DE19523864A1 - Washing compsn., giving better soil release - contains surfactant, silicate or zeolite binding calcium and poly:amino acid or anhydride as co-builder, and is free from inorganic sulphate - Google Patents

Abstract

A washing compsn. contains (a) 5-40 wt.% surfactant, (b) 5-50 wt.% Ca-binding silicate or zeolite, and (c) 1-20 wt.% of a polyamino acid or anhydride, and contains no appreciable amt. of inorganic sulphate. Pref. polyaspartic acid or a salt, pref.an alkali salt, are used. The mol. wt. is 500-20000. The compsn. is a solid and contains less than 3% (less than 1%) of inorganic sulphate, and 1-12% of citric acid or salt.

Description

The present invention relates to a preferably low or phosphate-free, Zeolite-containing and sulfate-free detergent system and a process for To wash.

The development of detergent builders has been general in recent years a spread of phosphate-free detergents has been influenced. As more common Zeolite A is used as a builder substitute for phosphate. Due to the long Stronger exchange kinetics of the zeolite for Ca ions require phosphate-free powder and liquid detergents and cleaning agents next to the main builder Zeolite A or P so-called cobuilders, such as. B. soda, polycarboxylates, NTA, silicates or hydroxy carboxylates.

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. B. in DE-A 20 25 238, DE-A 20 44 601, EP-A 0 137 669 or DE-A 36 04 223 can be described.

Polymerization products from aspartic acid have also become known or maleic acid and ammonia or NH₃-supplying starting materials see z. B. EP-A-256 366 and US-A-4 839 461. Further reference is made to EP-A-454 126 (= US-A-5 328 631)) EP-A-561 452, EP-A-561 464, EP-A-511 037, EP-A-581 452 (= US-A-5 266 237), EP-A-592 265 and EP-A-612 842.

These products contribute to the washing effectiveness of detergents by doing this Improve dirt-carrying capacity: On the one hand, they prevent dirt back on the laundry and become annoying due to a graying of the Textiles have an impact and on the other hand they reduce the deposit of inorganic Salts (incrustation) on the same.  

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

It has been shown that the secondary washing by the polycarboxylates effective graying and incrustation could be reduced, but is one To further optimize these cobuilders to strive for the effectiveness of To increase detergent and, at the same time, the performance characteristics of the To further improve textiles.

Now it has become known that the above Detergent systems in the presence of sulfate have good washing results. So is in EP-A 592 265 about 30% Na₂SO₄, in EP-0 A 612 842 up to 85% Na₂SO₄, in EP-A 581 452 (US 5 266 237) up to 50% Na₂SO₄, in EP 454 126 20 to 23% Na₂SO₄, in US 4,325,829 26.3% Na₂SO₄ and in WO 94/10282 12.5% Na₂SO₄ have been used as auxiliary.

It is known from US-A-5 116 513 and S. Sarig and F. Shifrin Natl. Counc. Res. Dev. [Rep.] NCRD (Isr.) 1977, (NCRD 8-76, Seawater Desaling) 150-7 that Polycarboxylates u. a. the structure claimed dispersed very well on CaSO₄ act and that this effect is more pronounced than the dispersing effect on CaCO₃.

Sulfate-free detergent systems would be ecologically cheaper (no sulfate Emission, lower transport weight, smaller pack volume) on the on the other hand also more economical (transport costs, higher proportion to be dried Goods etc.).

The task is a low or phosphate-free, zeolite-containing but sulfate-free To provide detergent system with improved cobuilder.

The invention relates to a detergent composition containing by weight percent

5 to 40 at least one surface active compound
5 to 50 at least one Ca-binding silicate or zeolite
1 to 20 at least one polycarboxylic acid or a salt thereof,

characterized in that the polycarboxylic acid is a polyamino acid or Anhydride thereof is and that the detergent composition is not essential Contains amounts of inorganic sulfate.

The average molecular weight (Mw) can vary within a wide range move, taking into account that molecules with too low poly degree of washing have less good washing properties, while too high Molecular weights have an undesirable thickening effect. Thus are polyamino acids usable with molecular weights between 500 and 500,000 g / mol, preferred but are 1,000 to 100,000 g / mol or, even better, 1,000 to 50,000 g / mol.

