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

Process for making compact cleaner containing surfactants Download PDF

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Publication number
EP0929644B1
EP0929644B1 EP97910336A EP97910336A EP0929644B1 EP 0929644 B1 EP0929644 B1 EP 0929644B1 EP 97910336 A EP97910336 A EP 97910336A EP 97910336 A EP97910336 A EP 97910336A EP 0929644 B1 EP0929644 B1 EP 0929644B1
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EP
European Patent Office
Prior art keywords
weight
detergent
alkali metal
surfactants
metal hydroxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP97910336A
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German (de)
French (fr)
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EP0929644A1 (en
Inventor
Dieter Hemm
Günter Hellmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ecolab GmbH and Co OHG
Original Assignee
Henkel Ecolab GmbH and Co KG
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Filing date
Publication date
Priority claimed from DE1996139118 external-priority patent/DE19639118A1/en
Application filed by Henkel Ecolab GmbH and Co KG filed Critical Henkel Ecolab GmbH and Co KG
Publication of EP0929644A1 publication Critical patent/EP0929644A1/en
Application granted granted Critical
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/044Hydroxides or bases
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2068Ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02Inorganic compounds
    • C11D7/04Water-soluble compounds
    • C11D7/06Hydroxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/261Alcohols; Phenols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/263Ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/32Organic compounds containing nitrogen
    • C11D7/3218Alkanolamines or alkanolimines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/32Organic compounds containing nitrogen
    • C11D7/3227Ethers thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/32Organic compounds containing nitrogen
    • C11D7/3245Aminoacids

Definitions

  • 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.
  • the cleaning agents contain the desired firm consistency Glycols, glycol derivatives and / or certain alkanolamines and alkali metal hydroxide in solid form.
  • 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.
  • 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 cleaning agents must also be provided at the same time Requirements such as good cleaning power, fat dissolving power, etc. must be met.
  • 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.
  • 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.
  • a solid alkali metal hydroxide with a aqueous solution of an alkali metal hydroxide mixed by wet grinding 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.
  • 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.
  • solid alkali metal hydroxide added.
  • Other components for example builder substances, bleach, Surfactants, defoamers or paraffin oil, are already formed thickened paste-like preparation.
  • 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.
  • 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.
  • 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.
  • 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.
  • the water content is also a critical parameter; it lies between 10 and 35% by weight, advantageously between 20 and 30% by weight.
  • the pH of those produced according to the invention is Detergent over 13.
  • 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.
  • 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.
  • 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.
  • 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.
  • Surfactant content which can usually be up to 20 wt .-%.
  • 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.
  • 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.
  • 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.
  • 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.
  • water-soluble builder components are e.g. B. organic Polymers of native or synthetic origin, especially polycarboxylates.
  • polycarboxylates 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.
  • hydroxycarboxylic acids such as B. mono-, dihydroxy-succinic acid, ⁇ -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 ( ⁇ -Na 2 Si 2 O 5 )
  • Na-SKS -7 ⁇ -Na 2 Si 2 O 5 , natrosilite
  • Na-SKS-11 ⁇ -Na 2 Si 2 O 5
  • Na-SKS-6 ⁇ -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.
  • 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.
  • Defoamer 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.
  • thickeners such as 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.
  • the process is at 20 ° C up to 50 ° C, preferably at 30 to 48 ° C, particularly preferably at 38-42 ° C.
  • 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.
  • a particular advantage of the invention is that the stirrability and associated advantages are already given at room temperature.
  • preferred Potash and sodium hydroxide solution particularly preferably sodium hydroxide solution
  • Adding the solid ingredients may be beneficial to reduce viscosity to go up slightly with the temperature.
  • 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.
  • 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.
  • Components for example foam inhibitors, builder substances, paraffin oils and / or surfactants and / or polyhydroxy compounds, preferably glycerin become.
  • 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.
  • 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.
  • a container capacity e.g. 0.5 to 10 kg
  • the detergent thus released is used, e.g. B. is metered into a dishwasher.
  • 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.
  • 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.
  • 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.
  • 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 NaOH (solid) (microprills) 20th Paraffin oil - Paraffin oil 1 Paraffin oil 3.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant - Sodium tripolyphosphate 22 Sodium tripolyphosphate 22 Chlorine carrier (coated) 5.8 Chlorine carrier (coated) 5.8 Chlorine carrier (coated) 5.8 Chlorine carrier (coated)
  • 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 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant 2.6 Surfactant
  • 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.
  • 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.
  • 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 Paraffin defoamers 1.5 Sodium tripolyphosphate 20th 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 Na
  • 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.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

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

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung wasserhaltiger Reinigungsmittel auf Basis von Alkalimetallhydroxyd mit verzögerter, kontrollierter und variierbarer Aushärtdauer. Zur Einstellung der gewünschten festen Konsistenz enthalten die Reinigungsmittel Glykole, Glykolderivate und/oder bestimmte Alkanolamine und Alkalimetallhydroxyd in fester Form. Durch eine spezifisch-sequentielle Zugabe von Paraffinöl und/oder Tensiden und weiteren Komponenten aus der Gruppe der Polyhydroxyverbindungen läßt sich die Durchhärtung des wasserhaltigen Reinigungsmittels verzögem.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.

Hochalkalische Reinigungsmittel sind heute in den verschiedensten Darbietungsformen im Handel erhältlich, z. B. als Pulver, als Granulat, als Flüssigkeit, als Schmelzblock oder als durch Verpressen hergestellte Tablette.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.

Jede Darbietungsform hat für einen definierten Verwendungszweck ganz spezifische Vorteile und Nachteile. Zum Reinigen von textilen Oberflächen oder zum manuellen mechanischen Reinigen von harten Oberflächen haben sich Pulver, Granulate oder Flüssigkeiten bewährt, während zum maschinellen Reinigen von harten Oberflächen, z. B. maschinellen Reinigen von Geschirr, neben Pulvern, Granulaten oder Flüssigkeiten zunehmend auch durch Verpressen hergestellte Tabletten oder durch Schmelzen und anschließendes Erkaltenlassen erhaltene blockförmige Reiniger (Schmelzblöcke) verwendet werden. Tabletten und Schmelzblöcke bieten gegenüber. Pulvem den Vorteil einer zielgenauen und einfachen Dosierung, stauben nicht und sind leicht handhabbar.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.

