DE19509973A1 - Powdery for granular detergents or cleaning agents - Google Patents

Abstract

The purpose is to prepare heavy washing or cleaning agents, especially those containing tensides, which, when dissolved in water, exhibit no gel formation or a very small and therefore negligible tendency thereto. The aim is achieved in that at least two different types of tensides are used where all of them are in raw material form or are in a single compound, or at least one tenside is in raw material form and at least one is in a compound and, where there are more than two tensides, at least one is in raw form and at least one is in at least one compound, or even where there are more than two different tensides, they are contained in at least two different tenside compounds, whereby for the entire tenside-containing washing or cleaning agent and each tenside-containing compound in a salt solution containing 50 wt.% of the washing or cleaning agent or the compound, 2.1 wt.% sodium carbonate and 47.9 wt.% water, at 25 DEG the flow limit is lower than 10 Pa and the gel disintegration limit is lower than 5 % strain.

Description

The invention particularly relates to heavy powdery to granular Detergents or cleaning agents with a bulk density of at least 500 g / l by no or a significantly reduced tendency to training mark gels when dissolved in water. The same applies to Invention a method for producing such washing or cleaning medium.

The increasing increase in the bulk density of commercial detergent granules is mainly due to an increasingly compact grain structure of the Granules reached, whereby the porosity of the granules up to one almost complete removal of the connected pore system decreases. However, with the decrease in porosity, there is generally an Desired detachment linked to detergent deposits granules on textiles.

This undesirable release delay is also caused by the fact that many surfactants, especially non-ionic surfactants, or surfactant mixtures tend to form gel phases. Dispersions are used under gels stood, which in addition to a reduction in viscosity due to shear a reduction and build-up of binding forces depending on the shear time between molecules or particles. Only when the gel phase is destroyed is, for example, by a longer shear, the bin forces are broken, the viscosity decreases again and the Mi Schung reaches a flowable state again.

With the help of dynamic rheology, the gel break limit can be set directly determine. In the oscillation test shows the length of the linear viskoelasti range (in% strain), from what mechanical stress (strain) the gel breaks.  

As gelling inhibitors or structure breakers are a number both solid as well as liquid substances that are hydrophilic, water soluble or in Water dispersible are known. Some of them, for example mentioned in the international patent application WO-A-93/02176. To this include, for example, lower polyalkylene glycols, which differ from straight derived or branched glycols with 2 to 6 carbon atoms, preferably polyethylene glycol or polypropylene glycol, and a relative Have molecular weights between 200 and 12,000, in particular up to 2000. Wei Other gelling inhibitors and structure breakers are the sulfates and ins especially the disulfates of lower polyalkylene glycol ethers and in particular those of polyethylene glycol and 1,2-polypropylene glycol with a right latent molecular mass between 600 and 6000. The disulfates originate in the rule of polyglycol ethers as they - caused by low water traces - arise in the alkoxylation of alcoholic components can, from.

Another group of known gelation preventers consists of the water-soluble salts of mono- and / or disulfosuccinates of the lower Polyalkylene glycol ether. The are of particular importance corresponding polyethylene glycol ether and polypropylene glycol ether compound in particular a molecular weight between 600 and 6000 exhibit.

The anionically modified polyalkylene glycol ethers can be supplied in the form biger salts, especially as sodium and potassium salts.

Furthermore, the adducts can also be from about 20 to about 80 moles Alkylene oxide, especially ethylene oxide, to 1 mole of an aliphatic alcohol hols with essentially 8 to 20 carbon atoms as a gel formation prevention serve or structure breakers and thus to better release speeds heavy detergents or cleaning agents. Are particularly important here the addition products of 20 to 60 moles of ethylene oxide to primary Alcohols, such as coconut oil alcohol or tallow oil alcohol Oleyl alcohols, on oxo alcohols, or on secondary alcohols with 8 to 18 Carbon atoms. Selected examples of this are tallow fatty alcohol with 30 EO or 40 EO.  

Another known group of gelation preventers consists of alkylene glycol monoalkyl ethers of the general formula RO (CH₂CH₂) _n H, in which R is a radical having 2 to 8 carbon atoms and n is a number from 1 to 8. Examples of this group are ethylene glycol monoethyl ether and diethylene glycol monobutyl ether.

In addition, one class of nonionic surfactants, the alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, such as those used in the japani The patent application JP 58/217598 are described or the preferred according to that described in international patent application WO-A-90/13533 NEN processes are known that they are not or only in ge ring circumference tend to gel.

However, the effect of these gelation preventers is not with all ten surfactants and surfactant mixtures as well as all heavy washing or cleaning average sufficient.

The object of the invention was therefore heavy washing or Rei cleaning agents, in particular those which contain surfactant mixtures, To be provided in the dissolution in water no or only a very have low and therefore negligible tendency to gel. A another task was to provide a general process after the heavy detergent or cleaning agent, which is especially surfactant contain mixtures can be obtained, which in the dissolution in the wash liquor has little or no tendency to gel, especially for the formation of low-viscosity gels with a relatively weak bin forces, and therefore an improved release speed in the fleet exhibit.

It has now been found that the viscosity of highly concentrated aqueous Surfactant phases is not critical to the dissolution rate of washing or detergents. Rather, the dissolving speed of compact tated detergents can be improved in that the surfactants in derar tiger form are used that this form or forms in highly concentrated  trated aqueous phase both a low modulus of elasticity and have a low gel breaking limit, so that the yield point as Product of these two factors is relatively low.