Among the polycarboxylic acids and poly to be used in the present invention In addition to the free acid, amino acids are the salts and the derivatives of Understand acids, especially anhydrides. It is also possible that the poly carboxylic acid has different substructures at the same time, e.g. B. free Acids and anhydrides.

In a particularly preferred embodiment, the polycarboxylic acid at least one of the following, optionally recurring structural units on:

where applies

R = H or a cation, in particular NH₄⊕, Na, K
n, m = 0 or an integer from 1 to 300
o, p, q = 0 or an integer from 1 to 10
r = 0 or an integer from 1 to 5
s = 0 or an integer from 1 to 10
n + m + o + p + q 300.

In a particularly preferred embodiment, the recurring Units A1, B1, A2 and B2 in the following distribution (% by weight) before:

A1 from 10 to 40%
B1 from 40 to 90%
I from 0 to 5%
A2 from 0 to 5%
B2 from 0 to 5%.

In the event that the polycarboxylic acid consists essentially of these with n, m, o, p, q, r and s indexed units, it has depending on the Reaction conditions, for example residence time and temperature of the thermal Polymerization, preferably a molecular weight after gel permeation chromatographic analyzes from Mw = 500 to 10,000, preferably 700 to 5,000, particularly preferably 1,000 to 4,500. In general, the share of beta form at more than 50%, preferably at more than 70%.

The polyamino acids according to the invention also include those under the selected reaction conditions compared to the corresponding starting compound applications have been chemically modified.

The molecular weight is determined by gel permeation chromatography (GPC) in LiChrospher Diol columns (Merck) and with phosphate buffer (pH = 7) as an eluent solution. Calibration can best be done with pure polyaspartic acid, e.g. B. Sigma, whose molecular weight by an absolute measurement method, at for example, LALLS was determined. The non-constant causes chemical composition of the polycarbonate to be used according to the invention acid an error in the absolute value of the molecular weight. This in general Known source of error cannot be easily eliminated, so everyone here information about the molecular weight as relative to the calibration Polyaspartic acid are to be understood.  

In principle, mixtures of polyamino acids can also be used with different compositions as well as with the same composition but different molecular weights.

The polyamino acids can be produced by known processes.

In addition, the reaction can be carried out appropriately and the starting materials selected other recurring units quantities may be included e.g. B.

• a) Malic acid units of the formulas: and
• b) Maleic and fumaric acid units of the formulas

The detergent according to the invention preferably contains (in% by weight)

The composition preferably contains 2 to 8 as compact detergent % By weight of polyamino acid and bleach activator.

If the detergent composition is a formulation as a liquid detergent then it preferably contains

For a formulation as a mild detergent, the detergent contains together settlement

Preferred corresponding components are given below.  

All individual components of the composition can be as pure substance or as Mixture of corresponding components are present. As calcium-binding silicate water-insoluble substances, in particular zeolites, are preferred Commitment.

In a preferred embodiment of the invention, the water-insoluble, silicate capable of binding calcium ions is a finely divided, bound Water-containing, synthetically produced, water-insoluble compound of general formula

(Kat _{2 / n} O) _x - Me₂O₃ - (SiO₂) _y (I),

in the
Kat a cation of valence n exchangeable with calcium,
n is a number from 1 to 3
x a number from 0.7 to 1.5
Me boron or aluminum and
y is a number from 0.8 to 6,
deploy.

Aluminum silicates or layered silicates are particularly preferably used, such as B. the layer silicates from Hoechst, preferably SKS6.

The aluminum silicates to be used can be amorphous or act crystalline products, of course also mixtures of Amorphous and crystalline products and also semi-crystalline products can be used are. The aluminum silicates can be naturally occurring or synthetic be manufactured products, with the synthetically produced products being preferred are. The production can e.g. B. by reaction of water-soluble silicates with water-soluble aluminates in the presence of water. To this end can mixed aqueous solutions of the starting materials or  one component in the solid state with the other as an aqueous one Solution present component are implemented. Also by mixing both components present in the solid state are obtained in the presence of water the desired aluminum silicates. Also from Al (OH) ₃, Al₂O₃ or SiO₂ can be reacted with alkali silicate or aluminate solutions Manufacture aluminum silicates. The production can also according to other known Procedure. Aluminum silicates which have a three are particularly preferred have dimensional spatial lattice structure.

