EP1017772B1 - Cleaning agent containing alcoholate - Google Patents
Cleaning agent containing alcoholate Download PDFInfo
- Publication number
- EP1017772B1 EP1017772B1 EP98954274A EP98954274A EP1017772B1 EP 1017772 B1 EP1017772 B1 EP 1017772B1 EP 98954274 A EP98954274 A EP 98954274A EP 98954274 A EP98954274 A EP 98954274A EP 1017772 B1 EP1017772 B1 EP 1017772B1
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- European Patent Office
- Prior art keywords
- agent
- solid
- surfactants
- relative
- cleaning
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- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
Definitions
- the present invention relates to water-containing cleaners with pasty to solid consistency based on alkali hydroxide.
- To set the desired Consistency contain the cleaning agents alcoholates.
- Addition of other components can be optionally the Check hardness and duration of curing of the cleaning agent.
- Highly alkaline detergents are today in the most diverse forms of presentation commercially available, for. B. as a powder, as granules, as a liquid, as a melted block or as a tablet made by compression.
- WO 96/27653 A1 describes a paste-like Detergents based on NaOH, by the thickening effect of certain glycols, Glycol derivatives and / or alkanolamines aqueous alkali oil eye uses.
- the object of the present invention is to provide highly alkaline, on alkali hydroxide, preferably potassium or sodium hydroxide, more preferably sodium hydroxide general-purpose cleaning agents for textile surfaces, preferably but those for cleaning hard surfaces, eg.
- alkali hydroxide preferably potassium or sodium hydroxide
- more preferably sodium hydroxide general-purpose cleaning agents for textile surfaces preferably but those for cleaning hard surfaces, eg.
- tableware and in particular to provide cleaning agents for the commercial cleaning of dishes, the advantages of powders and liquids on the one hand and the Advantages of tablets and fused blocks on the other hand unite.
- the means to provide cleaning agents that are one of the most diverse Application conditions have defined solubility, on the other hand but are stable to transport and storage stable and beyond fast, easy and to dose precisely, which are not dusty and without great technical Effort to produce and easy to fill.
- German Offenlegungsschrift DE-OS-31 38 425 the rheological Behavior of the cleaner described there described so 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 dosing pump and squeezed out of a spray nozzle leaves.
- Japanese Patent Publication JP 84/182870 describes solutions of alkali hydroxides in glycols or alcohols by neutralizing with long chain Carboxylic acids are viscous and by adding silicone oil a pasty Consistency, whereby they are used as pastes in the leather fatliquoring can.
- Japanese Patent Publication JP 86/296098 describes anhydrous solid detergents based on alkali hydroxides.
- the alkali carrier is in alkanolamines and water-soluble glycol ethers, thereby forming a solid Cleaner receives.
- a technical teaching for the variable reduction of strength and for controlling the hardening process is not described.
- the cleaning agents according to the invention have a finished state pasty or firm consistency, the transitions being fluid. she are preferably not pumpable at room temperature.
- consistency can also take the form of cut resistance, for example express. Many of the solid detergents according to the invention are during the Processing still pourable and shaping even after prolonged storage compressible.
- the agents can post-cure during storage. Especially with the addition of Solid fine alkali hydroxide, this curing process can very quickly run. Particularly advantageous is the use of up to 35 wt .-% preferably 2 to 25% by weight, particularly preferably 5 to 15% by weight, of solid Alkali hydroxide based on the total agent.
- surfactants Paraffin oil and polyhydroxy compounds can turn the curing process be delayed.
- the delayable curing time is measured by the stirring process is continued after addition of all components and until it stops is tracked as a result of curing.
- Purely phenomenological has the composition at the time that is called curing and the can be controlled, a consistency in which you can not, as desired, through a down at a production boiler located drain pipe can let, or can flow out of an upside down beaker.
- Another object of the invention is a process for the preparation of these Medium. They are obtained in the simplest case by stirring the alcoholates into the alkali solution. Especially preferred agents are obtained, if necessary after that, foam inhibitors and / or Builderkomponenten, then surfactants and / or paraffin oil and finally 0.1 to 35 wt.%, Preferably 2 to 25 wt.%, Based on the total Medium solid alkali hydroxide, preferably potassium or sodium hydroxide, especially preferably sodium hydroxide may be added.
- Another object of the invention is the use of these means for machine cleaning of dishes and surfaces and washing of Laundry.
- composition of matter are in the simplest case in addition to alkali, no other additives except the alkoxide as a thickener necessary to solidify the desired inventive solidifying To achieve effect in aqueous sodium hydroxide solution.
- the water content is a critical parameter; he lies between 10 and 35 wt .-%, advantageously between 20 and 30 wt .-%.
- the cleaning agents of the invention can over the already mentioned Ingredients addition to other common in alkaline cleaners ingredients contain, so far as the inventive variable strength not get lost.
- the cleaning agent of alkali lye preferably Potassium and caustic soda, particularly preferably sodium hydroxide solution, substance I. or the corresponding alcohol and optionally solid alkali hydroxide, preferably sodium hydroxide, as well as surfactants and / or paraffin oil as the carrier phase for other common in cleaning agents ingredients.
