EP0609777A2 - Detergent composition with improved soil removal ability, process for its production and use of a suitable polycarboxylate therefor - Google Patents

Abstract

2.1. Besides the main builder zeolite A, low-phosphate and phosphate-free detergents and cleaning agents require so-called co-builders, which increase the effectiveness of the detergents. Use of a novel co-builder is intended to decrease the secondary washing effects such as greying and encrustation. 2.2. In addition to the customary components such as surfactant, calcium-binding silicate, etc., the novel detergent contains at least 1% by weight of a polycarboxylate having the schematic structure (X, Y, Z), in which X is <IMAGE> Y is <IMAGE> and Z is -(F)q-. These carboxylates can be prepared from acrolein and, if desired, one or more comonomers by means of oxidising free radical donors without hydrolysing conditions and/or without subsequent Cannizzaro reaction. The novel co-builders show improvements in all basic detergent properties compared with co-builders conventionally used. 2.3. Detergent, detergent for delicate articles, colour detergent, liquid detergent, compact detergent.

Description

The present invention relates to a preferably low-phosphate or free, zeolite-containing detergent system, a process for its production and the use of a suitable polycarbonate therefor.

The development of detergent builders has been generally influenced by the spread of phosphate-free detergents in recent years. Zeolite A is used as the most common builder replacement for phosphate. Due to the slower exchange kinetics of the zeolite for Ca ions, phosphate-free powder and liquid detergents and cleaning agents need so-called cobuilders, such as z. B. soda, polycarboxylates, NTA, silicates or hydroxycarboxylates. Common builder additives are currently polymeric carboxylic acids and their salts. Preferred in the area of detergents and cleaning agents are e.g. B. homopolymers of acrylic acid or copolymers

based on acrylic acid with maleic acid such as z. B. in the specifications 20 25 238, 20 44 601, in EP 0 137 669 or DE 36 04 223 A1.

These products contribute to the washing effect of the detergents by improving the dirt-carrying capacity:

On the one hand, they prevent the dirt from being drawn back onto the laundry and have a disruptive effect due to the graying of the textiles, and on the other hand, they reduce the deposition of inorganic salts (incrustation) on them.

Polycarboxylates in connection with zeolites or layered silicates are u. a. known from EP 0 401 780.

It has been shown that the secondary washing effects of graying and incrustation could be reduced by the commercially available products of the polycarboxylates, but further optimization of these cobuilders is desirable in order to increase the effectiveness of the detergents and at the same time

to further improve the usage properties of the textiles.

The task is a low-phosphate or low-zeolite detergent system with an improved cobuilder.

This object is achieved with a detergent system according to claim 1.

In addition to a calcium ion-binding silicate, the new detergent system contains at least one (co) polymer, preferably of acrylic acid and acrolein. The invention also includes the use of these substances in phosphate-free or reduced phosphate powder or liquid detergents and cleaning agents.

wobei mindestens 1 Gew.-% der Zusammensetzung ein Polycarboxylat mit der schematischen Struktur (X,Y,Z) ist, worin X für

• Y für
  
  
  und Z für
  -(F)q-
  steht, worin
  • A = H, OH, Ci-6 Alkyl, CH₂CO(DECO)_r-1OM;
  • B = H, OH, C_1-6 Alkyl, COOM;
  • D = O, NH;
  • E = C_1-6 Alkyl, linear bzw. verzweigt;
  • F = ein copolymerisierbares Monomer;
  • M = H, Alkali- bzw. Erdalkalimetall, Ammonium, substituiertes Ammonium; bei X auch -(CH₂-CH₂-O)-_2-4M;
  • r = 1 - 5;
    ist und
  • m = 0 - 99,5 Mol %
  • n = 0,5 - 100 Mol %
  • q = 0 - 99,5 Mol %
    wobei m + n + q = 100 Mol %
  • bedeutet.

The detergent according to the invention contains

wherein at least 1% by weight of the composition is a polycarboxylate with the schematic structure (X, Y, Z), where X is

• Y for
  
  
  and Z for
  - (F) q-
  stands in what
  • A = H, OH, Ci-6 alkyl, CH ₂ CO (DECO) _r-1 OM;
  • B = H, OH, C _1-6 alkyl, COOM;
  • D = O, NH;
  • E = C _1-6 alkyl, linear or branched;
  • F = a copolymerizable monomer;
  • M = H, alkali or alkaline earth metal, ammonium, substituted ammonium; for X also - (CH ₂ -CH ₂ -O) - _2-4 M;
  • r = 1-5;
    is and
  • m = 0 - 99.5 mol%
  • n = 0.5 - 100 mol%
  • q = 0 - 99.5 mol%
    where m + n + q = 100 mol%
  • means.

wobei mind. 1 Gew.-% der Zusammensetzung ein Polycarboxylat ist, das aus Acrolein und ggf. einem oder mehreren Comonomeren mittels oxidierender Radikalspender ohne verseifende Bedingungen und/oder ohne anschließender Cannizzaro-Reaktion herstellbar ist
und/oder wobei mind. 1 Gew.-% der Zusammensetzung ein Polycarboxylat ist, das aus Acrolein und ggf. einem oder mehreren Comonomeren mittels oxidierender Radikalspender herstellbar ist und einen Anteil an funktionellen Gruppen des Typs -C(0)-0[-CH₂-CH₂-C(0)0]_rR' hat, worin R' für ein Alkali-, Erdalkali- oder Stickstoff-haltiges Kation steht
und/oder wobei mind. 1 Gew.-% der Zusammensetzung ein Polycarboxylat ist, das aus Acrolein und ggf. einem oder mehreren Comonomeren mittels oxidierender Radikalspender herstellbar ist und wobei das Polycarboxylat insbesondere auf einmal oder unmittelbar aufeinanderfolgend mit mehreren, insbesondere allen weiteren der o. g. Komponenten ggf. unter Zusatz von H₂0 vermischt und ggf. getrocknet wird.The detergent according to the invention can also be defined as follows:

wherein at least 1% by weight of the composition is a polycarboxylate which consists of acrolein and possibly one or more comonomers by means of oxidizing radical donors without saponifying conditions and / or can be produced without a subsequent Cannizzaro reaction
and / or wherein at least 1% by weight of the composition is a polycarboxylate, which can be prepared from acrolein and possibly one or more comonomers by means of oxidizing radical donors and a proportion of functional groups of the type -C (0) -0 [-CH ₂ -CH ₂ -C (0) 0] _r R ', wherein R' is an alkali, alkaline earth or nitrogen-containing cation
and / or wherein at least 1% by weight of the composition is a polycarboxylate, which can be prepared from acrolein and possibly one or more comonomers by means of oxidizing radical donors, and the polycarboxylate in particular at once or in succession with a plurality, in particular all other, of the abovementioned Components may be mixed with the addition of H ₂ 0 and dried if necessary.

In addition to the components mentioned, the inventive detergent according to the invention preferably contains at least one of the following components in the amount specified below

As a compact detergent, the composition contains 2-8% by weight of polycarboxylate and bleach activator.