Diese Vorteile lassen sich beispielsweise in Haushaltsgeschirrspülmaschinen nutzen, vor allem aber in kontinuierlich arbeitenden gewerblichen Geschirrspülmaschinen, in denen das zu reinigende Spülgut durch verschiedene Waschzonen gefahren wird. 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.

Es hat sich nun gezeigt, daß sehr harte Tabletten und sehr harte Schmelzblöcke Nachteile aufweisen. So können z.B. an solchen Tabletten Bruchschäden auftreten; solchermaßen geschädigte Tabletten bieten naturgemäß nicht mehr den Vorteil einer genauen Dosierung. Ein weiteres Problem bei Tabletten besteht darin, daß die gewünschte Wasserlöslichkeit nicht immer gewährleistet werden kann, d. h. Tabletten lösen sich bisweilen entweder zu schnell oder zu langsam. Bei Schmelzblöcken ist zwar beim Transport eine hohe Bruchfestigkeit zu erwarten, bei größeren Gebinden tritt aber ein Problem bei der Dosierung dieser sehr festen Reinigungsmittel auf. Darüber hinaus erfordern sowohl Tabletten als auch Schmelzblöcke bisher sehr aufwendige Herstellverfahren, die gerade bei der Verarbeitung von alkalischen Schmelzen besonders hohe Anforderungen an die verwendeten Materialien und die gewählten Bedingungen stellen.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.

Besonders erwünscht ist auch eine hohe Homogenität der erhaltenen Reiniger, die aber bei festen Reinigem oft nur schwierig zu realisieren ist. Dieses Problem tritt bei flüssigen Reinigem, die leicht gerührt werden können, weniger auf. Erwünscht wäre also die Homogenität einer Flüssigkeit, einer viskosen Flüssigkeit oder einer rührbaren Paste, die dann zu einem Feststoff kontrollierbar variierbarer Festigkeit erstarrt, um in diesem Stadium deren Vorteile bei Lagerung und Transport und Dosierung zu nutzen. Dabei wäre es besonders wünschenswert, wenn die Rührbarkeit bei Temperaturen bis zu ca 40 °C erhalten bliebe, da dann auch weniger temperaturstabile Bestandteile zugemischt werden könnten. Anwendungstechnisch wäre es von besonderem Vorteil eine frühzeitige Durchhärtung des Materials während des Produktionsprozesses in den Produktionsapparaturen zu verhindem. Ganz besonders wünschenswert wäre eine weitgehende Kontrolle der Parameter, die den Durchhärteprozeß entscheidend beeinflussenHigh 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

Aufgabe der vorliegenden Erfindung ist es, hochalkalische, auf Alkalimetallhydroxid, bevorzugt Kalium- oder Natriumhydroxid, besonders bevorzugt Natriumhydroxid basierende Reinigungsmittel allgemeiner Art für textile Oberflächen, vorzugsweise aber solche zum Reinigen von harten Oberflächen, z. B. Geschirr, und insbesondere Reinigungsmittel zum gewerblichen Reinigen von Geschirr bereitzustellen, die die Vorteile von Pulvem und Flüssigkeiten einerseits und die Vorteile von Tabletten und Schmelzblöcken andererseits in sich vereinen. Das heißt, es sollen Reinigungsmittel bereitgestellt werden, die eine unter den verschiedensten Anwendungsbedingungen definierte Löslichkeit besitzen, andererseits aber transportstabil und lagerstabil sind und darüber hinaus schnell, einfach und genau zu dosieren sind, die nicht stauben und ohne großen technischen Aufwand herstellbar und einfach abfüllbar sind. Besonders die Rührbarkeit bei der Herstellung, eine kontrolliert variierbare Festigkeit der Reinigungsmittel und eine verzögerte Durchhärtung bei der Herstellung und Lagerung würde große Vorteile bieten und sollen berücksichtigt werden. Dabei sollte ein Verfahren entwickelt werden, das es gestattet, weniger temperaturstabile Substanzen nötigenfalls auch unterhalb von 42 °C einzuarbeiten, ohne die anderen Aufgaben zu gefährdenThe 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

Selbstverständlich müssen gleichzeitig auch die an Reinigungsmittel zu stellenden Erfordemisse wie gute Reinigungskraft, Fettlösekraft, etc. erfüllt sein.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.

Im Stand der Technik sind bereits sowohl höherviskose bis pastöse Reinigungsmittel als auch feste Reinigungsmittel in Tabletten- oder Blockform beschrieben.The state of the art already includes both higher-viscosity and pasty cleaning agents as well as solid detergents in tablet or block form.

So wird z.B. in der deutschen Offenlegungsschrift DE-OS-31 38 425 das rheologische Verhalten der dort beschriebenen Reiniger so beschrieben, daß sich eine gelartige Paste durch Einwirkung mechanischer Kräfte, beispielsweise durch Schütteln oder Druckeinwirkung auf eine verformbare Vorratsflasche bzw. Tube oder mittels einer Dosierpumpe verflüssigt und leicht aus einer Spritzdüse ausdrücken läßt.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.

Die US-Patentschrift US 3,607,764 beschreibt Glasreinigungsmittel in fester Form, die zu einer versprühbaren Lösung verdünnt werden. Diese Mittel enthalten u.a. Natrium- oder Kaliumhydroxid, Natrium- oder Kaliumtripolyphosphat, Natrium- oder Kaliumpyrophosphat, Hydroxycarbonsäure-Builder, ein wasserlösliches nichtionisches Tensid, Alkylenglykolether und gegebenenfalls Natriumcarbonat. Eine Kontrolle der Viskosität oder der Festigkeit im Sinne der vorliegenden Erfindung wird nicht beschrieben.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.

Die japanische Patentschrift JP-A-84/182870 beschreibt Lösungen von Alkalimetallhydroxiden in Glycolen oder Alkoholen, die durch das Neutralisieren mit langkettigen Carbonsäuren viskos werden und durch Zugabe von Siliconöl eine pastöse Konsistenz erhatten, wodurch sie als Pasten in der Lederfettung verwendet werden können.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.

Die japanische Patentschrift JP-A-86/296098 beschreibt wasserfreie feste Reinigungsmittel basierend auf Alkalimetallhydroxiden. Hierbei wird der Alkaliträger in Alkanolamine und wasserlösliche Glycolether gemischt, wodurch man einen festen Reiniger erhält Eine technische Lehre zur variierbaren Verringerung der Festigkeit und zur Kontrolle des Härteprozesses wird nicht beschrieben. 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.