- Alcoholates become more commercial Alcohols, with the exception of the alcoholates of ethylene glycol and 1,2-propylene glycol used. They are alcoholates of Ethanol, propanol, isopropanol, glycerol and butylene glycol.
- the alkyl chain content is differentiated Properties achieved.
- the alkoxides can be prepared by the usual methods of organic chemistry easily manufactured.
- the amount of alcoholate added should be 0.5 to about 40% by weight, preferably about 1 to about 10 wt .-% based on the total Cleaning agent amount. Since the alkoxide with the corresponding Alcohol in equilibrium is possibly contained free alcohol mathematically included in the mecanicatmenge, in polyhydric alcohols as a monoalcoholate.
- surfactants both anionic surfactants and cationic surfactants, amphoteric surfactants and nonionic surfactants can be used.
- the cleaning performance is decisively influenced by the amount of surfactants. In particular, of their concentration but also depends on the curing time after addition of all components.
- weakly foaming surfactants especially nonionic surfactants, in an amount of up to 10 wt.%, Preferably 0.1 to 5 wt .-% and particularly preferably 0.5 to 4 wt .-% be included. Normally, extremely low-foam compounds are used for automatic dishwashing.
- a higher surfactant content which is usually up to 30 wt .-%, preferably 0.1 to 15 particularly preferred 1 to 10 wt .-% and most preferably 2 to 4 wt .-% based on the total means may be.
- nonionic, cationic and amphoteric surfactants especially anionic Surfactants, preferably from the group of alkylbenzenesulfonates, the fatty alcohol sulfates and the fatty alcohol ether sulfates.
- Paraffin oil which according to the invention may contain up to 10% by weight
- Long-chain hydrocarbons are understood as being branched or unbranched could be.
- they are the inventive Agents in amounts between 0.1 and 8 wt .-% particularly preferred between 0.5 and 5 wt .-% added.
- the cleaning agents may additionally builders in one Amount of up to 60 wt .-%, preferably 15 to 40 wt .-%, included.
- the builder contained in the cleaning agents according to the invention in principle, any substance can be that in the state of the art as in the broadest sense for washing and cleaning agent suitable builder is known.
- Preferably Water-soluble builder substances are used, these in the However, agents of the invention may be present undissolved.
- the Coated builders known in the art can be used and are even preferred when bleached with chlorine is working.
- alkali phosphates in question in the form of their Sodium or potassium salts may be present.
- alkali phosphates in question in the form of their Sodium or potassium salts may be present. Examples include: tetrasodium diphosphate, Pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium hexametaphosphate and the corresponding potassium salts or mixtures Sodium and potassium salts.
- complexing agents are mentioned, such as. B. nitrilotriacetate or ethylenediaminetetraacetate. Also soda and Borax count within the scope of the present Invention to the builders.
- water-soluble builder components are, for. B. organic Polymers of native or synthetic origin, especially polycarboxylates.
- Commercially available products are z. 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 (eg DE 42 28 786) and polyamino acids such as polyglutamic acid or polyaspartic acid, z.
- hydroxycarboxylic acids such as B. mono-, dihydroxy-succinic acid, ⁇ -hydroxypropionic acid, Citric acid, gluconic acid, and their salts.
- Citrates are preferably used in the form of trisodium citrate dihydrate.
- amorphous metasilicates or sheet silicates may furthermore be mentioned. Even crystalline phyllosilicates are suitable builders, provided that they are sufficiently stable to alkali; crystalline phyllosilicates are marketed by the company Hoechst AG (Germany) under the trade name Na-SKS, z.
- 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 ).
- builders from the group pentasodium triphosphate, Trisodium citrate, nitrilotriacetate, ethylenediaminetetraacetate, Sodium salts of polyacrylic acid and of maleic acid - acrylic acid - Copolymers, soda, alkali silicate and mixtures thereof.
- Bleaches customary in detergents and cleaners can also be used in the novel bleaches Be contained means, then preferably in amounts between 0.5 and 10% by weight, and more preferably between 1.5 and 10% by weight.
- These may be selected from the group of oxygen-based bleaching agents, such as 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-toluenesulfonic acid amide, Trichloroisocyanuric acid, alkali metal dichloroisocyanurate, alkali hypochlorites, and alkali hypochlorites releasing agents, with particularly alkali stable bleaching compositions are preferred.
- These can be both alkaline stable substances or by suitable methods such as surface coating or passivation be stabilized components.
- ingredients in the cleaners according to the invention are defoamers. These may be in concentrations between 0.1 and 5 wt.%, Preferably 0.5 and 3 wt .-% are used when a selected surfactant under foam too much in the given circumstances, or act foam-suppressing foaming food particles in the dishwasher. Under defoamers one understands all known in the prior art foam-damping substances, but preferably those based on silicone and paraffin, more preferably on Paraffin-based, as z. B. in DE 34 00 008, DE 36 33 518, the DE 30 00 483, DE 41 17 032, DE 4323410, WO 95/04124 and the DE 196 20 249 are. But other defoamers can be used.