The invention accordingly relates to a first embodiment form a powdery to granular detergent or cleaning agent, ins especially with bulk densities of at least 500 g / l, containing anionic and / or nonionic surfactants and other usual ingredients of Washing or cleaning agents, the washing or cleaning agent min contains at least 2 different types of surfactants, of which

• - all are available as raw materials or in a single compound or
• - At least one surfactant as a raw material and at least one surfactant in one compound, at least with more than two different surfactants a surfactant as a raw material and at least one surfactant in at least a compound is present or
• - Even if there are more than two surfactants in at least two un different surfactant compounds are contained,

with the proviso that for the entire surfactant-containing washing or cleaning medium and any surfactant-containing compound in a saline solution containing 50 % By weight of the washing or cleaning agent or of the compound, 2.1% by weight Sodium carbonate and 47.9 wt .-% water, at 25 ° C apply that the flow limit less than 10 Pa and the gel break limit less than 5 each % strain is.

Within the scope of this invention, granular agents also include those understood, for example by roller compaction or extrusion were obtained so that the definition "powdery to granular" all includes solid agents, which by spray drying, granulation, ver various known types of compaction and mixing of the raw materials or individual compounds produced by these methods can be obtained.

In a preferred embodiment of the invention the yield point is even less than 5 Pa each and / or the gel break limit in each case less than 2% strain.  

The invention opens up the possibility of also using such surfactants which normally can form gels under certain conditions gene, but now due to the specific A according to the invention batches of these surfactants the formation of gels in the dissolution of the Medium in water is largely suppressed.

All known anionic surfactants, nonionic surfactants, can be used as surfactants cationic surfactants, amphoteric surfactants and zwitterionic surfactants are also used are provided that their form of use and thus also the entire detergent or cleaning agent the above-mentioned physicochemical Obey conditions. In particular, however, anionic and / or nonionic surfactants used in the agents according to the invention.

Anionic surfactants are, for example, those of the sulfonate type and sulfates used.

As surfactants of the sulfonate type are preferably C₉-C₁₃-alkylbenzenesul fonates, olefin sulfonates, d. H. Mixtures of alkene and hydroxyalkane sulfones ten and disulfonates, such as those obtained from C₁₂-C₁₈ monoolefi with an internal or internal double bond by sulfonation with gas shaped sulfur trioxide and subsequent alkaline or acid hydrolysis who receives sulfonation products. Alkane is also suitable sulfonates made from C₁₂-C₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization be. The esters of α-sulfofatty acids (ester sul fonate), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm nuclear or tallow fatty acids, as well as their salts, which, for example can be obtained by saponification of the ester group.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Un The fatty acid glycerol esters are the mono-, di- and triesters and their To understand mixtures as they are produced by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of Triglycerides with 0.3 to 2 moles of glycerin can be obtained. Preferred sul The fatty acid glycerol esters are the sulfonation products of saturated ten fatty acids with 6 to 22 carbon atoms, for example the Capron  acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid re, stearic acid or behenic acid. If you start with fats and oils, then natural mixtures of different fatty acid glycerol esters it is necessary to get the feeds in themselves prior to sulfation ter saturate largely with hydrogen, d. H. on iodine numbers less than 5, advantageously less than 2 to harden. Typical examples ge Suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, Rape oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, Lard oil or lard. Because of their high natural content saturated fatty acids, however, have proven to be particularly advantageous from coconut oil, palm kernel oil or beef tallow. The sulfation the saturated fatty acids with 6 to 22 carbon atoms or the Mi Formations from fatty acid glycerol esters with iodine numbers less than 5, the fat contain acids with 6 to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent new Tralisierung with aqueous bases, as in the international patent message WO-A-91/09009 is specified.

The sulfonation products are a complex mixture, the mono-, di- and Triglyceride sulfonates with α and / or internal sulfonic acid grouping contains. Sulfonated fatty acids are formed as by-products salts, glyceride sulfates, glycerine sulfates, glycerin and soaps. If you go with the sulfonation of saturated fatty acids or hardened fatty acid glyce pure ester mixtures, the proportion of α-sulfonated fatty acid Depending on how the process is carried out, salts may be up to about 60% by weight.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from pri hard alcohols of natural and synthetic origin. As alk (en) yl sulfates become the alkali and especially the sodium salts of sweat rock acid half esters of C₁₂-C₁₈ fatty alcohols, for example from coconut fat alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C₁₀-C₂₀ oxo alcohols and those half esters of secondary alcohols this chain length preferred. Alk (en) yl sulfates are also preferred the chain length mentioned, which is a synthetic, on petrochemical Based straight-chain alkyl radical containing an analog Have the same degradation behavior as the adequate compounds based on  oleochemical raw materials. For washing technology interest are C₁₆-C₁₈- Alk (en) yl sulfates are particularly preferred. It can also be special Advantage and especially advantageous for machine detergents, C₁₆-C₁₈-alk (en) yl sulfates in combination with lower melting anion surfactants and especially with such anionic surfactants that have a lower Have power point and at relatively low washing temperatures of for example room temperature to 40 ° C a low crystallization Show enough to use. In a preferred embodiment of the inven The agents therefore contain mixtures of short-chain and long-chain gene fatty alkyl sulfates, preferably mixtures of C₁₂-C₁₄ fatty alkyl sulfa ten or C₁₂-C₁₈ fatty alkyl sulfates with C₁₆-C₁₈ fatty alkyl sulfates and ins special C₁₂-C₁₆ fatty alkyl sulfates with C₁₆-C₁₈ fatty alkyl sulfates. In another preferred embodiment of the invention, however not only saturated alkyl sulfates, but also unsaturated alkenyl sulfa te used with an alkenyl chain length of preferably C₁₆ to C₂₂. Mixtures of saturated, mainly from C₁₆ existing sulfated fatty alcohols and unsaturated, mostly from C₁₈ existing sulfated fatty alcohols preferred, for example those that differ from solid or liquid fatty alcohol mixtures of the type HD Derive Ocenol® (commercial product of the applicant). Here are weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and particularly preferred from about 5: 1 to 1: 1.

