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EP0929644A1 - Produits de nettoyage compacts contenant des tensioactifs - Google Patents

Produits de nettoyage compacts contenant des tensioactifs

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Publication number
EP0929644A1
EP0929644A1 EP97910336A EP97910336A EP0929644A1 EP 0929644 A1 EP0929644 A1 EP 0929644A1 EP 97910336 A EP97910336 A EP 97910336A EP 97910336 A EP97910336 A EP 97910336A EP 0929644 A1 EP0929644 A1 EP 0929644A1
Authority
EP
European Patent Office
Prior art keywords
weight
formula
surfactants
solid
group
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.)
Granted
Application number
EP97910336A
Other languages
German (de)
English (en)
Other versions
EP0929644B1 (fr
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE1996139118 external-priority patent/DE19639118A1/de
Application filed by Henkel Ecolab GmbH and Co KG filed Critical Henkel Ecolab GmbH and Co KG
Publication of EP0929644A1 publication Critical patent/EP0929644A1/fr
Application granted granted Critical
Publication of EP0929644B1 publication Critical patent/EP0929644B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 water-based cleaning agents based on alkali metal hydroxide with a delayed, controlled and variable curing time.
  • the cleaning agents contain glycols, glycol derivatives and / or certain alkanolamines and alkali hydroxide in solid form.
  • the hardening of the water-containing cleaning agent can be delayed by a specific sequential addition of paraffin oil and / or surfactants and other components from the group of the polyhydroxy compounds.
  • Highly alkaline cleaning agents are now commercially available in a wide variety of forms, e.g. B. as a powder, as granules, as a liquid, as a melting block or as a tablet produced by compression.
  • a high level of homogeneity of the cleaners obtained is also particularly desirable, but this is often difficult to achieve with solid cleaners. This problem is less common with liquid cleaners that can be easily stirred.
  • the homogeneity of a liquid, a viscous liquid or a stirrable paste would then be desired, which then solidifies into a solid, controllable, variable strength in order to utilize its advantages in storage and transport and metering at this stage. It would be particularly desirable if the stirrability were maintained at temperatures up to about 40 ° C., since then less temperature-stable components could also be mixed in.
  • the object of the present invention is to provide highly alkaline cleaning agents of a general nature for textile surfaces, based on alkali hydroxide, preferably potassium or sodium hydroxide, particularly preferably sodium hydroxide, but preferably those for cleaning hard surfaces, e.g. B. dishes, and in particular cleaning agents for the commercial cleaning of dishes, which combine the advantages of powders and liquids on the one hand and the advantages of tablets and melting blocks on the other.
  • cleaning agents are to be provided which have a solubility defined under the most varied of application conditions, but on the other hand are transport-stable and storage-stable and, moreover, can be dosed quickly, easily and precisely, which are not dusty and can be produced without great technical effort and are easy to fill .
  • stirrability during production a controlled variable strength of the cleaning agents and a delayed hardening during production and storage would offer great advantages and should be taken into account.
  • a method should be developed that allows less temperature-stable substances to be incorporated below 42 ° C if necessary, without endangering the other tasks
  • German published patent application DE-OS-31 38 425 theological behavior of the cleaners described there is described in such a way that a gel-like paste is liquefied and easily liquefied by the action of mechanical forces, for example by shaking or pressure on a deformable storage bottle or tube or by means of a metering pump can be squeezed out of a spray nozzle.
  • US Pat. No. 3,607,764 describes glass cleaning agents in solid form, which are diluted to form a sprayable solution. These agents contain, inter alia, sodium or potassium hydroxide, sodium or potassium tripolyphosphate, Sodium or potassium pyrophosphate, hydroxycarboxylic acid builder, a water-soluble nonionic surfactant, alkylene glycol ether and optionally sodium carbonate. A control of the viscosity or the strength in the sense of the present invention is not described
  • Japanese patent specification JA 84/182870 describes solutions of alkali metal hydroxides in glycols or alcohols which become viscous when neutralized with long-chain carboxylic acids and which have a pasty consistency when silicone oil is added, so that they can be used as pastes in leather greasing.
  • Japanese patent specification JA 86/296098 describes anhydrous solid cleaning agents based on alkali hydroxides.
  • the alkali carrier is mixed in alkanolamm and water-soluble glycol ethers, whereby a solid cleaner is obtained.