- abrasive ingredients are e.g. Dyes or alkali stable Perfumes.
- abrasive ingredients may in principle contain However, preferably the cleaning agents of the invention are free thereof.
- thickeners such as B. swellable phyllosilicates of Montmorillonite type, bentonite, kaolin, talc or carboxymethylcellulose optional can be used to vary the strength, they are to achieve the desired controllable solids properties and the consistency of Cleaning agent according to the invention not required, d. H. on such Thickener can be dispensed with.
- alcoholates as solidifying agents for water-based detergents for the automatic rinsing of dishes or for washing textiles containing alkali metal hydroxide Sodium hydroxide, with subsequent sequential addition of various Components, in particular of paraffin oil and / or surfactants in combination claimed with the subsequent addition of solid NaOH.
- a method for solidifying aqueous 42 to 55 wt.% Iger Alkali solution, preferably potassium and sodium hydroxide, more preferably sodium hydroxide claimed.
- the method is characterized in that one such Alkali solution with stirring an alkoxide is added and so a paste-like preparation, which is followed by one or more components from the classes of paraffin foam inhibitors and / or builders and / or paraffin oil and / or surfactants are added before solid Alkali hydroxide, preferably potassium or sodium hydroxide, more preferably Sodium hydroxide or a mixture of these substances is added to a delayed, controlled and variable curing of the cleaning material too to reach.
- the process at 20 ° C to 50 ° C is preferred at 30 to 48 ° C particularly preferably carried out at 38 to 42 ° C.
- the content NaOH in the aqueous solution also be more than 55 wt .-%. Accordingly, at lower temperatures, the NaOH content is also below 42 wt .-% are.
- the restriction to 42 to 55% by weight NaOH solutions is therefore limited essentially to temperatures of 20 ° C to 25 ° C.
- a particular advantage of the invention is that the stirrability and thus associated benefits are already given at room temperature.
- preferred Potassium and caustic soda particularly preferably sodium hydroxide
- preferred Potassium and caustic soda particularly preferably sodium hydroxide
- the consistency of the invention can but in almost all cases below 42 ° C, preferably between 38 ° C and 42 ° C be realized, so that less temperature-stable components, such as Example, chlorine-containing bleach in the detergents of the invention can be incorporated.
- an early hardening of the cleaning agent as a result of Addition of solid alkali hydroxide counteracted by previously other Components, for example foam inhibitors, builders, paraffin oils and / or surfactants are added.
- solid alkali hydroxide counteracted by previously other Components for example foam inhibitors, builders, paraffin oils and / or surfactants are added.
- foam inhibitors, builders, paraffin oils and / or surfactants are added.
- all or only certain substances of these classes can be added.
- a maximum curing time is achieved if all of the above Substances are added in this order, before firm Alkali hydroxide is mixed for solidification.
- a preferred Embodiment becomes after completion of the addition of the alcoholates for at least 3 minutes, preferably for 10 to 20 minutes before stirring you add the other components, after their addition, respectively is stirred for at least 3 minutes, preferably 8 to 15 minutes.
- the preparation of the cleaning agent for example, in a stirred tank at 20 to 50 ° C, preferably at 30 to 48 ° C, more preferably at 38 - 42 ° C take place.
- the detergent has procedurally by the sequence-bound Addition of paraffin oils and / or surfactants has the advantage that the curing of the detergent can be delayed so long that it no solid deposits can occur in the production equipment.
- the detergent can be stored at approx. 40 ° C in the sales container be bottled and e.g. via a cooling tunnel to about 20 ° C to reach the be cooled according to the invention consistency. But also other methods the filling and return to room temperature are conceivable.
- the application of the solid detergent according to the invention can, for. B. in the Make sure that in a container (capacity, for example, 0.5 to 10 kg) of controllable strength sprayed with water sprayed is and the so-dissolved detergent is used, for. In a dishwasher is metered.
- a container capacity, for example, 0.5 to 10 kg
- the so-dissolved detergent is used, for. In a dishwasher is metered.
- Pasty cleaners can be used with Help of suitable, strong pressure exerting devices directly into the Application liquor are dosed or also first with water in one brought liquid form and dosed in this form.
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Abstract
Description
Die vorliegende Erfindung betrifft wasserhaltige Reinigungsmittel mit pastöser bis fester Konsistenz auf Basis von Alkalihydroxyd. Zur Einstellung der gewünschten Konsistenz enthalten die Reinigungsmittel Alkoholate. Durch eine spezifischsequentielle Zugabe von weiteren Komponenten läßt sich gegebenenfalls der Härtegrad und die Dauer der Durchhärtung des Reinigungsmittels kontrollieren.The present invention relates to water-containing cleaners with pasty to solid consistency based on alkali hydroxide. To set the desired Consistency contain the cleaning agents alcoholates. By a specifically sequential Addition of other components can be optionally the Check hardness and duration of curing of the cleaning agent.