In der WO 95/18213 wird ein Verfahren zur Herstellung von festen, stark alkalischen Reinigungsmitteln beschrieben. Hierbei wird ein festes Alkalimetallhydroxid mit einer wäßrigen Lösung eines Alkalimetallhydroxids durch Naßvermahlung vermischt. Der so gebildeten alkalischen Matrix können weitere Komponenten, beispielsweise Sequestriermittel, Bleichmittel, Verdickungsmittel, Tenside oder Entschäumer, zugefügt werden. Dieses Verfahren bewirkt ein schnelles Erhärten der so hergestellten Reinigungsmittel.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.

Die WO 97/41203 zählt gemäß Artikel 54(3) EPÜ zum Stand der Technik. Diese Patentanmeldung betrifft Kompaktreiniger für gewerbliche Geschirrspülmaschinen auf Basis von Alkalimetallhydroxid. Zur Herstellung der Mittel wird eine wäßrige Alkalimetallhydroxidlauge mit einer Verbindung der Formel I und/oder II vermischt. Die genannten Formeln werden nachfolgend im Zusammenhang mit der vorliegenden Erfindung erläutert. Anschließend wird festes Alkalimetallhydroxid zugefügt. Weitere Komponenten, beispielsweise Buildersubstanzen, Bleichmittel, Tenside, Entschäumer oder Paraffinöl, werden der so gebildeten, bereits angedickten pastenförmigen Zubereitung zugemischt.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.

Gegenstand der vorliegenden Erfindung ist demgegebenüber ein Verfahren zur Herstellung eines festen Reinigungsmittels zur Reinigung von textilen oder harten Oberflächen mit einer verzögerten, kontrollierbaren und veränderlichen Aushärtdauer nach Vereinigung aller Komponenten, dessen Wassergehalt im Bereich von 10 bis 35 Gew.-% liegt, bei welchem

  • 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-xNHx 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.
  • Dabei wird die verzögerbare Aushärtdauer dadurch gemessen, daß der Rührvorgang nach Zugabe aller Komponenten fortgesetzt wird und bis zu seinem Stillstand infolge der Aushärtung verfolgt wird. Rein phänomenologisch hat die Zusammensetzung an dem Zeitpunkt, der als Aushärtung bezeichnet wird und der kontrolliert werden kann, eine Konsistenz, in der man sie nicht, wie gewünscht, durch ein unten an einem Produktionskessel befindliches Abflußrohr ausfließen lassen kann, oder aus einem umgedrehten Becherglas ausfließen lassen kann.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.

    Die erfindungsgemäß hergestellten Reinigungsmittel haben also z. B. eine Konsistenz bei der sie bei 20°C - 40°C nicht aus einem Behälter, z. B. einem umgedrehten offenen Becherglas, ausfließen können. Die erfindungsgemäße Konsistenz kann sich aber zum Beispiel auch in Form von Schnittfestigkeit äußem. Viele der erfindungsgemäß hergertellten Reinigungsmittel sind während der Verarbeitung und der Lagerung noch formgebend verpreßbar. 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.

    Im Rahmen des erfindungsgemäßen Verfahrens wird als wäßrige Alkalimetallhydroxidlauge bevorzugt eine 42 bis 55 Gew.-%ige Kali- und/oder Natronlauge, vorzugsweise in einer Menge von 35 bis 55 Gew.-% bezogen auf das Reinigungsmittel, eingesetzt. Ferner ist es erfindungsgemäß bevorzugt, als Verbindung der Formel I Ethylenglykol, 1,2-Propylenglykol, Butylglykol und/oder Butyldiglykol sowie als Verbindung der Formel II Ethanolamin, Diethanolamin und/oder Triethanolamin, vorzugsweise in einer Gesamtmenge von 1 bis 10 Gew.-% bezogen auf das Reinigungsmittel, einzusetzen. Als festes Alkalimetalthydroxid werden bevorzugt Kalium- und/oder Natriumhydroxid eingesetzt.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.

    Gemäß einer besonders bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens werden nach dem Einrühren der Verbindungen der Formel I und/oder II, zunächst Schauminhibitoren und Builderkomponenten, dann Tenside und/oder Paraffonöl und/oder Polyhydroxyverbindungen, und schließlich bis zu 35 Gew.-% vorzugsweise 2 bis 25 Gew.-%, bezogen auf das gesamte Mittel, festes Alkalimetallhydroxid, bevorzugt Kalium- oder Natriumhydroxid, besonders bevorzugt Natriumhydroxid zugegeben.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.

    Entscheidend für das Erreichen der gewünschten Konsistenz oder der verzögerten Durchhärtung ist die erfindungsgemäße Abstimmung aller Inhaltstoffe, der Reihenfolge der Inhaltsstoffe und deren Konzentration zum Erhalt spezifischer Merkmale aufeinander.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.

    So hat es sich beispielsweise gezeigt, daß die in US 3,607,764 beschriebenen festen Mischungen nicht einfach durch sukzessives Verdünnen mit Wasser in das erfindungsgemäß hergestellte teste Reinigungsmittel mit den gewünschten kontrollierbaren rheologischen Eigenschaften überführt werden können.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.

    Auch wurde gefunden, daß ein Einbringen von NaOH (flüssig) in Alkohole oder Glycole unter Zusatz von weiterem festen NaOH in den untersuchten Fällen keine homogenen Mittel ergibt, die auch nicht kontrollierbar durchhärten.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.

    Umgekehrt sind aber bei erfindungsgemäßer Wahl der Stoffzusammensetzung überraschenderweise auch keine weiteren Zusatzstoffe außer dem Verdickungsmittel und z. B. festem Alkalimetallhydroxid, bevorzugt Kalium- oder Natriumhydroxid, besonders bevorzugt Natriumhydroxid und Zugabe von Paraffinöl und/oder Tensiden und/oder Polyhydroxyverbindungen bevorzugt Glycerin nötig, um den gewünschten, erfindungsgemäßen, verfestigenden Effekt in wäßriger Natronlauge zu erzielen. Darüber hinaus ist zu betonen, daß auch die Zugabe der Stoffe der Formel I oder Formel II zusammen mit Alkalimetallhydroxidlauge, bevorzugt Kaliund Natronlauge, besonders bevorzugt Natlronlaugelalleine für die gewünschte kontrollierbare Festigkeit genügt. Diese Festigkeit wiederum kann durch die erfindungsgemäße Sequenz der Zugabe und die Konzentration von Paraffinöl, Tensiden, Polyhydroxyverbindungen bevorzugt Glycerin und festem NaOH über einen anwendungstechnisch günstigen Zeitraum, bei angemessener Temperatur in rührbarem Zustand gehatten werden, d.h. es kann eine kontrollierbare Verzögerung der Materialdurchhärtung erreicht werden.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.

