EP0929644B1 - Process for making compact cleaner containing surfactants - Google Patents

Abstract

A water-containing solid detergent having a delayed, controllable and variable hardening time after addition of all the components produced by providinga) aqueous 42 to 55% lye, in a quantity of 21 to 70% by weight,b) mixing with the aqueous lye a compound selected from the group corresponding to formula (I):in which R1 is a hydrogen atom or a methyl group and R2, independent of R1, is a hydrogen atom, a C1-4 alkyl group, a group CH2CH(R3)0R4 or a group CH2CH(R5)OCH2-CH(R6)OR7, where R3, R5, and R6 represent hydrogen atoms or methyl groups and R4and R7 represent hydrogen atoms or C1-4 alkyl groups, and compounds corresponding to formula II:in which R8 is a hydrogen atom or a methyl group and x is the number 0, 1 or 2, in a total quantity of 0.5 to 40% by weight, adding theretoc) a foam inhibitor, builder component, paraffin oil, or surfactants, or polyhydroxy compounds in the order given, and finally adding theretod) 2% to 25% by weight of solid alkali metal hydroxide, all weights being based on the weight of the detergent.

Description

The present invention relates to a method for producing water-based cleaning agents based on Alkali metal hydroxide with delayed, controlled and variable curing time. For The cleaning agents contain the desired firm consistency Glycols, glycol derivatives and / or certain alkanolamines and alkali metal hydroxide in solid form. Through a specific sequential addition of paraffin oil and / or Surfactants and other components from the group of Polyhydroxy compounds can be hardened through the water-containing Detergent delayed.

Highly alkaline cleaning agents are in a wide variety of forms commercially available, e.g. B. as a powder, as granules, as a liquid, as a melting block or as a tablet manufactured by compression.

Each form of presentation has very specific ones for a defined purpose Advantages and disadvantages. For cleaning textile surfaces or for manual mechanical cleaning of hard surfaces have powder, Granules or liquids have proven to be useful for machine cleaning hard surfaces, e.g. B. machine cleaning of dishes, in addition to powders, Granules or liquids increasingly also produced by pressing Tablets or obtained by melting and then cooling block-shaped cleaners (melting blocks) can be used. Tablets and Melting blocks offer opposite. Pulvem the advantage of a targeted and simple dosing, do not dust and are easy to handle.

These advantages can be found, for example, in household dishwashers use, but especially in continuously working commercial dishwashers, in which the wash ware to be cleaned through different washing zones is driven.

It has now been shown that very hard tablets and very hard enamel blocks Have disadvantages. For example, breakage of such tablets occur; tablets damaged in this way naturally no longer offer the benefit of accurate dosing. Another problem with tablets is in that the desired water solubility is not always guaranteed can, d. H. Tablets sometimes dissolve too quickly or too slowly. In the case of melting blocks, high breaking strength is required during transport expect, with larger containers there is a problem with the dosage of these very solid detergent. They also require both tablets also melting blocks have so far been very complex manufacturing processes, especially at processing of alkaline melts places particularly high demands on the materials used and the chosen conditions.

High homogeneity of the cleaners obtained is also particularly desirable, but which is often difficult to achieve with solid cleaners. This problem occurs less with liquid cleaners that can be easily stirred. The homogeneity of a liquid, a viscous one, would be desirable Liquid or a stirrable paste, which can then be controlled to a solid variable strength solidifies to at this stage its advantages in storage and to use transportation and dosing. It would be special desirable if the stirrability is maintained at temperatures up to approx. 40 ° C would remain, since then less temperature-stable components are also added could. In terms of application technology, it would be particularly advantageous to do this early Hardening of the material during the production process in the To prevent production equipment. Would be particularly desirable extensive control of the parameters affecting the hardening process decisively influence

The object of the present invention is to use highly alkaline, on alkali metal hydroxide, preferably potassium or sodium hydroxide, particularly preferably sodium hydroxide based cleaning agents of a general kind for textile surfaces, but preferably those for cleaning hard surfaces, e.g. B. dishes, and in particular cleaning agents for the commercial cleaning of dishes to provide the benefits of powders and liquids on the one hand and the On the other hand, combine the advantages of tablets and melting blocks. The means that cleaning agents should be provided, one of the most varied Have defined solubility, on the other hand, they are stable in transport and storage and, moreover, fast, are easy and precise to dose, they do not dust and without great technical Effort to manufacture and easy to fill. Especially that Stirability during production, a controlled variable strength of the Detergent and a delayed hardening in the manufacture and Storage would offer great advantages and should be taken into account. there a process should be developed that allows less if necessary, temperature-stable substances also below 42 ° C to incorporate without endangering the other tasks

Of course, the cleaning agents must also be provided at the same time Requirements such as good cleaning power, fat dissolving power, etc. must be met.