If the detergent composition is a liquid detergent formulation, then it contains

For a formulation as a mild detergent, the detergent composition contains

• Y für
  
  
  und Z für
  -(F)q-steht, worin
  • A = H, OH, Ci-6 Alkyl, CH₂CO(DECO)_r-1OM;
  • B = H, OH, Ci-6 Alkyl, COOM;
  • D = O, NH;
  • E = C_1-6 Alkyl, linear bzw. verzweigt;
  • F = ein copolymerisierbares Monomer;
  • M = H, Alkali- bzw. Erdalkalimetall, Ammonium, substituiertes Ammonium; bei X auch -(CH₂-CH₂-O)-_2-4M;
  • r = 1 - 5;
  
  ist und
  • m = 0 - 99,5 Mol %
  • n = 0,5 - 100 Mol %
  • q = 99,5 Mol %
  
  bedeutet, zu 1 - 20 Gew.-% in einer zu 5 - 50 Gew.-% ein calciumionenbindendes Silikat und zu 5 - 40 Gew.-% Tensid enthaltenden Waschmittelzusammensetzung.

The invention also relates to the use of a polycarboxylate of the schematic structure (X, Y, Z), in which X is

• Y for
  
  
  and Z for
  - (F) q-stands where
  • A = H, OH, Ci-6 alkyl, CH ₂ CO (DECO) _r-1 OM;
  • B = H, OH, Ci-6 alkyl, COOM;
  • D = O, NH;
  • E = C _1-6 alkyl, linear or branched;
  • F = a copolymerizable monomer;
  • M = H, alkali or alkaline earth metal, ammonium, substituted ammonium; for X also - (CH ₂ -CH ₂ -O) - _2-4 M;
  • r = 1-5;
  
  is and
  • m = 0 - 99.5 mol%
  • n = 0.5 - 100 mol%
  • q = 99.5 mol%
  
  means 1 to 20% by weight in a detergent composition containing 5 to 50% by weight of a calcium ion-binding silicate and 5 to 40% by weight of surfactant.

The use of a polycarboxylate, which can be prepared from acrolein and possibly one or more comonomers by means of oxidizing radical donors without saponifying conditions and / or without a subsequent Cannizzaro reaction, in an amount of 1 to 20% by weight in an amount of 5 to 50% by weight. a calcium ion-binding silicate and detergent composition containing 5-40% by weight of surfactant is also part of the invention.

• a) einen Anteil an funktionellen Gruppen des Typs -C(0)-0[-CH₂-CH₂C(0)0]_xR' hat, worin R' für ein Alkali-, Erdalkali- oder Stickstoff-haltiges Kation steht und x = 1-5 ist, zu 1 - 20 Gew.-% in einer zu 5 - 50 Gew.-% ein calciumionenbindendes Silikat und zu 5 - 40 Gew.-% Tensid enthaltenden Waschmittelzusammensetzung,
  und/oder
• b) wobei das Polycarboxylat mit mehreren, insbesondere allen Komponenten ggf. unter Zusatz von H₂0 vermischt und ggf. getrocknet wird, zu 1 - 20 Gew.-% in einer zu 5 - 50 Gew.-% ein calciumionenbindendes Silikat und zu 5 - 40 Gew.-% Tensid enthaltenden Waschmittelzusammensetzung.

Finally, the present invention also includes the use of a polycarboxylate which can be prepared from acrolein and possibly one or more comonomers by means of oxidizing radical donors and

• a) has a proportion of functional groups of the type -C (0) -0 [-CH ₂ -CH ₂ C (0) 0] _x R ', where R' is an alkali, alkaline earth or nitrogen-containing cation and x = 1-5, 1 to 20% by weight in a detergent composition containing 5 to 50% by weight of a calcium ion-binding silicate and 5 to 40% by weight of surfactant,
  and or
• b) wherein the polycarboxylate is mixed with several, in particular all components, if appropriate with the addition of H ₂ O and optionally dried, to 1 to 20% by weight in 5 to 50% by weight of a calcium ion-binding silicate and to 5 - Detergent composition containing 40% by weight of surfactant.

The invention also includes a method for producing the detergent compositions described above, in which the individual powdery components are mixed with one another by mixing and the liquid components are sprayed homogeneously with one another. Alternatively, water- and heat-insensitive components can first be processed into a slurry with water and then spray-dried; the remaining components are - as explained above - mixed.

In the case of compact detergents in particular, the components are advantageously agglomerated or extruded by forced mixing.

The liquid detergents are prepared by mixing with an appropriate amount of solubilizer or water and, if necessary, concentrated.

All individual components of the composition can be present as a pure substance or as a mixture of corresponding components. Water-insoluble substances, in particular zeolites, are preferably used as the calcium-binding silicate.

in der Kat ein mit Calcium austauschbares Kation der Wertigkeit n, x eine Zahl von 0,7 bis 1,5, Me Bor oder Aluminium und y eine Zahl von 0,8 bis 6 bedeuten, einsetzen.In a preferred embodiment of the invention, as the water-insoluble silicate capable of binding calcium ions, a finely divided, bound water-containing, synthetically produced, water-insoluble compound of the general formula

in the cat use a cation exchangeable with calcium of the valence n, x is a number from 0.7 to 1.5, Me boron or aluminum and y is a number from 0.8 to 6.

Aluminum silicates are particularly preferably used.

The aluminum silicates to be used can be amorphous or crystalline products, although mixtures of amorphous and crystalline products and also partially crystalline products can of course also be used. The aluminum silicates can be naturally occurring or else synthetically produced products, with the synthetically produced products being preferred. The production can e.g. B. by reaction of water-soluble silicates with water-soluble aluminates in the presence of water. For this purpose, aqueous solutions of the starting materials can be mixed with one another or a component present in the solid state can be reacted with the other component present as an aqueous solution. The desired aluminum silicates are also obtained by mixing the two components present in the solid state in the presence of water. Aluminum silicates can also be produced from Al (OH) ₃ , A1 ₂ 0 ₃ or Si0 ₂ by reaction with alkali silicate or aluminate solutions. The production can also be carried out by other known processes. In particular, the invention relates to aluminum silicates which have a three-dimensional space lattice structure.

The preferred calcium binding capacity, which is approximately in the range from 100 to 200 mg CaO / g active substance (AS), usually around 100 to 180 mg CaO / g AS, is found above all in compounds of the composition:
0.7 - 1.1 Na ₂ 0. Al ₂ O ₃ . 1.3-3.3 Si0 ₂

• a) 0,7 - 1,1 Na₂0 . Al₂O₃. 1,3 - 2,4 Si0₂
• b) 0,7 - 1,1 Na₂0 . Al₂O₃. 2,4 - 3,3 Si0₂

This molecular formula comprises two types of different crystal structures (or their non-crystalline precursors), which also differ in their molecular formulas. These are:

• a) 0.7 - 1.1 Na ₂ 0. Al ₂ O ₃ . 1.3 - 2.4 Si0 ₂
• b) 0.7 - 1.1 Na ₂ 0. Al ₂ O ₃ . 2.4-3.3 Si0 ₂

The different crystal structures are shown in the X-ray diffraction diagram.

The amorphous or crystalline aluminum silicate present in aqueous suspension can be separated from the remaining aqueous solution by filtration and at temperatures of e.g. B. Dry 50 to 400 _° C. Depending on the drying conditions, the product contains more or less bound water. It is advisable not to exceed 200 ° C if the aluminum silicate is intended for use in detergents and cleaning agents. However, the aluminum silicates do not need to be dried at all after their preparation in order to prepare a suspension according to the invention; rather - and this is particularly advantageous - an aluminum silicate that is still moist from manufacture can be used. However, it is also possible to use dried aluminum silicates at medium temperatures, for example at 80 to 200 _° C., until the adhering liquid water has been removed, in order to prepare suspensions according to the invention.