    Schließlich ist auch der Wassergehalt ein kritischer Parameter; er liegt zwischen 10 und 35 Gew.-%, vorteilhafterweise zwischen 20 und 30 Gew.-%.Finally, the water content is also a critical parameter; it lies between 10 and 35% by weight, advantageously between 20 and 30% by weight.

    Aufgrund des hohen NaOH-Gehaltes liegt der pH-Wert der erfindungsgemäß hergestellten Reinigungsmittel über 13.Due to the high NaOH content, the pH of those produced according to the invention is Detergent over 13.

    Die erfindungsgemäß hergestellten Reinigungsmittel können aber darüber hinaus noch in Kombination mit anderen Mittein verwendet werden, ohne daß die erfindungsgemäße variierbare Festigkeit verloren geht. In diesem Sinne wirkt das Reinigungsmittel aus Alkalimetallhydroxidlauge, bevorzugt Kali- und Natronlauge, besonders bevorzugt Natronlauge, Substanz I und/oder II und festem Alkalimetallhydroxid, bevorzugt Natriumhydroxid, sowie Tensiden und/oder Paraffinöl und/oder Polyhydroxyverbindungen bevorzugt Glycerinl als Trägerphase für andere in Reinigern übliche Inhaltstorfe.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.

    Als Tenside können sowohl Aniontenside als auch Kationtenside, amphotere Tenside und nicht-ionische Tenside eingesetzt werden. Insbesondere von ihrer Konzentration hängt die Aushärtdauer nach Zugabe aller Komponenten ab. Auch können schwach schäumende Tenside, vor allem nichtionische Tenside, in einer Menge von bis zu 10 Gew.-%, bevorzugt 1 bis 5 Gew.-% und besonders bevorzugt 2 bis 4 Gew.-% enthalten sein. Üblicherweise werden für das maschinelle Geschirrspülen extrem schaumarme Verbindungen eingesetzt. 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.

    Hierzu zählen vorzugsweise C12-C18-Alkylpolyethylenglykolpolypropylenglykolether mit jeweils bis zu 8 Mol Ethylenoxid- und Propylenoxideinheiten im Moiekül. Man kann aber auch andere als schaumarm bekannte nichtionische Tenside verwenden, wie z. B. C12-C18-Alkylpolyethylenglykolpolybutylenglykolether mit jeweils bis zu 8 Mol Ethylenoxid- und Butylenoxideinheiten im Molekül sowie endgruppenverschlossene Alkylpolyalkylenglykolmischether.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.

    Sollten die Mischungen gemäß der vorliegenden Erfindung zum maschinellen Waschen von Wäsche eingesetzt werden, so empfiehlt sich ein höherer Tensidgehalt, der in der Regel bis 20 Gew.-% betragen kann. Man verwendet dann neben nichtionischen, kationischen und amphoteren Tensiden besonders anionische Tenside aus der Gruppe der Alkylbenzolsulfonate, der Fettalkoholsulfate, der Fettalkoholethersulfate u. a. bekannter anionischer TensideShould 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

    Unter Paraffinöl, das erfindungsgemäß bis zu 10 Gew.-% enthalten sein kann, versteht man langkettige Kohlenwasserstoffe, die verzweigt oder nicht verzweigt sein können. In einer bevorzugten Ausführungsform werden sie den erfindungsgemäß hergestellten Mitteln zwischen 0,1 und 8 Gew.-%, besonders bevorzugt zwischen 0,5 und 5 Gew.-%, zugesetzt.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.

    Unter organischer Polyhydroxyverbindung wird bevorzugt Glycerin, verstanden. Aber auch andere Polyhydroxyverbindungen wie Glucose zeigen den erfindungsgemäßen Effekt. Funktionelle Gruppen stören den erfindungsgemäßen Erfolg in der Regel nicht So kann man, wenn auch weniger bevorzugt, auch Dialdehyde wie Glyoxal verwenden, das sich unter den stark alkalischen Bedingungen in substituierte Mono- oder Polyhydroxyverbindungen, wie z. B. Giycolsäure, umlagert.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.

    Fakultativ können die Reinigungsmittel zusätzlich eine Buildersubstanz in einer Menge von bis zu 60 Gew.-%, vorzugsweise 15 bis 40 Gew.-%, enthalten. Optionally, the cleaning agents can also contain a builder substance an amount of up to 60 wt .-%, preferably 15 to 40 wt .-%, contain.

    Die in den erfindungsgemäß hergestellten Reinigungsmitteln enthaltene Buildersubstanz kann im Prinzip jeder Stoff sein, der im Stand der Technik als im weitesten Sinne für Wasch- und Reinigungsmittel geeigneter Builder bekannt ist; vorzugsweise werden wasserlösliche Buildersubstanzen eingesetzt. Auch die im Stand der Technik bekannten gecoateten Buildersubstanzen können eingesetzt werden und sind sogar bevorzugt, wenn man mit chlorhaltigen Bleichmitteln arbeitet.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.

    Als BuHdersubstanzen kommen z. B. Alkaliphosphate, die in Form ihrer Natrium- oder Kaliumsalze vorliegen können, in Frage. Beispiele hierfür sind: Tetranatriumdiphosphat, Pentanatriumtriphosphat, sogenanntes Natriumhexametaphosphat sowie die entsprechenden Kaliumsalze bzw. Gemische aus Natriumhexametaphosphat sowie die entsprechenden Kaliumsalze bzw. Gemische aus Natrium- und Kaliumsalzen.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.

    Weiterhin sind Komplexbildner zu nennen, wie z. B. Nitrilotriacetat oder Ethylendiamintetraacetat. Auch Soda und Borax zählen im Rahmen der vorliegenden Erfindung zu den Buildersubstanzen.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.