The state of the art already includes both higher-viscosity and pasty cleaning agents as well as solid detergents in tablet or block form.

For example, in the German published application DE-OS-31 38 425 the rheological Behavior of the cleaners described there so described that a gel-like paste by the action of mechanical forces, for example by Shake or apply pressure to a deformable storage bottle or tube or liquefied by means of a metering pump and easily from a spray nozzle expresses.

The US patent US 3,607,764 describes glass cleaning agents in solid Form that are diluted into a sprayable solution. These funds included i.a. Sodium or potassium hydroxide, sodium or potassium tripolyphosphate, Sodium or potassium pyrophosphate, hydroxycarboxylic acid builder water-soluble nonionic surfactant, alkylene glycol ether and optionally Sodium. A check of viscosity or strength in the sense of present invention is not described.

Japanese patent JP-A-84/182870 describes solutions of alkali metal hydroxides in glycols or alcohols, which are neutralized with long-chain Carboxylic acids become viscous and a by adding silicone oil have pasty consistency, making them used as pastes in leather greasing can be.

Japanese patent JP-A-86/296098 describes anhydrous solid cleaning agents based on alkali metal hydroxides. Here, the alkali carrier in Alkanolamines and water-soluble glycol ethers mixed, making one solid cleaner receives a technical lesson to variably reduce the Strength and to control the hardening process is not described.

WO 95/18213 describes a process for the production of solid, strongly alkaline Detergents described. Here, a solid alkali metal hydroxide with a aqueous solution of an alkali metal hydroxide mixed by wet grinding. The Alkaline matrix formed in this way can include further components, for example Sequestering agents, bleaching agents, thickening agents, surfactants or defoamers, be added. This process causes a quick hardening of the so manufactured cleaning agents.

According to Article 54 (3) EPC, WO 97/41203 is part of the prior art. This Patent application relates to compact cleaners for commercial dishwashers based on alkali metal hydroxide. An aqueous solution is used to prepare the agents Alkali metal hydroxide solution mixed with a compound of formula I and / or II. The formulas mentioned are described below in connection with the present invention explained. Then solid alkali metal hydroxide added. Other components, for example builder substances, bleach, Surfactants, defoamers or paraffin oil, are already formed thickened paste-like preparation.

a) wäßrige Alkalimetallhydroxidlauge in einer Menge von 21 bis 70 Gew.-% und

b) zum Aufbau einer erhöhten Viskosität eine Verbindung der Formel I HOCH₂CH(R¹)OR² in der R¹ für ein Wasserstoffatom oder eine Methylgruppe steht und R² unabhängig davon ein Wasserstoffatom, eine C₁ bis C₄-Alkylgruppe, eine Gruppe CH₂CH(R³)OR⁴ oder eine Gruppe CH₂CH(R⁵)OCH₂CH(R⁶)OR⁷ bedeutet, worin R³, R⁵ und R⁶ für Wasserstoffatome oder Methylgruppen und R⁴ und R⁷ für Wasserstoffatome oder C₁ bis C₄-Alkylgruppen stehen, und/oder eine Verbindungen der Formel II, [HOCH₂CH(R⁸)]_3-xNH_x in der R⁸ für ein Wasserstoffatom oder eine Methylgruppe und x für eine der Zahlen 0,1 oder 2 steht, in einer Gesamtmenge von 0,5 bis 40 Gew.-%, vermischt werden und

c) danach Alkalimetallhydroxid als Feststoff sowie Paraffinöl und/oder Tenside und/oder Polyhydroxyverbindungen sowie gegebenenfalls Schauminhibitoren, Buildersubstanzen und weitere übliche Reinigungsmittelbestandteile zugegeben werden,
dadurch gekennzeichnet, daß nach dem Vermischen der wäßrigen Alkalimetallhydroxidlauge mit einer Verbindung der Formeln I und/oder II

d) gegebenenfalls zunächst 0,1 bis 5 Gew.-% Schauminhibitoren und bis zu 60 Gew.-% Buildersubstanzen,

e) sodann bis zu 10 Gew.-% Paraffinöl und/oder bis zu 10 Gew.-% Tenside und/oder bis zu 10 Gew.-% einer Polyhydroxyverbindung, ausgewählt aus Glycerin und Glucose, oder Glyoxal und

f) erst nachfolgend bis zu 35 Gew.-% festes Alkalimetallhydroxid zugefügt werden, wobei alle Gew.-%-Angaben auf das gesamte Reinigungsmittel bezogen sind.