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 detergents are today in the most diverse forms of presentation commercially available, for. B. as a powder, as granules, as a liquid, as a melted block or as a tablet made 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 Pulvern den Vorteil einer zielgenauen und einfachen Dosierung, stauben nicht und sind leicht handhabbar.Each type of presentation has its own specific purpose for a defined purpose Advantages and disadvantages. For cleaning textile surfaces or for manual mechanical cleaning of hard surfaces have powder, Granules or liquids proven, while for mechanical cleaning of hard surfaces, z. B. machine cleaning of dishes, in addition to powders, Granules or liquids increasingly produced by compression Tablets or obtained by melting and subsequent cooling block-shaped cleaners (melting blocks) can be used. Tablets and Melting blocks offer the advantage of targeted and powdered powders 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 continuous commercial dishwashers, in which the items to be cleaned through different wash 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 Reinigungsmittels 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 fused blocks Disadvantage. So z. B. on such tablets breakage occur: such damaged tablets naturally no longer provide the Advantage of a precise dosage. Another problem with tablets is in that the desired water solubility is not always guaranteed can, d. H. Sometimes tablets dissolve either too fast or too slowly. In the case of melting blocks, a high breaking strength is to be expected during transport, but with larger containers, there is a problem with the dosage of this very solid detergent. In addition, both tablets require also melted blocks so far very expensive manufacturing process, which is just at the processing of alkaline melts particularly high demands the materials used and the conditions chosen:
Besonders erwünscht ist auch eine hohe Homogenität der erhaltenen Reiniger, die aber bei festen Reinigern oft nur schwierig zu realisieren ist. Dieses Problem tritt bei flüssigen Reinigern, 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 herab zu etwa 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 verhindern. Ganz besonders wünschenswert wäre eine weitgehende Kontrolle der Parameter, die den Durchhärteprozeß entscheidend beeinflussen.It is also particularly desirable to have a high degree of homogeneity of the resulting cleaners, but this is often difficult to achieve with solid cleaners. This problem occurs less in liquid cleaners that can be easily stirred. He wishes So would be the homogeneity of a liquid, a viscous liquid or a stirrable paste which is then controllably variable to a solid Strength solidifies, at this stage their advantages in storage and Use transport and dosing. It would be particularly desirable if stirrability were maintained at temperatures as low as about 40 ° C, because then less thermally stable components are added could. From an application point of view, it would be of particular advantage to have an early one Curing of the material during the production process in the Prevent production equipment. Especially desirable would be a broad control of the parameters that the curing process decisively influence.
WO 96/27653 A1 beschreibt ein pastenförmiges Reinigungsmittel auf Basis von NaOH, indem man die verdickende Wirkung von bestimmten Glykolen, Glykolderivaten und/oder Alkanolaminen auf wässrige Alkaliöllauge nutzt.WO 96/27653 A1 describes a paste-like Detergents based on NaOH, by the thickening effect of certain glycols, Glycol derivatives and / or alkanolamines aqueous alkali oil eye uses.
Aufgabe der vorliegenden Erfindung ist es, hochalkalische, auf Alkalihydroxid, 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 Pulvern 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 Konsistenz und eine verzögerte Durchhärtung bei der Herstellung fester Reinigungsmittel würden 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 gefährden. Wie bei jedem technischen Verfahren gilt es natürlich auch einen gegebenen Effekt unter möglichst preisgünstigen Bedingungen bezüglich Rohstoffen und Produktionsbedingungen zu erzielen.The object of the present invention is to provide highly alkaline, on alkali hydroxide, preferably potassium or sodium hydroxide, more preferably sodium hydroxide general-purpose cleaning agents for textile surfaces, preferably but those for cleaning hard surfaces, eg. As tableware, and in particular to provide cleaning agents for the commercial cleaning of dishes, the advantages of powders and liquids on the one hand and the Advantages of tablets and fused blocks on the other hand unite. The means to provide cleaning agents that are one of the most diverse Application conditions have defined solubility, on the other hand but are stable to transport and storage stable and beyond fast, easy and to dose precisely, which are not dusty and without great technical Effort to produce and easy to fill. Especially the stirrability the production, a controlled variable consistency and a delayed Curing in the production of solid detergents would be great advantages offer and should be considered. A procedure should be developed It also allows less temperature stable substances if necessary below 42 ° C without endangering the other tasks. Of course, as with any technical process, there is a given Effect under the lowest possible conditions regarding raw materials and To achieve production conditions.
Selbstverständlich müssen gleichzeitig auch die an Reinigungsmittel zu stellenden Erfordernisse wie gute Reinigungskraft, Fettlösekraft, etc. erfüllt sein.Of course, at the same time to be placed on cleaning agents Requirements such as good cleaning power, fat dissolving force, etc. be fulfilled.
Im Stand der Technik sind bereits sowohl höherviskose bis pastöse Reinigungsmittel beschrieben worden, als auch feste Reinigungsmittel in Tabletten- oder Blockform.Both higher-viscosity and pasty cleaning agents are already known in the prior art described as well as solid detergents in tablet or block shape.