The preferred, approximately in the range of 100 to 200 mg CaO / g active substance (AS) calcium binding capacity is usually around 100 to 180 mg CaO / g AS especially with compounds of the composition:

0.7 - 1.1 Na₂O - Al₂O₃ - 1.3 - 3.3 SiO₂.

This molecular formula comprises two types of different crystal structures (or their non-crystalline precursors), which are also characterized by their empirical formulas differentiate. They are

• a) 0.7 - 1.1 Na₂O - Al₂O₃ - 1.3 - 2.4 SiO₂
• b) 0.7 - 1.1 Na₂O -Al₂O₃ - 2.4 - 3.3 SiO₂.

The different crystal structures can be seen in X-ray diffraction diagram.

The amorphous or crystalline aluminum silicate present in aqueous suspension can be separated by filtration from the remaining aqueous solution 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 go above 200 ° C if that Aluminum silicate is intended for use in detergents and cleaning agents. The aluminum silicates, however, need one after preparation to prepare them suspension according to the invention not to be dried at all; much more can - and this is particularly advantageous - one that is still moist from manufacture Aluminum silicate can be used. However, it can also be used for medium Temperatures, for example at 80 to 200 ° C, until the removal of  adhering liquid water dried aluminum silicates for frosting Use 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 μ and 0.1 mm. This information relates the primary particle size, d. that is, the size of the at the precipitation and optionally the subsequent crystallization resulting particles. With particular That advantage is used aluminum silicates, which are at least 80 wt .-% from particles with a size of 10 to 0.01 μ, in particular 8 to 0.1 μ consist.

These aluminum silicates preferably contain no primary or secondary particles more with diameters above 45 µ. As secondary particles Particles that form larger structures through agglomeration of the primary particles have arisen.

With regard to the agglomeration of the primary particles to form larger structures the use of aluminum silicates that are still damp from their manufacture proven particularly useful for the production of the suspensions according to the invention, since has shown that when using these still moist products Formation of secondary particles is practically completely prevented.

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

Such zeolite powder can according to DE-A-24 47 021, DE-A-25 17 218, DE-A-26 52 419, DE-A-26 51 420, DE-A-26 51 436, DE-A-26 51 445, DE-A-26 51 485 getting produced. They then have the particle distribution given there curve on.

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

The phosphate-free builder combination described in European patent application EP 164 514, which mainly contains crystalline phyllosilicates of a selected structural formula NaMSi _x O _{2 + 1} -yH₂O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number Are from 0 to 20 and preferred values for x are 2, 3 or 4 can be used. These layered silicates can be used as water softeners both separately and in detergents and cleaning agents together with other builders or co-builders such as phosphates, zeolite, other silicates, phosphonates and polycarboxylates. Reference is also made to the publications FJ Dany et al. "Crystalline layered silicate - a new builder", soap-oil-fat waxes 20/1990, 805 to 808, and K.-H. Bergk et al. "Manufacture and use of Magaditt as a phosphate substitute in detergents", soap-oil-fat waxes 15/1987, 555 to 561, and the literature cited therein.

DE-A 26 56 009 describes textile detergents containing 12 to 25% by weight zeolite, in particular of type 4A, 5 to 20 wt .-% of a sodium silicate, and a Contain peroxy bleach. According to the information in this reference unwanted deposits of water-insoluble zeolite particles on the laundry thereby preventing 0.3 to 3% by weight of a polymer from the group Carboxymethyl cellulose, lower alkyl cellulose, hydroxy-lower alkyl cellulose, Polyvinyl alcohol, polyvinyl acetate and / or polyvinyl pyrrolidone can be used.

Other builder components

The detergent should contain one or more detergent builders. From the The area of ion exchangers here is preferably synthetic sodium To mention aluminum silicates of the zeolite A type. Zeolite NaX is also suitable or zeolite P or layered silicate SKS6 or other SKS types from Hoechst and mixtures of the compounds mentioned. This detergent inventory part is in the recipe with 5 to 60% by weight, preferably with 10 to 40% by weight represented.

The polycarboxylates to be used according to the invention are in the range of 0.1 to 20% by weight, advantageously at least 0.5% by weight, preferably to at least 1% by weight, but in particular in the range from 2 to 10% by weight used.