The present invention accordingly provides a process for the production of a solid cleaning agent for cleaning textile or hard surfaces with a delayed, controllable and variable curing time after combining all components, the water content of which is in the range from 10 to 35% by weight, in which

a) aqueous alkali metal hydroxide solution in an amount of 21 to 70 wt .-% and

b) to build up an increased viscosity, a compound of formula I. HIGH ₂ CH (R ¹ ) OR ² in which R ^{1 represents} a hydrogen atom or a methyl group and R ² independently of it a hydrogen atom, a C ₁ to C ₄ alkyl group, a group CH ₂ CH (R ³ ) OR ⁴ or a group CH ₂ CH (R ⁵ ) OCH ₂ CH (R ⁶ ) OR ⁷ , in which R ³ , R ⁵ and R ^{6 represent} hydrogen atoms or methyl groups and R ⁴ and R ^{7 represent} hydrogen atoms or C ₁ to C ₄ alkyl groups, and / or a compound of the formula II, [HIGH ₂ CH (R ⁸ )] _3-x NH _x in which R ^{8 represents} a hydrogen atom or a methyl group and x represents one of the numbers 0.1 or 2, in a total amount of 0.5 to 40% by weight, and are mixed

c) then alkali metal hydroxide as a solid as well as paraffin oil and / or surfactants and / or polyhydroxy compounds and optionally foam inhibitors, builder substances and other customary detergent components are added,
characterized in that after mixing the aqueous alkali metal hydroxide solution with a compound of the formulas I and / or II

d) optionally initially 0.1 to 5% by weight of foam inhibitors and up to 60% by weight of builder substances,

e) then up to 10% by weight of paraffin oil and / or up to 10% by weight of surfactants and / or up to 10% by weight of a polyhydroxy compound selected from glycerol and glucose, or glyoxal and

f) only up to 35% by weight of solid alkali metal hydroxide are subsequently added, all the% by weight data being based on the entire cleaning agent.

The delayable curing time is measured in that the Stirring continues after adding all components and until his Standstill due to curing is tracked. From a purely phenomenological point of view Composition at the time known as curing and that can be controlled, a consistency in which you don't like it desired, through a drain pipe located at the bottom of a production boiler can flow out, or flow out of an inverted beaker can leave.

The cleaning agents produced according to the invention have, for. B. a consistency at 20 ° C - 40 ° C not from a container, e.g. B. an upside down open beaker, can flow out. The consistency according to the invention can but also manifest themselves, for example, in the form of cut resistance. Many of the Cleaning agents produced according to the invention are during processing and Storage still compressible.

In the context of the process according to the invention, is used as aqueous Alkali metal hydroxide solution preferably contains 42 to 55% by weight of potassium and / or Sodium hydroxide solution, preferably in an amount of 35 to 55 wt .-% based on the Detergent. It is also preferred according to the invention as Compound of the formula I ethylene glycol, 1,2-propylene glycol, butyl glycol and / or Butyl diglycol and as a compound of formula II ethanolamine, diethanolamine and / or triethanolamine, preferably in a total amount of 1 to 10% by weight based on the detergent. As a solid alkali metal hydroxide potassium and / or sodium hydroxide are preferably used.

According to a particularly preferred embodiment of the invention Procedure after stirring of the compounds of formula I and / or II, first foam inhibitors and Builder components, then surfactants and / or paraffin oil and / or Polyhydroxy compounds, and finally up to 35% by weight, preferably 2 to 25% by weight, based on the total agent, of solid alkali metal hydroxide is preferred Potassium or sodium hydroxide, particularly preferably sodium hydroxide added.

Crucial for achieving the desired consistency or delayed curing is the coordination of all Ingredients, the order of the ingredients and their concentration to Preservation of specific characteristics on each other.

For example, it has been shown that those described in US Pat. No. 3,607,764 solid mixtures not simply by successively diluting with water in the test detergent produced according to the invention with the desired controllable rheological properties can be transferred.

It was also found that the introduction of NaOH (liquid) into alcohols or Glycols with the addition of further solid NaOH in the examined cases does not result in homogeneous agents that do not harden through controllable.

Conversely, the choice of substance composition according to the invention Surprisingly, no other additives besides the thickener and Z. B. solid alkali metal hydroxide, preferably potassium or sodium hydroxide, particularly preferably sodium hydroxide and addition of paraffin oil and / or Surfactants and / or polyhydroxy compounds, preferably glycerol, are necessary in order to desired, strengthening effect according to the invention in aqueous To achieve sodium hydroxide solution. It should also be emphasized that the addition the substances of the formula I or formula II together with alkali metal hydroxide solution, preferably potassium and Sodium hydroxide solution, particularly preferably sodium hydroxide solution alone for the desired one controllable strength is sufficient. This strength in turn can be achieved through the sequence of addition and concentration of paraffin oil according to the invention, Surfactants, polyhydroxy compounds prefer glycerin and solid NaOH over an application-technically favorable period at an appropriate temperature be held in a stirrable state, i.e. it can be a controllable Delay in material hardening can be achieved.