The particle size of the individual aluminum silicate particles can be different and z. B. are in the range between 0.1 u and 0.1 mm. This refers to the primary particle size, i.e. that is, the size of the particles obtained during the precipitation and, if appropriate, the subsequent crystallization. It is particularly advantageous to use aluminum silicates which consist of at least 80% by weight of particles with a size of 10 to 0.01 u, in particular 8 to 0.1 u.

These aluminum silicates preferably no longer contain primary or secondary particles with diameters above 45 u. Secondary particles are particles that are formed by agglomeration of the primary particles into larger structures.

With regard to the agglomeration of the primary particles to form larger structures, the use of the aluminum silicates which are still moist from their production has been used to produce the suspensions of the invention Sions particularly proven, since it has been found that the formation of secondary particles is practically completely prevented when using these still moist products.

In a particularly preferred embodiment of the invention, powdered zeolite, in particular of type A, is advantageously used as calcium-binding silicate, with a particularly defined particle spectrum.

Such zeolite powder can according to DE-AS 24 47 021, DE-AS 25 17 218, DE-OS 26 52 419, DE-OS 26 51 420, DE-OS 26 51 436, DE-OS 26 51 437, DE-OS 26 51 445, DE-OS 26 51 485 are produced. They then have the particle distribution curves given there.

In a particularly preferred embodiment, a powdery zeolite of type A can be used, which has the particle size distribution described in DE-OS 26 51 485.

The polycarboxylates can be used both as an acid and as a salt or as a partially neutralized substance; metal ions and nitrogen-containing cations are suitable as counterions.

• - monoethylenisch ungesättigte, carboxylgruppenfreie Monomere. Z. B. Hydroxy(meth)acrylate mit (CH₂)_xOH als Estergruppe, wobei x = 2-4 ist. (Meth)acrylamid, (Meth)acrylonitril, Vinylsulfonsäure, Allylsulfonsäure, Dimethylaminoethyl(meth)acrylat, Diethylaminoethyl(meth)acrylat, 2-(meth)-acrylamido-2-methylpropan-sulfonsäure, Vinylphosphonsäure, Allylphosphonsäure, Allylalkohol, Vinylglykol, Vinylacetat, Allylacetat, N-Vinylpirrolidon, N-vinylformamid, N-Vinylimidazol, N-vinylimidazolin, 1-Vinyl, -2-methyl-2-imidazolin. Ester der (Meth)acrylsäure mit 1 - 8 C-Atome im Alkoholrest wie z. B. Methyl(meth)acrylat, Ethyl(meth)acrylat, Propyl(meth)acrylat, Butyl(meth)acrylat evtl. mit Alkohol- bzw. mit Aminogruppen funktionalisiert, Ethylen, Propylen, Methylvinylether, Ethylvinylether, Styrol und alphaMethylstyrol. Alle monomeren Säure und Basen können evtl. auch als Salze verwendet werden.
• - Mehrfachethylenisch ungesättigte Monomere. Z. B. Ester aus Ethylenglykol, Propylenglykol, Butandiol bzw. Hexandiol mit (Meth)acryl-, Malein- bzw. Fumarsäure, Ester aus Polyethylenglykol bzw. Copolymeren aus Ethylen- und Propylenglykol mit (Meth)acrylsäure, Maleinsäure bzw. Fumarsäure, zwei- bis dreifach mit (Meth)acryl- bzw. Maleinsäure veresterte Anlagerungsprodukte von Ethylenoxid und/oder Propylenoxid an Trimethylolpropan, mindestens zweifache Ester aus (Meth)acryl- bzw. Maleinsäure und Glycerin bzw. Pentaerythrit, Triallyamin, Tetraallylethylendiamin, Polyethylenglykoldivinylether, Trimethylolpropandiallylether, Butandioldiallylether, Pentaerythrittriallylether, Divinylharnstoff.

The polymers of structure (X, Y, Z) according to the invention are preferably copolymers of acrylic acid and acrolein. The distribution of the monomers in the polymer is usually statistical (random), the end groups of the polymer (X, Y, Z) are usually those which arise under the corresponding reaction conditions. The copolymerizable monomer F is advantageously chosen so that it does not impair the cobuilder effect of the entire polymer. Suitable monomers F are

• - Monoethylenically unsaturated, carboxyl-free monomers. For example, hydroxy (meth) acrylates with (CH ₂ ) _x OH as the ester group, where x = 2-4. (Meth) acrylamide, (meth) acrylonitrile, vinylsulfonic acid, allylsulfonic acid, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) -acrylamido-2-methylpropane-sulfonic acid, vinylphosphonic acid, allylphosphonic acid, allyl alcohol, vinyl glycol, vinyl acetate, Allyl acetate, N-vinyl pirrolidone, N-vinyl formamide, N-vinyl imidazole, N-vinyl imidazoline, 1-vinyl, -2-methyl-2-imidazoline. Esters of (meth) acrylic acid with 1 - 8 carbon atoms in the alcohol residue such as. B. methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate may be functionalized with alcohol or with amino groups, ethylene, propylene, methyl vinyl ether, ethyl vinyl ether, styrene and alpha-methyl styrene. All monomeric acids and bases can possibly also be used as salts.
• - Polyethylenically unsaturated monomers. For example, esters of ethylene glycol, propylene glycol, butanediol or hexanediol with (meth) acrylic, maleic or fumaric acid, esters of polyethylene glycol or copolymers of ethylene and propylene glycol with (meth) acrylic acid, maleic or fumaric acid, two to three times Addition products of ethylene oxide and / or propylene oxide with trimethylolpropane esterified with (meth) acrylic or maleic acid, at least two-fold esters of (meth) acrylic or maleic acid and glycerol or pentaerythritol, triallyamine, tetraallylethylenediamine, polyethylene glycol divinyl ether, trimethylolpropane diallyl ether, pentanediol Divinyl urea.

Monomers F also include those polymer building blocks which have been chemically modified under the chosen reaction conditions compared to the corresponding starting compounds.

For component Y, on the one hand, monoethylenically unsaturated aldehydes such as acrolein and methacrolein, which are oxidized to the corresponding acid during the polymerization, and monoethylenically unsaturated esters or higher esterification homologues and amides which correspond to the structural element Y are suitable.

For component X, monoethylenically unsaturated C ₃ to C ₈ mono- or dicarboxylic acids, such as. As acrylic acid, methacrylic acid, fumaric acid, maleic acid and maleic anhydride, itaconic acid, citraconic acid, crotonic acid. The esters and amides derived from these compounds and corresponding to structural element X are also suitable.

The polycarboxylates which are preferably used according to the invention are polymeric cobuilders which contain 0.5-100 mol% of the monomer structure - (CH ₂ -CH-COOR) -, where R = CH ₂ -CH ₂ -COOR 'and R' H or R and their salt form (e.g. alkali metals and ammonium compounds are suitable as counterions).

1 H-NMR is suitable for the quantitative determination of these ester-containing side chains, which appear to arise especially from the use of acrolein as a monomer.

1 shows a 1 H NMR spectrum of a copolymer of 80% acrolein and 20% acrylic acid in D ₂ 0. The spectrum was recorded on a Bruker AMX 500 spectrometer at 500.13 MHz. All low molecular weight components can be separated off by dialysis using a semi-permeable membrane with a cut-off limit of 2,000 g / mol (calibration using polyoxyethylene). The NMR spectrum of the polymer purified in this way (FIG. 2) allows quantitative determination of the ester structure bound to the polymer, which can be recognized by the clear signals at 4.2-4.4 ppm.