  • a technical lesson on variably reducing the strength and controlling the hardening process is not described
  • the present invention relates to a water-containing solid cleaning agent with a delayed, controllable and variable curing time after addition of all components, which can be produced by a process in which a) aqueous alkali metal hydroxide solution, preferably potassium and sodium hydroxide solution, particularly preferably sodium hydroxide solution, preferably 42-55% strength , in an amount of 21 to 70 wt .-%, preferably 35 to 55 wt .-%, and to build up an increased viscosity b) a compound of formula I.
  • aqueous alkali metal hydroxide solution preferably potassium and sodium hydroxide solution, particularly preferably sodium hydroxide solution, preferably 42-55% strength
  • R 1 represents a hydrogen atom or a methyl group and R 2 independently of it a hydrogen atom, a C 1 -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 alkyl groups, and / or compounds of the formula II,
  • foam inhibitors and builder components and / or paraffin oil and / or surfactants and / or polyhydroxy compounds preferably glycerols and / or alkali metal hydroxide, preferably potassium or sodium hydroxide, particularly preferably sodium hydroxide is added as a solid.
  • the delayable curing time is measured by continuing the stirring process after adding all the components and following it until it comes to a standstill as a result of the curing. From a purely phenomenological point of view, at the point in time known as curing and which can be controlled, the composition has a consistency in which it cannot, as desired, flow out through a drain pipe located at the bottom of a production kettle, or flows out of an inverted beaker can leave.
  • the cleaning agents according to the invention have, for. B. a consistency at 20 ° C - 40 ° C not from a container, e.g. B. an inverted open beaker can flow out.
  • the consistency according to the invention can also manifest itself, for example, in the form of cut resistance.
  • Many of the cleaning agents according to the invention can still be molded during processing and storage.
  • Particularly preferred agents are obtained if, after stirring in the compounds of the 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 hydroxide, preferably potassium or sodium hydroxide, particularly preferably sodium hydroxide.
  • Another object of the invention is a process for the preparation of these agents and the use of these agents for machine cleaning of dishes.
  • composition of the invention when choosing the composition of the invention, surprisingly, there are also no further additives apart from the thickener and z.
  • 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, necessary to achieve the desired strengthening effect according to the invention in aqueous To achieve sodium hydroxide solution.
  • alkali metal hydroxide solution preferably potassium and sodium hydroxide solution, particularly preferably sodium hydroxide solution alone, is sufficient for the desired controllable strength.
  • This strength in turn, can be kept in a stirrable state by the sequence according to the invention of the addition and the concentration of paraffin oil, surfactants, polyhydroxy compounds, preferably glycerol and solid NaOH, for a period of time which is advantageous in terms of application technology, at an appropriate temperature, ie a controllable delay in the hardening of the material can be achieved.
  • the water content is also a critical parameter; it is between 10 and 35% by weight, advantageously between 20 and 30% by weight.
  • the pH of the cleaning agents according to the invention is above 13.
  • the cleaning agents according to the invention can also be used in combination with other agents without losing the variable strength according to the invention.
  • the cleaning agent consisting of alkali solution, preferably potassium and sodium hydroxide solution, particularly preferably sodium hydroxide solution, substance I and / or II and solid alkali hydroxide, preferably sodium hydroxide and surfactants and / or paraffin oil and / or polyhydroxy compounds, preferably glycerol as carrier phase for others customary in cleaners Ingredients.
  • Both anionic surfactants and cationic surfactants, amphoteric surfactants and non-ionic surfactants can be used as surfactants.
  • the hardening time after adding all components depends in particular on their concentration.
  • Low-foaming surfactants, especially nonionic surfactants can also be present in an amount of up to 10% by weight, preferably 1 to 5% by weight and particularly preferably 2 to 4% by weight.
  • Extremely low-foaming compounds are usually used for automatic dishwashing.
  • C 12 -C 18 -Alkylipolyethylene glycol polypropylene glycol ethers, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule, are preferably used for this purpose.
  • nonionic surfactants known as low-foaming can also be used, such as BC 12 -C 1B alkyl polyethylene glycol glycol polybutylene glycol ether, each with up to to 8 moles of ethylene oxide and butylene oxide units in the molecule as well as end capped alkyl polyalkylene glycol mixed ether
  • a higher surfactant content is recommended, which can generally be up to 20% by weight.