Also 2,3-alkyl sulfates, which, for example, according to the US patents 3,234,258 or 5,075,041 are manufactured and sold as commercial products Shell Oil Company under the name DAN® can be obtained suitable anionic surfactants.

Also the sulfuric acid monoesters of ethoxy with 1 to 6 moles of ethylene oxide straight-chain or branched C₇-C₂₁ alcohols such as 2-methyl-ver branched C₉-C₁₁ alcohols with an average of 3.5 moles of ethylene oxide (EO) or C₁₂-C₁₈ fatty alcohols with 1 to 4 EO are suitable. You will be in wash due to their high foaming behavior only in relatively small quantities gene, for example in amounts of 1 to 5 wt .-%, used.  

Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, also known as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with Al alcohols, preferably fatty alcohols and especially ethoxylated fat represent alcohols. Preferred sulfosuccinates contain C₈- to C₁₈- Fatty alcohol residues or mixtures thereof. In particular, Sul preferred fosuccinates contain a fatty alcohol residue that differs from ethoxylated Derives fatty alcohols, which in themselves are non-ionic surfactants (see description below). Here again are sulfosuccinates, whose fatty alcohol residues are narrowed down from ethoxylated fatty alcohols derive ter homolog distribution, particularly preferred. It is the same possible, alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms men in the alk (en) yl chain or their salts. In addition to the or instead of the sulfosuccinates, isothionates, taurides or Sarcoside can be used.

Soaps, in particular, are particularly suitable as further anionic surfactants Quantities from 0.1 to 10 wt .-%, in particular from 0.2 to 5 wt .-%, each based on the finished funds. Saturated ones are suitable Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitin acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular dere from natural fatty acids, e.g. B. coconut, palm kernel or tallow fatty acid derived soap mixtures, as well as unsaturated fatty acid soaps, ins special salts of oleic acid or linoleic acid. But in particular preference is also given to those soap mixtures which are sown to 50 to 100% by weight Tigt C₁₂-C₂₄ fatty acid soaps and 0 to 50 wt .-% of oleic acid soap are composed.

The anionic surfactants can be in the form of their sodium, potassium or ammo nium salts and as soluble salts of organic bases, such as mono-, di- or Triethanolamine. The anionic surfactants are preferably in Form of their sodium or potassium salts, especially in the form of sodium salt before.  

Preferred nonionic surfactants are alkoxylated, advantageous generally ethoxylated, especially primary alcohols with preferably 8 up to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole Alcohol used in which the alcohol residue is linear or preferably in 2- Position can be methyl branched or linear and methyl branched radicals can be contained in the mixture, as is usually the case in oxo alcohol residues available. In particular, however, are alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, e.g. B. from coconut, Palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per Mole of alcohol preferred. Preferred ethoxylated alcohols include for example C₁₂-C₁₄ alcohols with 3 EO or 4 EO, C₉-C₁₁ alcohols with 7 EO, C₁₃-C₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C₁₂-C₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C₁₂- C₁₄ alcohol with 3 EO and C₁₂-C₁₈ alcohol with 5 EO. The specified ethoxy The degrees of lation represent statistical averages that are required for a special Product can be an integer or a fractional number. Preferred alcohol holethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition to these usual polyalkylene glycol ethers, polyalky can also be used lenglycolamines, for example coconut amines with about 2 to 10 EO, polyol ethers, for example glycerol with about 3 to 10 EO, and / or polyolamines, for example, triethanolamines with about 3 to 10 EO can be used.

In addition, other carbohydrate surfactants, in particular alkyl glycosides of the general formula RO (G) _x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, can be used as further nonionic surfactants C atoms and G is the symbol which stands for a glycose unit with 5 or 6 C atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferred non-ionic surfactants that either as the sole nonionic surfactant or in combination with their nonionic surfactants, especially together with alkoxylated Fatty alcohols and / or alkyl glycosides are used are alkoxy lated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the Alkyl chain, especially fatty acid methyl esters, as described, for example, in Japanese Patent Application JP 58/217598 are described or the preferably according to that in international patent application WO-A-90/13533 described methods are produced.

Equally, however, polyalkylene glycol esters, for example Fatty acid polyethylene glycol esters, preferably coconut fatty acids with about 2 to 12 EO, polyalkylene glycol amides, for example coconut fatty acid mono ethanolamide with about 2 to 12 EO, or polyol esters, for example coconut fatty acid monoglyceride with about 2 to 12 EO, can be used.