Finally, the water content is also a critical parameter; it lies between 10 and 35% by weight, advantageously between 20 and 30% by weight.

Due to the high NaOH content, the pH of those produced according to the invention is Detergent over 13.

However, the cleaning agents produced according to the invention can also in Combination with other agents can be used without the inventive variable strength is lost. The cleaning agent works in this sense from alkali metal hydroxide solution, preferably potassium and sodium hydroxide solution, in particular preferably sodium hydroxide solution, substance I and / or II and solid alkali metal hydroxide, preferably sodium hydroxide, and also surfactants and / or paraffin oil and / or Polyhydroxy compounds prefer glycerol as a carrier phase for others in Common peat cleaners.

Both anionic surfactants and cationic surfactants, amphoteric surfactants and non-ionic surfactants are used. In particular the curing time depends on their concentration after all components have been added from. Low foaming surfactants, especially non-ionic ones, can also be used Surfactants, in an amount of up to 10 wt .-%, preferably 1 to 5 wt .-% and particularly preferably 2 to 4 wt .-% may be included. Usually for machine dishwashing uses extremely low-foaming compounds.

These preferably include C ₁₂ -C ₁₈ alkyl polyethylene glycol polypropylene glycol ethers, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule. But you can also use other non-foaming non-foaming surfactants, such as B. C ₁₂ -C ₁₈ alkyl polyethylene glycol polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule and end-capped alkyl polyalkylene glycol mixed ether.

Should the mixtures according to the present invention be machined Washing laundry are used, so a higher is recommended Surfactant content, which can usually be up to 20 wt .-%. One uses then in addition to non-ionic, cationic and amphoteric surfactants anionic surfactants from the group of alkylbenzenesulfonates, fatty alcohol sulfates, the fatty alcohol ether sulfates u. a. known anionic surfactants

Paraffin oil, which according to the invention can contain up to 10% by weight, means long-chain hydrocarbons that are branched or not branched could be. In a preferred embodiment, they will Agents produced according to the invention between 0.1 and 8 wt .-%, particularly preferred between 0.5 and 5 wt .-% added.

Under organic polyhydroxy compound preferably glycerin, understood. But also other polyhydroxy compounds like glucose show the effect of the invention. Functional groups generally do not interfere with the success according to the invention So, although less preferred, also use dialdehydes such as glyoxal, which is among the strong alkaline conditions in substituted mono- or polyhydroxy compounds, such as B. Glycolic acid rearranged.

Optionally, the cleaning agents can also contain a builder substance an amount of up to 60 wt .-%, preferably 15 to 40 wt .-%, contain.

The builder substance contained in the cleaning agents produced according to the invention can in principle be any substance that is considered in the broadest sense in the prior art builders suitable for detergents and cleaning agents are known; preferably water-soluble builder substances are used. Also in the state of the Technically known coated builder substances can be used and are even preferred when working with bleaches containing chlorine.

As BuHdersubstanz come for. B. alkali phosphates in the form of their sodium or potassium salts may be present. Examples for this are: Tetrasodium diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate as well as the corresponding potassium salts or mixtures of sodium hexametaphosphate as well as the corresponding potassium salts or mixtures from sodium and potassium salts.

Furthermore, complexing agents are to be mentioned, such as. B. nitrilotriacetate or ethylenediaminetetraacetate. Soda and borax also count within the scope of the present Invention to builder substances.

Other possible water-soluble builder components are e.g. B. organic Polymers of native or synthetic origin, especially polycarboxylates. In Examples include polyacrylic acids and copolymers Maleic anhydride and acrylic acid as well as the sodium salts of these polymer acids. Commercial products are e.g. B. Sokalan® CP 5 and PA 30 from BASF, Alcosperse® 175 and 177 from Alco, LMW® 45 N and SPO2 ND from Norsohaas. Suitable native polymers include, for example, oxidized Starch (e.g. DE 42 28 786) and polyamino acids such as polyglutamic acid or polyaspartic acid, e.g. B. from the companies Cygnus, Bayer, Rohm & Haas, Rhône-Poulenc or SRCHEM.

Other possible builder components are naturally occurring hydroxycarboxylic acids such as B. mono-, dihydroxy-succinic acid, α-hydroxypropionic acid, Citric acid, gluconic acid and their salts. Citrates are preferred used in the form of trisodium citrate dihydrate.

Amorphous metasilicates or layered silicates can also be mentioned as builder substances. Crystalline layered silicates are also suitable builders insofar as they are sufficiently stable to alkali; Crystalline layered silicates are sold by Hoechst AG (Germany) under the trade name Na-SKS, e.g. B. Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O), Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O), makatite), Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS -7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-11 (τ-Na ₂ Si ₂ O ₅ ) and Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ).