  • nonionic, cationic and amphoteric surfactants particularly anionic surfactants from the group of Alkylbenzenesulfonates, the fatty alcohol sulfates, the fatty alcohol ether sulfates and other known anionic surfactants
  • Paraffin oil which according to the invention can contain up to 10% by weight, is understood to mean long-chain hydrocarbons which can be branched or not branched.
  • agents according to the invention they are between 0.1 and 8% by weight, particularly preferably between 0 , 5 and 5% by weight were added
  • Organic polyhydroxy compound is understood to mean in particular the polyhydric alcohols, preferably glycerol.
  • polyhydroxy compounds such as, for example, glucose
  • functional groups generally do not interfere with the success according to the invention.
  • B use glycolic acid, or also aldehydes or dialdehydes, such as glyoxal, which, under the strongly alkaline conditions, are substituted mono- or polyhydroxy compounds, such as.
  • the cleaning agents can thus optionally additionally contain a builder substance in an amount of up to 60% by weight, preferably 15 to 40% by weight
  • the builder substance contained in the cleaning agents according to the invention can in principle be any substance which is known in the prior art as a builder suitable in the broadest sense for detergents and cleaning agents; water-soluble builder substances are preferably used.
  • the coated builder substances known in the prior art can also be used and are even preferred when working with chlorine-containing bleaching agents.
  • B. alkali phosphates which may be in the form of their sodium or potassium salts, in question.
  • alkali phosphates which may be in the form of their sodium or potassium salts, in question.
  • examples of this are: tetrasodium diphosphate, pentasodium triphosphate, so-called sodium hexamaphosphate and the corresponding potassium salts or mixtures of sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • complexing agents are to be mentioned, such as. B. nitrilotriacetate or ethylenediaminetetraacetate. Soda and borax are also among the builder substances in the context of the present invention.
  • water-soluble builder components are e.g. B. organic polymers of native or synthetic origin, especially polycarboxylates.
  • polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids are suitable.
  • Commercial products are e.g. B. Sokalan® CP 5 and PA 30 from BASF, Alcosperse® 175 and 177 from Alco, LMW® 45 N and SP02 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. the companies Cygnus, Bayer, Rohm & Haas, Rh ⁇ ne-Poulenc or SRCHEM.
  • hydroxy carboxylic acids such as. B. mono-, dihydroxy-succinic acid, ⁇ -hydroxypropion- acid, citric acid, gluconic acid, and their salts. Citrates are preferably 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 0 45 xH 2 0, Kenyaite
  • Na-SKS-2 Na 2 Si 14 0 29 xH 2 0, magadiite
  • Na-SKS-3 Na 2 Si 8 0 17 xH 2 0
  • Na-SKS-4 Na 2 Si 4 0 9 xH 2 0
  • macatite Na-SKS-5 ( ⁇ -Na 2 Si 2 0 5 )
  • Na-SKS-7 ß-Na 2 Si 2 0 5l natrosilite
  • Na-SKS-11 ⁇ -Na 2 Si 2 0 5
  • Na-SKS-6 ⁇ -Na 2 Si 2 0 5 ).
  • Particularly preferred builder substances are those selected from the group consisting of pentasodium triphosphate, trisodium citrate, nitrilotriacetate, ethylenediaminetetraacetate and mixtures thereof.
  • Bleaching agents which are customary in cleaning agents can also be present in the agents according to the invention, then preferably between 0.5 and 10% by weight and particularly preferably between 1.5 and 10% by weight. These can be selected from the group of oxygen-based bleaches, such as. B Sodium perborate also in the form of its hydrates, or sodium percarbonate, or from the group of chlorine-based bleaches, such as N-chloro-p-toluenesulfonamide, trichloroisocyanuric acid, alkali metal dichloroisocyanurate, alkali metal hypochlorites, and alkali metal hypochlorite-releasing agents, with alkali-stable bleaching compositions being particularly preferred. These can be both alkali-stable substances or components stabilized by suitable processes such as surface coating or passivation.
  • defoamers are understood to mean all foam-damping substances known in the prior art, but preferably those based on silicone and paraffin, particularly preferably on a paraffin base, such as those found 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 Az 196 20 249 are described. But also others Defoamers can be used
  • ingredients optionally contained are further common cleaning agent components, such as, for example, dyes or alkali-stable perfume substances.