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 German Offenlegungsschrift DE-OS-31 38 425 the rheological Behavior of the cleaner described there described so 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 dosing pump and squeezed out of a spray nozzle leaves.
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.US Pat. No. 3,607,764 describes glass cleaner in solid Form, which are diluted to a sprayable solution. These funds included et al Sodium or potassium hydroxide, sodium or potassium tripolyphosphate, Sodium or potassium pyrophosphate, hydroxycarboxylic acid builder, a water-soluble nonionic surfactant, alkylene glycol ethers and optionally sodium carbonate. A control of the viscosity or the strength in the sense of the present Invention is not described.
Die japanische Patentschrift JP 84/182870 beschreibt Lösungen von Alkalihydroxiden in Glycolen oder Alkoholen, die durch das Neutralisieren mit langkettigen Carbonsäuren viskos werden und durch Zugabe von Siliconöl eine pastöse Konsistenz erhalten, wodurch sie als Pasten in der Lederfettung verwendet werden können.Japanese Patent Publication JP 84/182870 describes solutions of alkali hydroxides in glycols or alcohols by neutralizing with long chain Carboxylic acids are viscous and by adding silicone oil a pasty Consistency, whereby they are used as pastes in the leather fatliquoring can.
Die japanische Patentschrift JP 86/296098 beschreibt wasserfreie feste Reinigungsmittel basierend auf Alkalihydroxiden. 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 Publication JP 86/296098 describes anhydrous solid detergents based on alkali hydroxides. Here, the alkali carrier is in alkanolamines and water-soluble glycol ethers, thereby forming a solid Cleaner receives. A technical teaching for the variable reduction of strength and for controlling the hardening process is not described.
Gegenstand der vorliegenden Erfindung ist ein pastöses bis festes wasserhaltiges alkalisches Reinigungsmittel
enthaltend
und zum Aufbau einer erhöhten Viskosität
in einer Gesamtmenge von 0,5 bis 40 Gew.%, vorzugsweise 1 bis 10 Gew.-%, besonders bevorzugt 2 bis 8 Gew.%, alle Gew.-% Angaben bezogen auf das gesamte Reinigungsmittel,
und
and to build up an increased viscosity
in a total amount of from 0.5 to 40% by weight, preferably from 1 to 10% by weight, particularly preferably from 2 to 8% by weight, all percentages by weight based on the total cleaning agent,
and
Die erfindungsgemäßen Reinigungsmittel haben im fertigen Zustand eine pastenförmige oder feste Konsistenz, wobei die Übergänge fließend sind. Sie sind vorzugsweise bei Raumtemperatur nicht pumpfähig. Die erfindungsgemäße Konsistenz kann sich aber zum Beispiel auch in Form von Schnittfestigkeit äußern. Viele der erfindungsgemäßen festen Reinigungsmittel sind während der Verarbeitung noch gießbar und auch nach längerer Lagerung noch formgebend verpreßbar.The cleaning agents according to the invention have a finished state pasty or firm consistency, the transitions being fluid. she are preferably not pumpable at room temperature. The inventive However, consistency can also take the form of cut resistance, for example express. Many of the solid detergents according to the invention are during the Processing still pourable and shaping even after prolonged storage compressible.
Die Mittel können während der Lagerung nachhärten. Besonders bei Zusatz von festem feinteiligem Alkalihydroxyd kann dieser Aushärteprozeß sehr schnell verlaufen. Besonders günstig ist dabei der Einsatz von bis zu 35 Gew.-% bevorzugt 2 bis 25 Gew.% besonders bevorzugt 5 bis 15 Gew.% festem Alkalihydroxid bezogen auf das gesamte Mittel. Durch Zusatz von Tensiden, Paraffinöl und Polyhydroxyverbindungen kann der Aushärteprozeß wiederum verzögert werden.The agents can post-cure during storage. Especially with the addition of Solid fine alkali hydroxide, this curing process can very quickly run. Particularly advantageous is the use of up to 35 wt .-% preferably 2 to 25% by weight, particularly preferably 5 to 15% by weight, of solid Alkali hydroxide based on the total agent. By addition of surfactants, Paraffin oil and polyhydroxy compounds can turn the curing process be delayed.
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 by the stirring process is continued after addition of all components and until it stops is tracked as a result of curing. Purely phenomenological has the composition at the time that is called curing and the can be controlled, a consistency in which you can not, as desired, through a down at a production boiler located drain pipe can let, or can flow out of an upside down beaker.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung dieser Mittel. Man erhält sie im einfachsten Fall durch Einrühren der Alkoholate in die Alkalilauge. Besonders bevorzugte Mittel werden erhalten, wenn danach ggf. Schauminhibitoren und/oder Builderkömponenten, dann Tenside und/oder Paraffinöl und schließlich 0,1 bis 35 Gew.% vorzugsweise 2 bis 25 Gew.%, bezogen auf das gesamte Mittel festes Alkalihydroxid, bevorzugt Kalium- oder Natriumhydroxid, besonders bevorzugt Natriumhydroxid zugegeben werden.Another object of the invention is a process for the preparation of these Medium. They are obtained in the simplest case by stirring the alcoholates into the alkali solution. Especially preferred agents are obtained, if necessary after that, foam inhibitors and / or Builderkomponenten, then surfactants and / or paraffin oil and finally 0.1 to 35 wt.%, Preferably 2 to 25 wt.%, Based on the total Medium solid alkali hydroxide, preferably potassium or sodium hydroxide, especially preferably sodium hydroxide may be added.