The average molecular weight (Mw) of the copolymers can vary within a wide range, taking into account that molecules with too low a degree of polymerization have less good washing properties, while too high molecular weights have an undesirable thickening effect. Copolymers having a molecular weight between 500 and 500,000 g / mol can thus be used, but are preferred 2,000 to 100,000 g / mol or, even better, 5,000 to 50,000 g / mol.

The molecular weight is determined by gel permeation chromatography (GPC) on LiChrospher diol columns (Merck) and with phosphate buffer (pH = 7) as an eluent solution. A calibration can best be done with narrowly distributed polyacrylic acid. The non-constant chemical composition of the copolymers of interest for this patent causes an error in the absolute value of the molecular weight. This well-known source of error cannot easily be eliminated, so that all the molecular weight information given here is to be understood as relative to the calibration with polyacrylic acid.

In principle, mixtures of polymers can also be used, both with a different composition and with the same composition but different molecular weights.

The acrylic acid polymers can be prepared by known processes. Helpful hints can be found in "Acrylic and Methacrylic Acid Polymers", JW Nemec and W. Bauer jr, and in "Radical Polymerization", CH Baumford, in Vol. 1 and 13 of the "Encyclopedia of Polymer Science and Technology", John Find Wiley & Sons, New York 1990. Such processes are also described, for example, in "Acrylic acid polymers", M.L. Mitter in "Encyclopedia of polymer science and technology", vol. 1 Interscience Publishers, New York 1964.

The (co) polymers can be prepared by all customary free-radical polymerization processes. For example, the following production methods are mentioned: solution polymerization, the monomers being dissolved in water or in another solvent or solvent mixture with any additions of low molecular weight organic and / or inorganic compounds. Precipitation polymerization in solvents in which the monomers are at least partially soluble and the polymers are not soluble. Emulsion and suspension polymerization in solvents in which the monomers are not soluble and the emulsions or suspensions are stabilized by adding low and / or high molecular weight substances.

Radiation-induced polymerization can also be used to prepare the polymers.

However, solution polymerization in water is preferred, as described in the text below.

The monomer concentration is between 5 and 70%, with 25 to 50% being preferred, depending on the viscosity of the resulting polymer solution.

Suitable initiators are both thermally decomposable radical donors which have sufficient solubility in the chosen solvent or in the monomers, and also multi-component redox initiators. However, water-soluble substances such as hydrogen peroxide and peroxodisulfates of the alkali metals or ammonium are preferred.

The polymerization temperature is used together with the amount of initiator to control the molecular weight of the desired polymer. It is between 30 and 1800 _° C, and it is advantageous to keep it between 60 and 130 _° C. Low temperatures usually lead to high molecular weight polymers, too high temperatures can cause polymer degradation and coloring.

The molecular weight can also be controlled by suitable regulators such as thio derivatives and low molecular weight alcohols. Are suitable for. B. thioglycolic acid, mercaptopropionic acid and their esters and 2-mercaptoethanol.

Similar polymers are known from DE 23 54 432 C3 and the literature mentioned herein. According to this document, however, such detergent polymers are used with zeolites which contain exclusively carboxyl groups, aldehydo groups, alcohols and vinyl groups. That is, some of the polymers were subjected to a Cannizzaro reaction and were generally prepared under those reaction conditions in which no ester groups but instead alcohol groups are formed in the acrolein polymerization. The water-soluble, practically uncrosslinked polycarboxylic acids known from DE-OS 24 08 873 are also such polymers.

Surfactants impart the desired cleaning effect via wetting and rewetting and guarantee the dirt-carrying capacity through oriented adsorption on pigment dirt and through solubilization of soluble contaminants, which is further expressed by other ingredients.

Surfactant combinations are always typical for detergent formulations, since mixtures of different surface-active substances have a synergistic effect. H. an increased performance compared to the addition of the individual effects.

Very powerful synergistic surfactant combinations are obtained from linear alkylbenzenesulfonates and fatty alcohol polyglycol ethers. For low washing temperatures (30 to 60 ° C), longer-chain soaps are replaced by customized silicone oils for foam regulation.

Some of the alkylbenzenesulfonates can be replaced by alkylsulfates, which moreover have more favorable anaerobic degradation behavior. In the case of fatty alcohol polyglycol ethers, there are alternatives for the hydrophobic part of the molecule, which is accessible either on the basis of renewable raw materials (fatty alcohols in the narrower sense) or petrochemically (oxo or Ziegler alcohols). The new surfactant class of alkyl polyglycosides, representatives of Nonionics "without ethylene oxide", which are only available on the basis of the renewable raw materials fatty alcohols (fats and oils) and starch or sugar, are currently used in particular for liquid detergents. In the case of fatty alcohol polyglycol ethers, the trend is towards lower ethoxylated products, which improve the washing out of grease soiling, especially at low temperatures.

In particular, products for oxidative removal of colored impurities are used as bleaching systems in detergents. The general trend of washing at a lower temperature and the increase in the proportion of blended fabrics that are more sensitive to cotton or linen make it necessary to use bleach activators, since sodium perborate is only effective above 60 to 70 _° C.

Activated bleaching at or below 60 ° C is based - when using N-acetyl compounds as bleach activators - on the formation of the peracetic acid anion in the wash liquor, which has a higher oxidation potential than the perhydroxide anion released from perborate by hydrolysis.

N, N, N ', N'-tetraacetylethylene diamine (TAED) and 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT) are suitable for transferring the acetyl group to the perhydroxide anion ). DADHT is somewhat more efficient than TAED at low washing temperatures and also has the advantage that, unlike TAED, all acetyl groups available in the molecule are used in bleaching (only two out of four in TAED)

The peracetic acid anion is most effective against hydrophilic, bleachable stains. Long-chain diperoxycarboxylic acids are particularly effective at lower temperatures, such as. B. Dodecane-1,12-diper acid. Use of alkanoyloxy-benzenesulfonates (AOBS) with alkyl chain lengths from C ₈ to C ₁₀ is advantageous, as is nonanoyloxy-benzenesulfonate (NOBS). In the nonane-1-peracid anion (p-hydroxybenzenesulfonate as a leaving group) formed from NOBS and perborate in the wash liquor, hydrophilicity and lipophilicity are so well balanced that the bleaching capacity in spite of the lower active oxygen values in the liquor compared to the TAED system is comparably good. NOBS is also nitrogen free.

In compact detergents in particular, sodium perborate tetrahydrate is replaced by the monohydrate.

For ecological reasons (reduction of boron pollution in the water) the perborate can be substituted by percarbonate, which has been problematic because of its lack of stability in detergents.

Sodium perborate also needs to be stabilized. Above all, the radical decomposition caused by heavy metals, especially copper ions, should be avoided, as a result of which fiber damage can also occur. The complexing agents previously used for this, such as EDTA, have now largely been replaced by the formulations due to the lack of biodegradability. Alternatives are e.g. B. certain protein hydrolyzates whose biuret structures are particularly suitable for complexing copper. In many cases, phosphonates also serve as stabilizers.

Enzymes are almost indispensable ingredients in universal detergents and in many other formulations for washing and cleaning. Pancreatin (trypsin), proteases, amylases, cellulases and lipases are used.