  • abrasive ingredients can be present, but the cleaning agents according to the invention are preferably free of them
  • thickeners such as swellable layered silicates of the montmo ⁇ llonit type, bentonite, kaolin, talc or carboxymethyl cellulose can optionally be used to vary the strength, they are not necessary to achieve the desired controllable solids properties and the consistency of the cleaning agents according to the invention, ie such thickeners can be dispensed with
  • a process for solidifying aqueous 42 to 55% by weight alkali hydroxide solution preferably potassium and sodium hydroxide solution, particularly preferably sodium hydroxide solution.
  • the process is characterized in that a compound of the formula I and / or Adds a compound of formula II and thus obtains a paste-like preparation which is subsequently added to several or all components from the classes of paraffin foam inhibitors, builder substances, paraffin oil and / or surfactants and / or polyhydroxy compounds, preferably glycerol, before solid alkali metal hydroxide, preferably potassium or sodium hydroxide, particularly preferably sodium hydroxide or a mixture of these substances, in order to achieve a delayed, controlled and variable hardening of the cleaning material.
  • the process at 20 ° C. to 50 ° C., preferably at 30 to 48 ° C., particularly preferably at 38 - 42 ° C Since the solubility of NaOH in water increases at higher temperatures, the NaOH content in the aqueous solution can then also be more than 55% by weight. Correspondingly, the NaOH content can also be below 42% by weight at lower temperatures.
  • the restriction to 42 to 55% by weight NaOH solutions is therefore essentially limited to temperatures from 20 ° C. to 25 ° C.
  • the surfactants in the cleaning agent which can be selected from all main classes, namely cationic, anionic, amphoteric and nonionic surfactants, are preferably used in concentrations of up to 10% by weight, but in particular in concentrations between 0.1 to 5% by weight 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 glycerol 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 the paraffins and / or surfactants and / or polyhydroxy compounds used, preferably glycerol depend on the desired curing time.
  • a particular advantage of the invention lies in the fact that the stirrability and the associated advantages are already present at room temperature.
  • the thickened alkali metal hydroxide solution preferably potassium and sodium hydroxide solution, particularly preferably sodium hydroxide solution
  • the consistency according to the invention can, however, be achieved in almost all cases below 42 ° C., preferably between 38 ° C. and 42 ° C., so that even less temperature-stable components, such as bleaches containing chlorine, can be incorporated into the cleaning agents according to the invention.
  • the application of the solid cleaning agents according to the invention can e.g. B. in such a way that the detergent of controllable strength in a container (capacity z. B. 0.5 to 10 kg) is sprayed with water and the detergent thus dissolved is used, for. B. is metered into a dishwasher.
  • a dosing device sold by Henkel Hygiene GmbH under the name Topmater® P40 or a solids dosing device V / VT-2000 sold by Henkel Ecolab can be used.
  • 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.
  • the sequence-bound addition of paraffin oils and / or surfactants gives the cleaning agent the advantage that the curing of the cleaning agent can be delayed so long that there are no solid deposits in the production equipment.
  • the cleaning agent can then be filled into the sales container at approx. 40 ° C and, for example, via a cooling tunnel to approx. 20 ° C to achieve the are cooled according to the invention.
  • other methods of filling and returning to room temperature are also conceivable.
  • the cleaning agents according to the invention cure depending on the time, which was determined by time-dependent measurements and is also strongly influenced by the respective concentrations of surfactants and / or paraffin oils in the cleaning agent composition.
  • Detergents of the following compositions 1 to 9 were produced with differences in the order in which the components were added and the composition of the detergents.
  • 50% aqueous sodium hydroxide solution was placed in a 2 liter beaker and heated to 38-40 ° C.
  • With slow stirring in of 1,2-propylene glycol (60 rpm) the temperature rises to approx. 46 ° C.
  • Stirring was continued for 15 min, then the paraffin foam inhibitor was added and the mixture was stirred again for 10 min.
  • the temperature is then reduced to 38 to 40 ° C and kept constant.
  • the other components of the compositions were added in the order shown in the table and each was stirred for 10 minutes.