Particularly preferred builder substances are those selected from the group Pentasodium triphosphate, trisodium citrate, nitrilotriacetate, ethylenediaminetetraacetate, Soda, alkali metal silicate or mixtures thereof.

Bleaching agents customary in cleaning agents can also be used in the inventive Prepared agents are included, then preferably between 0.5 and 10 wt .-% and particularly preferably between 1.5 and 10% by weight. These can be from the Group of oxygen-based bleaches, such as. B sodium perborate also in Form of its hydrates, or sodium percarbonate, or from the group of Chlorine-based bleaches, such as N-chloro-p-toluenesulfonamide, Trichloroisocyanuric acid, alkali dichloroisocyanurate, alkali hypochlorites, and alkali hypochlorites releasing agents, particularly alkali-stable bleaching compositions are preferred. These can be both alkali-stable substances or by suitable methods such as surface coating or passivation are stabilized components.

According to a further preferred embodiment of the invention Processes are carried out after the addition of compounds of the formulas I and / or II to aqueous alkali metal hydroxide solution, first paraffin foam inhibitors, then one or more builder components, then paraffin oil, then one or several surfactants, then solid sodium hydroxide and finally bleach added.

Other possible ingredients in the cleaners produced according to the invention are Defoamer. These can be in concentrations between 0.1 and 5 wt .-%, preferably 0.5 and 3% by weight are used when a selected surfactant foams too much under the given circumstances. They also work foam-dampening on foaming leftovers in the dishwasher. Defoamers are understood to mean all known in the prior art foam-suppressing substances, but preferably those based on silicone and paraffin, particularly preferred on a paraffin base, as z. B, in DE 34 00 008, DE 36 33 518, DE 30 00 483, DE 41 17 032, DE 4323410, WO 95/04124 and the as yet unpublished German application with the Ref .: 196 20 249. But other defoamers can also be used.

Optional ingredients are other common detergent ingredients, such as B. dyes or alkali-stable perfume substances. Abrasive In principle, ingredients can be included, but they are preferred Cleaning agent produced according to the invention, however, free of it.

Although in addition thickeners such. B. swellable layered silicates from Montmorillonite type, bentonite, kaolin, talc or carboxymethyl cellulose optional Can be used to vary the strength, they are to be achieved the desired controllable solids properties and the consistency of the Cleaning agents produced according to the invention are not required, d. H. on such Thickeners can be omitted.

Also the use of high-melting paraffins or high-melting polyethylene glycols for solidifying mixtures is here to achieve the invention Success not necessary, but also not excluded. Also the use of long chain fatty acids and long chain fatty acid salts, as used in the soap industry (chain lengths between C12 and C18) is not necessary to achieve the strength according to the invention. Also the production of liquid crystalline structures for thickening unnecessary.

Generally the process is at 20 ° C up to 50 ° C, preferably at 30 to 48 ° C, particularly preferably at 38-42 ° C.

Since the solubility of NaOH in water increases at higher temperatures, then the NaOH content in the aqueous solution is also more than 55% by weight be. Accordingly, the NaOH content can be at lower temperatures are also below 42% by weight. The restriction to 42 to 55% by weight NaOH solutions are therefore essentially limited to temperatures of 20 ° C to 25 ° C. Surfactants in detergents that are made up of all main classes, namely cation, anion, amphoteric and non-ionic Surfactants that can be selected are used in concentrations up to 10% by weight. used, but especially in concentrations between 0.1 to 5 wt .-% and very particularly preferably between 0.5 and 3.7% by weight. The paraffin oils are used in concentrations of up to 10% by weight, preferably between 0.1 and 8% by weight, particularly preferably between 0.5 and 5% by weight and in particular between 0.9 and 4.1% by weight. The polyhydroxy compounds, preferably glycerin, are used in concentrations of up to 10% by weight, preferably between 0.1 and 8% by weight, particularly preferably between 0.5 and 5 % By weight. The proportional concentrations of paraffins used and / or surfactants and / or polyhydroxy compounds, preferably glycerol on the desired curing time.

A particular advantage of the invention is that the stirrability and associated advantages are already given at room temperature. In some Cases, e.g. with greatly increased viscosity of the thickened alkali metal hydroxide solution, preferred Potash and sodium hydroxide solution, particularly preferably sodium hydroxide solution, can be used Adding the solid ingredients may be beneficial to reduce viscosity to go up slightly with the temperature. The invention In almost all cases, consistency can be below 42 ° C, preferably between 38 ° C and 42 ° C can be realized, so that less temperature stable Ingredients such as chlorine-containing bleach in the invention manufactured cleaning agents can be incorporated.