Proteases break down - usually high-molecular - protein soiling, such as blood and egg stains, which cannot be removed from the fiber by surfactants alone. The a-amylases, which are mostly used together with proteases, serve both to break down the starch-containing dirt and to cleave the adhesive-like bond between fiber and particle dirt, which is mediated by starch itself and its degradation products, the dextrins.

The cellulases (cellulose-degrading enzymes) not only enable cleaning, but also "softening" and refreshing the color of cotton textiles.

Lipases, i.e. fat-splitting enzymes, are important for increasing washing power. Above all, they can help to limit the increased use of surfactants at low washing temperatures.

Optical brighteners, also called (fluorescence) whiteners (fluorescent whitening agents, FWA), absorb the UV component of sunlight that is invisible to the human eye in the wavelength range around 350 nm and emit blue (depending on the structure also blue-green) fluorescence radiation around 440 nm (500 nm). The fluorescent radiation of the z. B. on textile fibers tinted white adds to the reflected visible light, so that not only a possible yellow tinge of a white fabric, as it can appear after repeated use and cleaning, "added" again to white, but overall a more intense, a "brighter" white is achieved.

Stilbene derivatives are particularly suitable. In addition, coumarin and quinolone (carbostyryl) and 1,3-diphenylpyrazoline structures, naphthalenedicarboxylic acid and cinnamic acid derivatives and combinations of benzoxazole or benzimidazole structures with conjugated systems also play a certain role.

Recently, polymers have also been used in detergents to prevent color transfer from one fabric to another. Special polyvinylpyrrolidones and homopolymers of vinylimidazole are particularly suitable for this. In general detergent formulations that contain color transfer inhibitors, bleaching systems and whiteners are mostly dispensed with.

Carbonate such as soda is used to enhance the washing effect (alkali reserve).

Fillers such as As sodium sulfate, can be added to improve manageability and flowability.

More silicate, e.g. B. water glass, acts as a corrosion inhibitor; or z. As magnesium silicate, acts (like phosphonate) as a stabilizer. However, amorphous and crystalline disilicates can now also be used as cobuilders and in special detergents as main builders.

Hydroxycarboxylic acids can be used as cobuilders in addition to polymer and zeolite A, namely they take on a so-called carrier function for Ca ions.

Graying inhibitors suspend the detached dirt in the wash liquor.

In addition to zeolite A, phosphates can be used as main builders in p-reduced formulations or, in smaller quantities, phosphate acts as a carrier cobuilder in the detergent.

Solubilizers are preferably used in liquid detergents. Are suitable for. B. polyethylene glycols with different degrees of polymerization and molar mass for mixing with surfactants, alcohol or water.

Furthermore, conventional or newer components can be contained in the detergent compositions, such as. As dyes, perfume oils, plasticizers or the color transfer inhibitors described above.

The invention is explained in more detail below with the aid of examples and figures.

• Fig. 1 ein NMR-Spektrum eines erfindungsgemäß einzusetzenden Polymeren;
• Fig. 2 ein NMR-Sepktrum des Polymeren aus Fig. 1 nach Dialyse;
• Fig. 3 Vergrauungswerte nach der 10. Wäsche;
• Fig. 4 Vergrauungswerte nach der 25. Wäsche;
• Fig. 5 Inkrustationswerte nach der 10. Wäsche;
• Fig. 6 Inkrustationswerte nach der 25. Wäsche;
• Fig. 7 Vergleichende Waschversuche ohne Zeolith, Vergrauungswerte nach der 10. Wäsche;
• Fig. 8 Vergrauungswerte nach der 25. Wäsche;
• Fig. 9 Inkrustationswerte nach der 10. Wäsche; und
• Fig. 10 Inkrustationswerte nach der 25. Wäsche.

Show it

• 1 shows an NMR spectrum of a polymer to be used according to the invention;
• FIG. 2 shows an NMR spectrum of the polymer from FIG. 1 after dialysis;
• 3 graying values after the 10th wash;
• 4 graying values after the 25th wash;
• 5 incrustation values after the 10th wash;
• 6 incrustation values after the 25th wash;
• 7 Comparative washing tests without zeolite, graying values after the 10th washing;
• 8 graying values after the 25th wash;
• 9 incrustation values after the 10th wash; and
• Fig. 10 incrustation values after the 25th wash.

Production of the polycarboxylates example 1

720 parts by weight of demineralized water and 424 parts of H ₂ O ₂ (50%) are placed in a reactor equipped with a cooler, stirrer and temperature control devices and heated to 70.degree. With vigorous stirring, 950 parts of acrolein, 245 parts of acrylic acid and 424 parts of 50% H ₂ O ₂ are metered in simultaneously for four hours through separate lines. 105 minutes after the start of the feed line, the metering of a total of 1000 parts of deionized water begins, which flows in at 300 parts / hour.

After a total reaction time of seven hours, the temperature is brought to 95 _° C. for a three-hour post-reaction.

After cooling, the contents of the reactor are adjusted to pH 7-9 using NaOH solution.

This creates a 35.1% polymer solution with a viscosity of 400 mPa.s. The polymer has an average molecular weight of 8000 g / mol.

By 1 H-NMR of a dialyzed sample, approximately 12% by weight of the structure -CH ₂ -CH- (COO-CH ₂ -CH ₂ -) _r COOR '- was detected.

Example 2

In a similar reactor as in Example 1, 450 parts of deionized water and 150 parts be presented 50% H ₂ 0 ₂ and heated to 90 ° C. With vigorous stirring, 525 parts of acrylic acid, 225 parts of acrolein and 150 parts of 50% H ₂ O _{2 are passed} into the reactor for three hours. The temperature is then set to 97 ° C. and left to react for a further five hours. After cooling, a 50.2% polymer solution with a viscosity of 1800 mPa.s. The polymer has Mw = 25,000 g / mol. About 10% by weight of the structure -CH ₂ -CH- (COO-CH ₂ -CH ₂ -) _r COOR'- can be detected by 1H-NMR.

Example 3

Using a procedure similar to that in Example 2, 600 parts of acrylic acid and 150 parts of acrolein are used as monomers. The dosing time is 2 hours. The 50.5% polymer solution obtained has a viscosity of 2200 mPa.s. The polymer has an average molecular weight of 20,000 g / mol. About 4% by weight of the structure -CH ₂ -CH- (COO-CH ₂ -CH ₂ -) _r COOR'- can be detected by 1 H-NMR.

Example 4

Following the procedure of Example 2, 675 parts of acrylic acid and 75 parts of acrolein are used as monomers. The 52.5% solution obtained with a viscosity of 6700 mPa.s contains a polymer with Mw = 21,000 g / mol and approx. 1% by weight of the structure -CH ₂ -CH- (COO-CH ₂ -CH ₂ -) _r COOR'-.

Example 5

200 parts by weight of demineralized water are placed in a reactor as in Example 1 and heated to 95.degree. A solution of 53 parts of sodium peroxodisulfate in 320 parts of demineralized water, 510 parts of β-carboxyethyl acrylate, 90 parts of acrylic acid and 320 parts of demineralized water are simultaneously fed in with vigorous stirring within two hours. This is followed by a post-reaction at 98-100 ° C for 1.5 hours.