Other inorganic builders such as Na or K carbonate or silicates (in kri stalliner and amorphous form) can complement or complete the builder system  standing. Both types of substance can each range between 0 to 30 wt .-%, but preferably between 3 to 15 wt .-% are used.

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

Phosphates can be used in a range from 0 to 5%.

Surfactants impart the desired cleaning via wetting and rewetting effect and ensure by oriented adsorption on pigment dirt and by solubilizing soluble contaminants the dirt-carrying capacity, which is further characterized by other ingredients. Surfactant is preferred combinations, as mixtures of different surfactants syner show gistic effect, d. H. one compared to the addition of the individual effects increased performance. Very powerful synergistic combination of surfactants ions are obtained from linear alkylbenzenesulfonates and fatty alcohol polyglycol ether. For low washing temperatures (30 to 60 ° C) foam control Long-chain soaps are replaced by tailor-made silicone oils.

Some of the alkylbenzenesulfonates can be replaced by alkylsulfates which also show more favorable anaerobic degradation behavior. With the fatty alcohol poly Glycol ethers are alternatives to the hydrophobic part of the molecule, either based on renewable raw materials (fatty alcohols in the narrower sense) or petro is chemically accessible (oxo or Ziegler alcohols). The new surfactant class of Alkyl polyglycosides, representatives of Nonionics "without ethylene oxide", which are made from finally based on the renewable raw materials fatty alcohols (fats and oils) and starch or sugar are currently available, especially for liquid detergent used. With fatty alcohol polyglycol ethers, the trend is towards lower ethoxylated products, which wash out fat ver Improve dirt especially at low temperatures.

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 are used  as well as non-ionic surfactants. The percentage of anionic surfactants should amount to at least 5% by weight and is preferably in the range between 5 and 10 % By weight. Organic anionic detergents are particularly useful Sulfates and sulfonates have a practical meaning. The sulfonates include for example alkylbenzenesulfonates, 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 To name tallow fatty alcohols. Nonionic surfactants include e.g. B. Polyethylene oxide condensation products of primary and secondary aliphatic alcohols, alkylphenols or alkylpolyglycosides in the range between 0 to 20% by weight, preferably between 0 to 10% by weight.

As bleaching systems, products for oxidative use are used in particular in detergents Removal of colored contaminants used. The general trend in wash lower temperature, as well as the increase in the proportion of compared Cotton or linen blend fabrics that are more sensitive to temperature make it Use of bleach activators is necessary, as sodium perborate only above 60 to 70 ° C is effective.

The activated bleaching at or below 60 ° C is based - when using N-acetylver bonds as bleach activators - on the formation of the peracetic acid anion in the wash liquor, which has a higher oxidation potential than that due to hydrolysis Perhydroxate anion released from perborate.

The acetyl group can be transferred to the perhydroxide anion N, N, N ', N'-tetraacetylethylenediamine (TAED) and 1,5-diacetyl-2,4-dioxo hexahydro-1,3,5-triazine (DADHT). DADHT is at low wash temperatures somewhat more powerful than TAED and also has the advantage that the difference For the TAED, all acetyl groups available in the molecule are used in the bleach (only two out of four in the TAED).

The peracetic acid anion is more resistant to hydrophilic, bleachable stains most effective. Long-chain diperoxycarboxylic acids are also particularly important lower temperatures effectively such. B. Dodecane-1,2-dipersoic acid. A stake of alkanoyloxy-benzenesulfonates (AOBS) with alkyl chain lengths of C₈-C₁₀ as well as nanonoyloxy-benzenesulfonate (NOBS) advantageous. In the in the  Wash liquor formed from NOBS and perborate nonan-1-peracid anion (p-hydroxybenzenesulfonate as a leaving group) hydrophilicity and Lipophilia is such a good balance that the bleaching power despite the compared to the TAED system lower active oxygen levels in the fleet overall is equally good. NOBS is also nitrogen-free.

In the case of bleaches which supply H₂O₂ in water, sodium in particular perborate tetrahydrate or monohydrate or coated percarbonates a practical Meaning. They are preferably in the range between 0 to 30% by weight used between 10 to 25 wt .-%.