Ein weiterer Gegenstand der Erfindung ist die Verwendung dieser Mittel zum maschinellen Reinigen von Geschirr und Oberflächen und zum Waschen von Wäsche.Another object of the invention is the use of these means for machine cleaning of dishes and surfaces and washing of Laundry.
Bei erfindungsgemäßer Wahl der Stoffzusammensetzung sind im einfachsten Fall neben Alkalilauge keine weiteren Zusatzstoffe außer dem Alkoholat als Verdickungsmittel nötig, um den gewünschten erfindungsgemäßen verfestigenden Effekt in wäßriger Natronlauge zu erzielen. Dabei kann die Konsistenz durch die bevorzugte weitere Zugabe geeigneter Mengen von Paraffinöl, Tensiden und festem Alkalihydroxid über einen anwendungstechnisch günstigen Zeitraum, bei angemessener Temperatur in leicht rührbarem Zustand gehalten werden, d.h. es kann eine kontrollierte Verzögerung der Materialdurchhärtung erreicht werden.In the inventive choice of the composition of matter are in the simplest case in addition to alkali, no other additives except the alkoxide as a thickener necessary to solidify the desired inventive solidifying To achieve effect in aqueous sodium hydroxide solution. Here, the consistency by the preferred further addition of suitable amounts of paraffin oil, surfactants and solid alkali hydroxide over a period of application favorable period, at be maintained in an easily stirrable condition, i. e. it a controlled delay of material curing 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 a critical parameter; he lies between 10 and 35 wt .-%, advantageously between 20 and 30 wt .-%.
Aufgrund des hohen NaOH-Gehaltes liegt der pH-Wert der erfindungsgemäßen Reinigungsmittel über 13. Due to the high NaOH content, the pH of the invention Detergent above 13.
Die erfindungsgemäßen Reinigungsmittel können über die bereits genannten Inhaltsstoffe hinaus noch andere in alkalischen Reinigern übliche Inhaltsstoffe enthalten, soweit dadurch die erfindungsgemäße variierbare Festigkeit nicht verloren geht. In diesem Sinne wirkt das Reinigungsmittel aus Alkalilauge, bevorzugt Kali- und Natronlauge, besonders bevorzugt Natronlauge, Substanz I oder dem korrespondierenden Alkohol und gegebenenfalls festem Alkalihydroxid, bevorzugt Natriumhydroxid, sowie Tensiden und/oder Paraffinöl als Trägerphase für andere in Reinigern übliche Inhaltstoffe.The cleaning agents of the invention can over the already mentioned Ingredients addition to other common in alkaline cleaners ingredients contain, so far as the inventive variable strength not get lost. In this sense, the cleaning agent of alkali lye, preferably Potassium and caustic soda, particularly preferably sodium hydroxide solution, substance I. or the corresponding alcohol and optionally solid alkali hydroxide, preferably sodium hydroxide, as well as surfactants and / or paraffin oil as the carrier phase for other common in cleaning agents ingredients.
Als Alkoholate werden handelsüblicher Alkohole, mit Ausnahme der Alkoholate von Ethylenglykol und 1,2-Propylenglykol verwendet. Es sind Alkoholate von Ethanol, Propanol, Isopropanol, Glycerin und Butylenglykol. Dabei werden bei zunehmendem Alkylkettenanteil durchaus differenzierte Eigenschaften erreicht. So scheint mit zunehmender Kettenlänge die verdickende Wirkung der Alkoholate graduell abzunehmen. Auch Verzweigungen in der Alkylkette scheinen eine Veränderung des Verdickungsprozesses zu bewirken. Dabei können die Alkoholate nach den üblichen Methoden der organischen Chemie leicht hergestellt werden. Es gibt ebenfalls die Möglichkeit, die Alkoholate in situ zu erzeugen, indem man die entsprechenden Alkohole zu der AlkalihydroxidLösung zutropfen läßt. Je nach Lage des Gleichgewichtes verbleibt eine betimmte Menge des zum Alkoholat korrespondierenden Alkohols als solcher in der Lösung.As alcoholates become more commercial Alcohols, with the exception of the alcoholates of ethylene glycol and 1,2-propylene glycol used. They are alcoholates of Ethanol, propanol, isopropanol, glycerol and butylene glycol. At the same time, the alkyl chain content is differentiated Properties achieved. Thus, with increasing chain length, the gradually decrease the thickening effect of alcoholates. Also branches In the alkyl chain, a change in the thickening process seems to be effected. there The alkoxides can be prepared by the usual methods of organic chemistry easily manufactured. There is also the option of the alcoholates in situ by adding the corresponding alcohols to the alkali hydroxide solution drops. Depending on the position of the balance remains one the amount of alcohol corresponding to the alcoholate as such in the solution.
