JPH07331288A - Detergent composition and its preparation - Google Patents

Abstract

PURPOSE: To obtain the subject composition containing a surfactant, a calcium- binding silicate, and a specified polycarboxylate, containing little or no phosphate, reduced in the deposition of washing residues, and not darkening.

CONSTITUTION: The objective composition comprises (A) 5-40 wt.% surfactant, (B) 5-50 wt.% calcium-bonding silicate (desirably, type A zeolite), (C) 1-20 wt.% polycarboxylate having a structure of the formula (X, Y, Z) [wherein X is formula I (wherein A is H, OH, or the like; B is H, a 1-6C alkyl, or the like; M is H, an alkali metal, or the like; and (m) corresponds to 0-99.5 mol.%); Y is formula II (wherein D is O or NH; E is a 1-6C alkyl; (n) corresponds to 0.5-100 mol.%; (r) is 1-5); and Z is (F)_q (wherein F is a copolymerizable monomer; and (q) corresponds to 0-99.5 mol.%)], (D) 0-30 wt.% another silicate, (E) 0-30 wt.% carbonate, (F) 0-10 wt.% organic complexing agent, (G) 0-5 wt.% phosphonate, (H) 0-30 wt.% phosphate, and (I) 0-20 wt.% hydroxycarboxylic acid, or the like.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

The present invention relates to zeolite-containing detergent systems, which are preferably phosphate-poor or phosphate-free, a process for their preparation and the use of polycarboxylic acid salts suitable therefor.

[0002]

BACKGROUND OF THE INVENTION The development of detergent builders has been generally influenced by the development of phosphate-free detergents for several years. Zeolite A is used as a modern builder alternative to phosphates. Due to the slow exchange kinetics of zeolites for Ca ions, phosphate-free powdered and liquid detergents and cleaners are used in addition to the main builder, zeolite A, as well as so-called cobuilders, such as soda, poly A carboxylate, NTA, silicate or hydroxycarboxylate is required.

Conventional builder additives are currently high molecular weight carboxylic acids and their salts. In the field of detergents and cleaners, for example, homopolymers of acrylic acid or copolymers of acrylic acid with maleic acid are advantageous, which are described, for example, in publication 20252.
38, 2044601, EP 0137669.
No. or German Patent Application Publication No. 360422
3A1.

These products contribute to the cleaning effect of detergents by improving their dirt-carrying capacity.

These products, on the one hand, prevent dirt from redepositing on the laundry and adversely affecting the darkening of the fibers, and, on the other hand, depositing anionic salts on the laundry (laundry residue). Inkrustierung) is reduced.

Polycarboxylic acid salts in the context of zeolites or layered silicic acids are known from EP 0401780.

Although commercial products of polycarboxylates have been shown to have a secondary cleaning effect which avoids darkening and laundry residue buildup, optimization of these auxiliary builders enhances the effectiveness of the detergent and thus At the same time, one must strive to improve the use properties of the fibers.

[0008]

The object of the present invention is therefore a phosphate-poor or phosphate-free zeolite-containing detergent system with improved auxiliary builders.

[0009]

The problem is solved by a detergent system according to claim 1.

The novel detergent system contains, in addition to the calcium ion-binding silicate, at least one (co) polymer, preferably acrylic acid and acrolein.
The use of the substances mentioned above in phosphate-free or reduced-phosphate powdered or liquid detergents and cleaners also belongs to the invention.

The detergent according to the invention comprises the following components: surfactant 5-40% by weight calcium-binding silicate 5-50% by weight polycarboxylic acid salt 1-20% by weight other silicates 0-30% by weight. % Carbonate 0-30% by weight Organic complexing agent 0-10% by weight Phosphonate 0-5% by weight Phosphate 0-30% by weight Hydroxycarboxylic acid 0-20% by weight Bleach 0-30% by weight Bleach Activator 0 to 10% by weight Optical brightener 0 to 5% by weight Enzyme 0 to 30% by weight Anti-darkening agent 0 to 5% by weight Antifoaming agent 0 to 8% by weight Filler 0 to 40% by weight, At that time, 1% by weight or more of the composition has the following structure (X, Y, Z) [where X is

[0012]

[Chemical 3]

And Y is

[0014]

[Chemical 4]

And Z represents-(F) _q-- , where A = H, OH, C ₁ -C ₆ alkyl, CH ₂ CO (DEC
_{O) r-1 OM; B} = H, OH, C 1 ~C 6 alkyl, COOM; D = O, NH ; E = C 1 ~C 6 alkyl, linear or branched; F = copolymerizable monomers; M = H, alkali metal or alkaline earth metal, ammonium, substituted ammonium, for X - (CH ₂ -C
H ₂ —O) _2-4 M; also represents r = 1 to 5, m = 0 to 99.5 mol%, n = 0.5 to 100 mol%, q = 0 to 99.5 mol%, m + n + q = representing 100 mol%)].

The detergent according to the invention comprises the following components: surfactant 5-40% by weight calcium-binding silicate 5-50% by weight polycarboxylic acid salt 1-20% by weight other silicates 0-30% by weight. % Carbonate 0-30% by weight Organic complexing agent 0-10% by weight Phosphonate 0-5% by weight Phosphate 0-30% by weight Hydroxycarboxylic acid 0-20% by weight Bleach 0-30% by weight Bleach Activator 0 to 10% by weight Optical brightener 0 to 5% by weight Enzyme 0 to 30% by weight Anti-darkening agent 0 to 5% by weight Antifoaming agent 0 to 8% by weight Filler 0 to 40% by weight, In that case, 1% by weight or more of the composition comprises acrolein and optionally one or more comonomers with an oxidizing radical donor under non-saponification conditions and /
Or a polycarboxylic acid salt which can be prepared without subsequent Cannialo reaction, and / or in which case 1% by weight or more of the composition is oxidizable radicals from acrolein and optionally one or more comonomers. Can be produced with a donor, and type:
_{-C (O) -O [-CH 2} -CH 2 C (O) O] x R '
(In the formula, R ′ is an alkali metal cation, an alkaline earth metal cation or a nitrogen-containing cation, and x = 1 to 5
Is a polycarboxylic acid salt having a proportion of functional groups of 1) and / or 1% by weight or more of the composition,
A polycarboxylic acid salt which can be prepared from acrolein and optionally one or more comonomers with an oxidizable radical donor, wherein the polycarboxylic acid salt is a plurality of, in particular all, one at a time or directly in succession. It may be limited to the above-mentioned components, optionally mixed with the addition of H ₂ O, and optionally dried.

Advantageously, the above-mentioned detergent according to the invention is
In addition to the components mentioned above, it contains at least the following components in the amounts indicated below: Surfactant 7 to 30% by weight, in particular 10 to 20% by weight Polycarboxylate 2 to 10% by weight Other silicates. 3 to 15% by weight Carbonate 3 to 15% by weight Organic complexing agent 0.5 to 5% by weight Phosphonate 0.1 to 1% by weight Phosphate 0 to 5% by weight Particularly 0 to 1% by weight Hydroxycarboxylic acid 2 to 10% by weight Bleach 10 to 25% by weight Bleach activator 2 to 8% by weight Optical brightener 0.1 to 0.3% by weight Enzyme 0.3 to 1% by weight Anti-darkening agent 0.5 to 1.5% by weight Defoamer 0-3.5% by weight Filler 0-20% by weight As a compact detergent, the composition contains 2-8% by weight of polycarboxylate and bleach activator, respectively.