The water-thin 42.1% solution obtained is cloudy and tends to separate phases; after neutralization with 1M NaOH, complete solubility is achieved. The polymer has an Mw of 5200 g / mol and, according to NMR analysis, contains about 85% by weight of the structure -CH ₂ -CH- (COO-CH ₂ -CH ₂ -), COOR'-.

Description of the detergent formulations

The use of the copolymers based on acrylic acid / acrolein in detergents is of particular practical importance since they substantially reduce the disadvantages of the known detergents. In addition to the novel copolymers, these detergents according to the invention also contain conventional substances, which will be described in more detail below:

A) surfactants

The proportion of the surfactant component in the total detergent formulation is between 5 to 40% by weight, preferably between 7 to 30% by weight and especially between 10 to 20% by weight. Both anionic and nonionic surfactants are used. The proportion of anionic surfactants should be at least 5% by weight and is preferably in the range between 5-10% by weight. As anionic detergent substances, sulfates and sulfonates in particular are of practical importance. The sulfonates include, for example, alkylbenzene sulfonates, preferably with straight-chain alkyl radicals, olefin, alkane or also fatty acid ester sulfonates.

As surfactants of the sulfate type, fatty alcohol sulfates are e.g. B. from coconut oil or tallow fatty alcohols.

Nonionic surfactants include e.g. B. polyethylene oxide condensation products of primary and secondary aliphatic alcohols, alkylphenols or also alkypolyglycosides in the range between 0-20% by weight, preferably between 0-10% by weight.

B) Builder components

The detergent should contain one or more detergent builders. From the area of ion exchangers, synthetic sodium aluminum silicates of the zeolite A type should preferably be mentioned here. Zeolite NaX or Zeolite P and a mixture of the compounds mentioned are also suitable. This detergent component is represented in the recipe with 5-50% by weight, preferably with 10-30% by weight.

The polycarboxylates according to the invention are advantageously in the range of 0.1-20% by weight.

0.5% by weight, preferably at least 1% by weight, but in particular in the range from 2 to 10% by weight.

Other inorganic builders such as Na or K carbonate or silicates (in crystalline and amorphous form) can supplement or complete the builder system. Both types of substance can each be used in the range between 0-30% by weight, but preferably between 3-15% by weight.

Complex-forming substances such as nitrilotriacetic acid, the proportion of which is 0-10% by weight, preferably 0.5-5%, and di- or polyphosphonic acids in the range between 0-5% by weight, preferably 0.1-1% or derivatives of hydroxycarboxylic acids such as citrate or tartrate in the range between 0-20%, preferably between 2-10%, can be used as builder components.

Phosphates can be used in a range of 0 - 30%.

C) Bleach / Bleach Activators

In the case of the bleaching agents which supply H ₂ 0 ₂ in water, sodium perborate tetrahydrate or monohydrate or coated percarbonates in particular are of practical importance. They are used in the range between 0-30% by weight, preferably between 10-25% by weight.

Organic N-acyl or O-acyl compounds such as, for. B. TAED of practical importance. They are used in the range between 0-10% by weight, preferably 2-8% by weight.

D) enzymes

Enzymes specific to certain types of dirt, for example proteases, amylases or lipases, can also be incorporated into the detergent formulation. Combinations of are preferred

Enzymes with different effects are used. Their range of application is between 0-3% by weight, preferably in the range between 0.3-1% by weight.

E) Optical brighteners

Detergents can contain, as optical brighteners, in particular derivatives of the following compounds: stilbene, biphenylstilbene, diphenylpyrazoline, coumarin or combinations of benzoxazole or benzamidozole. They are used in the range from 0 to 5% by weight, preferably in the range from 0.1 to 0.3%.

F) Additional graying inhibitors

The detergents can additionally contain graying inhibitors which suspend the dirt detached from the fibers in the washing liquor. Methyl or carboxymethyl celluloses can be mentioned here as an example. Their proportion in the detergent can be 0-5% by weight, in particular 0.5-1.5% by weight.

G) defoamer

Foam inhibitors are generally used in amounts of 0-8% by weight. Soaps, silicone oils or hydrophobic silicas are common. In the case of non-surfactant defoamers, amounts of 0-3.5% by weight are generally sufficient because of the stronger action compared to soaps.

Carrying out washing tests

The good effect of the new copolymers described above could be found in comparative washing tests with commercially available detergent polymers. The market products (MP) were a homopolymer (MP1) based on polyacrylate and an Mw of 120,000 g / mol and a copolymer (MP2) based on acrylic / maleic acid (about 30/70) with Mw = 70,000 g / mol. The structure -CH ₂ -CH- (COO-CH ₂ -CH ₂ -) _r COOH- was not detectable in these products.

These products were tested in comparative washing tests according to DIN 44983 with the copolymers from Example 1 to Example 5 (described in the following figures as B1, B2, B3, B4, B5).

A) Composition of the detergent (% by weight)

The polymers used in the detergents were neutralized with NaOH and resulted in an active ingredient content of 40 - 54%.

In the detergent formulation, only the polymers were varied, the other detergent ingredients were kept the same for each formulation. The active content of the polymers used was calculated to be 4%. The balance in the recipe, due to the different solids content of the polymers, was achieved with sulfate.

B) Washing conditions

• Waschmaschinentyp: Miele W 763
• Programm: Koch- /Buntwäsche ohne Vorwäsche
• Temperatur / Härte: 60 °C / 20 dH
• Waschmittelmenge: 130 g (10,0 g/I)
• Ballaststoff: 20 St. Baumwolle,weiß 3 St. Frottee 2 St, Handtücher Gewicht = 3,3 kg
• Weißgewebe: Frottee, Handtuch, Baumwolle und Baumwolle-grüne Streifen (WFK) 0,8 kg
• Aufhärtung: zu jedem ungeraden Waschgang Blut (EMPA 111) Standard (EMPA 101) Hautfett (WFK 10 D) Tee, (WFK 10)
• Sekundärwaschvermögen: 1 Zyklus, 25 Wäschen bestimmt wurden Inkrustation und Vergrauung nach der 10. und 25. Wäsche

The washing conditions are summarized in the following table:

• Washing machine type: Miele W 763
• Program: Cottons without pre-wash
• Temperature / hardness: 60 ° C / 20 dH
• Detergent amount: 130 g (10.0 g / l)
• Dietary fiber: 20 pieces of cotton, white 3 pieces of terry cloth 2 pieces, towels weight = 3.3 kg
• White fabric: terry cloth, towel, cotton and cotton-green stripes (WFK) 0.8 kg
• Hardening: for every odd wash cycle blood (EMPA 111) standard (EMPA 101) skin fat (WFK 10 D) tea, (WFK 10)
• Secondary washability: 1 cycle, 25 washes incrustation and graying were determined after the 10th and 25th wash

Laundry Research Krefeld (WFK) and the Swiss Federal Material Testing Institute (EMPA) Switzerland sell test soils for washing trials. These test soils are called z. B. EMPA 111 for blood stains etc.

3.) Determination of the measured values for determining the secondary washing ability

The graying or dirt reduction is determined via the reflection R 457 nm by means of a spectrophotometer (DC 3890) from Datacolor. The whiteness of the new fabrics is determined as a zero value before the washing cycle. The results of the graying are given as a reduction in reflectance (delta R = R zero value -R measured). 5 measuring points are determined for each white tissue and the mean value and scatter are calculated therefrom. The LSD value (smallest significant difference) is calculated in accordance with DIN 44983 Part 50. The ranking results from a grading of the individual measured values determined on the different tissues.