Die Menge des zugesetzten Alkoholats soll 0,5 bis etwa 40 Gew.-%, vorzugsweise etwa 1 bis etwa 10 Gew.-% bezogen auf das gesamte Reinigungsmittel betragen. Da das Alkoholat mit dem korrespondierenden Alkohol im Gleichgewicht steht, ist eventuell enthaltener freier Alkohol rechnerisch in die Alkoholatmenge einzubeziehen, bei mehrwertigen Alkoholen als Monoalkoholat. The amount of alcoholate added should be 0.5 to about 40% by weight, preferably about 1 to about 10 wt .-% based on the total Cleaning agent amount. Since the alkoxide with the corresponding Alcohol in equilibrium is possibly contained free alcohol mathematically included in the Alkoholatmenge, in polyhydric alcohols as a monoalcoholate.
Als Tenside können sowohl Anionentenside als auch Kationentenside, amphotere Tenside und nicht-ionische Tenside eingesetzt werden. Die Reinigungsleistung wird von der Menge der Tenside entscheidend beeinflußt. Insbesondere von ihrer Konzentration hängt aber auch die Aushärtdauer nach Zugabe aller Komponenten ab. Je nach Anwendungsbereich können z. B. beim Reinigen von Geschirr und Oberflächen schwach schäumende Tenside, vor allem nichtionische Tenside, in einer Menge von bis zu 10 Gew.%, bevorzugt 0,1 bis 5 Gew.-% und besonders bevorzugt 0,5 bis 4 Gew.-% enthalten sein. Üblicherweise werden für das maschinelle Geschirrspülen extrem schaumarme Verbindungen eingesetzt. Hierzu zählen vorzugsweise C12-C18-Alkylpolyethylenglykolpolypropylenglykolether mit jeweils bis zu 8 Mol Ethylenoxid- und Propylenoxideinheiten im Molekül. 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.As surfactants, both anionic surfactants and cationic surfactants, amphoteric surfactants and nonionic surfactants can be used. The cleaning performance is decisively influenced by the amount of surfactants. In particular, of their concentration but also depends on the curing time after addition of all components. Depending on the application z. B. in the cleaning of dishes and surfaces weakly foaming surfactants, especially nonionic surfactants, in an amount of up to 10 wt.%, Preferably 0.1 to 5 wt .-% and particularly preferably 0.5 to 4 wt .-% be included. Normally, extremely low-foam compounds are used for automatic dishwashing. These include preferably C 12 -C 18 -Alkylpolyethylenglykolpolypropylenglykolether each with up to 8 moles of ethylene oxide and propylene oxide in the molecule. But you can also use other known as low-foaming nonionic surfactants such. B. C 12 -C 18 -Alkylpolyethylenglykolpolybutylenglykolether each with up to 8 moles of ethylene oxide and butylene oxide in the molecule and endgruppenverschlossene Alkylpolyalkylenglykolmischether.
Sollen die Mischungen gemäß der vorliegenden Erfindung zum maschinellen Waschen von Wäsche eingesetzt werden, so empfiehlt sich ein höherer Tensidgehalt, der in der Regel bis 30 Gew.-%, bevorzugt 0,1 bis 15 besonders bevorzugt 1 bis 10 Gew.-% und äußerst bevorzugt 2 bis 4 Gew.-% bezogen auf das gesamte Mittel betragen kann. Man verwendet dann neben oder anstelle von nichtionischen, kationischen und amphoteren Tensiden besonders anionische Tenside, vorzugsweise aus der Gruppe der Alkylbenzolsulfonate, der Fettalkoholsulfate und der Fettalkoholethersulfate.If the mixtures according to the present invention for machine Washing are used, it is recommended that a higher surfactant content, which is usually up to 30 wt .-%, preferably 0.1 to 15 particularly preferred 1 to 10 wt .-% and most preferably 2 to 4 wt .-% based on the total means may be. You then use next to or instead of nonionic, cationic and amphoteric surfactants especially anionic Surfactants, preferably from the group of alkylbenzenesulfonates, the fatty alcohol sulfates and the fatty alcohol ether sulfates.
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 erfindungsgemäßen Mitteln in Mengen zwischen 0,1 und 8 Gew.-% besonders bevorzugt zwischen 0,5 und 5 Gew.-% zugesetzt. Paraffin oil, which according to the invention may contain up to 10% by weight, Long-chain hydrocarbons are understood as being branched or unbranched could be. In a preferred embodiment, they are the inventive Agents in amounts between 0.1 and 8 wt .-% particularly preferred between 0.5 and 5 wt .-% added.
Fakultativ können die Reinigungsmittel zusätzlich Buildersubstanzen in einer Menge von bis zu 60 Gew.-%, vorzugsweise 15 bis 40 Gew.-%, enthalten.Optionally, the cleaning agents may additionally builders in one Amount of up to 60 wt .-%, preferably 15 to 40 wt .-%, included.