  • the period of time up to the degree of hardness of the composition was determined by a person skilled in the art which made the stirring at 38 to 40 ° C. very difficult or impossible at all. From a purely phenomenological point of view, after this point in time the composition had a consistency in which it could not, as desired, flow out through a drain pipe at the bottom of a production kettle, or flow out of an inverted beaker
  • a comparison of tests B1, B2 and B3 shows that each has a relatively short curing time of only about 5 minutes. This is shown in Example B2 in the case where, after addition of the propylene glycol, paraffin foam inhibitor, then solid NaOH and finally paraffin oil and then surfactants are added. With the same sequence, it is irrelevant for the curing time whether the addition of paraffin oil (B1) or surfactants (B3) is omitted.
  • Example B4 the sequence is changed in that a builder component is now added after the addition of the foam inhibitors. Then, in example B5, paraffin oil is added (no paraffin oil was added in experiment B4), then surfactants and finally solid NaOH and chlorine carrier. The positions of solid NaOH and the builder component are thus exchanged. With this addition sequence, the curing time increases to 30 minutes if no paraffin oil is present (B4), or even to 90 minutes if paraffin oil has been added, as in Example B5.
  • 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.
  • the thickened stirrable pastes according to the parent application can be extended depending on the amount of glycerol compared to the other components, for example R4 and R6 to about 180 min
  • both the sequence and the concentration of the added components influence the curing time.
  • the longest curing time is achieved when both paraffin oil and surfactants and polyhydroxy compounds are preferably added with glycerin and solid NaOH is only stirred in after their addition

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP97910336A 1996-09-24 1997-09-23 Procede pour produire des agents de nettoyage compacts contenant des agents tensioactifs Expired - Lifetime EP0929644B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE1996139118 DE19639118A1 (de) 1996-09-24 1996-09-24 Tensidhaltiger Kompaktreiniger
DE19639118 1996-09-24
DE19648107 1996-11-21
DE19648107 1996-11-21
PCT/EP1997/005218 WO1998013466A1 (fr) 1996-09-24 1997-09-23 Produits de nettoyage compacts contenant des tensioactifs

Publications (2)

Publication Number Publication Date
EP0929644A1 true EP0929644A1 (fr) 1999-07-21
EP0929644B1 EP0929644B1 (fr) 2001-11-21

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP97910336A Expired - Lifetime EP0929644B1 (fr) 1996-09-24 1997-09-23 Procede pour produire des agents de nettoyage compacts contenant des agents tensioactifs

Country Status (15)

Country Link
US (1) US6331518B2 (fr)
EP (1) EP0929644B1 (fr)
JP (1) JP2001500915A (fr)
AT (1) ATE209246T1 (fr)
AU (1) AU727115B2 (fr)
BR (1) BR9713218A (fr)
CA (1) CA2266068A1 (fr)
DE (1) DE59706068D1 (fr)
DK (1) DK0929644T3 (fr)
ES (1) ES2168614T3 (fr)
NO (1) NO991403D0 (fr)
NZ (1) NZ334801A (fr)
PL (1) PL332140A1 (fr)
SK (1) SK39299A3 (fr)
WO (1) WO1998013466A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19741874A1 (de) * 1997-09-23 1999-04-01 Henkel Ecolab Gmbh & Co Ohg Alkoholathaltiger Reiniger
US8974386B2 (en) 1998-04-30 2015-03-10 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US6949816B2 (en) 2003-04-21 2005-09-27 Motorola, Inc. Semiconductor component having first surface area for electrically coupling to a semiconductor chip and second surface area for electrically coupling to a substrate, and method of manufacturing same
US8688188B2 (en) 1998-04-30 2014-04-01 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US9066695B2 (en) 1998-04-30 2015-06-30 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8465425B2 (en) 1998-04-30 2013-06-18 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US6175752B1 (en) 1998-04-30 2001-01-16 Therasense, Inc. Analyte monitoring device and methods of use
US8480580B2 (en) 1998-04-30 2013-07-09 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8346337B2 (en) 1998-04-30 2013-01-01 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
JP2002534130A (ja) * 1999-01-14 2002-10-15 ノバルティス アクチエンゲゼルシャフト アデノウイルスベクター、パッケージ細胞系、組成物および製法および使用法
US6560471B1 (en) 2001-01-02 2003-05-06 Therasense, Inc. Analyte monitoring device and methods of use
WO2002078512A2 (fr) 2001-04-02 2002-10-10 Therasense, Inc. Dispositif et procede de recherche de glucose dans le sang
US7033988B2 (en) * 2002-01-23 2006-04-25 The Procter & Gamble Company Detergent tablets comprising solubility aids
GB2390853A (en) * 2002-07-16 2004-01-21 Reckitt Benckiser Nv Cleaning composition containing hydrophobic component
US6900167B2 (en) 2002-10-09 2005-05-31 Ecolab, Inc. Solid composition with rheology modifier
US6903062B2 (en) * 2002-12-19 2005-06-07 Ecolab, Inc. Rheology modifier concentrate
US7811231B2 (en) 2002-12-31 2010-10-12 Abbott Diabetes Care Inc. Continuous glucose monitoring system and methods of use
ITBS20030015A1 (it) * 2003-02-20 2004-08-21 Bettari Detergenti S R L Metodo per la preparazione di un agglomerato detergente di aspetto solido e prodotto risultante.
