DE4203031A1 - METHOD FOR THE PRODUCTION OF SOLID DETERGENT AND CLEANING AGENT WITH HIGH SHOCK WEIGHT AND IMPROVED SOLUTION SPEED - Google Patents

Abstract

The purpose is to produce solid washing and cleaning agents with a high powder density or a component therof by the addition of solid and liquid detergent raw materials with simultaneous or subsequent shaping and, if desired, drying, in which the agents containing the usual components like anionic tensides, builder substances, alkalising agents and liquid niotensides and, if required, water or aqueous solutions exhibit an improved rate of dissolution at temperatures between 15 and 60 DEG C. This is achieved in that firstly all the solid components are mixed together and then the liquid components are added. To improve the dissolving properties, an additive is introduced into the process after the solid components have been mixed. The additive to improve the dissolving properties consists of fatty alkyl sulphate, olefine sulphate, alkyl-aromatic sulphonates or mixtures thereof. The additive which is solid per se may be either introduced as the last solid component or added to the other already mixed solid components, or it may be introduced into the process in the form of an aqueous mixture, preferably in a 25 to 60 wt % aqueous solution. The per se solid additive content of the agent is preferably 0.5 to 8 wt %.

Description

The invention relates to a method for producing solid washing and Detergents or components of solid washing and cleaning agents which are characterized by improved dissolution behavior, in particular at low temperatures, as well as the use of certain Anionic surfactants as additives to improve the dissolution behavior in solid Detergents and cleaning agents.

Solid detergents with high bulk density, i.e. H. Means with a bulk density above 500 g / l, often have due to their compact form and from the resulting smaller surface area lower dissolving speed, especially at low temperatures 15 to 60 ° C, on as an agent with a comparable composition, the but have a bulk density of, for example, only 300 g / l.

From the international patent application WO 91/02 047 a method for Manufacture of compacted granules known in washing and cleaning means are used. A homogeneous premix under Zu Set of a plasticizer and / or lubricant at high pressures between 25 and 200 bar extruded. This application teaches that as Pla stifying and / or lubricant surfactants can be used. Here it is possible that the plasticizers and / or lubricants limited men containing auxiliary liquids. These auxiliary liquids include also higher-boiling, optionally polyethoxylated alcohols, at room temperature or moderately elevated temperatures flowable polyalkoxylates and the like.  

While the slow release speed in machine application The means is less disruptive, these means are manual when doing it Application, for example in the application in the hand wash basin, from Ver users generally not accepted.

The object of the invention was a solid washing and cleaning high bulk density or a component therefor make the usual ingredients, including ethoxylated alcohols as nonionic surfactants, and that at temperatures between 15 and 60 ° C has an improved dissolving speed. Another The object of the invention was to provide ingredients of washing and cleaning agents find agents that improve the dissolution behavior of the solid detergents and cleaning agents can be used.

The invention accordingly relates to a first embodiment form a process for the production of solid detergents and cleaning agents with high bulk density or a component of a solid washing and rice detergent with high bulk density by joining solid and liquid detergent raw materials with simultaneous or subsequent Shaping and drying if desired, using anionic surfactants, Builders and alkalizers and liquid nonionic surfactants as well optionally uses water or aqueous solutions, initially all solid components mixed together and then the liquid Components are added and to improve the dissolution behavior tens an additive from the group of fatty alkyl sulfates, olefin sulfonates, alkyl aromatic sulfonates and mixtures of these after mixing of the solid components is introduced into the process.

The suitable additives are solid per se, but can be introduced into the process in solid or pasty to liquid form, for example in the form of an aqueous solution. As suitable additives of the fatty alkyl sulfate type, alkyl sulfates having 8 to 18 carbon atoms are preferably used alone or in mixtures. In particular, the use of C ₈ alkyl sulfate, C ₁₂ alkyl sulfate, mixtures of C ₁₂ to C ₁₈ alkyl sulfates, C ₁₂ and C ₁₄ alkyl sulfates and C ₈ to C ₁₆ alkyl sulfates is preferred. Suitable additives of the olefin sulfonate type are preferably olefin sulfonates having 12 to 18 carbon atoms, in particular C ₁₃ to C ₁₈ olefin sulfonate and, with very particular advantage, C ₁₃ -C ₁₇ olefin sulfonate. Particularly preferred additives of the alkyl aromatic sulfonate type are toluenesulfonate and cumene sulfonate.

The solid additives per se are definitely after mixing the other solid components, d. H. the rest of the stock per se parts that are mixed together in solid form and not in liquid Form, for example in the form of an aqueous solution, are used in brought the procedure. The additive is preferred in one Embodiment in solid form as the last solid component to the rest added mixed solid ingredients.

In a further preferred embodiment, the solid per se Substitute in the form of an aqueous mixture, preferably in the form of a 25th up to 60 wt .-% and in particular in a 30 to 45 wt .-% aqueous Solution introduced into the process. In the case of adding the per se fixed Additives in the form of an aqueous solution still apply that the Lö solution containing the additive after mixing the solid loading Components are introduced into the process, however, the addition of these The solution is then not tied to any other chronological order. So it is possible Lich that the aqueous solution containing the additive before the Zu Give the other liquid components together with the other rivers components or as the last component in the process as a whole ren is introduced. In a preferred embodiment, the per se solid additive in the form of an aqueous solution before the addition of other liquid components introduced into the process. In a Another preferred embodiment is the per se solid additive Form of an aqueous solution with the liquid nonionic surfactants or Non-ionic surfactant mixtures intensively mixed and together with them in the ver drive introduced. The solid additive per se is preferred introduced into the process in such quantities that its content is 0.5 to 8 % By weight, based on the average. It is particularly advantageous the per se solid additive is introduced into the process in the amounts, that its content 0.5 to 5 wt .-%, preferably 0.8 to 4 wt .-% and ins particularly 1 to 3 wt .-%, each based on the agent. Here  it is particularly preferred that the content of alkyl aromatic zu Substitutes is not above 3 wt .-%.