Organic N-acyl or O-acyl compounds such as e.g. B. TAED of practical importance. You will be in Range between 0 to 10 wt .-%, preferably from 2 to 8 wt .-% used.

In compact detergents in particular, sodium perborate tetrahydrate is Monohydrate replaced. For ecological reasons (reduction of boron pollution in the Water) the perborate can be substituted by percarbonate.

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 due to the lack of biodegradability from the formulations. 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. A stabilizer is not necessary for the polycarboxylates used here, since the Cu ²⁺ ions are bound sufficiently well by the polycarboxylate.

Enzymes that are suitable for certain types of dirt are specific, for example proteases, amylases, Cellulases or lipases. Combinations of enzymes with are preferred different effects used. Their application range is between 0 to 3% by weight, preferably in the range between 0.3 to 1% by weight.  

Preferred enzymes are pancreatin (trypsin), proteases, amylases, cellulases and lipases.

Proteases build - mostly high molecular weight - protein contaminations such as blood and Egg stains, which cannot be removed from the fiber by surfactants alone. The α-amylases mostly used together with proteases serve both Breakdown of the starchy dirt as well as the splitting of the starch itself and their degradation products, the dextrins, mediate adhesive-like bonding between fiber and particle dirt.

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 the enhancement of Washing power. Above all, they can help increase the use of surfactants to be kept within limits at low washing temperatures.

Detergents can be used as optical brighteners, especially derivatives of the following Compounds contain: stilbene, biphenylstilbene, diphenylpyrazoline, coumarin or combinations of benzoxazole or benzamidozole. You will be in the area from 0 to 5% by weight, preferably in the range from 0.1 to 0.3%.

Optical brighteners, also (fluorescence) whiteners (fluorescent whitening agents, FWA), cause not only a possible yellow tinge to itself white tissue, as it can appear after repeated use and cleaning, back to "added" to white, but overall a more intense one "Brighter" white is achieved.

The detergents can additionally contain graying inhibitors which Suspend dirt detached from the fiber in the wash liquor. As an an example methyl or carboxymethyl celluloses should be mentioned here. Your share in Detergent can be 0 to 5% by weight, in particular 0.5 to 1.5% by weight.

To prevent color transfer from one fabric to another especially special polyvinyl pyrrolidones and homopolymers of vinyl imidazole used.  

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

More silicate, e.g. B. water glass, acts as a corrosion inhibitor, or z. B. Magnesium silicate (like phosphonate) acts as a stabilizer. Amorphous and crystalline Disilicate can also be used as a cobuilder and in special detergents Find main builders.

Hydroxycarboxylic acids can be used as cobuilders in addition to polymer and zeolite A are used, in particular as a carrier for Ca ions. Are preferred Citric acid and its Na salts, tartaric acid, malic acid, particularly preferred Citric acid.

Graying inhibitors suspend the detached dirt in the wash liquor. Carboxymethyl cellulose (CMC) and methyl cellulose are preferred.

Phosphates can be the main builders alongside Zeolite A in p-reduced form stations are used or in smaller quantities than phosphate Carrier cobuilder function in the detergent.

Foam inhibitors are generally used in amounts of 0 to 8% by weight. used. Soaps, silicone oils or hydrophobic are common Silicas. In the case of non-surfactant defoamers, because of the comparison for soaps with stronger action, generally amounts of 0 to 3.5% by weight. Prefers Baysilone is used.

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

Furthermore, other components can be combined in the detergent Settlements may be included, such as B. dyes, perfume oils or plasticizers.

The invention also relates to a method for producing the invention Detergent compositions in which the individual powdered compo components by mixing and the liquid components by spraying on are mixed homogeneously. Alternatively, water and heat can sensitive components are first processed into a slurry with water and  then spray dried; the remaining components are - like listed above - mixed.

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

The liquid detergents are made by mixing with an appropriate amount of Solubilizer or prepared in water and optionally concentrated.

All individual components of the composition can be as pure substance or as Mixture of corresponding components are present. As calcium-binding silicate water-insoluble substances, in particular zeolites, are preferred Commitment.

The invention is illustrated below with the aid of examples executed and applies to detergents, fine, color, liquid and especially for Compact detergent.  