When the detergent composition is a liquid detergent formulation, it comprises the following components: anionic surfactant 5-15% by weight nonionic surfactant 10-20% by weight calcium-binding silica. Acid salt 10 to 25% by weight Polycarboxylic acid salt 1 to 5% by weight Bleach 0% by weight Bleach activator 0% by weight Auxiliary builder 0 to 8% by weight Dissolution aid 0 to 30% by weight Water 0 to 50% by weight contains.

For the preparation as a finishing detergent, the detergent composition comprises the following components: anionic surfactant 5-15% by weight nonionic surfactant 1-10% by weight calcium-binding silicate 10-50% by weight. % Polycarboxylic acid salt 1 to 5% by weight Bleach 0% by weight Bleach activator 0% by weight Carbonate 0 to 20% by weight.

The present invention is based on the illustrated structure (X, Y, Z), where X is

[0021]

[Chemical 5]

Represents Y and Y is

[0023]

[Chemical 6]

And Z represents-(F) _q-- , where A = H, OH, C ₁ -C ₆ alkyl, CH ₂ CO (DEC
_{O) r-1 OM; B} = H, OH, C 1 ~C 6 alkyl, COOM; D = O, NH ; E = C 1 ~C 6 alkyl, linear or branched; F = copolymerizable monomers; M = H, alkali metal or alkaline earth metal, ammonium, substituted ammonium, for X - (CH ₂ -C
H ₂ —O) _2-4 M; also represents r = 1 to 5, m = 0 to 99.5 mol%, n = 0.5 to 100 mol%, and q = 0 to 99.5 mol%) ] The polycarboxylic acid represented by
It also relates to the use of up to 1 to 20% by weight in a detergent composition containing% by weight and 5 to 40% by weight of surfactant.

A polycarboxylic acid which can be prepared from acrolein and optionally one or more comonomers with a radical donor that oxidizes, without saponification conditions and / or subsequently without a Cannialo reaction,
1-20 in a detergent composition containing 5-50% by weight of calcium-binding silicate and 5-40% by weight of surfactant
The use of up to wt% is likewise part of the invention.

Finally, acrolein and optionally 1
It can be prepared from one or more comonomers using a radical donor that oxidizes and a) —C (O) —O [—CH ₂ —CH ₂ C (O) O] _x
R '(wherein R'represents an alkali metal, alkaline earth metal or nitrogen-containing cation, x = 1-5)
The proportion of functional groups of the type: 5 to 50% by weight of calcium ion-binding silicate and 5 to 40% by weight of surfactant.
1 to 20% by weight and / or b) a polycarboxylic acid salt in an amount of 5 to 50% by weight of calcium-binding silicate and 5 to 40% by weight of surfactant. in an amount of detergent compositions 1 to 20% by weight containing a plurality of, in particular the whole of the component, when the mixed addition of H ₂ O, optionally also present invention the use of polycarboxylic acids to dried Belong to

The present invention also relates to the above-mentioned method for producing a detergent composition, in which the individual powdery components are mixed and the liquid components are uniformly mixed by spraying. Second, the water and heat insensitive ingredients are first slurried and processed with water, followed by spray drying and the remaining ingredients post-mixed as described above.

Particularly in the case of compact detergents, it is advantageous for these components to be agglomerated and extruded by forced mixing.

Liquid detergents are prepared by mixing with a corresponding amount of solubilizer or water and are optionally concentrated.

All individual components of the composition can be present as pure substances or as a mixture of the corresponding components. As calcium-binding silicates, it is advantageous to use substances which are preferably water-insoluble, in particular zeolites.

In a particularly preferred embodiment of the invention, the water-insoluble, calcium ion-binding silicates have the general formula: (Kat _{2 / n} O) _x .Me ₂ O _3. (SiO _{2 2} ) _y (I) [In the formula, Kat represents an n-valent cation exchangeable with calcium, x represents a number of 0.7 to 1.5, Me represents boron or aluminum, and y represents 0. Representing a number from 8 to 6], a finely dispersed synthetic water-insoluble compound containing bound water is used.

It is particularly advantageous to use aluminum silicate.

The aluminum silicates to be used can be amorphous or crystalline products, of course also using mixtures of amorphous and crystalline products as well as partially crystalline products. You can The aluminum silicates may be naturally derived or synthetically produced products, the synthetically produced products being preferred. This production is performed, for example, by reacting a water-soluble silicate with water-soluble aluminum in the presence of water. For this purpose, it is also possible to mix aqueous solutions of the starting materials with one another or to react the components which are present in the solid state with the components which are present as other aqueous solutions.
It is also possible to obtain the desired aluminum silicate by mixing the components which are present in both solid states in the presence of water. Similarly, Al (OH) ₃ , Al ₂ O ₃ or Si
Aluminum silicate can also be produced from O ₂ by reaction with an alkali metal silicate solution or an aluminate solution. This production can also be performed by a known method. In particular, the present invention relates to aluminum silicate having a three-dimensional spatial lattice structure.

Approximately 100-200 mg of active substance (AS)
Within the range of CaO / g, usually AS almost 100
Preferred calcium binding ability in the range of ~180mg CaO / g has the following _{composition: 0.7~1.1Na 2 O · Al 2 O} 3 · 1.3~3.3S
This is especially the case for compounds of iO ₂ .

This summation formula includes two types of different crystal structures (or their uncrystallized intermediates):
These can also be distinguished by their summation formula.
It is as _{follows: a) 0.7~1.1Na 2 O · Al} 2 O 3 · 1.3~
2.4 SiO ₂ b) 0.7 to 1.1 Na ₂ O · Al ₂ O ₃ · 2.4 to
3.3 SiO ₂ Different crystal structures are shown in the X-ray diffractogram.

Amorphous or crystalline aluminum silicate, which is present in the form of an aqueous suspension, is isolated by filtration of the remaining aqueous solution and dried, for example at temperatures of 50 to 400 ° C. Depending on the drying conditions, the product contains more or less bound water. When considering aluminum silicates for use in detergents and cleaning agents, the temperature preferably does not exceed 200 ° C. However, this aluminum silicate does not have to be dried at all after its preparation for the preparation of the suspension according to the invention; rather (although this is particularly advantageous), the aluminum silicate still moist from the preparation. Can also be used. But at moderate temperatures,
Aluminum silicate, which has been dried at a temperature of 80 to 200 ° C. until the adhering liquid water has been removed, can also be used for the preparation of the suspension according to the invention.

The particle size of the individual aluminum silicate particles can vary, for example in the range 0.1 μ to 0.1 mm. This figure relates to the primary particles, ie the size of the particles produced during precipitation and optionally subsequent crystallization. 10 to at least 80% by weight
It is advantageous to use aluminum silicates which consist of particles with a size of 0.01 μ, in particular 8 to 0.1 μ.

The aluminum silicate advantageously does not contain primary or secondary particles with a diameter of more than 45 μ. The secondary particles are particles that generate larger structures due to aggregation of the primary particles.

With regard to the agglomeration of the primary particles into larger structures, it is particularly suitable to use the aluminum silicate still moist from its production for producing the suspensions according to the invention, This is because it is clear that when the moist product is still used, the formation of secondary particles does not actually occur completely.