In particular, an early hardening of the cleaning agent due to the Addition of solid alkali metal hydroxide counteracted by previously others Components, for example foam inhibitors, builder substances, paraffin oils and / or surfactants and / or polyhydroxy compounds, preferably glycerin become. Depending on the desired curing time, all or only certain Substances of these classes can be added. A maximum curing time will achieved when all of the above substances are added in that order before solid alkali metal hydroxide is added for solidification. In a preferred embodiment is after completion of the addition of the compounds of the formula I and / or II for at least 3 minutes, preferably between 10 and 20 Minutes, stirred before adding the other components. After every further addition of material is preferably also at least 3 minutes, preferred between 8 and 15 minutes.

The cleaning agents produced according to the invention are preferably found Use for machine cleaning of dishes.

The use of the solid cleaning agents prepared according to the invention can, for. B. in the way that the in a container (capacity e.g. 0.5 to 10 kg) of detergent of controllable strength with water is sprayed on and the detergent thus released is used, e.g. B. is metered into a dishwasher. Here is an example one from Henkel Hygiene GmbH under the name Topmater® P40 dispenser or a solid dispenser sold by Henkel Ecolab V / VT-2000 on.

The cleaning agent can be produced, for example, in a stirred tank at 20 to 50 ° C, preferably at 30 to 48 ° C, particularly preferably at 38 - 42 ° C respectively. Technically, the detergent has the sequence-linked addition of paraffin oils and / or surfactants has the advantage that the curing of the cleaning agent can be delayed so long that it there can be no solid deposits in the production equipment. The cleaning agent can then be put into the sales container at approx. 40 ° C be filled and e.g. via a cooling tunnel to approx. 20 ° C to reach the are cooled according to the invention. But also other methods filling and return to room temperature are conceivable.

The cleaning agents produced according to the invention harden depending on the sequence of added components depending on the time after what through time-dependent measurements was determined and also by the respective Concentrations of surfactants and / or paraffin oils in the detergent composition is strongly influenced.

Examples

Detergents of the following compositions 1 to 15 were used Differences in the order of adding the components and the Composition of detergents made. 50% aqueous Sodium hydroxide solution was placed in a 21-beaker and heated to 38-40 ° C. With the slow stirring in of 1,2-propylene glycol (60 rpm), the Temperature to approx. 46 ° C. Stirring was continued for 15 min, then Paraffin foam inhibitor added and stirred again for 10 min. The temperature is then reduced to 38 to 40 ° C and remains constant held. The other components of the compositions were in the in added the order shown in the table and stirred for 10 min each. After adding the last component (chlorine carrier) was carried out by a specialist determines the length of time until the degree of hardness of the composition that the Stirring at 38 to 40 ° C was very difficult or no longer allowed. From a purely phenomenological point of view, the composition after this time a consistency in which you can not get it as desired by a bottom of one Production boiler located drain pipe can flow out, or from can flow out of an inverted beaker

The amounts in the following table relate to the% by weight of the present components. The influence of the order of the added Components on the curing time must be considered in comparison.

All mixtures can be stirred homogeneously and filled into containers. The hardening process but is different in speed.

The various constituents or their order of admixing and to a lesser extent also their concentration have different effects on the variable curing time of the material. This will be briefly explained in the following. Ingredient B1 Ingredient B2 Ingredient B3 Sodium hydroxide solution (50% aq) 42.1 Sodium hydroxide solution (50% aq) 41.1 Sodium hydroxide solution (50% aq) 41.1 1,2 propylene glycol 6 1,2 propylene glycol 6 1,2 propylene glycol 6 Paraffin defoamers 1.5 Paraffin defoamers 1.5 Paraffin defoamers 1.5 NaOH (solid) (microprills) 20th NaOH (solid) (microprills) 20th NaOH (solid) (microprills) 20th Paraffin oil - Paraffin oil 1 Paraffin oil 3.6 Surfactant 2.6 Surfactant 2.6 Surfactant - Sodium tripolyphosphate 22 Sodium tripolyphosphate 22 Sodium tripolyphosphate 22 Chlorine carrier (coated) 5.8 Chlorine carrier (coated) 5.8 Chlorine carrier (coated) 5.8 approximate max. Stirring time in min 5 approximate max. Stirring time in min 5 approximate max. Stirring time in min 5