Also nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may be suitable. The amount of this is not Ionic surfactants is preferably no more than that of the ethoxylators ten fatty alcohols, especially not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

in the R²CO for an aliphatic acyl radical with 6 to 22 carbon atoms men, R³ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 Carbon atoms and [Z] for a linear or branched polyhydro xyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands. The polyhydroxy fatty acid amides are known Substances commonly used by reductive amination of a reducing  Sugar with ammonia, an alkylamine or an alkanolamine and subsequently acylation with a fatty acid, a fatty acid alkyl ester or a Fatty acid chloride can be obtained.

Also mono-, di- and / or triglycerides, which optionally ethoxylate can be ent and possibly branched and / or unsaturated alkyl radicals can hold, are suitable nonionic surfactants.

In particular, it is preferred that the agents at least as anionic surfactants Alkylbenzenesulfonates and / or alkylsulfates, advantageously alkylsulfa te or contain alkylbenzenesulfonates and alkyl sulfates. In addition to the Anionic surfactants preferably also contain nonionic surfactants such as ethoxylated and / or ethoxylated and propoxylated alcohols, esp special fatty alcohols, but also ethoxylated fatty acid esters, in particular ethoxylated fatty acid methyl esters. Other preferred nonionic ten side are polyethylene glycol fatty acid esters, alkyl polyglycosides, in particular their alkyl polyglucosides, and polyhydroxy fatty acid amides, in particular Glucamide.

The distribution of the surfactants throughout the detergent or cleaning agent is preferably heterogeneous. This means that all used Surfactants, for example, as a raw material in a homogeneous mixture or - if the finished product consists of only one granulate - together Men can be present in this granulate in a homogeneous distribution, as long as the agents meet the above-mentioned physicochemical conditions. It however, it is preferred to incorporate the surfactants in various ways Introduce detergents or cleaning agents. So see preferred execution form the invention that either at least one surfactant as a raw material and at least one surfactant in one compound, with more than two different the existing surfactants at least one surfactant as raw material and min at least one surfactant in at least one compound or at least two ver different surfactant compounds are available. It can be particularly beneficial be if different surfactants are also strictly separated from each other, for example in different compounds or on the one hand in compounds and on the other hand, can be used as a raw material or raw materials. Here is  especially the separation of less gelling surfactants such as ethoxylated Fatty acid esters and gel thickening surfactants such as polyalkylene glycol ethers of particular advantage.

In the context of this invention, compounds include both liquid and solid forms of use, in particular granular forms of use of surfactants understood that in addition to the surfactants and possibly existing Verun cleanings, which can result from the manufacture of the surfactants, too other ingredients, especially common ingredients of washing or cleaning agents in substantial amounts or in which the surfactants through a special process into a granular structure were transferred. The granular compounds can be spray dried, spray granulated, granulated, roller compacted, extruded or after each of the known other processes. Examples of derar term compounds are spray-dried compounds with a content of 5 to 30 % By weight of anionic surfactants, for example alkyl sulfates and / or the alkylbenzenesul fonaten, usually as so-called tower powder in detergent, however can also be used in cleaning agents and in addition to the tensides contain special builder substances and inorganic salts. Another one An example would be a granulated and simultaneously dried surfactant gra nulate, which advantageously very high amounts of surfactants, for example as between 40 and almost 100 wt .-%, based on the corresponding Compound. The latter granules can, for example, after the Teaching of the international patent application WO-A-93/04162 can be obtained. Another preferred embodiment for a compound also provides a so-called carrier grain made of essentially inorganic constituents such as builder substances and inorganic salts, which with tensides and in particular with liquid to wax-like liquids at the processing temperature has been treated with surfactants.

The total surfactant content in the finished washing or cleaning agents is in preferred embodiments 5 to 40 wt .-%, preferably example 10 to 35 wt .-% and in particular 15 to 30 wt .-%.

For the other ingredients of detergents or cleaning agents and In addition to the surfactants mentioned, compounds include, in particular, inorganic  and / or organic builder substances, ingredients that contain the fats Sustainably increase washability, the known and above-mentioned soluble improving the quality, alkaline salts, graying inhibitors (dirt ger), foam inhibitors, bleaches and bleach activators, optical on lighter, enzymes, possibly fabric softening substances, colors and fragrances as well as neutral salts such as sulfates and chlorides in the form of their sodium or Potassium salts.

Zeolites in particular come as inorganic builder substances, but also amorphous and / or crystalline silicates as well as carbonates, possibly in Mi. with silicates.

The fine crystalline, synthetic and bound water used ent Holding zeolite is preferably detergent grade zeolite NaA. Ge however, zeolite X and zeolite P and mixtures of A, X are also suitable and / or P. The zeolite can be used as a spray-dried powder or as undried, stabilized suspensions that are still moist from their manufacture sion are used. In the event that the zeolite as a suspension is set, this small addition of nonionic surfactants as Stabilizers contain, for example 1 to 3 wt .-%, based on Zeo lith, on ethoxylated C₁₂-C₁₈ fatty alcohols with 2 to 5 ethylene oxide groups pen, C₁₂-C₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated ten isotridecanols. Suitable zeolites have an average particle size of less than 10 µm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight bound water.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula (II) NaMSi _x O _{2x + 1} · _y H₂O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number is from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline sheet silicates of the formula (II) are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na₂Si₂O₅ · _y H₂O are preferred.