In a particularly preferred embodiment of the present invention, the calcium-binding silicate is powdered zeolite,
In particular, it is advantageous to use type A zeolites, particularly preferably type A zeolites having a specific particle size distribution.

Zeolites of this kind are known from German Patent Application Publication No. 2447021, German Patent Application Publication No. 2517218, German Patent Application Publication No. 2652419, German Patent Application Publication No. 2651420, German Federal Republic of Germany. Published German patent application 2651436, published German patent application 2651437, published German patent application No. 2
No. 651445, German Patent Application Publication No. 26
No. 51485 specification. These have the particle size distribution curves described herein.

In a particularly advantageous embodiment, it is possible to use the powdered zeolites of type A with the particle size distribution described in DE-A-2651485.

The polycarboxylic acid salts can be used both as acids and as salts or as partially neutralized substances; metal ions as well as nitrogen-containing cations are suitable as counterions.

The polymers according to the invention of the structure (X, Y, Z) are preferably copolymers of acrylic acid and acrolein. The distribution of the monomers in the polymer is usually random, the end groups of the polymer (X, Y, Z) being the groups which form under the corresponding reaction conditions. This copolymerizable monomer F is advantageously chosen such that it does not adversely affect the co-builder action of the overall polymer. Suitable monomers F are: monoethylenically unsaturated,
A monomer containing no carboxyl group, for example, a hydroxy (meth) acrylate having (CH ₂ ) _x OH (where x = 2 to 4) as an ester group. (Meth) acrylamide, (meth) acrylonitrile, vinyl sulfonic acid, allyl sulfonic 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-vinylpyrrolidone, N
-Vinylformamide, N-vinylimidazole, N-
Vinyl imidazoline, 1-vinylyl-2-methyl-2-
Imidazoline. Esters of (meth) acrylic acid having 1 to 8 C atoms in the alcohol group, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, optionally an alcohol group or Amino functionalized, ethylene, propylene, methyl vinyl ether, ethyl vinyl ether, styrene and α-methyl styrene. The acids and bases of all monomers can optionally be used in salt form.

Multi-ethylenically unsaturated monomers. For example, ethylene glycol, propylene glycol or hexanediol and (meth) acrylic acid, maleic acid or fumaric acid ester, polyethylene glycol or a copolymer of ethylene glycol and propylene glycol, (meth) acrylic acid, maleic acid or An ester consisting of fumaric acid, an addition product of ethylene oxide and / or propylene oxide 2-3 times esterified with (meth) acrylic acid or maleic acid and trimethylolpropane, (meth) acrylic- or maleic acid, At least double ester consisting of glycerin or pentaerythritol, triallylamine, tetraallylethylenediamine, polyethylene glycol divinyl ether, trimethylolpropanedi Rirueteru, butanediol diallyl ether, pentaerythritol allyl ether, divinyl urea.

Suitable monomers F are also polymeric building blocks which have been chemically modified with the corresponding starting materials under the chosen reaction conditions.

For component Y, monoethylenically unsaturated aldehydes such as acrolein and methacrolein, which are oxidized to the corresponding acids during polymerization, as well as monoethylenically unsaturated esters or higher esterified analogues and The amide corresponding to the corresponding structural element Y is suitable.

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

The polycarboxylic acid salts which can be used advantageously according to the invention are polymeric auxiliary builders,
This monomer structure :-( CH ₂ -CH-COOR) -
(In the formula, R = CH ₂ —CH ₂ —COOR ′ is represented and R ′
Represents H or R) as well as its salt form (for example alkali metal and ammonium compounds are suitable as counterions) 0.5 to 100%.

1H-NMR is particularly suitable for the quantitative measurement of ester-containing side chains which result from the use of acrolein as monomer.

In FIG. 1, acrolein 8 in D ₂ O
1H-of a copolymer of 0% and 20% acrylic acid
The NMR spectrum is shown. This spectrum is 500 on a Bruker AMX 500 spectrometer.
Recorded at 13 MHz. All low molecular weight components can be separated by dialysis using a semipermeable membrane with a resolution of 2000 g / mol (calibrated for polyoxyethylene). The NMR spectrum of the polymer thus purified (FIG. 2) allows a quantitative measurement of the ester structure bound to the polymer, which results in a clear signal of 4.2-
It was identified at 4.4 ppm.

The average molecular weight (Mw) of the copolymers can be varied within wide limits, with molecules having a too low degree of polymerization having poor washing properties, while too high a molecular weight is undesirable thickening. Must be taken into consideration. Therefore, 500-500000g
/ Mol, preferably 2000 to 100,000 g / mol or more preferably a copolymer having a molecular weight between 5,000 and 50,000 g / mol can be used.

This average molecular weight measurement is carried out by gel permeation chromatography of a LiChrospher Diol column (Merck) using a phosphate buffer (pH = 7) as an elution solution. Calibration is best done with narrowly dispersed polyacrylic acid. In this case, the non-constant chemical composition of the copolymer of interest in the present invention causes an error in the absolute value of the molecular weight. Since this generally known source of error cannot easily be ruled out, all numerical values for the molecular weights given here must be understood as comparisons to calibrations with polyacrylic acid.

In principle, it is also possible to use mixtures of polymers having different compositions, as well as mixtures of polymers having the same composition but different molecular weights.

The acrylic acid polymer can be produced by a known method. A detailed suggestion for this is
"Acrylic and methacrylic acid polymer" (Acrylic an
d Methacrylic Acid Polymers, JW Nemec and W.
Bauer jr) and "Radical Polymerization"
isation, CH Baumford), "Encyclopedia of Polymer Science and Technolo"
gy, John Wiley & Sons, New York 1990), respectively. A method of this kind is, for example, an "Acrylic acid polymer".
s), ML Mitter, "Encyclopedia of Polymer Science and Technology," Vol. 1 (Interscience Publishers, New York)
1964).

The (co) polymer can be produced by any conventional radical polymerization method. For example, the following preparation methods may be mentioned: solution polymerization in which the monomers are dissolved in water or other solvents or solvent mixtures optionally with additives of low molecular weight organic and / or inorganic compounds. Precipitation polymerization in a solvent in which the monomers are at least partially soluble and the polymer is insoluble. Emulsion and suspension polymerization in solvents where the monomer is not soluble and the emulsion or suspension is stabilized by the addition of low and / or high molecular weight substances.

Radiation-induced polymerization can also be used for the preparation of the polymer.

However, solution polymerization in water as described below is advantageous.

The monomer concentration varies between 5 and 70%, depending on the viscosity of the resulting polymer solution, it is between 25 and 70%.
50% is advantageous.

Suitable initiators are thermally decomposable radical donors which have sufficient solubility in the selected solvent or monomer, as well as multicomponent redox initiators. However, water-soluble substances such as hydrogen peroxide and alkali metal or ammonium peroxodisulfates are preferred.

Polymerization temperature is utilized with the amount of initiator to control the molecular weight of the desired polymer. The polymerization temperature is between 30 and 180 ° C, in which case it is between 60 and 130 ° C.
It is advantageous to keep Lower temperatures often result in higher molecular weight polymers, and higher temperatures can cause polymer degradation and discoloration.

The molecular weight can be adjusted with suitable regulators such as thio derivatives and low molecular weight alcohols. Suitable are, for example, thioglycolic acid, mercaptopropionic acid and its esters and 2-mercaptoethanol.