The liquid constituents of the agent include, in particular, liquid nonionic surfactants which are preferably derived from ethoxylated fatty alcohols having 8 to 20 carbon atoms and an average of 1 to 15 moles of ethylene oxide per mole of alcohol and in particular primary alcohols preferably having 9 to 18 carbon atoms and an average of 1 to 12 Derive moles of ethylene oxide per mole of alcohol in which the alcohol residue may be linear or methyl-branched in the 2-position, or may contain linear and methyl-branched residues in the mixture, as are usually present in oxo alcohol residues. However, linear residues of alcohols of native origin with 12 to 18 carbon atoms, such as coconut oil, tallow oil or oleyl alcohol, are particularly preferred. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a restricted homolog distribution (narrow range ethoxylates, NRE). In particular, alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups. The preferred ethoxylated alcohols include, for example, C ₉ -C ₁₁ oxo alcohol with 7 EO, C ₁₃ -C ₁₅ oxo alcohol with 3 EO, 5 EO or 7 EO and in particular C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 5 EO.

In particular, it is preferred to include nonionic surfactant mixtures in the process bring which the liquid nonionic surfactants in intimate mixing with a Structure breaker included. It is preferred that the weight ver ratio of the liquid nonionic surfactants to the structure breaker 10: 1 to 1: 2 is.

A number of both solid and liquid are suitable as structure breakers ger substances that are hydrophilic, water-soluble or water-dispersible are. Lower polyalkylene glycols, for example, are suitable straight-chain or branched glycols with 2 to 6 carbon atoms derive, preferably polyethylene glycol or polypropylene glycol, and a  have a molecular weight between 200 and 12,000. In particular are Polyethylene glycols with a molecular weight between 200 and 4000 preferred, the liquid polyethylene glycols having a relative Mo especially up to 2000 and especially between 200 and 600 have partial properties.

Likewise, the sulfates and especially the disulfates of lower poly alkylene glycols, in particular polyethylene glycol and 1,2-polypropylene glycol suitable. The sul are particularly preferred fate and / or disulfates, which differ from polyethylene glycols and poly propylene glycols with a molecular weight between 600 and 6000 and derive in particular between 1000 and 4000. The disulfates originate usually from polyglycol ethers, such as - caused by low Traces of water - ent in the alkoxylation of alcoholic components can stand from.

Another group of suitable structure breakers consists of the water-soluble salts of mono- and / or disulfosuccinates of the lower Polyalkylene glycols. The ent are of particular importance speaking polyethylene glycol and polypropylene glycol compounds, wherein Sulfosuccinate and disulfosuccinate of polyglycol ethers with a rela tive molecular mass between 600 and 6000, in particular between 1000 and 4000, are particularly preferred.

For the use of the anionically modified polyalkylene glycols as Structural breakers are any salts, but preferably the alkali metal salts, especially the sodium and potassium salts, and ammonium salts and / or salts of organic amines, for example of tri ethanolamine. The most important for practical use Salts are the sodium salts of sulfates, disulfates, sulfosuccinates and Disulfosuccinate of polyethylene glycol and polypropylene glycol.

Mixtures of the polyalkylene glycols and theirs are also preferred ionically modified derivatives in any mixing ratio used. In particular, there is a mixture of polyalkylene glycol and the sulfosuccinates and / or disulfosuccinates of the polyalkylene glycols  prefers. A mixture of polyalkylene glycol and is also suitable the corresponding sulfates and / or disulfates and a mixture of Polyalkylene glycol and the corresponding sulfates and / or disulfates so such as the corresponding sulfosuccinates and / or sulfodisuccinates.

Furthermore, suitable and preferred are within the meaning of this invention Structure breakers set the add-on products from about 20 to about 80 moles Ethylene oxide in 1 mol of an aliphatic alcohol with essentially 8 to 20 carbon atoms, the long-known ingredients of Represent detergents and cleaning agents. The An are particularly important Storage products from 20 to 60 moles and in particular from 25 to 45 moles Ethylene oxide to primary alcohols, such as coconut fatty alcohol or Tallow fatty alcohol, on oleyl alcohol, on oxo alcohols, or on secondary alcohols get with 8 to 18 and preferably 12 to 18 carbon atoms. Examples for particularly preferred structure breakers from the group of highly ethoxy gated alcohols are tallow fatty alcohol with 30 EO and tallow fatty alcohol with 40 EO. It is also preferred to use mixtures which are highly ethoxylated Contain alcohols, for example mixtures of tallow fatty alcohol with 40 EO and water or from tallow fatty alcohol with 40 EO and polyethylene glycol with a molecular weight between 200 and 2000.

Other suitable structure breakers are ethoxylated, vicinal internal columns Some alkanediols or 1,2-alkanediols with a carbon chain with 8 to 18 carbon atoms and 4 to 15 moles of ethylene oxide per mole of diol. It is it is possible that only one of the two OH groups or both OH groups of the Alkanediols are ethoxylated.