Description of the detergent formulations

The use of polycarbonylate is of particular practical importance (Polyamino acid) based on maleic acid / NH₃ in detergents, since they are the after reduce parts of the known detergents significantly. This invention Detergents also contain conventional substances, which are detailed below To be described in more detail: surfactants (see above), builders (see above), and bleaching agents (see above), bleach activators (see above), enzymes, optical brighteners (see above), Graying inhibitors (see above), defoamers (see above) and others.

The washing and / or cleaning agents according to the invention are preferably in the form of free-flowing, powdery or granular preparations, which are conventional in themselves Way, for example by mixing, granulating and / or by spray drying can be produced with subsequent compression if necessary. in the the known details of the associated printed documents apply here State of the art. At least partially, these funds or individual comm components or sub-combinations of several elements in a conventional manner can be obtained by spray drying in the dry form, which then with in particular temperature-sensitive components are mixed.

A particular embodiment of the agent according to the invention comprises Detergent with bulk densities of at least 650 g / l, preferably of 700 g / l to 1200 g / l and in particular 800 g / l to 1000 g / l. With these it can by granulation processes, for example by wet granulation and subsequent drying, in particular fluidized bed drying agents act. Of course, pressed washing-active preparations, produced by, for example, compacting or pelleting, the invention according to the co-builder.

In this context, preference is given to using the method of international patent application WO 91/2047 manufactured product. It acts by extrusion of a homogeneous premix, which can optionally be carried out with the addition of a plasticizer Hole shapes, which preferably have an opening width of 0.5 mm to 5 mm , then crushing the extrudate by means of a cutter direction and subsequent treatment in a rounding machine  Detergent or intermediate detergent, which is also mixed with other Detergent ingredients can be used.

The same also applies to super compact detergents made from mixtures of zeolites and layered silicates (e.g. zeolite A or P and SKS6 (Hoechst)).

A preferred embodiment of a solid granular universal detergent according to the invention with a bulk density in the range from 700 g / l to 1200 g / l, in particular from 800 g / l to 1000 g / l
15% to 25% anionic surfactant
1% to 15% by weight of nonionic surfactant,
15% by weight to 40% by weight of alkali alumosilicate, in particular zeolite NaA,
2% by weight to 15% by weight of cobuilder according to the invention,
10% by weight to 30% by weight of bleach,
2% by weight to 10% by weight of bleach activator,
up to 10% by weight, preferably 1% by weight to 5% by weight alkali silicate,
up to 15% by weight, preferably 3% by weight to 12% by weight alkali carbonate,
0.1% by weight to 10% by weight of at least one substance from the group of foam inhibitors, enzymes, graying inhibitors, optical brighteners, dyes, adjusting agents, fillers, and
1 to 20% by weight of water.

A further preferred embodiment of the agents according to the invention relates to mild detergents and colored detergents with a bulk density in the range from 700 g / l to 1200 g / l, in particular from 800 g / l to 1000 g / l, based on the following composition:
5% by weight to 15% by weight, in particular 6% by weight to 13% by weight, of anionic surfactant, in particular from the group of the fatty alcohol sulfates,
10% by weight to 22% by weight, in particular 12% by weight to 20% by weight, of nonionic surfactant, in particular from the group of the alkyl polyethylene glycol ether,
20% by weight to 45% by weight, in particular 25% by weight to 30% by weight of alkali aluminum silicate, in particular zeolite NaA,
5% by weight to 20% by weight of cobuilder according to the invention,
2% by weight to 10% by weight, in particular 4% by weight to 8% by weight of alkali carbonate,
up to 10% by weight, in particular 1% by weight to 5% by weight, alkali silicate,
0.1 to 2.5% by weight foam inhibitor,
0.5% by weight to 5% by weight of color transfer inhibitor, in particular polyvinyl pyrrolidone,
0.1% by weight to 3% by weight of one or more substances from the group of textile softeners, graying inhibitors, dyes and fragrances, and
5% to 20% water by weight.

Carrying out washing tests

The effect of co-builders in a standard compact detergent at 95 ° C without prewash was tested. The following products were used and tested against each other:
Product A: basic compact detergent and co-builder, according to the invention (see Table 1, supplemented with 5% polyaspartic acid Na salt)
Product B: Basic compact detergent without co-builder (see Table 1).