A comparison of tests B1, B2 and B3 shows that each has a relatively short curing time of only about 5 minutes be added. With the same sequence, it is irrelevant for the curing time whether the addition of paraffin oil (B1) or surfactants (B3) is omitted. Ingredient B4 Ingredient B5 Ingredient B6 Sodium hydroxide solution (50% aq) 42.1 Sodium hydroxide solution (50% aq) 41.1 Sodium hydroxide solution (50% aq) 41.1 1,2 propylene glycol 6 1,2 propylene glycol 6 1,2 propylene glycol 6 Paraffin defoamers 1.5 Paraffin defoamers 1.5 Paraffin defoamers 1.5 Sodium tripolyphosphate 20th Sodium tripolyphosphate 20th Sodium tripolyphosphate 20th Paraffin oil - Paraffin oil 1 Paraffin oil 3.6 Surfactant 2.6 Surfactant 2.6 Surfactant - NaOH (solid) (microprills) 22 NaOH (solid) (microprills) 22 NaOH (solid) (microprills) 22 Chlorine carrier (coated) 5.8 Chlorine carrier (coated) 5.8 Chlorine carrier (coated) 5.8 approximate max. Stirring time in min 30th approximate max. Stirring time in min 90 approximate max. Stirring time in min 90

In example B4, as in all the following examples, the order is changed in that now after adding the foam inhibitors Builder component is added. The addition is then made in example B5 of paraffin oil (no paraffin oil was added in experiment B4), then of Surfactants and finally solid NaOH and chlorine carrier. The positions of solid NaOH and the builder component are therefore exchanged. At this Addition sequence increases the curing time to 30 min if no paraffin oil is present (B4), or even for 90 min, if paraffin oil - as in example B5 - has been added.

In example B6, compared to example B5, the influence of the surfactant component is examined in more detail by the fact that no surfactant has been added. Such a composition and sequence of the components added leads to a curing time of 90 min. Ingredient B7 Ingredient B8 Ingredient B9 Sodium hydroxide solution (50% aq) 44.7 Sodium hydroxide solution (50% aq) 43.7 Sodium hydroxide solution (50% aq) 41.1 1.2 propylene glycol 6 1,2 propylene glycol 6 1,2 propylene glycol 6 Paraffin defoamers 1.5 Paraffin defoamers 1.5 Paraffin defoamers 1.5 Sodium tripolyphosphate 20th Sodium tripolyphosphate 20th Sodium tripolyphosphate 20th Paraffin oil - Paraffin oil 1 Paraffin oil - Surfactant - Surfactant - Surfactant 3.6 NaOH (solid) (microprills) 22 NaOH (solid) (microprills) 22 NaOH (solid) (microprills) 22 Chlorine carrier (coated) 5.8 Chlorine carrier (coated) 5.8 Chlorine carrier (coated) 5.8 approximate max. Stirring time in min 5 approximate max. Stirring time in min 5 approximate max. Stirring time in min 45

In experiment B7, both the addition of paraffin oil and surfactants refrain from checking. In fact, despite the changed order in in this case there is no increase in the curing time. It is - how in tests B1, B2 and B3 - 5 min. This is through experiments 4, 5, 6 and 7 shown that both the paraffin oil and the surfactants are added at positions 5 and 6 to extend the curing time. in the Experiment B8, the surfactant component was not added and the proportion of Paraffin component reduced to 1% by weight compared to experiment B6. Also in this case the curing time is only 5 minutes.

In example B9, no paraffin oil is added, and a possible compensatory effect by increasing the proportion of surfactant is examined. In fact, the curing time with a surfactant content of 3.6% by weight increases to 45 minutes in comparison to experiment B4 (30 minutes). Ingredient B10 (% by weight) B11 (% by weight) B12 (% by weight) B13 (% by weight) B14 (% by weight) B15 (% by weight) Sodium hydroxide solution (50% aq) 43 39 40 39 38.8 38.8 1.2 propylene glycol 5 6 5 6 6 6 Sodium tripolyphosphate (coated) 23 23 23 23 18.5 23 Soda (calc.) 7 7 5 7 6 6 Paraffin oil - - 5 - - - Glycerin - - - 3rd - 3rd Glyoxal (40%) - - - - 7.5 - Surfactant / foam suppressor 1 4th 1 1 1.2 1.2 NaOH (solid) (microprills) 21 21 21 21 22 22 approximate max. Stirring time in min about 10 about 40 about 90 about 180 approx. 120 about 180

The thickened stirrable pastes according to Examples B10, B11 and B12 can vary depending on the amount of glycerin over the others Components are extended, so in the example B13 and B15 to approx. 180 min.

Also the addition of aqueous glyoxal (which can be found among the strongly alkaline conditions spontaneously to glycolic acid or 3-hydroxypropanoic acid, implemented) leads to a delayed hardening (in Example B14 this is 120 min). However, the addition causes a lot violent jump in temperature, so that when incorporating temperature-unstable Substances on this delay medium should be avoided. Polyhydroxy compounds of the glucose type lead at the high pH values u. U. to brown discoloration and are then not special prefers. When using ethylene glycol it happens with higher ones Concentrations to inhomogeneities. The strongly alkaline conditions result to a precipitate, which also does not meet the conditions of a homogeneous Sales product fulfilled.