    Weitere mögliche wasserlösliche Builderkomponenten sind z. B. organische Polymere nativen oder synthetischen Ursprungs, vor allem Polycarboxylate. In Betracht kommen beispielsweise Polyacrylsäuren und Copolymere aus Maleinsäureanhydrid und Acrylsäure sowie die Natriumsalze dieser Polymersäuren. Handelsübliche Produkte sind z. B. Sokalan® CP 5 und PA 30 von BASF, Alcosperse® 175 und 177 von Alco, LMW® 45 N und SPO2 ND von Norsohaas. Zu den geeigneten nativen Polymeren gehören beispielsweise oxidierte Stärke (z. B. DE 42 28 786) und Polyaminosäuren wie Polyglutaminsäure oder Polyasparaginsäure, z. B. der Firmen Cygnus, Bayer, Rohm & Haas, Rhône-Poulenc oder SRCHEM.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.

    Weitere mögliche Builderkomponenten sind natürlich vorkommende Hydroxycarbonsäuren wie z. B. Mono-, Dihydroxy-bemsteinsäure, α-Hydroxypropionsäure, Citronensäure, Gluconsäure, sowie deren Salze. Citrate werden vorzugsweise in Form von Trinatriumcitrat-Dihydrat eingesetzt.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.

    Als Buildersubstanzen sind weiterhin amorphe Metasilikate oder Schichtsilikate zu nennen. Auch kristalline Schichtsilikate sind geeignete Builder, soweit sie hinreichend alkalistabil sind; kristalline Schichtsilikate werden von der Fa. Hoechst AG (Deutschland) unter dem Handelsnamen Na-SKS vertrieben, z. B. Na-SKS-1 (Na2Si22O45·xH2O, Kenyait), Na-SKS-2 (Na2Si14O29·xH2O, Magadiit), Na-SKS-3 (Na2Si8O17·xH2O), Na-SKS-4 (Na2Si4O9·xH2O), Makatit), Na-SKS-5 (α-Na2Si2O5), Na-SKS-7 (β-Na2Si2O5, Natrosilit), Na-SKS-11 (τ-Na2Si2O5) und Na-SKS-6 (δ-Na2Si2O5).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 ).

    Besonders bevorzugte Buildersubstanzen sind die ausgewählt aus der Gruppe Pentanatriumtriphosphat, Trinatriumcitrat, Nitrilotriacetat, Ethylendiamintetraacetat, Soda, Alkalimetallsilikat bzw. deren Mischungen.Particularly preferred builder substances are those selected from the group Pentasodium triphosphate, trisodium citrate, nitrilotriacetate, ethylenediaminetetraacetate, Soda, alkali metal silicate or mixtures thereof.

    Auch in Reinigungsmitteln übliche Bleichmittel können in den erfindungsgemäß hergestellten Mitteln enthalten sein, dann bevorzugt zwischen 0.5 und 10 Gew.-% und besonders bevorzugt zwischen 1,5 und 10 Gew.-%. Diese können aus der Gruppe der Bleichmittel auf Sauerstoffbasis, wie z. B Natriumperborat auch in Form seiner Hydrate, oder Natriumpercarbonat, oder aus der Gruppe der Bleichmittel auf Chlorbasis, wie N-Chlor-p-toluolsulfonsäureamid, Trichlorisocyanursäure, Alkalidichiorisocyanurat, Alkalihypochlorite, und Alkalihypochlorite freisetzende Mittel, wobei besonders alkalistabile Bleichmittelzusammensetzungen bevorzugt sind. Dies können sowohl alkalistabile Substanzen sein, oder durch geeignete Verfahren wie beispielsweise durch Oberflächenbeschichtung oder -passivierung stabilisierte Komponenten sein. 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.

    Nach einer weiteren bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens werden nach erfolgter Zugabe von Verbindungen der Formeln I und/oder II zur wäßrigen Alkalimetallhydroxidlauge zunächst Paraffin-Schauminhibitoren, danach eine oder mehrere Builderkomponenten, danach Paraffinöl, danach ein oder mehrere Tenside, danach festes Natriumhydroxid und schließlich Bleichmittel hinzugefügt.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.

    Weitere mögliche Inhaltsstoffe in den erfindungsgemäß hergestellten Reinigern sind Entschäumer. Diese können in Konzentrationen zwischen 0,1 und 5 Gew.-%, bevorzugt 0,5 und 3 Gew.-% zum Einsatz kommen, wenn ein gewähltes Tensid unter den gegebenen Umständen zu stark schäumt. Auch wirken sie schaumdämpfend auf schäumende Speisereste in der Geschirrspülmaschine. Unter Entschäumern versteht man alle im Stand der Technik bekannten schaumdämpfenden Stoffe, bevorzugt aber solche auf Silikon- und Paraffinbasis, besonders bevorzugt auf Paraffinbasis, wie sie z. B, in der DE 34 00 008, der DE 36 33 518, der DE 30 00 483, der DE 41 17 032, der DE 4323410, der WO 95/04124 und der noch nicht veröffentlichten deutschen Anmeldung mit dem Az.: 196 20 249 beschrieben sind. Aber auch andere Entschäumer können verwendet werden.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.

    Fakultativ enthaltene Inhaltsstoffe sind weitere übliche Reinigungsmittelbestandteile, wie z. B. Farbstoffe oder alkalistabile Parfumstoffe. Abrasiv wirkende Inhaltsstoffe können zwar prinzipiell enthalten sein, vorzugsweise sind die erfindungsgemaß hergestellten Reinigungsmitte jedoch frei davon.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.

    Obwohl zusätzlich Verdickungsmittel wie z. B. quellfähige Schichtsilikate vom Montmorillonit-Typ, Bentonit, Kaolin, Talk oder Carboxymethylcellulose fakultativ eingesetzt werden können, um die Festigkeit zu variieren, sind sie zur Erreichung der gewünschten kontrollierbaren Feststoffeigenschaften und der Konsistenz der erfindungsgemäß hergestellten Reinigungsmittel nicht erforderlich, d. h. auf solche Verdickungsmittel kann verzichtet werden.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.

    Auch der Einsatz hochschmelzender Paraffine oder hochschmelzender Polyethylenglycole zur Verfestigung von Mischungen ist hier zur Erzielung des erfindungsgemäßen Erfolges nicht notwendig, aber auch nicht ausgeschlossen. Auch der Einsatz von langkettigen Fettsäuren und langkettigen Fettsäuresalzen, wie sie in der Seifenindustrie eingesetzt werden (Kettenlängen zwischen C12 und C18) ist zur Erzielung der erfindungsgemäßen Festigkeit nicht erforderlich. Ebenfalls ist die Erzeugung von flüssigkristallinen Strukturen zur Verdickung nicht notwendig. 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.