The incrustation is determined via the ash content (double determination). 2 g of tissue are annealed in a pre-incinerator at 500 ° C (for 1 hour) and then incinerated in a muffle furnace at 800 ° C for 1 hour. The crucibles are weighed back.

Results

• Gute Waschresultate an Frottee (F) sind besonders beim Beispiel 1 mit einem ΔR von 4,13 festzustellen. Beispiel 3 (AR = 2,81) und 5 (AR = 2,85) zeigen signifikant vergleichbare Ergebnisse zu den Marktprodukten MP1 (AR = 2,89) und MP2 (AR = 2,75), da der LSD-Wert 0,27 beträgt. Beispiel 2 (AR = 1,47) und 4 (AR = 2,65) zeigen im Vergleich zu den beiden Marktprodukten abfallende Leistungen an Frottee.

Graying after the 10th wash (Fig. 3):

• Good washing results on terry cloth (F) are particularly noticeable in Example 1 with a ΔR of 4.13. Example 3 (AR = 2.81) and 5 (AR = 2.85) show significantly comparable results for the market products MP1 (AR = 2.89) and MP2 (AR = 2.75), since the LSD value 0, 27 is. Example 2 (AR = 1.47) and 4 (AR = 2.65) show decreasing terry services compared to the two market products.

On the test fabric cotton with green stripes (BW / GS), example 2 (ΔR = 5.26) shows the best results, followed by examples 1 and 3 (both equally important: ΔR = 4.84) and example 4 (ΔR = 3.76) . The market products show poorer graying inhibition on these fabrics. The AR value for MP1 = 2.51 and for MP2 = 3.4. The determined LSD value was 0.24.

The market products (ΔR of MP1 = 7.02 MP2 = 7.94) also show a drop in performance compared to the examples according to the invention in the graying inhibition on the barley grain towel (H). Only example 4 (ΔR = 7.61) is significantly comparable with the performance of MP2. Examples 1, 2, 3 and 5 have AR values> 8.85. The best results are shown in Example 1 (ΔR = 9.85) and Example 3 (ΔR = 9.77). The LSD was found to be 0.41.

On cotton test fabrics (BW), example 3 (ΔR = 3.94) shows the best washing results, followed by example 2 (ΔR = 3.41), example 1 (ΔR = 2.28) and example 5 (ΔR = 2.01). Market product 1 (ΔR = 1.69), example 4 (ΔR = 1.35) and market product 2 (ΔR = 1.13) brought worse results. The LSD value was 0.20 in this series of measurements.

Graying after the 25th wash (Fig. 4)

On terry, the polymers from Example 1 (AR = 6.64), Example 2 (AR = 7.01) and Example 3 (AR = 6.97) show the best graying inhibition followed by Example 5 (AR = 4.94) and Market product 1 (AR = 4.76). The worst results in this series show market product 2 (AR = 3.8) and example 4 (AR = ₃ , ₅₀ ). The LSD is 0.53.

In BW / GS, the good performances of Example 2 (AR = 8.83) and Example 1 (AR = 8.39) are particularly noteworthy. Example 3 (ΔR = 7.65) and Example 5 (ΔR = 7.34) show somewhat poorer washing performance, which, on the basis of the LSD value of 0.41, can be classified as equivalent. Market product 2 (ΔR = 6.54), example 4 (ΔR = 6.06) and market product 1 (5.01) show a further drop in graying inhibition.

The best result on the barley grain towel is shown in Example 3 (ΔR = 13.61), followed by Example 1 (ΔR = 13.19), which should be regarded as equivalent with an LSD value of 0.41. Example 2 (ΔR = 12.6) and Example 5 (ΔR = 12.42) show slightly decreasing reflections and are also to be regarded as equivalent. Further falling results again show hard product 1 (ΔR = 11.83), market product 2 (ΔR = 10.24) and example 4 (ΔR = 9.53).

On the test fabric cotton, example 3 (ΔR = 7.92) again shows advantages over the other polymers, followed by example 2 (ΔR = 7.22), example 1 (ΔR = 6.08), example 5 (ΔR = 4.7 ), MP1 (ΔR = 4.45) and MP2 (ΔR = 3.67). The values of example 5 and market product 1 are to be regarded as equivalent with an LSD value of 0.27.

In the overall assessment of the graying inhibition of all examined fabrics after the 25th wash, the newly developed polymers again show advantages over the market products except for example 4. The ranking in the overall assessment looks as follows: graying inhibition B3> B2> B1> B5> MP1> MP2> B4

Encryption after the 10th wash

When evaluating the laundry crustation after the 10th wash (Fig. 5), all 5 examples clearly show significant advantages over the market products due to the low ash values, namely for all examined types of fabric. The mean value of the ash content determined from the four fabrics terry cloth, cotton / green stripes, barley grain towel and cotton / white increases with the acrylic acid content in the individual polymers from 0.9% ash (B1), 1.1% (B2), 1 , 3% (B3) to 1.4% (B4). Example 5 shows results comparable to B3. The two market products, on the other hand, show declining performances: their ash content is 1.9% (MP1) and 2.0% (MP2).

The ranking for incrustation reduction results in:
B1>B2> B3 = B5>B4>MP1> MP2

This advantage remains even after the 25th wash (Fig. 6) for the developed polymer types. While the ash content for the new polymers is only slightly between 0.1 and 0.2% compared to the 10th wash (B1 = 1.1%, B2 = 1.2%, B3 = 1.4%, B4 = 1, 5%, B5 = 1.4%), the market products show incrustation values of 3.4% (MP1) and 3.2% (MP2).

The ranking of the newly developed polymers remains the same as after the 10th wash, only the ranking of the market products is about:
B1>B2> B3 = B5>B4>MP2> MP1

Washing attempts without zeolite A

These washing tests show that the polymers to be used according to the invention achieve their superior effect, in particular together with zeolites. The above-mentioned detergent formulation was chosen as the basis for the following experiment. Only the zeolite A was replaced by the washing alkalis sodium carbonate and sodium disilicate. Example B1 and the market product MP1 were chosen as the polymer. Since Wessalith CS is a granulated zeolite A, which in addition to zeolite A also contains 2% CMC, 1.7% NaS0 ₄ and 2.6% nonionic surfactant, these substances were assigned to the corresponding product groups, so that the recipes only differ from the active substances Differentiate builder content.

Results:

Graying after the 10th wash (Fig. 7)

Good washing results on terry cloth (F) could be achieved with formulation B1a with a ΔR value of 4.61. Declining performances showed MP1 b (ΔR = 1.77) followed by B1 b (ΔR = 1.05) followed. The LSD was 0.6.

B1a (ΔR = 4.74) also performed best on the test fabric cotton with green stripes, followed by formulation B1 b (ΔR = 1.08) and MP1 b (ΔR = 0.63) with an LSD value of 0, 24th

The good performance of recipe B1a (ΔR = 10.51) is also confirmed for the barley grain towel (H). The graying values of B1 and MP1 are to be regarded as equivalent with ΔR = 6.58 and 6.56 with an LSD value of 0.37.

The same trend can be seen in the test fabric cotton (BW). B1a shows the best value with ΔR = 3.39, followed by B1B and MP1b, which can be regarded as equally important with an LSD value of 0.26 with ΔR = 0.53 and 0.44.