The washing tests were tested with the following water hardness:
14 ° d (2.5 mmol / l).

The co-builder was dosed uniformly at 5% of the total amount of detergent taking into account the active ingredient content of the products.

The fabric types *) listed below are available and described by Detergent Research Institute Krefeld (WFK).

The following criteria for the washing effectiveness of these products should be recorded will:

• - Primary washing effect on test fabrics with different stains
• - Graying after 25 wash cycles on white test fabrics
• - Color graying (redeposition) after 25 washes on CO 11 A *
• - Inorganic and organic incrustation after 25 washing cycles CO 11 A *
• - Damage factor after 25 washes on CO 11 A * (standard cotton according to DIN 53 919, IEC 2267).

The basic formulation of the compact detergent consists of the following compos nenten:  

Table 1

Basic detergent without a co-builder

The liquid components (anionic surfactants and nonionic surfactants) become one Prepared stock solution. The powdered ingredients are for everyone Weighing attempt weighed. The basic detergent is reduced by 5% per wash of the various co-builders added. The total amount of detergent (basic detergent medium and co-builder) is 21 g / kg dry wash per wash.

The washing trials were carried out in four Miele Novo household washing machines tronic W 918 made to avoid accumulating machines specific differences were used alternately (= cyclically interchanged). It was 95 ° C in the cook-wash program without pre-washing on a machine load of 4.5 kg of normally soiled household laundry. The Washing tests were carried out at a water hardness of 2.5 mmol / l (14 ° d).  

The washing effect was determined with the addition of by average soiled household laundry with washed test fabrics. As Test fabrics were used:

- Wash cycle control strips fabric 53 919 G according to DIN 53 919-T2 (Art.no.11A)

After 25 washes, the graying (including color graying), the Damage factor that measured inorganic and organic incrementation.

The following are also used as test fabrics for the graying measurement:

- wfk-CO terry cloth (item no.12 A)
- wfk-PES / CO fabric (item no.20 A).

These types of fabric were washed 25 times and then over Remission measurements evaluated in accordance with DIN 44 983-T21.

The bleaching effect is based on the bleaching intensity BI on the bleaching test fabric after 25 washes determined according to item 4.2 of DIN 44 983-T21.

- wfk bleaching test fabric (Art.No. 10 E).

They were calculated using the following formula:

a = reflectance value of the undyed, white starting tissue
b = mean value from 4 measurements of the unwashed wfk bleach test fabric
c = mean value from 4 measurements of the wfk bleaching test fabric washed 25 times.

The tissue ash, the information about deposits on the tissue during the Washing there is, on standard cotton fabrics according to DIN 53 919-T01 after 25 Washing cycles according to DIN 44 983 E-T21 (= inorganic incrustation)  determined. In addition, the organic incrustation by extraction with Determined methanol.

The damage factor s is a measure of the chemical fiber degradation of the cotton during washing. It is determined on the wash cycle control strip using DIN 44 983-T 21, section 4.5 and DIN 54 270-T 03 (EWNN _{mod. (NaCl)} method).

In addition, 4 carrier fabrics 40 _* 50 cm² made of PES / CO were added to each washing process, onto which the following fabric test pieces of 10 _* 10 cm² were sewn to assess the dirt removal:

- wfk-CO pigment / skin fat acc. to Bey (item no. 10 C)
- wfk-PES / CO pigment / skin fat acc. to Bey (item no.20 C)
- CFT-CO pigment / oil (item no.AS-8)
- wfk-CO-cocoa (Art.No. 10-F)
- CFT-CO tea (art.no.BC-1)
- CFT-CO blood (art.no.CS-1)
- CFT-CO pigment / oil / milk (item no.AS-10)

The dirt-proof fabric samples were washed once, dried and opened of the left side not to be measured carefully ironed smooth. The The cleaning effect was based on DIN 44 983-T21 point 4.1 Measurement of the reflectance on the washed dirty tissues determined. From the The total measured individual remission values was the mean value for each tissue type and the corresponding confidence interval for 95% statistical certainty calculated.  

4. Results of the investigation 4.1 Results with a water hardness of 2.5 mmol / l (14 ° d)

The results of the washing effect at 2.5 mmol / l (14 ° d) water hardness are in the Tables 1 and 2 are shown.