    Im allgemeinen wird das Verfahren bei 20°C bis 50°C bevorzugt bei 30 bis 48°C besonders bevorzugt bei 38 - 42°C durchgeführt. Generally the process is at 20 ° C up to 50 ° C, preferably at 30 to 48 ° C, particularly preferably at 38-42 ° C.

    Da bei höheren Temperaturen die Löslichkeit von NaOH in Wasser steigt, kann dann der Gehalt an NaOH in der wäßrigen Lösung auch mehr als 55 Gew.-% betragen. Entsprechend kann bei niedrigeren Temperaturen der NaOH-Gehalt auch unter 42 Gew.-% liegen. Die Einschränkung auf 42 bis 55 Gew-%ige NaOH-Lösungen beschränkt sich daher im wesentlichen auf Temperaturen von 20°C bis 25°C. Tenside im Reinigungsmittel, die aus allen Hauptklassen, nämlich Kation, Anion-, amphotere und nicht-ionische Tenside, ausgewählt werden können, werden in Konzentrationen bis zu 10 Gew.-% verwendet, insbesondere aber in Konzentrationen zwischen 0,1 bis 5 Gew.-% und ganz besonders bevorzugt zwischen 0,5 und 3,7 Gew.-%. Die Paraffinöle werden in Konzentrationen bis zu 10 Gew.-% eingesetzt, bevorzugt zwischen 0,1 und 8 Gew.%, besonders bevorzugt zwischen 0,5 und 5 Gew.-% und insbesondere zwischen 0,9 und 4,1 Gew.-%. Die Polyhydroxyverbindungen, bevorzugt Glycerin, werden in Konzentrationen bis zu 10 Gew.-% eingesetzt, bevorzugt zwischen 0,1 und 8 Gew.% besonders bevorzugt zwischen 0,5 und 5 Gew.-%. Die eingesetzten anteilmäßigen Konzentrationen der Paraffine und/oder Tenside und/oder Polyhydroxyverbindungen, bevorzugt Glycerin, hängen von der gewünschten Aushärtdauer ab.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.

    Ein besonderer Vorteil der Erfindung liegt darin, daß die Rührbarkeit und die damit verbundenen Vorteife bereits bei Raumtemperatur gegeben sind. In manchen Fällen, z.B. bei stark erhöhter Viskosität der verdickten Alkalimetallhydroxidlauge, bevorzugt Kali- und Natronlauge, besonders bevorzugt Natronlauge, kann es vor Zugabe der festen Inhaltstoffe günstig sein, zur Verringerung der Viskosität geringfügig mit der Temperatur nach oben zu gehen. Die erfindungsgemäße Konsistenz kann aber in fast allen Fällen unterhalb 42 °C, bevorzugt zwischen 38 °C und 42 °C realisiert werden, so daß auch weniger temperaturstabile Bestandteile wie zum Beispiel chlorhaltige Bleichmittel in die erfindungsgemaß hergestellten Reinigungsmittel eingearbeitet werden können. 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.

    Insbesondere wird einer frühen Aushärtung des Reinigungsmittels infolge der Zugabe von festem Alkalimetallhydroxid dadurch entgegengewirkt, daß zuvor andere Komponenten, beispielsweise Schauminhibitoren, Buildersubstanzen, Parafinöle und/oder Tenside und/oder Polyhydroxyverbindungen, bevorzugt Glycerin, zugesetzt werden. Je nach der gewünschten Aushärtdauer können alle oder nur gewisse Substanzen dieser Klassen hinzugefügt werden. Eine maximale Aushärtdauer wird erreicht, wenn alle oben genannten Substanzen in dieser Reihenfolge hinzugegeben werden, ehe festes Alkalimetallhydroxid zur Verfestigung beigemischt wird. In einer bevorzugten Ausführungsform wird nach Beendigung der Zugabe der Verbindungen der Formel I und/oder II noch mindestens 3 Minuten, bevorzugt zwischen 10 und 20 Minuten, nachgerührt, bevor man die anderen Komponenten zusetzt. Nach jeder weiteren Stoffzugabe wird vorzugsweise auch mindestens 3 Minuten, bevorzugt zwischen 8 und 15 Minuten, gerührt.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.

    Die erfindungsgemäß hergestellten Reinigungsmittel finden vorzugsweise Verwendung zum maschinellen Reinigen von Geschirr. The cleaning agents produced according to the invention are preferably found Use for machine cleaning of dishes.

    Die Anwendung der erfindungsgemäß hergestellten festen Reinigungsmittel kann z. B. in der Weise erfolgen, daß das in einem Gebinde (Fassungsvermögen z. B. 0,5 bis 10 kg) befindliche Reinigungsmittel kontrollierbarer Festigkeit mit Wasser angesprüht wird und das so gelöste Reinigungsmittel zur Anwendung kommt, z. B. in eine Geschirrspülmaschine eindosiert wird. Hier bietet sich beispielsweise ein von der Henkel Hygiene GmbH unter der Bezeichnung Topmater® P40 vertriebenes Dosiergerät oder ein von Henkel Ecolab vertriebenes Feststoffdosiergerät V/VT-2000 an.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.

    Die Herstellung des Reinigungsmittels kann beispielsweise in einem Rührkessel bei 20 bis 50°C, bevorzugt bei 30 bis 48°C, besonders bevorzugt bei 38 - 42°C erfolgen. Das Reinigungsmittel besitzt verfahrenstechnisch durch die sequenzgebundene Zugabe von Paraffinölen und/oder Tensiden den Vorteil, daß die Aushärtung des Reinigungsmittels so lange verzögert werden kann, daß es zu keinen festen Ablagerungen in den Produktionsapparaturen kommen kann. Anschließend kann das Reinigungsmittel bei ca. 40°C in das Verkaufsgebinde abgefüllt werden und z.B. über einen Kühltunnel auf ca 20 °C zur Erreichung der erfindungsgemäßen Konsistenz abgekühlt werden. Aber auch andere Methoden der Abfüllung und Rückführung auf Raumtemperatur sind denkbar.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.

    Die erfindungsgemäß hergestellten Reinigungsmittel härten je nach Sequenz der zugegebenen Komponenten abhängig von der Zeit nach, was durch zeitabhängige Messungen ermittelt wurde und auch von den jeweiligen Konzentrationen von Tensiden und/oder Paraffinölen in der Reinigungsmittelzusammensetzung stark beeinflußt wird. 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.