US8066639B2 (en) 2003-06-10 2011-11-29 Abbott Diabetes Care Inc. Glucose measuring device for use in personal area network
WO2005023971A1 (fr) * 2003-09-03 2005-03-17 Johnsondiversey, Inc. Composition de nettoyage
EP1718198A4 (fr) 2004-02-17 2008-06-04 Therasense Inc Procede et systeme de communication de donnees dans un systeme de controle et de gestion de glucose en continu
US8112240B2 (en) 2005-04-29 2012-02-07 Abbott Diabetes Care Inc. Method and apparatus for providing leak detection in data monitoring and management systems
US7766829B2 (en) 2005-11-04 2010-08-03 Abbott Diabetes Care Inc. Method and system for providing basal profile modification in analyte monitoring and management systems
US7620438B2 (en) 2006-03-31 2009-11-17 Abbott Diabetes Care Inc. Method and system for powering an electronic device
US8226891B2 (en) 2006-03-31 2012-07-24 Abbott Diabetes Care Inc. Analyte monitoring devices and methods therefor
US20080071158A1 (en) 2006-06-07 2008-03-20 Abbott Diabetes Care, Inc. Analyte monitoring system and method
US8732188B2 (en) 2007-02-18 2014-05-20 Abbott Diabetes Care Inc. Method and system for providing contextual based medication dosage determination
US8930203B2 (en) 2007-02-18 2015-01-06 Abbott Diabetes Care Inc. Multi-function analyte test device and methods therefor
US8123686B2 (en) 2007-03-01 2012-02-28 Abbott Diabetes Care Inc. Method and apparatus for providing rolling data in communication systems
US7928850B2 (en) 2007-05-08 2011-04-19 Abbott Diabetes Care Inc. Analyte monitoring system and methods
US8665091B2 (en) 2007-05-08 2014-03-04 Abbott Diabetes Care Inc. Method and device for determining elapsed sensor life
US8461985B2 (en) 2007-05-08 2013-06-11 Abbott Diabetes Care Inc. Analyte monitoring system and methods
US8456301B2 (en) 2007-05-08 2013-06-04 Abbott Diabetes Care Inc. Analyte monitoring system and methods
JP5324207B2 (ja) * 2008-12-19 2013-10-23 ディバーシー株式会社 自動食器洗浄機用固形洗浄剤の製法およびそれによって得られる自動食器洗浄機用固形洗浄剤
US8103456B2 (en) 2009-01-29 2012-01-24 Abbott Diabetes Care Inc. Method and device for early signal attenuation detection using blood glucose measurements
US9226701B2 (en) 2009-04-28 2016-01-05 Abbott Diabetes Care Inc. Error detection in critical repeating data in a wireless sensor system
WO2010138856A1 (fr) 2009-05-29 2010-12-02 Abbott Diabetes Care Inc. Systèmes d'antenne de dispositif médical comportant des configurations d'antenne externe
WO2010140561A1 (fr) * 2009-06-01 2010-12-09 ユケン工業株式会社 Composition dégraissante et procédé de fabrication de celle-ci
WO2011026147A1 (fr) 2009-08-31 2011-03-03 Abbott Diabetes Care Inc. Dispositif et procédés de traitement de signal d'analyte
EP2473099A4 (fr) 2009-08-31 2015-01-14 Abbott Diabetes Care Inc Système de surveillance de substance à analyser et procédés de gestion de l'énergie et du bruit
US9320461B2 (en) 2009-09-29 2016-04-26 Abbott Diabetes Care Inc. Method and apparatus for providing notification function in analyte monitoring systems
JP6443802B2 (ja) 2011-11-07 2018-12-26 アボット ダイアベティス ケア インコーポレイテッドAbbott Diabetes Care Inc. 分析物モニタリング装置および方法