Modified nonionic surfactants with a terminal acid group are also suitable as structure breakers. These are nonionic surfactants, in particular fatty alcohols, in which an OH group has been converted into a group with a carboxyl group. Nonionic surfactants with a terminal acid group thus include esters or partial esters of a nonionic surfactant with a polycarboxylic acid or a polycarboxylic anhydride. Examples of acid-terminated nonionic surfactants are the known polyether carboxylic acids and esters or half esters of C ₈ -C ₁₈ alcohols with succinic anhydride, maleic anhydride, maleic acid or citric acid.

Another group of suitable structure breakers consists of alkylene glycol monoalkyl ethers of the general formula RO (CH ₂ CH ₂ O) _n H, in which R represents a radical with 2 to 6 carbon atoms and n represents a number from 1 to 8. Examples of this group of additives are ethylene glycol monoethyl ether and diethylene glycol monobutyl ether.

According to the invention, the liquid nonionic surfactants, especially the ethoxy fatty alcohols mixed intimately with the structure breaker set. This intimate mixture is achieved by either a homogeneous solution or a dispersion of those according to the invention set liquid nonionic surfactants and the hydrophilic, water-soluble cover produces water-dispersible structure breakers. The Structure breakers cause very small amounts, based on the Sum of liquid nonionic surfactant and structure breaker, another improvement tion of the dissolution behavior of the finished funds. Preferably they are in a weight ratio of liquid nonionic surfactant: structure breaker of 8: 1 used up to 1: 2.

In addition, nonionic surfactants can also be alkyl glycosides in the general formula RO- (G) _x , in which R is a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms branched in the 2-position, G is a symbol , which stands for a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10, preferably between 1 and 2 and in particular is significantly less than 1.4, for example in amounts of 1 to 10 wt .-%, in liquid to pasty form or mixed with the liquid ethoxylated alcohols.

The content of the agents in accordance with the invention as nonionic surfactants set ethoxylated alcohols is preferably 1 to 15 wt .-% and in particular 2 to 10% by weight. The content of the agent according to the invention The structure breakers used inevitably result from this. Preferential the agents contain up to 5% by weight, in particular 1 to 3% by weight,  on polyethylene glycol with a molecular weight between 200 and 1500.

The anionic surfactants are preferably in solid form, for example in spray-dried or granulated form, and not in the form of a pasty one to liquid mixture introduced into the process. So you count the fixed components of the funds used in the first stage of the procedure be mixed together. It is particularly preferred that the Anionic surfactants featured as the first ingredient in the first stage of the process be placed and the other solid components are added.

Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are alkylbenzenesulfonates (C ₉ -C ₁₅ -alkyl), olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates such as are obtained, for example, from C ₁₂ -C ₁₈ monoolefins with a terminal and internal double bond through sul form with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are dialcan sulfonates which are obtainable from C ₁₂ -C ₁₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and in particular the esters of o-sulfo fatty acids (ester sulfonates), for example the α-sulfonated ones Methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie from fatty alcohols, for example coconut oil alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C ₁₀ -C ₂₀ oxo alcohols, and those secondary alcohols of these chains are long. The sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol of ethylene oxide, are also suitable. Sulfated fatty acid monoglycerides are also suitable.

Furthermore, for example, soaps from natural or synthetic, preferably saturated fatty acids can be used. Soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids, are particularly suitable. Preferred are those which are composed of 50 to 100% of saturated C ₁₂ -C ₁₈ fatty acid soaps and 0 to 50% of oleic acid soaps.

The fatty alkyl sulfates and olefin sulfonates mentioned thus both belong to the anionic surfactants as well as the additives. As part of this inven only then do the fatty alkyl sulfates and olefin sulfates become per se solid additives counted if they according to the invention in the temporal Ranking after mixing the other solid components in the Ver driving. However, follows after the addition of the fatty alkyl sulfates and the olefin sulfonates still add another per se solid constituent in solid form, the fatty alkyl sulfates and Olefin sulfonates within the scope of this invention belong to the remaining solid inventory parts of anionic surfactants presented in the first process stage. The Ver The dissolution behavior is improved by the fatty alkyl sulfates and oils finsulfonate as well as by the alkyl aromatic sulfonates only then achieved when they are introduced as additives in the process.

The anionic surfactants and the anionic surfactant additives can in Form of their sodium, potassium and ammonium salts and as soluble salts organic bases, such as mono-, di- or triethanolamine. The Ge hold detergents according to the invention on anionic surfactants and anionts Sidic additives is preferably 5 to 40, in particular 8 to 35% by weight. It is particularly advantageous if the content of the funds of sulfonates and / or sulfates 10 to 35% by weight, in particular 15 to 30 % By weight, and the soap content up to 8% by weight, in particular 0.5 to 5 % By weight.

The amounts of the surfactants are preferably incorporated into the process brings that the sum of surfactants and additive 15 to 50 wt .-% and in particular 20 to 45% by weight, in each case based on the agent. The weight ratio of the sum of anionic surfactants and anionic surfactants Additive: nonionic surfactant is preferably at least 1: 1 and especially 2: 1 to 10: 1.  

The other solid components are before the addition of the additive preferably builder substances, alkalizing agents and - if before hand - bleach introduced into the process.

Weakly acidic are suitable as organic and inorganic builders er, neutral or alkaline reacting soluble and / or insoluble com components that are able to precipitate or bind complex ions. Suitable and in particular ecologically harmless builder substances, such as finely crystalline, synthetic water-containing zeolites of the type NaA, the a Have calcium binding capacity in the range of about 100 to 200 mg CaO / g, find a preferred use. Their average particle size is above Licher in the range of 1 to 10 microns (measurement method: Coulter Counter, Vo lumen distribution). The zeolite content of the compositions is in general up to 50% by weight, preferably at least 10% by weight and in particular 18 to 40% by weight, based on anhydrous substance.