    BeispieleExamples

    Es wurden Reinigungsmittel der folgenden Zusammensetzungen 1 bis 15 mit Unterschieden in der Reihenfolge bei der Zugabe der Komponenten und der Zusammensetzung der Reinigungsmittel hergestellt. 50 %ige wäßrige Natronlauge wurden in einem 21-Becherglas vorgelegt und auf 38-40° C erwärmt. Unter langsamem Einrühren von 1,2-Propylenglykol (60 U/min)) steigt die Temperatur auf ca. 46° C an. Für 15 min wurde nachgerührt, danach wurde Paraffin-Schauminhibitor zugegeben und abermals 10 min nachgerührt. Nachfolgend wird die Temperatur auf 38 bis 40° C reduziert und konstant gehalten. Die weiteren Komponenten der Zusammensetzungen wurden in der in der Tabelle gezeigten Reihenfolge zugegeben und jeweils 10 min nachgerührt. Nach Zugabe der letzten Komponente (Chlorträger) wurde von einem Fachmann die Zeitdauer bis zu jenem Härtegrad der Zusammensetzung ermittelt, der das Rühren bei 38 bis 40° C nur noch sehr schwer oder überhaupt nicht mehr zuließ. Rein phänomenologisch hatte die Zusammensetzung nach diesem Zeitpunkt eine Konsistenz, in der man sie nicht, wie gewünscht, durch ein unten an einem Produktionskessel befindliches Abflußrohr ausfließen lassen kann, oder aus einem umgedrehten Becherglas ausfließen lassen kannDetergents 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

    Die Mengenangaben der folgenden Tabelle beziehen sich auf die Gew.-% der vorliegenden Komponenten. Der Einfluß der Reihenfolge der zugegebenen Komponenten auf die Aushärtdauer muß im Vergleich betrachtet werden.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.

    Alle Mischungen sind homogen rührbar und in Behälter abfüllbar. Der Durchhärteprozeß ist aber unterschiedlich schnell.All mixtures can be stirred homogeneously and filled into containers. The hardening process but is different in speed.

    Die verschiedenen Bestandteile bzw. ihre Reihenfolge beim Zumischen und in geringerem Ausmaß auch ihre Konzentration wirkt sich unterschiedlich auf die variierbare Aushärtdauer des Materials aus. Dies soll im folgenenden kurz erklärt werden. Inhaltstoff B1 Inhaltstoff B2 Inhaltstoff B3 Natronlauge (50% aq) 42,1 Natronlauge (50% aq) 41,1 Natronlauge (50% aq) 41,1 1,2 Propylenglycol 6 1,2 Propylenglycol 6 1,2 Propylenglycol 6 Paraffin-Entschäumer 1,5 Paraffin-Entschäumer 1,5 Paraffin-Entschäumer 1,5 NaOH (fest) (Microprills) 20 NaOH (fest) (Microprills) 20 NaOH (fest) (Microprills) 20 Paraffinöl - Paraffinöl 1 Paraffinöl 3,6 Tensid 2,6 Tensid 2,6 Tensid - Natriumtripolyphosphat 22 Natriumtripolyphosphat 22 Natriumtripolyphosphat 22 Chlorträger (gecoatet) 5,8 Chlorträger (gecoatet) 5,8 Chlorträger (gecoatet) 5,8 ungefähre max. Rührzeit in min 5 ungefähre max. Rührzeit in min 5 ungefähre max. Rührzeit in min 5 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

    Der Vergleich der Versuche B1, B2 und B3 zeigt, daß jeweils eine relativ kurze Aushärtdauer von nur ungefähr 5 min vorliegt In Beispiel B2 wird dies für den Fall gezeigt, daß nach Zugabe des Propylenglykols, Paraffinschauminhibitor, dann festes NaOH und schließlich Paraffinöl und dann Tenside hinzugegeben werden. Bei gleicher Reihenfolge ist es für die Aushärtdauer unerheblich, ob die Zugabe von Paraffinöl (B1) oder von Tensiden (B3) unterbleibt. Inhaltstoff B4 Inhaltstoff B5 Inhaltstoff B6 Natronlauge (50% aq) 42,1 Natronlauge (50% aq) 41,1 Natronlauge (50% aq) 41,1 1,2 Propylenglycol 6 1,2 Propylenglycol 6 1,2 Propylenglycol 6 Paraffin-Entschäumer 1,5 Paraffin-Entschäumer 1,5 Paraffin-Entschäumer 1,5 Natriumtripolyphosphat 20 Natriumtripolyphosphat 20 Natriumtripolyphosphat 20 Paraffinöl - Paraffinöl 1 Paraffinöl 3,6 Tensid 2,6 Tensid 2,6 Tensid - NaOH (fest) (Microprills) 22 NaOH (fest) (Microprills) 22 NaOH (fest) (Microprills) 22 Chlorträger (gecoatet) 5,8 Chlorträger (gecoatet) 5,8 Chlorträger (gecoatet) 5,8 ungefähre max. Rührzeit in min 30 ungefähre max. Rührzeit in min 90 ungefähre max. Rührzeit in min 90 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 Beispiel B4 wird ebenso wie in allen folgenden Beispielen die Reihenfolge insofem verändert, als nun nach der Zugabe der Schauminhibitoren eine Builderkomponente hinzugefügt wird. Danach erfolgt im Beispiel B5 die Zugabe von Paraffinöl (in Versuch B4 wurde kein Paraffinöl hinzugefügt), dann von Tensiden und schließlich von festem NaOH und von Chlorträger. Die Positionen von festem NaOH und der Builderkomponente sind also ausgetauscht. Bei dieser Zugabesequenz erhöht sich die Aushärtdauer auf 30 min, wenn kein Paraffinöl vorliegt (B4), oder gar auf 90 min, wenn Paraffinöl - wie in Beispiel B5 - zugemischt worden ist.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 Beispiel B6 wird, verglichen mit Beispiel B5, der Einfluß der Tensidkomponente dadurch näher beleuchtet, daß kein Tensid hinzugefügt worden ist. Eine solche Zusammensetzung und Reihenfolge der zugegeben Komponenten führt zu einer Aushärtdauer von 90 min. Inhaltstoff B7 Inhaltstoff B8 Inhaltstoff B9 Natronlauge (50% aq) 44,7 Natronlauge (50% aq) 43,7 Natronlauge (50% aq) 41,1 1.2 Propylenglycol 6 1,2 Propylenglycol 6 1,2 Propylen - glycol 6 Paraffin-Entschäumer 1,5 Paraffin-Entschäumer 1,5 Paraffin-Entschäumer 1,5 Natriumtripolyphosphat 20 NatriumtripolyPhosphat 20 Natriumtripolyphosphat 20 Paraffinöl - Paraffinöl 1 Paraffinöl - Tensid - Tensid - Tensid 3,6 NaOH (fest) (Microprills) 22 NaOH (fest) (Microprills) 22 NaOH (fest) (Microprills) 22 Chlorträger (gecoatet) 5,8 Chlorträger (gecoatet) 5,8 Chlorträger (gecoatet) 5,8 ungefähre max. Rührzeit in min 5 ungefähre max. Rührzeit in min 5 ungefähre max. Rührzeit in min 45 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 Versuch B7 wurde sowohl die Zugabe von Paraffinöl als auch von Tensiden als Kontrolle unterlassen. Tatsächlich ist trotz der veränderten Reihenfolge in diesem Fall keine Verlängerung der Aushärtdauer festzustellen. Sie beträgt - wie in den Versuchen B1, B2 und B3 - 5 min. Damit ist durch die Versuche 4, 5, 6 und 7 gezeigt, daß sowohl das Paraffinöl als auch die Tenside durch die Zugabe an den Positionen 5 und 6 zur Verlängerung der Aushärtdauer beitragen. Im Versuch B8 wurde die Tensidkomponente nicht hinzugefügt und der Anteil der Paraffinkomponente im Vergleich zum Versuch B6 auf 1 Gew.-% reduziert. Auch in diesem Fall beträgt die Aushärtdauer nur 5 min.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.