Ranking: B1a> B1b = MP1b

Graying after 25 washes (Fig. 8)

After 25 washes, formula B1a with ΔR = 6.78 on terry cloth still shows the best results, followed by formulation MP1b and B1b which are of equal importance with ΔR = 0.88 and 0.59 with an LSD value of 0.48.

The same trend can be seen in the fabric of cotton / green stripes. The LSD value is 0.3, the ΔR values of B1 are 8.49, of B1b 0.37 and of MP1 b 0.23.

For barley grain towel, formula B1a with ΔR = 13.34 shows the best results, followed by formulation 81 b (ΔR = 4.38) and MP1 b with ΔR = 3.2. The LSD is 0.43.

MP1b (ΔR = -1.68) again shows the worst washing performance on the cotton fabric. Formulations B1 b (ΔR = -1.4) and B1 b (ΔR = 6.26) show better results. The LSD value is 0.23.

Ranking: B1a> B1b> MP1b

Incrustations 10. laundry (Fig. 9)

The lowest ash content on the terry, cotton / green stripes, barley grain towel and cotton fabrics shows with values of 0.7%, 1.1%, 0.7% and 0.8% Example B1a with an average of all test fabrics of 0, 8th %. Formulation B1 b shows declining performance with ash contents of 1.8% (terry cloth), 2.9% (cotton / green stripes), 4.2% (barley grain towel) and 3.5% (cotton). The average is 3.1%. The ash contents of example MP1b showed the following values for the same soiling: 2.2% (terry cloth), 4.0% (cotton / green stripes), 4.7% (barley grain towel) and 4.0 % (Cotton). The average is 3.7%.

Ranking: B1a> B1b> MP1b b Incrustation 25. Wash (Fig. 10)

The same ranking was shown as after 10 washes. In example B1a, the incrustation on the various fabrics increased after 25 washes to 0.9% (terry cloth), 1.5% (cotton / green stripes), 1.4% in the barley grain towel and in the cotton fabric. The average is 1.3%. Formulations B1 and MP1 b have significantly higher incrustation. Formulation B1 showed the following results: 4.2% residue in terry cloth, 5.5% in cotton / green stripes, 9.2% in barley grain towel and 8.8% in cotton fabric. The average of all ash residues was 6.9%. The following values were obtained for formulation MP1b: 4.9% for terry cloth, 6.1% for cotton / green stripes, 9.2% for barley grain towel and 8.7% for cotton. The average is 7.2%.

Ranking: B1a> B1b> MP1b b Result

B1 a is clearly superior to B1 b and MP1 b, B1 b shows hardly any advantages over MP1 b.

Claims (19)

1. Containing detergent composition

wherein at least 1% by weight of the composition is a polycarboxylate with the schematic structure (X, Y, Z), where X is

Y for

and Z for
- (F) q-
stands in what A = H, OH, Ci-6 alkyl, CH ₂ CO (DECO) _r-1 OM; B = H, OH, C _1-6 alkyl, COOM; D = O, NH; E = C _1-6 alkyl F = a copolymerizable monomer; M = H, alkali or alkaline earth metal, ammonium, substituted ammonium; wherein X and - (CH ₂ -CH ₂ -0) ₂ - ₄ M; r = 1-5;
is and m = 0 - 99.5 mol% n = 0.5 - 100 mol% q = 0 - 99.5 mol%
means. 2. Containing detergent composition

at least 1% by weight of the composition being a polycarboxylate which can be prepared from acrolein and possibly one or more comonomers by means of oxidizing radical donors without saponification conditions and / or without a subsequent Cannizzaro reaction. 3. Detergent composition containing in particular according to claim 2

where at least 1% by weight of the composition is a polycarboxylate which can be prepared from acrolein and possibly one or more comonomers by means of oxidizing radical donors and a proportion of functional groups of the type -C (0) -0 [-CH ₂ -CH ₂ C (0) 0] _x R ', where R' is an alkali, alkaline earth or nitrogen-containing cation and x = 1-5. 4. Containing detergent composition

wherein at least 1% by weight of the composition is a polycarboxylate, which can be prepared from acrolein and possibly one or more comonomers by means of oxidizing radical donors, and wherein the polycarboxylate is mixed with several, in particular all components, if appropriate with the addition of H ₂ O, and if necessary is dried. 5. detergent composition according to any one of the preceding claims,
characterized,
that it contains at least one of the following components

6. detergent composition according to any one of the preceding claims,
marked by
containing a formulation as a compact detergent

7. detergent composition according to any one of claims 1 to 3,
marked by
containing a formulation as a liquid detergent

8. detergent composition according to any one of claims 1 to 5,
marked by
containing a formulation as a mild detergent

9. Use of a polycarboxylate of the schematic structure (X, YZ), wherein X for

Y for

and Z for
- (F) q-
stands in what A = H, OH, Ci-6 alkyl, CH ₂ CO (DECO) _r-1 OM; B = H, OH, Ci-6 alkyl, COOM; D = O, NH; E = C _1-6 alkyl, linear or branched; F = a copolymerizable monomer; M = H, alkali or alkaline earth metal, ammonium, substituted ammonium; wherein X and - (CH ₂ -CH ₂ -0) ₂ - ₄ M; r = 1-5;
is and m = 0 - 99.5 mol% n = 0.5 - 100 mol% q = 0 - 99.5 mol%
means 1 to 20% by weight in a detergent composition containing 5 to 50% by weight of a calcium ion-binding silicate and 5 to 40% by weight of surfactant. 10. Use of a polycarboxylate, which can be prepared from acrolein and possibly one or more comonomers by means of oxidizing radical donors without saponifying conditions and / or without a subsequent Cannizzaro reaction, in an amount of 1 to 20% by weight in an amount of 5 to 50% by weight. % a calcium ion-binding silicate and detergent composition containing 5-40% by weight of surfactant. 11. Use of a polycarboxylate which can be prepared from acrolein and possibly one or more comonomers by means of oxidizing radical donors and a proportion of functional groups of the type -C (0) -0 [-CH ₂ -CH ₂ C (0) OJ _x R 'has, in which R' stands for an alkali, alkaline earth or nitrogen-containing cation and x = 1-5, 1 - 20 wt .-% in a 5 - 50 wt .-% a calcium ion-binding silicate and Detergent composition containing 5-40% by weight of surfactant. 12. Use of a polycarboxylate which can be prepared from acrolein and, if appropriate, one or more comonomers by means of oxidizing radical donors and where the polycarboxylate is mixed with several, in particular all components, if appropriate with the addition of H ₂ O and optionally dried, to 1-20 % By weight in a detergent composition containing 5-50% by weight of a calcium ion-binding silicate and 5-40% by weight of surfactant. 13. A method for producing a detergent composition according to any one of claims 1 to 5 or 8,
characterized,
that the individual powdery components by mixing and the liquid components by Spray on to be mixed homogeneously. 14. A method for producing a detergent composition according to any one of claims 1 to 5 or 8,
characterized,
that water- and heat-insensitive components are processed into a slurry with water and then spray-dried. 15. The method according to claim 14,
characterized,
that other components are mixed by mixing or spraying. 16. A method for producing a detergent composition according to claim 6,
characterized,
that the individual powdery components are mixed homogeneously by mixing and the liquid components by spraying and agglomerated or extruded by forced mixing. 17. A method for producing a detergent composition according to claim 7,
characterized,
that the individual components are mixed with an appropriate amount of solubilizer or water and, if necessary, concentrated.

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