Suitable substitutes or partial substitutes for the zeolite are also Layered silicates of natural and synthetic origin, as in for example from the patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405 are known. Their usability is not specific zial composition or structural formula limited. Are preferred here however, smectites, especially bentonites.

Amorphous silicates can also be used as inorganic builder substances will. The term "amorphous" is also used in the context of the invention "X-ray amorphous" understood. This means that the silicates at Röntgenbeu experiments do not provide sharp X-ray reflections as they are for kri stalline substances are typical, but at most one or more measures xima of the scattered x-rays that are several degrees wide have units of the diffraction angle. However, it can very well even lead particularly good builder properties when the silicate particles Electron diffraction experiments blurred or even sharp diffraction deliver xima. This is to be interpreted as meaning that the products are microcritical stalline ranges from size 10 to a few hundred nm, where Values up to max. 50 nm and in particular up to max. 20 nm are preferred. Be silicates and silicate compounds according to the older German patent application P 44 00 024.3. Even builder compounds amorphous silicates and alkali carbonates, especially sodium carbonates, are preferred.

The content of the inorganic builder substances in the finished agents can vary widely. In preferred embodiment it is tion forms 20 to 60 wt .-%, based on anhydrous active substance, wherein also mixtures of several inorganic builder substances such as zeolite and crystalline layered disilicates or zeolite and amorphous Silicates or zeolite and soda-silicate compounds or amorphous silicates and crystalline layered disilicates or soda-silicate compounds and crystalline layered disilicates can be used.

Useful organic builder substances are preferred, for example polycarboxylic acids, such as lemons, used in the form of their sodium salts acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids,  Aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such an is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as Ci tronic acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Suitable polymeric polycarboxylates are, for example, the sodium salts polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Ge Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with malein have proven particularly suitable proven acid, the 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% Ma contain linseic acid. Their relative molecular mass, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and especially 50,000 to 100,000.

Terpolymers are also particularly preferred, for example those which according to DE-A-43 00 772 as monomer salts of acrylic acid and malein acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and 2-alkylallylsul contain fonic acid and sugar derivatives.

Other suitable builder systems are oxidation products from carboxylgrup pen-containing polyglucosans and / or their water-soluble salts, such as them for example in international patent application WO-A-93/08251 be written or their production, for example, in the internatio Nale patent application WO-A-93/16110 is described.

Also known are the other preferred builder substances To name polyaspartic acids or their salts and derivatives.

Other suitable builder substances are polyacetals, which are converted tion of dialdehydes with polyol carboxylic acids which have 5 to 7 carbon atoms and have at least 3 hydroxyl groups, for example as in euro European patent application EP-A-0 280 223 can be obtained  nen. Preferred polyacetals are made from dialdehydes such as glyoxal and glutar aldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acid Ren such as gluconic acid and / or glucoheptonic acid obtained.

Organic builder substances are preferably in amounts of 1 to 20 Wt .-%, especially in amounts of 2 to 15 wt .-% in the agents ten.

In a preferred embodiment, Com contains anionic surfactants pounds, which additionally zeolite as builder substance, but none of the usual contain known solubility improvers or structure breakers, either zeolite or anionic surfactants in a substantial excess, at for example in a weight ratio of 2: 1 to 5: 1 or from 1: 2 to 1: 5, but not around 1: 1, the amounts of zeolite always being anhydrous Active substance can be obtained. It is particularly preferred that the Weight ratio of zeolite to anionic surfactants in these compounds more than 2.5: 1 or 1: 2.5 to 1: 4.

However, in another preferred embodiment of the invention Zeolite as a builder as well as known solubility verbs serer or structure breaker used. Here it has been shown that the Weight ratio of zeolite to anionic surfactant in areas of upper half and around 1: 1 can be particularly advantageous. Surprisingly the tendency to gel formation including the zeolite, in particular of the zeolite stabilized with nonionic surfactants, by the addition a non-surfactant solubility improver or structure breaker, preferably modified by polyethylene glycol in such a way that Ge weight ratios of zeolite to anionic surfactant become particularly attractive by 1, while weight ratios below 1: 2 to very high elasticity mo Dulen can lead and are therefore less preferred. Here are weights ratios of 3: 1 to 1: 1 preferred.

However, surfactant solubility improvers or structure breakers such as used ethoxylated and propoxylated fatty alcohols, so Ge Weight ratios of zeolite to anionic surfactant in the range from 3.5: 1 to 1: 3 preferred embodiments.  

In addition, the agents can also contain components which and grease washability from textiles positively. This effect becomes particularly clear when a textile that is already soiled is soiled previously several times with a detergent according to the invention that this oil and contains fat-dissolving component, is washed. Among the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with one type partly in methoxyl groups of 15 to 30 wt .-% and in hydroxypropoxyl group pen of 1 to 15 wt .-%, each based on the nonionic cellulose ether, and the phthalene polymers known from the prior art acid and / or terephthalic acid or their derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates ten or anionic and / or nonionic modified derivatives of this.

In addition to the measures according to the invention for preventing the gel education or to reduce gel formation can of course known solubility improvements already described in detail above rer and structure breaker can be used. Are of interest here especially polyethylene glycol ethers with low molecular weights between 200 and 2000 as well as tallow fatty alcohols with 30 or 40 EO. You can for example in amounts between 0.5 and 10% by weight.