    Im Beispiel B9 wird kein Paraffinöl hinzugesetzt, und ein etwaiger kompensatorischer Effekt durch die Erhöhung des Tensidanteils untersucht. Tatsächlich verlängert sich die Aushärtdauer bei einem Tensidanteil von 3,6 Gew.-% auf 45 min im Vergleich zum Versuch B4 (30 min). Inhaltstoff B10 (Gew.-%) B11 (Gew.%) B12 (Gew.-%) B13 (Gew.-%) B14 (Gew.-%) B15 (Gew.-%) Natronlauge (50% aq) 43 39 40 39 38,8 38,8 1.2 Propylenglycol 5 6 5 6 6 6 Natriumtripolyphosphat (gecoatet) 23 23 23 23 18,5 23 Soda (calc.) 7 7 5 7 6 6 Paraffinöl - - 5 - - - Glycerin - - - 3 - 3 Glyoxal (40 % ig) - - - - 7,5 - Tensid/Schaumdämpfer 1 4 1 1 1,2 1,2 NaOH (fest) (Microprills) 21 21 21 21 22 22 ungefähre max. Rührzeit in min ca. 10 ca. 40 ca. 90 ca. 180 ca. 120 ca. 180 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

    Die verdickten rührbaren Pasten gemäß den Beispielen B10, B11 und B12 können in Abhängigkeit von der Menge von Glycerin gegenüber den anderen Komponenten verlängert werden, so im Beispiel B13 und B15 auf ca. 180 min.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.

    Auch die Zugabe von wässrigem Glyoxal (welches sich unter den herschenden stark alkalischen Bedingungen spontan zu Glycolsäure, bzw. 3-Hydroxypropansäure, umsetzt) führt zu einer verzögerten Aushärtung (im Beispiel B14 sind dies 120 min). Die Zugabe verursacht allerdings einen sehr heftigen Temperatursprung, so daß bei der Einarbeitung von temperaturlabilen Substanzen auf dieses Verzögerumgsmedium verzichtet werden sollte. Polyhydroxyverbindungen vom Typ der Glucose führen bei den hohen pH-Werten u. U. zu bräunlichen Verfärbungen und sind dann nicht besonders bevorzugt. Bei der Verwendung von Ethylenglycol kommt es bei höheren Konzentrationen zu Inhomogenitäten. Die stark alkalischen Bedingungen führen zu einem Niederschlag, der ebenfalls nicht die Bedingungen eines homogenenen Verkaufsproduktes erfüllt.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.

    Zusammenfassend kann festgestellt werden, daß sowohl die Reihenfolge als auch die Konzentration der zugefügten Komponenten die Aushärtdauer beeinflussen. Die längste Aushärtdauer wird dann erreicht, wenn sowohl Paraffinöl als auch Tenside und Polyhydroxyverbindungen, bevorzugt Glycerin, hinzugegeben werden und erst im Anschluß an deren Zugabe festes NaOH eingerührt wird.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 C1-4 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 C1-4 alkyl groups, and/or compounds corresponding to formula (II): [HOCH2CH(R8)3-xNHx 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.
    EP97910336A 1996-09-24 1997-09-23 Process for making compact cleaner containing surfactants Expired - Lifetime EP0929644B1 (en)

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    DE1996139118 DE19639118A1 (en) 1996-09-24 1996-09-24 Solid water-containing cleaning agent with retarded hardening
    DE19639118 1996-09-24
    DE19648107 1996-11-21
    DE19648107 1996-11-21
    PCT/EP1997/005218 WO1998013466A1 (en) 1996-09-24 1997-09-23 Compact cleaner containing surfactants

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    EP0929644A1 EP0929644A1 (en) 1999-07-21
    EP0929644B1 true EP0929644B1 (en) 2001-11-21

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    AU727115B2 (en) 2000-11-30
    CA2266068A1 (en) 1998-04-02
    WO1998013466A1 (en) 1998-04-02
    AU4777397A (en) 1998-04-17
    NO991403L (en) 1999-03-23
    NZ334801A (en) 2001-04-27
    ATE209246T1 (en) 2001-12-15
    JP2001500915A (en) 2001-01-23
    EP0929644A1 (en) 1999-07-21
    ES2168614T3 (en) 2002-06-16
    DK0929644T3 (en) 2002-05-21
    SK39299A3 (en) 1999-07-12
    PL332140A1 (en) 1999-08-30
    US6331518B2 (en) 2001-12-18
    US20010034317A1 (en) 2001-10-25
    BR9713218A (en) 2000-04-04
    DE59706068D1 (en) 2002-02-21
    NO991403D0 (en) 1999-03-23

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