As additional builder components, especially together with the Zeo lithen can be used, come in (co) polymeric polycarboxylates Consider, such as polyacrylates, polymethacrylates and especially copolymers acrylic acid with maleic acid, preferably from 50% to 10% Maleic acid. The relative molecular weight of the homopolymers is generally mean between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative Molecular mass from 50,000 to 100,000. Suitable, if less preferred compounds of this class are copolymers of acrylic acid or Methacrylic acid with vinyl ethers, such as vinyl methyl ethers, in which the proportion the acidity is at least 50%. Polyacetal carbon can also be used acids, such as those in US Pat. Nos. 4,144,226 and 41 46 495 are described, as well as polymeric acids by Polymeri sation of acrolein and subsequent disproportionation using alkalis be obtained and be from acrylic acid units and vinyl alcohol units or acrolein units are constructed. The content of funds (Co) polymeric polycarboxylates is preferably up to 10% by weight and in particular 2 to 8% by weight.  

Useful organic builder substances are preferred, for example polycarboxylic acids, such as lemons, used in the form of their sodium salts acid and nitrilotriacetate (NTA), if such use from eco logical reasons is not objectionable.

Other suitable solid constituents of the agents are water-soluble inorganic alkalizing agents such as bicarbonates, carbonates or silicates; in particular, alkali carbonate and alkali silicate, especially sodium silicate with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.0, are used. The sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight. The sodium silicate content of the compositions is generally up to 10% by weight and preferably between 2 and 8% by weight.

Among the compounds used as bleaching agents, have applications _2-providing Verbin in water H ₂ O, the sodium perborate tetrahydrate (NaBO ₂ .H ₂ O ₂ • 3 H ₂ O) and sodium perborate monohydrate (NaBO ₂ .H ₂ O ₂₎ of particular importance . Further bleaching agents that can be used are, for example, peroxy carbonate (Na ₂ CO ₃ .1.5 H ₂ O ₂ ), peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -supplying peracid salts or peracids such as perbenzoates, peroxaphthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate.

Other ingredients that can be used in solid form are, for example, bleach activators, graying inhibitors, Foam inhibitors, optical brighteners, enzymes, stabilizers for enzymes and bleaches, fabric softening agents and neutral salts.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples of these are N-acyl or O-acyl compounds which form organic peracids with H ₂ O ₂ , preferably N, N'- tetraacylated diamines, such as N, N, N ', N'-tetraacetylethylenediamine, furthermore carboxylic acid anhydrides and esters of polyols like glucose pentaacetate. The bleach activator content of the bleach-containing agents is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.

Graying inhibitors have the task of removing the fiber Keeping dirt suspended in the fleet and thus turning graying prevent. For this purpose, water-soluble colloids are mostly organic in nature is suitable, such as the water-soluble salts of polymeric carboxylic acid ren, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids the starch or the cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also contain water-soluble, acidic groups Polyamides are suitable for this purpose. Furthermore, soluble starch preparations and other starch products than those mentioned above use, for example degraded starch, aldehyde starches, etc. Also poly vinyl pyrrolidone is useful. Carboxymethyl cellulose is preferred (Na salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof and polyvinylpyrrolidone, in particular in amounts of 0.5 to 5% by weight, based on the agent used.

The foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; A reduction can also be achieved by adding non-surfactant-like organic substances. A reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, for example sulfates and / or sulfonates with nonionic surfactants and / or with soaps. In the case of soaps, the foam-suppressing effect increases with the degree of saturation and the C number of the fatty acid ester. Soaps of natural and synthetic origin that contain a high proportion of C ₁₈ -C ₂₄ fatty acids are therefore suitable as foam-inhibiting soaps. Suitable non-surfactant-like foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffin, waxes, microcrystalline waxes and their mixtures with silanized silica. Bisacylamides derived from C ₁₂ -C ₂₀ alkylamines and C ₂ -C ₆ dicarboxylic acids can also be used. Mixtures of various foam inhibitors are also advantageously used, for example those made from silicone and paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance or are mixed with the plasticizer and / or lubricant.

The detergents can be used as optical brighteners, derivatives of the diamino style Contain bendisulfonic acid or its alkali metal salts. Ge For example, salts of 4,4′-bis (2-anilino-4-morpholino-1,3,5- triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or of a similar structure Compounds that have a diethanolamino group instead of the morpholino group, a methylamino group, an anilino group or a 2-methoxyethylamino wear group. Brighteners of the substituted type can also be used 4,4'-distyryl-di-phenyls be present; for example the connection 4,4′- Bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the above mentioned brighter can be used.

According to a further preferred embodiment of the invention, a uniformly white granulate is obtained if, apart from the customary optical brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5, preferably around 0.1 to 0.3% by weight. , also contains small amounts, for example 10 ^-6 to 10 ^-3 wt .-%, preferably around 10 ^-5 wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (product name of Ciba-Geigy).

Enzymes come from the class of proteases, lipases and amyl asen or their mixtures in question. Are particularly well suited from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic substances obtained. Proteases of the subtilisin type and in particular Protea are preferred sen, which are obtained from Bacillus lentus. The enzymes can NEN adsorbed on carriers and / or embedded in shell substances to protect them against premature decomposition.

The stabilizers come in particular for per-compounds and enzymes Salts of polyphosphonic acids, especially 1-hydroxyethane-1,1-diphosphone acid (HEDP) into consideration.  

