25 ° C).

Example 16

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and Dosiervor¬ direction 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 ⁰ C, a pH of 6.7 was set at this temperature with 50 wt .-% sodium hydroxide solution. Finally, another 100.0 g of distilled water was added.

It was a polymer solution having a solids content of 41, 1 wt .-% and a K value of 60.4 (measured at pH 7 in 1 wt .-% aqueous solution at 25 ° C).

Example 17

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering device, 95.0 g of distilled water and 1.10 g of 50% strength by weight phosphorous acid were heated to an internal temperature of 99 ° C. with introduction of nitrogen and stirring. 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 zuge¬. After about 2.5 h, 100.0 g of distilled water were added. After completion of Natriumpersulfatzulauf 1 h at 99 ⁰ C was stirred. After cooling to 5O ⁰ C de wur¬ at this temperature with 50 wt .-% sodium hydroxide solution is einge¬ a pH of 6.5.

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.degree. C.) was obtained.

Example 18

In a pressure reactor with stirrer, nitrogen inlet, reflux condenser and metering device, 240.0 g of distilled water and 120.0 g of the monomer (B4) (2.3 mol%) were heated to internal temperature 95 ° C. with introduction of 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 given zu¬. After stirring for one hour at 95 ° C and cooling to 6O ⁰ 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 were added.

A polymer solution having a solids content of 47.3% by weight and a K value of 61.7 (measured at pH 7 in 1% strength by weight aqueous solution at 25.degree. C.) was obtained. 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% strength by weight phosphorous acid were heated to an internal temperature of 95 ° C. with introduction of nitrogen and stirring. Then, in four separate feeds, 198.3 g (97.8 mol%) of acrylic acid were continuously added over 4 h, and 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 in 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 ⁰ C and cooling to 60 ⁰ C, a pH of 6.5 was adjusted 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 Dosiervor- direction 150.0 g of distilled water and 2.17 g of 85 wt .-% phosphoric acid was heated under nitrogen and with stirring at 95 ⁰ C internal temperature. Then, in four separate feeds, 375.4 g of acrylic acid (99.2 mol%) were continuously added in four hours, 63.6 g of a 50% 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 stirring at 95 ° C. and cooling to 50 ° C., a pH of 6.7 was set in 1.5 h with 50% strength by weight sodium hydroxide solution. Then, while maintaining a temperature of 50 to 60 ⁰ C 2.12 g of a 50 wt .-% aqueous hydrogen peroxide solution in 30 min were added. Finally, stirring was continued for 30 minutes 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) Examination 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 added over a torque pickup. The previously mixed solid components were then uniformly metered in over 4 minutes, the slurry being stirred further at 150 rpm. After completion of the addition, the slurry was stirred with constant Umdre¬ tion number 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 slurries.

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

In Tables 2 to 4, the torques obtained in each case after 30 minutes zusammen¬ provided. 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

Table 2 Table 4

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 slurries with a higher concentration. Thus, in the case of the composition Slurry 1 without the addition of a copolymer according to the invention only reaches a total solids content of 68 wt .-% (compared to 73.5 wt .-% with the addition of 1 wt .-% of the copolymer of Example 4) become.

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 1 δmaligem washing, the ash content of the test fabric was determined by ashing at 700 ⁰ 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

Table 6: Washing conditions Table 7

Claims

claims

1. A process for the preparation of granular or pulverulent Waschmittelzu¬ compositions, comprising the preparation of a detergent base powder by drying an aqueous Waschmittellurries, characterized in that the slurry is added to a copolymer which by free radical copolymerization of

(B) 0.5 to 20 mol% of an alkoxylated monoethylenically unsaturated Mo¬ nomers of the formula I.

in which the variables have the following meaning:

R ^{1 is} hydrogen or methyl; R ² - (CHz) _x -O-, -CH ₂ -NR ⁵ -, -CHz-O-CHz-CR ^ -CHz-O- or -CONH-; R ^{3 are} 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%; R ^{4 is} hydrogen, C ₁ -C ₄ -alkyl, -SO ₃ M or -PO ₃ M ₂ ; R ^{5 is} 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 For¬ mel I - [R ³ -O] _n - ; R ^{7 is} hydrogen or ethyl; M alkali metal or hydrogen; n 4 to 250; x 0 or 1,

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

and

(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 ⁰ C).

2. The method according to claim 1, characterized in that one uses a copolymer which is obtainable by free-radical copolymerization of 80 to 99.5 mol% of the monomers (A) and 0.5 to 20 mol% of the monomers (B) ,

3. The method according to claim 1, characterized in that one uses a copolymer which by free radical copolymerization of 60 to 98 mol% of Mo¬ nomeren (A), 1 to 15 mol% of the monomers (B) and 1 to 30 mol% of Mono¬ mers (C) is available.

4. Process according to claims 1 to 3, characterized in that one uses a copolymer based on acrylic acid as the monomer (A).

5. Process according to claims 1 to 4, characterized in that one uses a copolymer based on ethoxylated allyl ethers with 10 to 100 mol ethylene oxide / mol as monomer (B).

6. Process according to claims 1 or 3 to 5, characterized in that one uses a copolymer based on maleic acid as the monomer (C).

7. A process for lowering the viscosity of aqueous Waschmittelslurries, da¬ characterized in that the slurry is a copolymer according to the Ansprü¬ Chen 1 to 6 added.

8. Waschmittelslurries containing a copolymer according to claims 1 to 6.

9. Detergent compositions comprising a copolymer according to An¬ claims 1 to 6.

10. Use of copolymers according to claims 1 to 6 as an additive in detergent compositions. Process for the preparation of granular or pulverulent detergent compositions

Summary

A process for the preparation of granular or pulverulent detergent compositions which comprises the preparation of a detergent base powder by drying an aqueous detergent slurry, characterized in that a copolymer is added to the slurry which is obtained by free-radical copolymerization of

(A) 50 to 99.5 mol% of a monoethylenically unsaturated monocarboxylic acid and / or a salt thereof, (B) 0.5 to 20 mol% of an alkoxylated monoethylenically unsaturated monomer IR ¹

H ₂ C:: C-R ^ RO - ^ - R ⁴

with the following meaning of the variables: R ^{1 is} hydrogen or methyl; R ² - (CH ₂ ) _X -O-, -CH ₂ -NR ⁵ -, -CHz-O-CHz-CR ^ -CHz-O- or -CONH-; R ^{3 are the} same or different C ₂ -C ₄ -alkylene radicals which may be arranged blockwise or statically, the proportion of ethylene radicals being at least 50 mol%; R ^{4 is} hydrogen, C ₁ -C ₄ -alkyl, -SO ₃ M or -PO ₃ M ₂ ; R ^{5 is} hydrogen or -CH ₂ -CR ¹ = CH ₂ ; R ^{6 is} -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 is} hydrogen or ethyl; M alkali metal or hydrogen; n 4 to 250; x is 0 or 1, (C) 0 to 50 mol% of a monoethylenically unsaturated dicarboxylic acid, an anhydride and / or a salt thereof and (D) 0 to 20 mol% of a further 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).