Similar polymers are known from the German patent DE 2354432C3 and the references cited therein. However, according to this document, detergent polymers which contain exclusively carboxyl groups, aldehyde groups, alcohols and vinyl groups together with zeolites are used. That is, the polymer is partly subjected to a Canniano reaction or is generally produced under such reaction conditions, in the case of acrolein polymerization, the ester groups are not formed, whereas the alcohol groups are formed. Federal Republic of Germany Patent Application Publication No. 24
The water-soluble, practically non-crosslinked polycarboxylic acids known from 08873 are such polymers.

Surfactants mediate the washing effect achieved via wetting and ambient wetting, the dirt-carrying capacity being ensured by the directed adsorption on pigment soils and by the solubilization of soluble soils, which soils are guaranteed. The loading bath is more prominent due to other contents.

For detergent preparations, the combination of surfactants is always common, as the mixture of different surfactants shows an interaction, ie a higher performance (compared to the sum of the single effects). performance).

A combination of remarkably good interactive surfactants is obtained from linear alkyl benzene sulphonates and fatty alcohol polyglycol ethers. For foaming control at low washing temperature (30-60 ° C),
The long chain soap is replaced by a silicone oil corresponding to its length.

Part of the alkylbenzene sulfonate is
It can be replaced by an alkyl sulfonate which exhibits advantageous anaerobic degradation properties. In the case of fatty alcohol polyglycol ethers, there is another for the hydrophobic molecular part, which is based on the raw material that follows (fat alcohol in a narrow sense) or petrochemical (oxo- or Ziegler-). Alcohol). A new class of surfactants of alkyl polyglucosides, non-ionic representatives without ethylene oxide, which can be obtained exclusively on the basis of the following raw fatty alcohols (fats and oils) and starches or sugars, are currently , Especially used for liquid detergents. In the case of fatty alcohol polyglycol ethers, there is a tendency towards low ethoxylation products, which improves the washout of fatty soils, especially at low temperatures.

As bleaching system, products are used in detergents for the oxidative removal of particularly colored soils. The general trend of washing at lower temperatures and increasing the proportion of temperature sensitive blends compared to cotton or flax requires the use of bleach activators, since sodium perborate is 60 70
This is because it is effective at a temperature higher than ° C.

The bleaching agent which is activated at 60 ° C. or lower, when an N-acetyl compound is used as the bleaching agent activator,
Due to the formation of the peracetic acid-anion in the wash liquor, this anion has a higher oxidizing capacity than the perhydroxide-anion which is liberated from the perborate by hydrolysis.

To convert the acetyl group to the perhydroxide anion, N, N, N ', N'-tetraacetylethylenediamine (TAED) and 1,5-diacetyl-2,4-dioxohexahydro-1, 3,5-triazine (DADHT) is suitable. DADHT has some performance advantages over TAED at low wash temperatures and, unlike TAED, has the advantage of using all available acetyl groups in the molecule in bleaching (for TAED 2 out of 4 Only one).

The peracetic acid-anion is most effective against hydrophilic bleachable stains. Long chain diperoxycarboxylic acids such as dodecane-1,12-diperacid are also especially
Effective at low temperatures. Alkanoyloxy having an alkyl chain length of C ₈ -C ₁₀ - benzenesulfonate (AO
The use of BS) is likewise advantageous as nonanoyloxy-benzenesulfonate (NOBS). NOB in washing liquid
Nonane-1-peracid formed from S and perborate-
In the anion (p-hydroxybenzene sulfonate as a leaving group), hydrophilicity and lipophilicity seem to be comparable in total to the bleaching ability despite the small amount of active oxygen in the washing liquid as compared with the TAED system. It maintains a good balance. Furthermore, NOBS is nitrogen-free.

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

Environmental reasons (reduction of boron load in water)
So perborate can be replaced by percarbonate, but this was problematic due to its low stability in detergents.

Sodium perborate must also be stabilized. In particular, radical decomposition caused by heavy metals, especially copper ions, should be avoided, which may also result in fiber damage. For that, other conventional complexing agents, such as EDTA, are well replaced from the preparations due to their low biodegradability. The other is, for example, certain protein hydrolysates, the biuret structure of which is particularly suitable for complexing copper.
Phosphonates are often still used as stabilizers.

Enzymes are almost necessary contents substances in common detergents and in many other preparations for washing or cleaning. Pancreatin (trypsin), proteases, amylases, cellulases and lipases are used.

Proteases break down mostly high molecular weight proteins, such as blood and protein stains, which cannot be dissolved from the fiber by the surfactant alone. Alpha-amylases, which are mostly used with proteases, are used for degrading starch-containing soils and for degrading the bonds between the adhesive-like fibers and the particle soils caused by the starch itself and the degradation products of starch.

Cellulases (cellulolytic enzymes) not only allow washing, but also softening and recovery of color of cotton fibers.

Lipases (lipolytic enzymes) are important for enhancing detergency. This can contribute in particular to keeping the high surfactant usage at low wash temperatures in the normal range.

Fluorescent whitening agent (similar to fluorescent white toner (fl
uorescent whitening agent, FWA))
Absorbs UV rays in the wavelength range of 350 nm of sunlight, which is invisible to human eyes, and is 440 in blue (blue-green depending on the structure)
Emit fluorescent radiation in the nm range (500 nm). For example, the fluorescent radiation of the white toner deposited on the textile fibers is added to the visible light that is reflected, resulting in the possible yellowing of the white textile, which may occur after several uses and washings, and again the whiteness. Not only is it replenished, but a bright, "shining" whiteness is achieved.

Special stilbene derivatives are suitable. In addition, the combination of coumarin- and quinolone- (carbostyryl-) and 1,3-diphenylpyrazoline structures, naphthalene dicarboxylic acid- and cinnamic acid derivatives and complex systems with benzoxazole- or benzimidazole-structures is specified. Have the role of.

Recently, polymers have also been used in detergents which prevent color transfer from one fiber to the other. For this reason, the special homopolymers of polyvinylpyrrolidone and vinylimidazole are particularly suitable. For this reason, bleaching systems and white toners are usually not used in general-purpose detergents containing color transfer inhibitors.

Carbonates, such as soda, are used to enhance the cleaning action (preliminary alkali).

Fillers such as sodium sulphate can be added to improve handling and flowability.

Other silicates, eg water glass, act as corrosion inhibitors; or eg magnesium silicate, act as stabilizers (eg phosphate). However, the amorphous and crystalline disilicates can also be used as auxiliary builders (Cobuilder) and, in special detergents, as the main builders.

Hydroxycarboxylic acids are used in addition to polymers and zeolite A as auxiliary builders, ie they have a so-called carrier function for Ca ions.

The darkening inhibitor suspends dissolved stains in the wash liquor.

Phosphates can be used as the main builder in zeolite p-reduction agents in addition to zeolite A, or in small amounts the phosphates have the auxiliary builder function in detergents as carriers.

Dissolution aids are advantageously used in liquid detergents. For example, polyethylene glycols having different degrees of polymerization and having a molar mass for mixing with surfactants, alcohols or water are suitable.

Furthermore, it is also possible to include in the detergent compositions still customary or novel ingredients, such as colorants, perfume oils, softeners or the abovementioned anti-transfer agents.

The present invention will be described in detail with reference to the following examples and drawings.