Other suitable ingredients of the agents are water-soluble inorganic cal salts such as bicarbonates, carbonates, amorphous silicates or mixtures from these; in particular alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na₂O: SiO₂ of 1: 1 up to 1: 4.5, preferably from 1: 2 to 1: 3.5. The salary of the Sodium carbonate is preferably up to 20% by weight, advantageously between 5 and 15% by weight. Especially when soda sili Kat compounds are used as builder substances, it is possible that the carbonate content of the agents at higher values between 10 and 20% by weight lies. The silicate content is then correspondingly high between 10 and 40 % By weight.  

According to the teaching of German patent application DE 43 19 578, alkali carbonates also by sulfur-free, 2 to 11 carbon atoms and given if necessary, a further carboxyl and / or amino group ren and / or their salts are replaced. It is within the scope of this invention preferred that a partial to complete exchange of the Alka licarbonate by glycine or glycinate.

Among the serving as bleach, H₂O₂ in water supplying verb have sodium perborate tetrahydrate and sodium perborate mono hydrate special meaning. Other useful bleaches are in for example sodium percarbonate, peroxypyrophosphates, citrate perhydrates so such as H₂O₂ supplying peracidic salts or peracids such as perbenzoates, per oxophthalates, diperazelaic acid or diperdodecanedioic acid. The salary of the Bleaching agent is preferably 5 to 25% by weight and in particular especially 10 to 20 wt .-%, advantageously perborates or percar bonate can be used.

To improve when washing at temperatures of 60 ° C and below To achieve bleaching effects, bleach activators can be incorporated into the preparations be worked. Examples of this are organic peracids with H₂O₂ forming N-acyl or O-acyl compounds, preferably N, N'-tetraacylier te diamines, p- (alkanoyloxy) benzenesulfonates, also carboxylic anhydrides and esters of polyols such as glucose pentaacetate. Other well-known bleachers tivators are acetylated mixtures of sorbitol and mannitol as they are for example in European patent application EP-A-0 525 239 be written. The bleach content of the bleaching agents activators is in the usual range, preferably between 1 and 10 % By weight and in particular between 3 and 8% by weight. Particularly preferred Bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED), 1,5-di acetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated Sorbi Tol Mannitol Mixtures (SORMAN).

When used in machine washing processes, it can be an advantage Add usual foam inhibitors. Suitable as foam inhibitors soaps of natural or synthetic origin, for example have a high proportion of C₁₈-C₂₄ fatty acids. Suitable non-surfactant  Like foam inhibitors are, for example, organopolysiloxanes and their Mixtures with microfine, possibly silanized silica and paraffins, Waxes, microcrystalline waxes and their mixtures with silanized pebbles acid or bistearylethylenediamide. Mixtures are also advantageous various foam inhibitors used, e.g. B. those made of silicone, Pa refined or waxing. The foam inhibitors are preferred, in particular other silicone and / or paraffin-containing foam inhibitors, to a granu lare, water-soluble or dispersible carrier substance bound. Ins mixtures of paraffins and bistearylethylenediami are special that preferred.

The salts of polyphosphonic acids are preferably the neutral react sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, Diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylene phosphonate used in amounts of 0.1 to 1.5 wt .-%.

Enzymes come from the class of proteases, lipases or lipo litically acting enzymes, amylases, cellulases or their mixtures in Question. Bacterial strains or fungi such as are particularly well suited Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymatic active substances. Preferably be Subtilisin-type proteases, and in particular proteases derived from Bacillus lentus are used. There are enzyme mixtures, for example example of protease and amylase or protease and lipase or lipolytic acting enzymes or protease and cellulase or from cellulase and Lipa or lipolytic enzymes or from protease, amylase and lipa se or lipolytic enzymes or protease, lipase or lipoli table-acting enzymes and cellulase, but especially protease and / or mixtures containing lipase or mixtures with lipolitic agents Enzymes of special interest. Examples of such lipolytic we Known enzymes are the well-known cutinases. Also peroxidases or oxidases have proven to be suitable in some cases. The enzymes can Carriers may be adsorbed and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, En enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5 % By weight, preferably 0.1 to about 2% by weight.  

The stabilizers come in particular for per-compounds and enzymes salts of polyphosphonic acids mentioned above.

Graying inhibitors have the task of removing the fiber To keep dirt suspended in the fleet and thus turn graying prevent. For this purpose, water-soluble colloids are mostly organic in nature suitable, for example the water-soluble salts of polymeric carboxylic acids, Glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids Starch or the cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Furthermore, soluble ones Use starch preparations and other starch products than those mentioned above, e.g. B. degraded starch, aldehyde starches, etc. . Polyvinylpyrrolidone is also useful. However, cellulose ethers such as carboxymethyl cellu are preferred loose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as Methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxy methyl cellulose and mixtures thereof, and polyvinyl pyrrolidone, for example as used in amounts of 0.1 to 5 wt .-%, based on the agent.

The agents can, as optical brighteners, derivatives of the diaminostilbene contain sulfonic acid or its alkali metal salts. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) style ben-2,2'-disulfonic acid or similar compounds, which replace the morpholino group with a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type can also be used be essential, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4′-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 ′ - (2- sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used.