Table 1

Primary washing results (remission values)

Table 2

Secondary wash results

The good effect of the co-builders mentioned is therefore surprising since one synergistic effect of Na₂SO₄ and co-builders is detectable, which in those detergent formulations described in the prior art to bear comes, but here according to the invention is not present, since no Na₂SO₄ used becomes.

Synergistic effect of polycarboxylate of the formula (I) and Na₂SO₄:
Modified test according to BASF (see Sokalan brochure, BASF specialty chemicals)

Test description Regulation for determining the calcium carbonate dispersing capacity (CCDK) execution

It is particularly important for all measurements that all with the measuring solution in Parts coming into contact are as free as possible from crystallization nuclei. This can be done by rinsing the affected parts thoroughly with dilute hydrochloric acid and then rinse with distilled water.

To determine the CCDK, 1.5 g of the substance to be investigated are in Dissolved 90 ml of distilled water and with hydrochloric acid or sodium hydroxide solution neutralized. The solution is thermostatted to 25.0 ° C and with 10.00 ml a sodium carbonate solution, w (Na₂CO₃) = 0.10. By adding 1N Hydrochloric acid or 1N sodium hydroxide solution, the pH of the solution is adjusted to 1 liter. During the titration, the pH is measured using pH stat. kept constant.

With an addition rate of 0.5 ml / min the measuring solution becomes 0.1 molar Calcium acetate standard solution added. The extent of the turbidity that arises as a loss of light transmission using an optical fiber photometer at λ = 650 nm measured and recorded with an X / t recorder whose paper feed Should be 2 cm / min. The measurement of the titration is from 100% Transmission carried out up to approx. 30%.

The end point of the titration is linearized through the intersection of the Extension of the course before and after the onset of turbidity shown. The volume of calcium consumed is determined acetate solution to the end point.

The CCDK is the calculated mass of that which has arisen up to the end point Calcium carbonates per gram of co-builder used.  

Sodium sulfate effect on CCDK

Objective: To determine the influence of sodium sulfate on the CCDK value
Use: 1.5 g each of polycarbonylate (polyamino acid) according to formula (I)
0.94 molar sodium sulfate solution

Claims (12)

1. Detergent composition containing in percent by weight: 5 to 40 at least one surface-active compound
5 to 50 at least one Ca-binding silicate or zeolite
1 to 20 at least one polycarboxylic acid or a salt thereof, characterized in that the polycarboxylic acid is a polyamino acid or an anhydride thereof and that the detergent composition contains no substantial amounts of inorganic sulfate. 2. Detergent composition according to claim 1, characterized in that that the polycarboxylic acid is a polyaspartic acid or a salt thereof. 3. Detergent composition according to at least one of the above going claims, characterized in that the polycarboxylic acid as Alkali salt is included. 4. Detergent composition according to at least one of the preceding claims, characterized in that the polycarboxylic acid has at least one of the following recurring structural units where R = H or a cation
n, m = 0 or a number from 1 to 300
o, p, q = 0 or a number from 1 to 10
r = 0 or a number from 1 to 5
s = 0 or a number from 1 to 10
n + m + o + p + q 300. 5. Detergent composition according to at least one of the above claims that they contain less than 5 wt .-% inorganic sulfate contains. 6. Detergent according to at least one of the preceding claims, that it contains less than 3% by weight of inorganic sulfate. 6a. Detergent according to at least one of the preceding claims, that it contains less than 1% by weight of inorganic sulfate. 7. Detergent composition according to at least one of the above outgoing claims, characterized in that they additionally 1 to Contains 12 wt .-% citric acid or a salt thereof. 8. Detergent composition according to at least one of the above going claims, characterized in that they as a solid formu lation exists. 9. Detergent composition according to at least one of the above outgoing claims, characterized in that the molecular weight Mw is between 500 and 20,000.   10. Detergent composition according to claim 4, characterized in that the repeating units A1, B1, I, A2 and B2 are present in the following distribution (% by weight): A1 from 10 to 40%
B1 from 40 to 90%
I from 0 to 5%
A2 from 0 to 5%
B2 from 0 to 5%. 11. Process for washing textiles with a detergent, thereby characterized in that a detergent according to at least one of the preceding claims is used.