Polycarboxylate Example 1 A reactor equipped with a condenser, stirrer and temperature controller was charged with 720 parts by weight of VE-water and 424 parts of H ₂ O ₂ (50%) and heated at 70 ° C. . 950 parts of acrolein and 50% H through a separate conduit with vigorous stirring
₂ O ₂ was fed simultaneously during 4 hours. Start of supply 105
After a minute, a total of 1000 parts of V flowing in at 300 parts / hour
E-water supply was started.

After a total reaction time of 7 hours, the temperature for the post reaction of the reaction of 3 hours was brought to 95 ° C.

After cooling, the reaction contents were adjusted to pH 7-9 with NaOH solution.

In this case, a 35.1% polymer solution having a viscosity of 400 mPa.s resulted. This polymer had an average molecular weight of 8000 g / mol.

By 1 H-NMR of the dialyzed sample, the structure: —CH ₂ —CH— (COO—CH ₂ —CH ₂ —) _r CO
OR'-about 12% by weight was detected.

Example 2 In the same reactor as in Example 1, 450 parts of VE-water and 50 parts of
% H ₂ O ₂ 150 parts and charged at 90 ° C. While stirring vigorously, 525 parts of acrylic acid and 2 of acrolein
It was introduced into the reactor during 25 parts of 50% H ₂ 0 ₂ 0.99 parts of 3 hours. Then, the temperature was adjusted to 97 ° C., and the post-reaction was continued for 5 hours. 1800m after cooling
A 50.2% polymer solution having a viscosity of Pa · s was obtained. This polymer has an average molecular weight (Mw) of 2500.
It had 0 g / mol. This structure: -CH ₂ -CH
_{- (COO-CH 2 -CH 2} -) r COOR'- is 1H-
Up to about 10% by weight was detected by NMR.

Example 3 Using the same method as in Example 2, 600 parts of acrylic acid and 150 parts of acrolein were used as monomers. The feeding time was 2 hours. The obtained 50.5% polymer solution had a viscosity of 2200 mPa · s. This polymer had an average molecular weight of 20000 g / mol. _{Structure: -CH 2 -CH- (COO-CH} 2 -CH 2
-) _R COOR'- is about 4% by weight by 1H-NMR.
Was detected up to.

Example 4 Acrylic acid 675 as monomer according to the method of Example 2
Parts and 75 parts of acrolein were utilized. 6700mP
The resulting 52.5% solution with a viscosity of a · s has an average molecular weight (Mw) = 21000 g / mol and a structure:
_{-CH 2 -CH- (COO-CH 2} -CH 2 -) r COO
It contained a polymer having R'-.

Example 5 In a reactor similar to that of Example 1 was charged 200 parts of VE-water,
Heated at 95 ° C. Within 2 hours, 53 parts of sodium peroxodisulfate, 510 parts of β-carboxyethyl acrylate, 90 parts of acrylic acid and V in 320 parts of VE-water.
A solution consisting of 320 parts of E-water was fed simultaneously with vigorous stirring. Subsequently, a post reaction was carried out at 98 to 100 ° C. for 1.5 hours.

The resulting 42.1% solution diluted with water was cloudy and tended to separate layers; 1M NaO.
Complete solubility was achieved after neutral adjustment with H 2. This polymer has an average molecular weight (Mw) of 5200 g / mol and has the structure: —CH ₂ —C by NMR evaluation.
_{H- (COO-CH 2 -CH 2} -) r COOR'- about 85
% By weight was included.

Description of Detergent Formulations From a practical point of view, acrylic acid / acrolein-based copolymers are applied in detergents because they significantly reduce the drawbacks of known detergents. In addition to the novel copolymers, the detergents according to the invention contain the usual substances detailed below: A) Surfactants The proportion of surfactant components in the total detergent formulation is 5-4.
0% by weight, preferably 7-30% by weight and especially 10-20
% By weight. Anionic as well as nonionic surfactants can also be used. The proportion of anionic surfactant is at least 5% by weight, advantageously in the range 5 to 10% by weight. Of particular importance as anionic detersive active substances are sulphates and sulphonates. Sulfonates include, for example, alkylbenzene sulfonates, preferably those with straight chain alkyl groups,
Olefins, alkanes or like fatty acid ester sulphonates belong.

As a sulfate type surfactant,
Examples include fatty alcohol sulphates consisting of coconut fat or tallow fatty alcohol.

Nonionic surfactants include, for example, the first
Of the secondary and secondary aliphatic alcohols, alkylphenols or polyethylene oxide condensation products of alkyl polyglycosides in the range of 0 to 20% by weight, preferably 0 to 10% by weight, are included.

B) Builder Component The detergent preferably contains one or more detergent builders. From the field of ion exchangers, preference is given here to zeolite A type synthetic sodium aluminum silicates. In addition, zeolite NaX or zeolite P and mixtures of the compounds mentioned are suitable.
This detergent component is present in the formulation in an amount of 5 to 50% by weight, preferably 10%.
Those having ˜30% by weight are typical. The polycarboxylic acid salts according to the invention are in the range of 0.1 to 20% by weight,
0.5% by weight or more, more preferably 1% by weight or more,
In particular, it is used within the range of 2 to 10% by weight.

Other anionic builders such as Na-
Or K-carbonates or silicates (crystalline or amorphous form) supplement or complete the builder system.
Both substance species are each comprised between 0 and 30% by weight, preferably between 3 and
It can be used within the range of 15% by weight.

Complexing substances such as nitrilotriacetic acid,
(This proportion is 0-10% by weight, preferably 0.5-5%), as well as di- or polyphosphonic acids (0-5% by weight, preferably 0.1-1%) or hydroxycarboxylic acids, such as Derivatives of citric acid or tartaric acid (0-20
%, Preferably 2-10%) can also be used as builder component. Phosphate can be used within the range of 0 to 30%.

C) Bleach / Bleacher Activator In the case of bleaches providing H ₂ O ₂ in water, in particular sodium perborate tetrahydrate or monohydrate or a gecoatete percarbonate salt. Is really important.

Organic N-acyl or O-acyl compounds, such as TAED, are of practical importance as bleach activators for peroxides. The bleach activator is used in the range of 0 to 10% by weight, preferably 2 to 8% by weight.

D) Enzymes It is possible to incorporate further into the detergent formulation enzymes which are specific for a particular type of soil, for example proteases, amylases or lipases. It is advantageous to use a combination of enzymes with diverse actions. Its range of application is 0 to 3% by weight, preferably 0.3 to 1% by weight.

E) Optical brighteners The detergents can contain, as optical brighteners, derivatives of the following compounds: stilbene, biphenylstilbene,
A combination from diphenylpyrazoline, coumarin or benzoxazole or benzamidazole. The optical brightener is used in the range of 0 to 5% by weight, preferably 0.1 to 0.3% by weight.

F) Additional Darkening Inhibitor The detergent may contain an additional darkening inhibitor which suspends the dissolved stains from the fibers in the dye liquor. Examples of this include methyl- or carboxymethyl cellulose. Its proportion in the detergent can be 0 to 5% by weight, in particular 0.5 to 1.5% by weight.

G) Defoamers Foam inhibitors are generally used in amounts of 0-8% by weight.
Usually this is soap, silicone oil or hydrophobic silicic acid. In the case of a non-surfactant type defoaming agent, 0 to 3.5% by weight is generally sufficient because it has a stronger action than soap.