In summary it can be said that both the order and also the concentration of the added components the curing time influence. The longest curing time is achieved if both Paraffin oil as well as surfactants and polyhydroxy compounds, preferably glycerin, be added and only after their addition solid NaOH is stirred.

Claims (14)

1. A process for the production of a solid detergent for cleaning textile or hard surfaces with a delayed, controllable and variable hardening time after combination of all the components and with a water content of 10 to 35% by weight, in which

   a) aqueous alkali metal hydroxide lye in a quantity of 21 to 70% by weight
   and, to build up a high viscosity,

   b) a compound corresponding to formula (I): HOCH₂CH(R¹)OR² in which R¹ is a hydrogen atom or a methyl group and R², independently of R¹, is a hydrogen atom, a C_1-4 alkyl group, a group CH₂CH(R³)OR⁴ or a group CH₂CH(R⁵)OCH₂CH(R⁶)OR⁷, where R³, R⁵ and R⁶ represent hydrogen atoms or methyl groups and R⁴ and R⁷ represent hydrogen atoms or C_1-4 alkyl groups, and/or compounds corresponding to formula (II): [HOCH₂CH(R⁸)_3-xNH_x in which R⁸ is a hydrogen atom or a methyl group and x is the number 0, 1 or 2,
   in a total quantity of 0.5 to 40% by weight, are mixed and

   c) solid alkali metal hydroxide and paraffin oil and/or surfactants and/or polyhydroxy compounds and optionally foam inhibitors, builders and other typical detergent ingredients are added,
   characterized in that, after the aqueous alkali metal hydroxide lye has been mixed with a compound corresponding to formulae I and/or II,

   d) first 0.1 to 5% by weight of foam inhibitors and up to 60% by weight of builders,

   e) then up to 10% by weight of paraffin oil and/or up to 10% by weight of surfactants and/or up to 10% by weight of a polyhydroxy compound selected from glycerol or glyoxal and

   f) afterwards up to 35% by weight of solid alkali metal hydroxide

   are optionally added, all percentages by weight being based on the detergent as a whole.
2. A process as claimed in claim 1, characterized in that a 42 to 55% by weight potash or soda lye is used as the aqueous alkali metal hydroxide lye, preferably in a quantity of 35 to 55% by weight, based on the detergent.
3. A process as claimed in claim 1 or 2, characterized in that ethylene glycol, 1,2-propylene glycol, butyl glycol and/or butyl diglycol is present as the compound corresponding to formula I while ethanolamine, diethanolamine and/or triethanolamine is/are present as the compound corresponding to formula II, preferably in a total quantity of 1 to 10% by weight, based on the detergent.
4. A process as claimed in one or more of claims 1 to 3, characterized in that paraffin oil is used in a quantity of 0.1 to 8% by weight and preferably 0.5 to 5% by weight, based on the detergent.
5. A process as claimed in one or more of claims 1 to 4, characterized in that anionic, cationic, amphoteric or nonionic surfactants are used as the surfactants.
6. A process as claimed in claim 6, characterized in that the surfactants are used in a quantity of 0.1 to 5% by weight and preferably 1 to 5% by weight, based on the detergent.
7. A process as claimed in one or more of claims 1 to 6, characterized in that glycerol is used as the polyhydroxy compound, preferably in a quantity of 0.1 to 8% by weight, based on the detergent.
8. A process as claimed in one or more of claims 1 to 7, characterized in that a compound selected from the group consisting of pentasodium triphosphate, trisodium citrate, nitrilotriacetate, ethylenediamine tetraacetate, soda, alkali metal silicate or mixtures thereof is used as the builder.
9. A process as claimed in claim 8, characterized in that the builder is used in a quantity of 15 to 40% by weight, based on the detergent.
10. A process as claimed in one or more of claims 1 to 9, characterized in that potassium and/or sodium hydroxide is/are used as the solid alkali metal hydroxide, preferably in a quantity of 2 to 25% by weight, based on the detergent.
11. A process as claimed in one or more of claims 1 to 10, characterized in that a bleaching agent is used as another typical detergent ingredient in a quantity of 0.5 to 10% by weight and preferably 1.5 to 10% by weight, based on the detergent.
12. A process as claimed in claim 11, characterized in that, after the addition of compounds I and/or II to the aqueous alkali metal hydroxide lye, first paraffin-based foam inhibitors, then one or more builder component(s), then paraffin oil, then one or more surfactants, then solid NaOH and, finally, bleaching agent are added.
13. A process as claimed in one or more of claims 1 to 12, characterized in that the addition of compounds corresponding to formula I and/or formula II to the aqueous alkali metal hydroxide lye is followed by stirring for at least 3 minutes and preferably for 10 to 20 minutes before other components are added.
14. A process as claimed in claim 13, characterized in that the addition of every other component is followed by stirring for at least 3 minutes and preferably for 8 to 15 minutes.