US9968306B2 (en) 2012-09-17 2018-05-15 Abbott Diabetes Care Inc. Methods and apparatuses for providing adverse condition notification with enhanced wireless communication range in analyte monitoring systems
US10184097B2 (en) 2013-02-08 2019-01-22 Ecolab Usa Inc. Protective coatings for detersive agents and methods of forming and detecting the same
CN112341720B (zh) * 2020-11-30 2023-05-16 黎明职业大学 一种环氧树脂清洗胶的制备方法及其应用

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607764A (en) * 1968-01-31 1971-09-21 Grace W R & Co Glass washing compound and process
US4342739A (en) 1979-01-09 1982-08-03 Fuji Photo Film Co., Ltd. Novel material for immunological assay of biochemical components and a process for the determination of said components
DE3138425A1 (de) 1981-09-26 1983-04-14 Henkel KGaA, 4000 Düsseldorf "verwendung eines pastoesen reinigers in geschirrspuelmaschinen"
JPS59182870A (ja) 1983-04-01 1984-10-17 Nitto Kagaku Kk ペ−スト状クリ−ナ−兼艶出剤
DE3400008A1 (de) 1984-01-02 1985-07-11 Henkel KGaA, 4000 Düsseldorf Zur verwendung in tensidhaltigen mitteln geeignetes schaumregulierungsmittel
JPS61296098A (ja) * 1985-06-25 1986-12-26 ティーポール株式会社 固体洗浄剤
US4753755A (en) * 1986-08-25 1988-06-28 Diversey Wyandotte Corporation Solid alkaline detergent and process for making the same
DE3633518A1 (de) 1986-10-02 1988-04-14 Philips Patentverwaltung Getakteter gleichspannungswandler
DE4117032A1 (de) 1991-05-24 1992-11-26 Henkel Kgaa Silikonhaltiges entschaeumergranulat
DE4228786A1 (de) 1992-08-29 1994-03-03 Henkel Kgaa Geschirrspülmittel mit ausgewähltem Builder-System
DE4323410A1 (de) 1993-07-13 1995-01-19 Henkel Kgaa Schüttfähiges, phosphatfreies Schaumregulierungsmittel
ATE159045T1 (de) 1993-08-02 1997-10-15 Henkel Kgaa Schaumregulatorgranulat und verfahren zu seiner herstellung
CA2175456C (fr) 1993-12-30 2005-05-17 Keith E. Olson Procede de production de compositions de nettoyage solides fortement alcalines
DE19507532C2 (de) * 1995-03-03 2000-01-05 Henkel Ecolab Gmbh & Co Ohg Pastenförmiges Reinigungsmittel
US6028113A (en) * 1995-09-27 2000-02-22 Sunburst Chemicals, Inc. Solid sanitizers and cleaner disinfectants
DE19620249A1 (de) 1996-05-21 1997-11-27 Henkel Kgaa Teilchenförmiges Schaumregulierungsmittel auf Paraffin-Basis
DE19617215A1 (de) * 1996-04-30 1997-11-06 Henkel Ecolab Gmbh & Co Ohg Kompaktreiniger für gewerbliche Geschirrspülmaschinen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9813466A1 *

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AU4777397A (en) 1998-04-17
WO1998013466A1 (fr) 1998-04-02
EP0929644B1 (fr) 2001-11-21
PL332140A1 (en) 1999-08-30
DE59706068D1 (de) 2002-02-21
BR9713218A (pt) 2000-04-04
DK0929644T3 (da) 2002-05-21
CA2266068A1 (fr) 1998-04-02
NZ334801A (en) 2001-04-27
AU727115B2 (en) 2000-11-30
ES2168614T3 (es) 2002-06-16
ATE209246T1 (de) 2001-12-15
US6331518B2 (en) 2001-12-18
US20010034317A1 (en) 2001-10-25
SK39299A3 (en) 1999-07-12
NO991403L (no) 1999-03-23
NO991403D0 (no) 1999-03-23
JP2001500915A (ja) 2001-01-23

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