Implementation of Laundry Test The good action of the novel copolymers described above can be confirmed in a comparative wash test with commercially available detergent polymers. The commercial product (MP) has a polyacrylate-based average molecular weight (Mw) of 120,000 g /
Homopolymer (MP1) with mol and average molecular weight (M) based on acrylic / maleic acid (about 30/70)
w) copolymer with 70,000 g / mol (MP
2). The structure in this product is: --CH ₂ --CH-(C
_{OO-CH 2 -CH 2 -)} r COOR'- was detected.

These products were tested according to DIN 44983 in comparative washing tests with the copolymers of Examples 1 to 5 (these are B1, B2, B3, B4, B.
5 as the following abbreviations).

A) Detergent Composition (wt%) The polymer used in the detergent is neutralized with NaOH,
40-54% of active agent was produced.

[0116] In the detergent formulation, only the polymer was changed and the other detergent contents were the same for each formulation. The active content of the polymer used was calculated as 4%. Guarantees in the formulations caused by the different solids contents of the polymers were achieved by the sulfate salts.

Marlon ARL 9.38 Dehydol TA5 0.80 Dehydol LT7 3.20 Edenor HT35 2.80 Blancophor 0.15 Tinopal CBS-X 0.02 Relatin HC-Comp 1.10 Trilon B 0.23 Soda 10.00 Perborate.4H ₂ O 20.00 Portil N 3.00 Wessalith CS 32 .90 TAED 3.18 Alcalase 2.5T 0.50 Polymer Sodium Sulfate B1 8.00 4.74 B2 7.89 4.85 B3 8.49 4.25 B4 7.94 4.80 B5 9.83 2.91 MP1 10.0 2.74 MP2 10.0 2.74 B) Washing conditions The washing conditions are summarized in the following table: Washing machine type: Miele (Miele W 763) Program: Underwear / color pattern without preliminary cleaning Temperature / hardness: 60 ° C / 20dH Detergent amount: 130g (10.0g / l) Contents: 20 cotton cloths, 3 white towels Two handkerchiefs Weight = 3.3 kg White fabric: towel, handkerchief, cotton cloth and green striped cotton cloth (WFK) 0.8 kg Curing: for each odd washing step Blood (EMPA 111) Standard (EMPA 101) Sebum ( WFK 10 D) Black tea (WFK 10) Secondary wash capacity: 1 cycle, 25th wash Laundry residue adhesion and darkening were measured after 10 and 25th wash.

Krefeld Cleaning Laboratory (WF
K) and the Swiss Federal Institute for Materials Testing (EMPA) sell soil test specimens for washing tests. This stain test product is called EMPA 111 or the like for blood stains, for example.

3. ) Examination of measurements for the measurement of secondary cleaning capacity Darkening or redeposition of soils is possible with Reflextion R
Datacolor, Inc. (Fa. Datacolor) via 457 nm
It was measured using a Spectral Photometer (DC3890). For the new fabric, whiteness was measured as a wash cycle zero value. The result of the darkening is indicated by the reduction of diffuse reflection (delta R = R zero value-R measured value). The measurement was carried out at 5 measuring points per white fabric, and then the average value and the scattering were calculated. LSD values (least significant difference) are calculated according to DIN 44983 Teil 50. Ranking was done using the scores of the individual measurements measured on the various fabrics.

The measurement of laundry dregs is carried out via the ash content (double measurement). 2g of each fabric, 500 ℃
It was ignited by preliminary ashing (1 hour) and then ashed at 800 ° C. in a muffle furnace for 1 hour. The crucible was collected.

Results Darkening after the 10th wash (FIG. 3): Good wash results for towel (F), especially in the case of Example 1, ΔR4.
You can check it at 13. Example 3 (ΔR = 2.81)
And Example 5 (ΔR = 2.85), the commercially available MP1 (ΔR = Δ85)
The results are clearly comparable to R = 2.89) and MP2 (ΔR = 2.75). Example 2 (ΔR = 1.4
7) and Example 4 (ΔR = 2.65) show a lower effect on towels compared to both commercial products.

A cotton fabric having a green striped pattern of the test fabric (B
For W / GS, Example 2 (ΔR = 5.26) gave the best results, Examples 1 and 3 (both have the same value: ΔR
= 4.84) and Example 4 (ΔR = 3.76) follows. The commercial product showed a worse darkening inhibitory effect on this fabric. These ΔR values were MP1 = 2.51 and MP = 3.4. The measured LSD value is 0.24
Met.

Handkerchief (coarse towel cloth (Gerstenkornhand
Regarding the darkening inhibitory effect on tuch)) (H), the commercial products (ΔR MP1 = 7.02, MP2 = 7.94) also showed a worse effect compared to the examples according to the invention. Only Example 4 (ΔR = 7.61) was clearly comparable to the effect of MP2. Examples 1, 2, 3 and 5 are 8.85
Showed a larger ΔR value. The best result is Example 1 (Δ
R = 9.85) and Example 3 (ΔR = 9.77). The LSD value was measured up to 0.41.

Example 3 for a cotton cloth (BW) (ΔR = 3.9)
4) shows the best cleaning effect, Example 2 (ΔR = 3.4)
1), Example 1 (ΔR = 2.28) and Example 5 (ΔR = 2.
019) follows. The worst result is the commercial product 1 (Δ
R = 1.69), Example 4 (ΔR = 1.35) and commercial product 2 (ΔR = 1.13). The LSD value was 0.20 in this measurement sequence.

Darkening after the 25th wash (FIG. 4):
For towels, Example 1 (ΔR = 6.64), Example 2 (ΔR
= 7.01) and Example 3 (ΔR = 6.97) showed the best darkening inhibitory effect, while Example 5 (ΔR =
4.94) and commercial product 1 (ΔR = 4.76) follow. The worst result among them is the commercial product 2 (ΔR =
3.8) and Example 4 (ΔR = 3.50). LS
The D value was 0.53.

For BW / GS, Example 2 (ΔR = 8.8)
The good results of 3) and Example 1 (ΔR = 8.39) are particularly excellent. Example 3 (ΔR = 7.6) with slightly worse washing effect
5) and Example 5 (ΔR = 7.34), which are ranked in the same rank based on an LSD value of 0.41. A lower value for the inhibition of darkening is obtained by the commercial product 2
(ΔR = 6.54), Example 4 (ΔR = 6.06) and commercial product 1 (5.01).

The best results for handkerchiefs (coarse towels) are shown in Example 3 (ΔR = 13.61) and Example 1 (ΔR
= 13.19) followed by an LS of 0.41
Considered to be at the same level in D value. Example 2 (Δ
R = 12.6) and Example 5 (ΔR = 12.42) show a mildly diminished effect and are also considered equivalent. The result of further reduction is the commercially available product 1 (ΔR = 11.1.
83), commercial product 2 (ΔR = 10.24) and Example 4 (Δ
R = 9.53).

For the test textile cotton cloth, again, Example 3 (Δ
R = 7.92) is advantageous compared to other polymers,
Example 2 (ΔR = 7.22), Example 1 (ΔR = 6.08), Example 5 (ΔR = 4.7), MP1 (ΔR = 4.45) and MP2 (ΔR = 3.67) follow. . The values for Example 5 and Commercial 1 are considered to be the same at an LSD value of 0.27.