In a further preferred embodiment of the invention, according to mixing the solid components and following the addition of the Additive and the liquid nonionic surfactants or the liquid mixtures, which contain the nonionic surfactants, one or more aqueous solutions knows Other, per se fixed components introduced into the process. That's the way it is For example, it is possible that, for example, the (co) poly meren polycarboxylates and / or the alkali silicates optionally as solid Be components in solid form or partially or completely in liquid form as aqueous solution can be used. The quantities already mentioned, in which these components may contain in the funds agree on the total amount in solid and / or liquid form per se fixed components. In particular, it is preferred that at least one aqueous solution of a homo- or copolymeric polycarboxy lats, for example a 30 to 55 wt .-% aqueous solution, then the addition of the liquid nonionic surfactants or the liquid mixtures, which contain the nonionic surfactants is introduced into the process.

Merging the solid and liquid detergent raw materials under simultaneous or subsequent shaping and, if desired, drying nung can by all known methods in which washing and cleaning detergent with high bulk density, d. H. with a bulk density above 500 g / l, preferably above 600 g / l and in particular between 700 and 1000 g / l, are produced, are carried out. Examples of derar Some known and preferred processes are granulation processes in which either the solid ingredients of a detergent or cleaning agent or a spray-dried washing and cleaning agent or a mixture of spray-dried and non-spray-dried ingredients of washing and Detergents, if necessary including the additive, in compacted in a high-speed mixer and at the same time in it Mixer or subsequently in another device, for example given in a fluidized bed, with the liquid components if mixed with the aqueous solution of an additive or is acted upon.

In particular, however, a method is preferred which is described in detail in the international patent application WO 91/02 047 is described. Doing so  a solid homogeneous premix with the addition of a plasticizer and / or Lubricant over hole shapes with opening widths of the predetermined granu lat dimension at high pressures between 25 and 200 bar strand-like ver presses. The strand is immediately after leaving the hole shape a cutting device to the predetermined granule dimension cut. The application of the high working pressure causes the plastifi of the premix during the formation of granules and provides the cutting ability of the freshly extruded strands. The premix exists partly from solid, preferably finely divided common ingredients of detergents and cleaning agents that invent the liquid components are mixed appropriately. The solid ingredients can be sprayed drying tower powders, but also agglomerates, each ge chose mixture components as pure substances, which in the finely divided Zu stood to be mixed together, as well as mixtures of these. in the Following this, the liquid ingredients including the selected plasticizer and / or lubricant mixed. As Plasticizers and / or lubricants become aqueous solutions of polymers Polycarboxylates and nonionic surfactants are preferred. For detailed Description of the suitable ingredients of the premix and the appropiate neten plasticizers and / or lubricants is based on the disclosure of in referenced international patent application WO 91/02 047.

The liquid nonionic surfactants are preferably used in the production of Detergents and cleaning agents by intimate extrusion under high pressure Mixing with structure breakers used, the weight ratio liquid nonionic surfactant: structure breaker in the mixtures 5: 1 to 1: 2 and in particular 10: 3 to 2: 3.

Kneaders of any configuration can preferably be used as the homogenizing device tion, for example 2-screw kneader can be selected. The intense Wed The creation process can in itself result in a desired one Lead to an increase in temperature. Thereby moderately elevated temperatures of for example, usually not exceeded 60 to 70 ° C. In a preferred embodiment, the premix is preferably continuous Lich fed to a 2-screw kneader (extruder), its housing and its extruder pelletizing head to the predetermined extrusion temperature  tempered, for example heated to 40 to 60 ° C. Under the The premix is sheared by the extruder screws when pressing 25 to 200 bar, preferably above 30 bar and especially at pressures compressed from 50 to 180 bar, plasticized, in the form of fine strands the perforated die plate extruded in the extruder head and finally the extru dat preferably spherical by means of a rotating cutting knife reduced to cylindrical granules. The hole diameter in the perforated nozzle plate and the strand cut length are on the ge selected pellet size. In this embodiment, the Production of granules of a substantially uniform predetermined baren particle size, the absolute particle sizes in particular intended application may be adapted. Generally will Particle diameter up to at most 0.8 cm is preferred. Important execution forms see here the production of uniform granules with through knives in the millimeter range, for example in the range of 0.5 to 5 mm and especially in the range of about 0.8 to 3 mm. The length / through The knife ratio of the chopped off primary granules is in an important embodiment in the range from about 1: 1 to about 3: 1. It is further preferred that the still plastic, moist primary granules to supply a further shaping processing step; be there edges present on the raw granulate are rounded, so that ultimately spherical shaped or at least approximately spherical granules are obtained can. At this stage, if desired or necessary, small Amounts of dry powder, for example zeolite powder such as zeolite NaA Powder to be used. This shape can be found on the market Rounding machines, for example in rounding machines with rotating bases disc, done. The granules are then preferably dried tion step, for example a fluidized bed dryer. About It has now surprisingly been found that extruded granules which Peroxy compounds as bleaching agents, for example perborate monohydrate, included, at supply air temperatures up to 150 ° C without any significant ver desire for active oxygen can be dried. The content of the getrock neten granules in free water is preferably up to about 3% by weight, in particular between 0.1 to 1% by weight. Alternatively, it is also possible Drying step immediately after extrusion of the  Primary granules and thus vorgenom before a desired to carry out their final shaping in a rounding machine.

To achieve an increased bulk density, it is advantageous to use the ge if necessary, dry the granules again with finely divided dry powder powder. Examples of such dry powder are again Zeolite NaA powder, but also precipitated or pyrogenic silica, such as them for example as Aerosil® or Sipernat® (products of the company Degussa) are commercially available. Hochkon are also preferred centered, at least 90 wt .-% fatty alcohol sulfate powder, which we substantial, i.e. at least 90% of particles with one particle size smaller than 100 µm exist. In particular, mixtures of Zeo lith and fatty alcohol sulfate powder preferred.