The bulk density of the preferred granular agents is generally 300 to 1200 g / l, in particular 500 to 1100 g / l. Your manufacture can by any of the known methods such as mixing, spray drying, granules ren and / or extrusion. Are suitable according to the invention special such procedures that allow subcomponents to  for example spray-dried components and granulated and / or extru dated components are mixed together. It is also possible Lich that spray-dried or granulated components subsequently in preparation, for example with nonionic surfactants, in particular ethoxylated fatty alcohols, applied according to the usual procedures will. Methods of this type are particularly advantageous in which Detergents or cleaning agents are obtained, which are a heterogeneous distribution effect of the individual surfactants. Especially in granulation and Extrusion process, it is preferred to include any ionic surfactants in the form of a spray-dried, granulated or extruded Compounds either as an admixture in the process or as an additive to be used later for other granules. It is preferred that the anionic surfactant compounds, if they should contain zeolite at all ten, anionic surfactants compared to zeolite, again based on anhydrous Active substance), contained in excess, weight ratios of zeolite to anionic surfactant from 1: 2.5 to 1: 4 are particularly preferred. Likewise it is possible and can be advantageous depending on the recipe, if further individual components of the agent, for example carbonates, Citrate or citric acid or other polycarboxylates or polycarbonate acids, polymeric polycarboxylates, zeolite and / or layered silicates for example layered crystalline disilicates, to be sprayed afterwards dried, granulated and / or extruded components, the gege if necessary with non-ionic surfactants and / or others during processing tion temperature liquid to waxy ingredients are mixed in. A method is preferred in which the Surface of partial components of the agent or of the entire agent for Reducing the stickiness of the granules and / or rich in nonionic surfactants is subsequently treated to improve their solubility. Suitable Surface modifiers are known from the prior art. No ben further suitable are finely divided zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts, for example calcium stearate, but especially mixtures of zeolite and silica or Zeolite and calcium stearate are particularly preferred.

The finished washing or cleaning agents can also consist of several Partial extrudates, which contain the above-mentioned ingredients  have and the physicochemical conditions specified according to the invention meet requirements. In another embodiment of the invention the extrudates, however, with other ingredients from washing or cleaning agents processed agents. This can look like the washing or Rei cleaning agent obtained by mixing several different granules of which an extrudate or various partial extrudates are the main Form component and preferably more than 60 wt .-%, in particular more make up as 70% by weight.

From international patent application WO-A-91/02047, for example known a process for producing high density extrudates, with a solid and free-flowing premix under pressure is pressed. The solid and free-flowing premix contains a plastic Fizier- and / or lubricant, which causes the premix under the pressure or the entry of specific work plastically softened and there becomes extrudable. After exiting the hole shape act on it System no longer shear forces and the viscosity of the system increases in such a way that the extruded strand to predetermined Extrudate dimensions can be cut.

A preferred embodiment of the invention now provides that extruding premix is not fully homogenized that much more the premix is produced under such gentle conditions, that heterogeneity in the distribution of individual content substances and especially the surfactants both in the premix and in the fer extrudate remains intact. According to the invention this is the case make sure that not only the extrudates or partial extrudates, but also the Compounds used to make the heterogeneous premix will obey the above physicochemical conditions.

Examples example 1 Containing gel starch from surfactant mixtures in a salt solution 2.1% by weight sodium carbonate and 47.9% by weight water

To determine the yield point and the gel breaking limit of different high Concentrated surfactant-containing phases were given in Table 1 benen mixtures prepared and the corresponding flow limits and gel breaking limits using a Rheometrics RFS II rheometer Right.

These examples (see also Table 1) show that the viscosity of the Detergent gels are not the only decisive factor for the strength of these gels. For example, comparative example V3 has a viscosity that in the range of viscosities of examples according to the invention such as the examples 4 and 5 lies. The modulus of elasticity is also not the only factor bend. Comparative example V3, in addition to being relatively minor gene viscosity also a relatively low modulus of elasticity, the ge is ringer than the module of example 4 or 5 and the invention Module of Example 6 according to the invention is the same. However, this points Example V3 has a very high gel breaking limit and therefore a corresponding one high yield point. This achieves a gel strength that ty no longer use detergents in household washing machines is tolerable.  

Table 1

Gel strength of mixtures 1 to 8 according to the invention and typical comparative detergent gels V1 to V3 (data in% by weight of active substance)

The viscosity Eta was measured at 25 ° C and a shear rate of 10 s ^-1 . The elastic modulus G 'was measured at 25 ° C.

The gel break limit was also at 25 ° C as the length of the viscoelastic Range measured in the oscillation test at 10 Hz; the yield point at 25 ° C results from the product of the modulus of elasticity and the gel break border.

Example 2

Rheology of zeolite-C₉-C₁₃-alkylbenzenesulfonate mixtures (figures in% by weight) in water at 25 ° C

Table 2

Example 3 application

According to the teaching of international patent application WO-A-91/02047 Extrudates of the following composition produced (data in% by weight):  

Table 3

To determine the dissolution behavior, a double-walled and 20 ° C thermostatted measuring vessel with conductivity measuring cell and magnetic stirring Fill in 400 ml tap water at 16 ° d (20 ° C), the magnet stirrer switched on at a speed of 240 revolutions per minute and the conductivity measuring cell is immersed. Then 3.2 g of each Added by means. The conductivity values were determined after 15, 30, 60, 120, Read 240, 300, 600, 1200 and 1800 seconds. If the values change A distinction was made between 1200 and 1800 seconds until the measurement was constant of conductivity measurements extended. Then there was a sub traction of the initial value without detergent (blank value) from the measurement results nissen and a calculation of the percentage conductivity, the con  constant end value was set to 100%. From the representation of the temporal In the course of the conductivity, the time was interpolated in seconds, at that reached 75% of the final conductivity.