In the overall evaluation of the darkening-inhibiting effect of all tested fabrics after the 25th wash, again Example 4
Up to the above, the newly developed polymer is advantageous in comparison with commercial products. The ranking in the comprehensive evaluation is as follows: Darkening inhibition B3>B2>B1>B5>MP1> MP2
> B4 Latent Adhesion After 10th Laundering In the evaluation of laundering deposits after the 10th laundering (FIG. 5), all five examples resulted in low ash values for all tested fabric types. Based on this, significant advantages can be confirmed as compared with the commercial products. The average ash content, measured from four fabrics, towels, cotton / green stripes, handkerchiefs (coarse towels) and cotton / white, together with the acrylic acid content in the individual polymers was 0.9% ash ( 1.1% from B1)
(B2), 1.3% (B3) and 1.4% (B4). Example 5 showed comparable results with B3. In contrast, the two commercial products showed a low effect: their ash content was 1.9% (MP1) and 2.0% (MP2).

The ranking in the reduction of laundry dregs is as follows: B1>B2> B3 = B5>B4>MP1> MP2 This advantage is retained for the developed polymer type even after the 25th wash. (Fig. 6). The ash content for the new polymer was only 0.1-0.2% (B1 = 1.1%, B2 = 1.2) compared to after 10 washes.
%, B3 = 1.4%, B4 = 1.5%, B5 = 1.4
%), But it is 3.4% (MP
Adhesion values of 1) and 3.2% (MP2) were shown.

The rank of newly developed polymers is 10.
Similar to after multiple washes, only the order of the commercial products was reversed: B1>B2> B3 = B5>B4>MP2> MP1 Washing test without zeolite A This washing test is used according to the invention The polymer to be
It is shown to achieve excellent action especially with zeolite. This detergent formulation described above was selected as the basis for the following tests. Zeolite A was simply replaced with washed alkali, sodium carbonate and sodium disilicate. B1 and the commercial product MP1 were selected as polymers. Wessalith CS is a granulated zeolite A, and in addition to zeolite A, CMC 2%, NaSO
₄ 1.7% and Niotensid 2.6%
As a result, this substance is supplemented with the corresponding product groups, the active substance formulations differ only in the builder content.

B1a B1b MP1b Marlon ARL 9.38 9.38 9.38 Dehydol TA5 0.8 1.66 1.66 Dehydol LT7 3.2 3.2 3.2 Edenol Edenor HT35) 2.8 2.8 2.8 Blankophor 0.15 0.15 0.15 Tinopal CBS-X 0.02 0.02 0.02 Relatin HC-Comp 1 .1 1.8 1.8 Trilon B 0.23 0.23 0.23 Perborate.4H ₂ O 20 20 20 TAED 3.18 3.18 3.18 Alcalase (Alcalase 2.5T) 0.5 0.5 0.5 Na sulfate 4.74 5.31 3.3 Wessalith CS 32.9 Polymer 8.0 8.0 8.0 Soda 10 30 30 30 Portil N 3 13.78 13.78 Results: Darkening after 10th wash (Fig. 7) Good wash results on towel (F) Is the formulation B1a
Can be achieved with a ΔR-value of 4.61. The decreasing effect is shown by MP1b (ΔR = 1.77), followed by B1b (ΔR = 1.05). The LSD value is at 0.6.

For the cotton fabric with the green stripes of the test fabric, B1a (ΔR = 1.74) is also the best, as is formulation B1b (ΔR = 1.08) and MP1b.
(ΔR = 0.63) follows with an LSD value of 0.24.

In the case of a handkerchief (coarse towel cloth) (H), the good effect of the formulation B1a (ΔR = 10.51) is confirmed. This darkening value of B1b and MP1b are considered the same rank with ΔR = 6.58 and 6.56 with an LSD value of 0.37.

A similar trend was demonstrated for cotton (BW) test fabrics. B1a showed the best value at ΔR = 3.39, and B1b and M considered to be the same rank with ΔR = 0.53 and 0.44 at an LSD value of 0.26.
P1b follows.

Rank: B1a> B1b = MP1b Darkening after the 25th wash (FIG. 8) After the 25th wash, the formulation B1a had ΔR = 6.78.
Still shows the best results for towels, 0.4
Formulations MP1b and B1b, which are of the same rank with ΔR = 0.88 and 0.59 at an LSD value of 8, follow.

The same tendency is shown for the woven cotton / green stripes. LSD value is 0.3, ΔR of B1a
The value is 8.49, B1b is 0.37 and MP1b
Is 0.23.

In the case of a handkerchief (coarse towel cloth) (H), formulation B1a showed the best results with ΔR = 13.34, formulation B1b (ΔR = 4.38) and MP1b.
(ΔR = 3.2) follows. The LSD value is 0.43.

Regarding the cotton fabric, again, MP1b (Δ
R = -1.68) shows the worst washing action. B1b
(ΔR = −1.4) and B1a (ΔR = 6.26) show better results. The LSD value is 0.23.

Rank order: B1a>B1b> MP1b Adhesion of laundry residue after the 10th wash (FIG. 9) The lowest ash content for woven towels, cotton / green stripes, handkerchiefs (coarse towels) and cotton cloths. To 0.7
B1a shows values of%, 1.1%, 0.7% and 0.8% with an average value of 0.8% from all test fabrics.
Blend B1b is 1.8% (towel), 2.9% (cotton cloth /
Green stripes show a decreasing effect with an ash content of 4.2% (handkerchief (coarse towel cloth)) and 3.5% (cotton cloth). This average value is 3.1%. The ash content of Example MP1b showed the following values for the same stain: 2.2% (towel), 4.0% (cotton cloth / green stripes), 4.7% (handkerchief (coarse towel cloth)) and 4 0.0% (cotton cloth). This average value is 3.7%.

Rank: B1a>B1b> MP1b Adhesion of laundry residue after the 25th washing (FIG. 10) The same rank order as that after the 10th washing was shown.
In the case of Example B1a, after the 25th wash, the residue on the various textiles is 0.9% (towels), 1.5% (cotton cloth / green stripes), 1.4% (handkerchief (coarse towel cloth). ) And cotton cloth). This average value is 1.3%. In the case of formulations B1b and MP1b, a significantly higher deposit of laundry dregs was shown. Formulation B1b showed the following results: 4.2% residue on towel, 5.5% residue on cotton cloth / green stripes, 9.2% residue on handkerchief (coarse towel cloth) and residue on cotton cloth. Material 8.8%. The average value from all ash residues is 6.9%. The following values were obtained for formulation MP1b: 4.9% for towels, 6.1% for cotton / green stripes, 9.2% for handkerchiefs (coarse towels) and 8.7 for cotton.
%. The average value is 7.2%.

Rank: B1a>B1b> MP1b Results: B1a clearly outperforms B1b and MP1b, and B1b has no advantage compared to MP1b.

[Brief description of drawings]

1 is a NMR spectrum of the polymer used according to the present invention.

2 NMR spectrum of the polymer from FIG. 1 after dialysis

FIG. 3 is a diagram showing darkening values after the 10th washing.

FIG. 4 is a diagram showing darkening values after the 25th wash.

FIG. 5 is a diagram showing an adhesion value of laundry dregs after 10th washing.

FIG. 6 is a diagram showing an adhesion value of laundry residue after the 25th wash.

FIG. 7 is a diagram showing darkening values after 10th washing in a comparative washing test without zeolite.