The washing and cleaning agents can consist of extrudates are made, which have the above-mentioned ingredients. The fer term agents can, however, also from a mixture of several different Granules are obtained, of which, for example, those according to the invention Extrudates are the main ingredient. For example, the Bleach activator, the enzymes as well as colors and fragrances Extrudates are added. It is preferred to use the bleach activator and the enzymes each in compacted granular form, for example as extrudates produced separately, which by means of a kneader receive the configuration described above or via a pellet press will be used.

In a further embodiment, the invention relates to the use of an additive from the group of fatty alkyl sulfates and olefin sulfonates to improve the dissolving behavior of solid washing and cleaning agents. It is preferred that alkyl sulfates with 8 to 18 carbon atoms, alone or in mixtures, preferably C ₈ alkyl sulfate, C ₁₂ alkyl sulfate, mixtures of C ₁₂ to C ₁₈ alkyl sulfates, C ₁₂ and C ₁₄ alkyl sulfates and C ₈ - to C ₁₆ alkyl sulfates, as the dissolving additive th additives used in detergents. It is further preferred that olefin sulfonates having 12 to 18 carbon atoms, preferably C ₁₃ -C ₁₈ olefin sulfonate and in particular C ₁₃ -C ₁₇ olefin sulfonate, are used as additives which improve the dissolving behavior in detergents and cleaning agents. The per se solid additive is preferably used in such amounts that its Ge content is 0.5 to 8 wt .-%, based on the agent. However, the per se solid additive is advantageously used in smaller amounts, so that its content is 0.5 to 5% by weight, preferably 0.8 to 4% by weight and in particular 1 to 3% by weight, based in each case the mean is.

Examples example 1

A solid premix of C ₉ -C ₁₃ alkylbenzenesulfonate sodium salt (90% by weight of active substance), C ₁₂ -C ₁₈ fatty alkyl sulfate powder (in a batch mixer equipped with a cutter head chopper) 91% by weight of active substance), C ₁₂ -C ₁₈ sodium fatty acid soap, Wessalith P® (zeolite NaA; commercial product from Degussa, Federal Republic of Germany), anhydrous sodium carbonate, Sokalan CP5® powder (copoly mer from acrylic acid and maleic acid; commercial product from Company BASF, Federal Republic of Germany), foam inhibitor concentrate, containing 15% by weight of silicone oil, 33% by weight of sodium sulfate, 35% by weight of sodium carbonate and 10% by weight of water glass as an inorganic carrier, C ₁₆ -C ₁₈ fatty alcohol with 5 EO, sodium perborate monohydrate, 1-hydroxyethane-1,1-diphosphonic acid tetranium salt (HEDP) and (as a solid additive) Texapon® K12 (sodium lauryl sulfate; 90% active substance, commercial product of the applicant) submitted.

With mixing tools running, this mixture was mixed with a mixture of polyethylene glycol with a relative molecular weight of 400, C ₁₂ -C ₁₄ fatty alcohol with 3 EO and C ₁₂ -C ₁₈ fatty alcohol with 5 EO (ratio 1: 4) and tallow alcohol with 40 EO offset.

A 30% by weight aqueous Sokalan CP-5 solution was then added siert. (82% by weight of the total amount of Sokalan CP 5 as powder and 18 % By weight used in the form of a solution.) The total amount of the mixture carried 5000 g.

The mixture was homogenized for 2 minutes and then one 2-screw extruder supplied, the housing including the extru the pelletizing head was heated to 45 ° C.  

The premix was under the shear of the extruder screws plasticized and then at a pressure of 120 bar by the Ex perforated nozzle plates to fine strands with a diameter of 1.2 min extruded, which after the nozzle exit by means of a knife were crushed into approximately spherical granules (length / through knife ratio about 1, hot cut). The resulting product was about 1 minute in a standard rounder of the type Marumerizer Add small amounts of zeolite NaA rounded and then at a Supply air temperature of 70 ° C in the fluidized bed dryer until it is reached ner exhaust air temperature of 53 ° C dried.

The low-dust product was passed through a sieve with a mesh size of 1.6 mm sieved. The proportion above 1.6 min was below 3%. The product obtained had a bulk density of 887 g / l.

The extruded and dried granules had the following composition:

12.88 wt .-% C₉-C₁₃ alkylbenzenesulfonate
6.63% by weight of C₁₂-C₁₃ fatty alkyl sulfate powder
0.96% by weight of C₁₂-C₁₈ fatty acid soap
2.23% by weight of C₁₂-C₁₄ fatty alcohol with 3 EO and C₁₂-C₁₈ fatty alcohol with 5 EO in a ratio of 1: 4
0.50% by weight of C₁₆-C₁₈ fatty alcohol with 5 EO
2.01% by weight additive: sodium lauryl sulfate
19.25% by weight of zeolite NaA (based on anhydrous active substance)
13.64% by weight sodium carbonate, anhydrous
6.07% by weight Sokalan CP5®
17.17% by weight sodium perborate monohydrate
1.00% by weight polyethylene glycol with a molecular weight of 400
1.00% by weight of C₁₆-C₁₈ fatty alcohol with 40 EO
Balance water, residual components, for example foam inhibitor concentrate and HEDP

The rate of dissolution of the granules was determined by the method of Leitfä ability measurement determines:

500 g of demineralized water (20 ° C.) were placed in a 1 liter glass jar filled, the propeller stirrer with a speed of 900 revolutions per Minute switched on and the conductivity measuring cell immersed. After that 5 g of the detergent granules were added. The change of the guidelines ability was recorded through a clerk. The measurement was made this way long until there was no increase in conductivity. The time until the conductivity is constant, the dissolution time of the whole Granules (100%). The dissolution time at 90% resolution was calculated determined.