Claims (15)

1. Powdery to granular detergent or cleaning agent, in particular with bulk densities of at least 500 g / l, containing anionic and / or nonionic surfactants and other conventional ingredients of washing or cleaning agents, characterized in that the washing or cleaning agent has at least 2 different Contains types of surfactants, of which

• - all present as a raw material or in a single compound, or
• - At least one surfactant as raw material and at least one surfactant in one compound, with more than two different surfactants at least one surfactant as raw material and at least one surfactant in at least one compound, or
• - Even if there are more than two surfactants present, they are contained in at least two different surfactant compounds,

with the proviso that for the entire surfactant-containing washing or cleaning detergent and any surfactant-containing compound in a saline solution holding 50% by weight of the washing or cleaning agent or the compound, 2.1 wt .-% sodium carbonate and 47.9 wt .-% water, at 25 ° C applies that the yield point in each case less than 10 Pa and the gel break limit in each case is less than 5% strain. 2. Composition according to claim 1, characterized in that the yield point in each case less than 5 Pa and / or the gel break limit in each case less than Is 2% strain. 3. Composition according to claim 1 or 2, characterized in that the surfactants are distributed heterogeneously in the finished agent. 4. Agent according to one of claims 1 to 3, characterized in that a surfactant as raw material and at least one surfactant in a compound, at least one if there are more than two different surfactants Surfactant as raw material and at least one surfactant in at least one Com pound or in at least two different surfactant compounds gene.   5. Agent according to one of claims 1 to 4, characterized in that it contains compounds containing anionic surfactants, which are also used as zeolite Have builder substance, but no usual known solubility contain improvements or structural breakdown, the weight ratio of zeolite (based on anhydrous active substance) to anion surfactants is between 2: 1 to 5: 1 or between 1: 2 to 1: 5. 6. Agent according to one of claims 1 to 5, characterized in that it contains compounds containing anionic surfactants and zeolite, the Ge Weight ratio of zeolite to anionic surfactants more than 2.5: 1 or 1: 2.5 to 1: 4. 7. Composition according to one of claims 1 to 4, characterized in that it contains compounds containing anionic surfactants, which are also used as zeolite Builder substance as well as known non-surfactant solubility ver better or structure breaker, preferably polyethylene glycols, ent hold, the weight ratio of zeolite to anionic surfactant in range Chen from 3: 1 to 1: 1. 8. Agent according to one of claims 1 to 4, characterized in that it contains compounds containing anionic surfactants, which are also used as zeolite Builder substance as well as known surfactant solubility improvers or structure breakers, preferably ethoxylated and propoxylated Contain fatty alcohols, the weight ratio of zeolite to An ionic surfactant ranges from 3.5: 1 to 1: 3. 9. A process for the preparation of powdery to granular detergents or cleaning agents, in particular with bulk densities of at least 500 g / l, containing anionic and nonionic surfactants and other conventional ingredients of detergents or cleaning agents, characterized in that at least 2 different types of surfactants are used who or from whom

• - all present as a raw material or in a single compound, or
• - At least one surfactant as raw material and at least one surfactant in one compound, with more than two different surfactants at least one surfactant as raw material and at least one surfactant in at least one compound, or
• - Even if there are more than two surfactants present, they are contained in at least two different surfactant compounds,

with the proviso that both for the entire surfactant-containing washing or Detergent as well as for any surfactant-containing compound in highly con centered aqueous phase be the yield point and the gel breaking limit are tuned and tensides and compounds are so coordinated be true that in a saline solution containing 50 wt .-% of Detergent or cleaning agent or the compound, 2.1 wt .-% sodium carbonate and 47.9 wt .-% water, the yield point at 25 ° C each less than 10 Pa and the gel break limit less than 2% strain is. 10. The method according to claim 9, characterized in that the yield point is less than 5 Pa and the gel break limit is less than 2% strain. 11. A method for producing a detergent or cleaning agent according to any one of claims 1 to 8, wherein the detergent or cleaning agent contains at least 2 different types of surfactants, or from which

• - all present as a raw material or in a single compound, or
• - At least one surfactant as raw material and at least one surfactant in one compound, with more than two different surfactants at least one surfactant as raw material and at least one surfactant in at least one compound, or
• - Even if there are more than two surfactants present, they are contained in at least two different surfactant compounds,

with the proviso that for the entire surfactant-containing washing or cleaning detergent and any surfactant-containing compound in a saline solution holding 50% by weight of the washing or cleaning agent or the compound 2.1 wt .-% sodium carbonate and 47.9 wt .-% water, at 25 ° C applies that the yield point in each case less than 10 Pa and the gel break limit in each case is less than 2% strain, or according to one of claims 9 or 10,  characterized in that the washing or cleaning agent by Mixture of different granules is obtained, one of which is an extrudate or different partial extrudates form the main component and before preferably make up more than 60% by weight, in particular more than 70% by weight. 12. The method according to claim 11, characterized in that the extru dierend premix is prepared under conditions such that both the premix and the finished extrudate a hete rogenicity regarding the distribution of the individual ingredients and in particular the surfactants.