FIG. 8 is a diagram showing darkening values after the 25th wash.

FIG. 9 is a diagram showing the adhesion value of laundry residue after the 10th wash.

FIG. 10 is a diagram showing the adhesion value of laundry residue after the 25th wash.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Beata-Maria Lorz, Federal Republic of Germany Wechtersbach Feldstraße 9 (72) Inventor Maurizio Ragnetti, Federal Republic of Germany Mainz-Kosheim Wallufer Strasse 30

Claims (13)

[Claims] 1. The following components: Surfactant 5-40% by weight Calcium-binding silicate 5-50% by weight Polycarboxylic acid salt 1-20% by weight Other silicates 0-30% by weight Carbonate 0 -30 wt% Organic complexing agent 0-10 wt% Phosphonate 0-5 wt% Phosphate 0-30 wt% Hydroxycarboxylic acid 0-20 wt% Bleach 0-30 wt% Bleach activator 0 10% by weight Optical brightener 0-5% by weight Enzyme 0-30% by weight Anti-darkening agent 0-5% by weight Defoamer 0-8% by weight Filler 0-40% by weight, composition at that time 1% by weight or more of the product has the following structure (X, Y, Z) [where X is And Y is The expressed, Z is - (F) _q - represents (wherein, A = H, OH, C 1 ~C 6 alkyl, CH ₂ CO (DEC
_{O) r-1 OM; B} = H, OH, C 1 ~C 6 alkyl, COOM; D = O, NH ; E = C 1 ~C 6 alkyl; F = copolymerizable monomers; M = H, alkali Metal or alkaline earth metal, ammonium, substituted ammonium; in the case of X,-(CH ₂ -C
H ₂ —O) _2-4 M; also represents r = 1 to 5, m = 0 to 99.5 mol%, n = 0.5 to 100 mol%, and q = 0 to 99.5 mol%) ] It is a polycarboxylic acid salt which has these. 2. The following components: Surfactant 5-40% by weight Calcium-binding silicate 5-50% by weight Polycarboxylic acid salt 1-20% by weight Other silicates 0-30% by weight Carbonate 0 -30 wt% Organic complexing agent 0-10 wt% Phosphonate 0-5 wt% Phosphate 0-30 wt% Hydroxycarboxylic acid 0-20 wt% Bleach 0-30 wt% Bleach activator 0 10% by weight Optical brightener 0-5% by weight Enzyme 0-30% by weight Anti-darkening agent 0-5% by weight Defoamer 0-8% by weight Filler 0-40% by weight, composition at that time 1% by weight or more of the product from acrolein and optionally one or more comonomers with oxidizing radical donors under non-saponification conditions and /
A detergent composition characterized in that it is a polycarboxylic acid salt which can be produced without causing a subsequent Cannialo reaction. 3. The following components: Surfactant 5-40% by weight Calcium-binding silicate 5-50% by weight Polycarboxylate 1-20% by weight Other silicates 0-30% by weight Carbonate 0 -30 wt% Organic complexing agent 0-10 wt% Phosphonate 0-5 wt% Phosphate 0-30 wt% Hydroxycarboxylic acid 0-20 wt% Bleach 0-30 wt% Bleach activator 0 10% by weight Optical brightener 0-5% by weight Enzyme 0-30% by weight Anti-darkening agent 0-5% by weight Defoamer 0-8% by weight Filler 0-40% by weight, composition at that time 1 wt% or more things, acrolein and optionally can be prepared by using an oxidizing radical donors from one or more comonomers, and the following types: -C (O) -O [-CH 2 -CH ₂ C (O)
O] _x R'wherein R'is an alkali metal cation, an alkaline earth metal cation or a nitrogen-containing cation,
3. The detergent composition according to claim 2, which is a polycarboxylic acid salt having a ratio of functional groups of x = 1 to 5). 4. The following components: Surfactant 5-40% by weight Calcium-binding silicate 5-50% by weight Polycarboxylic acid salt 1-20% by weight Other silicates 0-30% by weight Carbonate 0 -30 wt% Organic complexing agent 0-10 wt% Phosphonate 0-5 wt% Phosphate 0-30 wt% Hydroxycarboxylic acid 0-20 wt% Bleach 0-30 wt% Bleach activator 0 10% by weight Optical brightener 0-5% by weight Enzyme 0-30% by weight Anti-darkening agent 0-5% by weight Defoamer 0-8% by weight Filler 0-40% by weight, composition at that time 1% by weight or more of the product is a polycarboxylic acid salt which can be prepared from acrolein and optionally one or more comonomers with an oxidizing radical donor, wherein the polycarboxylic acid salt is a plurality of
In particular, a detergent composition characterized in that it is mixed with all the ingredients, optionally with the addition of H ₂ O and optionally dried. 5. One or more of the following components: surfactant 7 to 30% by weight, in particular 10 to 20% by weight polycarboxylic acid salt 2 to 10% by weight other silicates 3 to 15% by weight carbonates 3 to 3. 15% by weight Organic complexing agent 0.5-5% by weight Phosphonate 0.1-1% by weight Phosphate 0-5% by weight 0-1% by weight Hydroxycarboxylic acid 2-10% by weight Bleach 10- 25% by weight Bleach activator 2-8% by weight Optical brightener 0.1-0.3% by weight Enzyme 0.3-1% by weight Anti-darkening agent 0.5-1.5% by weight Antifoam 0 The detergent composition according to any one of claims 1 to 4, containing 0 to 3.5% by weight of a filler and 0 to 20% by weight of a filler. 6. The detergent according to claim 1, wherein the preparation contains the following components as a compact detergent: polycarboxylate 2 to 8% by weight bleach activator 2 to 8% by weight. Composition. 7. The formulation as a liquid detergent comprises the following components: anionic surfactant 5 to 15% by weight nonionic surfactant 10 to 20% by weight calcium-binding silicate 10 to 25% by weight polycarboxylic acid. Salt 1 to 5% by weight Bleach 0% by weight Bleach activator 0% by weight Supplementary builder 0 to 8% by weight Dissolution aid 0 to 30% by weight Water 0 to 50% by weight Any of claims 1 to 3. The detergent composition according to item 1. 8. The preparation has the following components as a finishing detergent: Anionic surfactant 5 to 15% by weight Nonionic surfactant 1 to 10% by weight Calcium-binding silicate 10 to 50% by weight Polycarboxylic acid The detergent composition according to any one of claims 1 to 5, containing 1 to 5% by weight of salt, bleaching agent of 0% by weight, bleaching agent activator of 0% by weight, and carbonate of 0 to 20% by weight. 9. A method according to claim 1, characterized in that the individual powdery components are mixed and the liquid components are sprayed so as to be homogeneously mixed with one another. A method for producing the detergent composition. 10. A process according to claim 1, wherein water and heat-insensitive components are processed into a slurry with water and subsequently spray-dried. A method for producing a detergent composition. 11. The method of claim 10 wherein the other ingredients are post-mixed by mixing or spraying. 12. The method according to claim 6, wherein the individual powdery components are mixed, the liquid components are sprayed to be mixed homogeneously with each other, and the mixture is forcedly mixed to agglomerate and extruded. A method for producing the detergent composition. 13. A process according to claim 7, characterized in that the individual components are mixed with a corresponding amount of solubilizer or water and optionally concentrated.