The dissolution time of the granules according to the invention was at 20 ° C. and 90% Dissolution on the day of manufacture 2.54 minutes and after a storage time of 3 weeks at 25 ° C for 2.03 minutes.

Example 2

A premix of composition similar to that in Example 1 was prepared, but with 7.63% by weight of C ₁₂ -C ₁₈ fatty alkyl sulfate powder and 1% by weight of sodium octyl sulfate additive, which as a 42% by weight aqueous solution ( Texapon® 842, commercial product of the applicant) was introduced into the process in intimate mixture with the mixture of liquid nonionic surfactant, tallow alcohol with 40 EO and polyethylene glycol.

The further processing was carried out as in Example 1.

The bulk weight was 892 g / l. The dissolving time of the G2 granules was 20 ° C and 90% resolution on the day of production 2.32 minutes.  

Example 3

A mixture of composition similar to that in Example 1 was produced, but with 7.63% by weight of C ₁₂ -C ₁₈ fatty alkyl sulfate powder and 1% by weight of additive C ₁₂ -C ₁₄ alkyl sulfate, which was 35% by weight. % aqueous solution (Texapon® LS 35, commercial product of the applicant) after the mixing of the solid components and before the addition of the other liquid components was introduced into the process.

Further processing is carried out as in Example 1.

The bulk density was 894 g / l. The dissolution time of the G3 granules was 20 ° C and 90% resolution on the day of production 2.39 minutes.

Example 4

A premix of composition similar to that in Example 1 was prepared, but with 6.85% by weight of C ₁₂ -C ₁₈ fatty alkyl sulfate powder and 1.78% by weight of additive C ₈ -C ₁₆ alkyl sulfate, which as 31% by weight aqueous solution (Sulfopon® 102, commercial product of the applicant) after the mixing of the solid components and before the addition of the further liquid components was introduced into the process.

The further processing was carried out as in Example 1.

The bulk weight was 862 g / l. The dissolving time of the G4 granules was 20 ° C and 90% resolution on the day of production 2.50 minutes and after a storage time of 3 weeks at 25 ° C 2.38 minutes.

Example 5

A premix of composition similar to that in Example 1 was prepared, but with 4.87% by weight of C ₁₂ -C ₁₈ fatty alkyl sulfate powder and 3.76% by weight of additive C ₁₃ -C ₁₇ olefin sulfonate, used as Hostapur® OSB (commercial product from Hoechst AG, Federal Republic of Germany, 90% active substance), which was the last solid component to be introduced into the process before the liquid components were added.

The further processing was carried out as in Example 1.

The bulk weight was 872 g / l. The dissolving time of the G5 granules was 20 ° C and 90% resolution on the day of production 2.56 minutes and after a storage time of 3 weeks at 25 ° C 2.35 minutes.

Comparative example

A premix of composition similar to that in Example 1 was prepared, but with 8.64% by weight of C ₁₂ -C ₁₈ fatty alkyl sulfate powder and without an additive.

The premix was extruded, cut, rounded as in Example 1, dried and sieved. The bulk weight was 903.5 g / l. The release time the granules V were at 20 ° C. and 90% dissolution on the day of manufacture position 3.43 minutes.

table

Dissolving times of the granules G1 to G5 and V at 20 ° and 90% resolution in minutes

Claims (31)

1. A process for the preparation of solid detergents and cleaning agents with a high bulk density or a component of a solid detergent and cleaning agent with a high bulk density by combining solid and liquid detergent raw materials with simultaneous or subsequent shaping and drying if desired, using anionic surfactants, builder substances, alkalizing agents and liquid nonionic surfactants and optionally water or aqueous solutions are used, characterized in that first all solid constituents are mixed with one another and then the liquid constituents are added, an additive from the group consisting of fatty alkyl sulfates, olefin sulfonates, alkyl aromatic sulfonates and mixtures of these being used to improve the dissolving behavior after mixing the solid constituents is introduced into the process. 2. The method according to claim 1, characterized in that as an additive alkyl sulfates with 8 to 18 carbon atoms alone or in mixtures, preferably C ₈ alkyl sulfate, C ₁₂ alkyl sulfate, mixtures of C ₁₂ - to C ₁₈ alkyl sulfates, C ₁₂ - And C ₁₄ alkyl sulfates and C ₈ - to C ₁₆ alkyl sulfates can be used. 3. The method according to claim 1, characterized in that as an additive olefin sulfonates having 12 to 18 carbon atoms, preferably C ₁₃ -C ₁₈ olefin sulfonate and in particular C ₁₃ -C ₁₇ olefin sulfonate are used. 4. The method according to claim 1, characterized in that as an additive Toluene sulfonate or cumene sulfonate can be used. 5. The method according to any one of claims 1 to 4, characterized in that the additive in solid form as the last solid component is added to the other mixed solid components.   6. The method according to any one of claims 1 to 4, characterized in that the per se solid additive in the form of an aqueous mixture, preferably in a 25 to 60% by weight and in particular in a 30 to 45 wt .-% aqueous solution introduced into the process becomes. 7. The method according to claim 6, characterized in that the per se solid additive in the form of an aqueous solution before adding the other liquid components is introduced into the process. 8. The method according to claim 6, characterized in that the per se solid additive in the form of an aqueous solution with the liquid Nonionic surfactants or nonionic surfactant mixtures are mixed intensively and together with them in the process. 9. The method according to any one of claims 1 to 8, characterized in that the per se solid additive in the amounts in the process is brought that its content 0.5 to 8 wt .-%, based on the Mean. 10. The method according to claim 9, characterized in that the per se solid additive is introduced into the process in the quantities that its content 0.5 to 5 wt .-%, preferably 0.8 to 4 wt .-% and in particular 1 to 3 wt .-%, each based on the agent. 11. The method according to any one of claims 1 to 10, characterized in that that the liquid nonionic surfactants are mixed intimately with a structure turbrecher in a weight ratio liquid nonionic surfactant: structure turbo breakers from 10: 1 to 1: 2 can be introduced into the process. 12. The method according to claim 11, characterized in that as a structural breakdown polyethylene glycol or polypropylene glycol with a relative molecular weight between 200 and 12,000, preferably between 200 and 4000, ethoxylated C ₈ -C ₁₈ fatty alcohols with 20 to 45 EO or mixtures of these are used. 13. The method according to claim 12, characterized in that as a structure turbrech polyethylene glycol with a relative molecular weight between between 200 and 2000, preferably between 200 and 600, tallow alcohol with 30 to 40 EO and mixtures of these can be used. 14. The method according to any one of claims 11 to 13, characterized in that that the weight ratio of liquid nonionic surfactant: structure breaker 8: 1 to 1: 2, preferably 5: 1 to 1: 2 and in particular 10: 3 to 2: 3 carries, preferably as an ethoxylated liquid nonionic surfactant Fatty alcohol is used. 15. The method according to any one of claims 1 to 14, characterized in that one or more aqueous solutions of other ingredients, before preferably at least one aqueous solution of a homo- or copolymer Polycarboxylate, following the addition of the liquid nonionic surfactants or the liquid mixtures containing the nonionic surfactants in the procedure be introduced. 16. The method according to any one of claims 1 to 15, characterized in that the anionic surfactants are used in solid form and preferably as first component in the first stage of the process. 17. The method according to any one of claims 1 to 16, that surfactants in the men gene that the sum of surfactants and additive 15th to 50 wt .-%, preferably 20 to 45 wt .-%, each based on the Mean. 18. The method according to any one of claims 1 to 17, characterized in that 5 to 40 wt .-%, preferably 8 to 35 wt .-% anionic surfactants and 1 to 15% by weight, preferably 2 to 10% by weight, nonionic surfactants each based on the average, the weight ratio Anionic surfactant: nonionic surfactant preferably at least 1: 1 and in particular which is 2: 1 to 10: 1. 19. The method according to any one of claims 1 to 18, characterized in that you use 0.5 to 5 wt .-%, based on the agent, of soap.   20. The method according to any one of claims 1 to 19, characterized in that as a further solid component zeolite in amounts of 18 to 50 wt .-%, preferably up to 40 wt .-%, each based on water free substance, begins. 21. The method according to any one of claims 1 to 20, characterized in that that bleaching agents, preferably as further solid components Perborate monohydrate in amounts of 5 to 25 wt .-%, based on the Medium, uses. 22. The method according to any one of claims 1 to 21, characterized in that as further components an optical brightener and a blue Dye are used. 23. The method according to any one of claims 1 to 22, characterized in that one by assembling and shaping by a process leads in which a solid homogeneous premix with the addition of a Plasticizer and / or lubricant over hole shapes with opening th of the predetermined granule dimension at high pressures between 25 and 200 bar extruded and the strand directly after the Exit from the hole shape by means of a cutting device on the predetermined granule dimension is cut. 24. The method according to claim 23, characterized in that the bleaching activator, the enzymes and fragrances after the extrudates be added. 25. The method according to any one of claims 1 to 22, characterized in that one by assembling and shaping by a process leads, in which either the solid ingredients of a washing and Detergent or a spray-dried washing and cleaning medium or a mixture of spray dried and not spray dried solid ingredients of washing and cleaning agents, if necessary including the additive, in a quick running mixer compacted and simultaneously in this mixer or then in another device with the liquid  Ingredients, optionally including the aqueous solution additive, is mixed or acted upon. 26. The method according to any one of claims 1 to 25, characterized in that you have a bulk density of detergents between cleaning 600 and 1000 g / l. 27. Use of an additive from the group of fatty alkyl sulfates and olefin sulfonates to improve the dissolution behavior of solid Detergents and cleaning agents. 28. Use according to claim 27, characterized in that alkyl sulfates having 8 to 18 carbon atoms, alone or in mixtures, preferably C ₈ alkyl sulfate, C ₁₂ alkyl sulfate, mixtures of C ₁₂ to C ₁₈ alkyl sulfates, C ₁₂ and C ₁₄ alkyl sulfates and C ₈ to C ₁₆ alkyl sulfates are used as additives in detergents and cleaning agents which improve the dissolving behavior. 29. Use according to claim 27, characterized in that olefin sulfonates having 12 to 18 carbon atoms, preferably C ₁₃ -C ₁₈ olefin sulfonate and in particular C ₁₃ -C ₁₇ olefin sulfonate, are used as the dissolving additives in detergents and cleaning agents be det. 30. Use according to any one of claims 27 to 29, characterized in net that the solid additive per se is used in the amounts that its content is 0.5 to 8 wt .-%, based on the agent. 31. Use according to claim 30, characterized in that the per se solid additive is used in quantities such that its content is 0.5 up to 5% by weight, preferably 0.8 to 4% by weight and in particular 1 to 3 % By weight, based in each case on the average.