Die in den erfindungsgemäßen 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, wobei diese in den erfindungsgemäßen Mitteln aber durchaus ungelöst vorliegen können. Auch die im Stand der Technik bekannten gecoateten Buildersubstanzen können eingesetzt werden und sind sogar bevorzugt, wenn man mit chlorhaltigen Bleichmitteln arbeitet.The builder contained in the cleaning agents according to the invention In principle, any substance can be that in the state of the art as in the broadest sense for washing and cleaning agent suitable builder is known. Preferably Water-soluble builder substances are used, these in the However, agents of the invention may be present undissolved. Also the Coated builders known in the art can be used and are even preferred when bleached with chlorine is working.
Als Buildersubstanzen kommen z. B. Alkaliphosphate in Frage, die in Form ihrer Natrium- oder Kaliumsalze vorliegen können. 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 builders z. As alkali phosphates in question, in the form of their Sodium or potassium salts may be present. Examples include: tetrasodium diphosphate, Pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium hexametaphosphate and the corresponding potassium salts or mixtures 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 mentioned, such as. B. nitrilotriacetate or ethylenediaminetetraacetate. Also soda and Borax count within the scope of the present Invention to the builders.
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 SP02 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, Rhöne-Poulenc oder SRCHEM.Further possible water-soluble builder components are, for. B. organic Polymers of native or synthetic origin, especially polycarboxylates. In Consider, for example, polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymeric acids. Commercially available products are z. 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 (eg DE 42 28 786) and polyamino acids such as polyglutamic acid or polyaspartic acid, z. B. the companies Cygnus, Bayer, Rohm & Haas, Rhone-Poulenc or SRCHEM.
Weitere mögliche Builderkomponenten sind natürlich vorkommende Hydroxycarbonsäuren wie z. B. Mono-, Dihydroxy-bernsteinsäure, 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 preferably 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).As builders, amorphous metasilicates or sheet silicates may furthermore be mentioned. Even crystalline phyllosilicates are suitable builders, provided that they are sufficiently stable to alkali; crystalline phyllosilicates are marketed by the company Hoechst AG (Germany) under the trade name Na-SKS, z. 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 bevorzugt werden Buildersubstanzen aus der Gruppe Pentanatriumtriphosphat, Trinatriumcitrat, Nitrilotriacetat, Ethylendiamintetraacetat, Natriumsalze von Poyacrylsäure und von Maleinsäure - Acrylsäure - Copolymerisaten, Soda, Alkalisilikat und deren Mischungen.Particularly preferred are builders from the group pentasodium triphosphate, Trisodium citrate, nitrilotriacetate, ethylenediaminetetraacetate, Sodium salts of polyacrylic acid and of maleic acid - acrylic acid - Copolymers, soda, alkali silicate and mixtures thereof.
Auch in Wasch- und Reinigungsmitteln übliche Bleichmittel können in den erfindungsgemäßen Mitteln enthalten sein, dann bevorzugt in Mengen 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, Alkalidichlorisocyanurat, 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.Bleaches customary in detergents and cleaners can also be used in the novel bleaches Be contained means, then preferably in amounts between 0.5 and 10% by weight, and more preferably between 1.5 and 10% by weight. These may be selected from the group of oxygen-based bleaching agents, such as 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-toluenesulfonic acid amide, Trichloroisocyanuric acid, alkali metal dichloroisocyanurate, alkali hypochlorites, and alkali hypochlorites releasing agents, with particularly alkali stable bleaching compositions are preferred. These can be both alkaline stable substances or by suitable methods such as surface coating or passivation be stabilized components.
Weitere mögliche Inhaltstoffe in den erfindungsgemäßen 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, bzw. wirken 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 DE 196 20 249 beschrieben sind. Aber auch andere Entschäumer können verwendet weden.Further possible ingredients in the cleaners according to the invention are defoamers. These may be in concentrations between 0.1 and 5 wt.%, Preferably 0.5 and 3 wt .-% are used when a selected surfactant under foam too much in the given circumstances, or act foam-suppressing foaming food particles in the dishwasher. Under defoamers one understands all known in the prior art foam-damping substances, but preferably those based on silicone and paraffin, more preferably on Paraffin-based, as z. B. in DE 34 00 008, DE 36 33 518, the DE 30 00 483, DE 41 17 032, DE 4323410, WO 95/04124 and the DE 196 20 249 are. But other defoamers can be used.
Weitere fakultativ enthaltene Inhaltsstoffe sind z.B. Farbstoffe oder alkalistabile Parfumstoffe. Abrasiv wirkende Inhaltsstoffe können zwar prinzipiell enthalten sein, vorzugsweise sind die erfindungsgemäßen Reinigungsmittel jedoch frei davon.Other optional ingredients are e.g. Dyes or alkali stable Perfumes. Although abrasive ingredients may in principle contain However, preferably the cleaning agents of the invention are free thereof.
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 erfindungsgemäßen Reinigungsmittel nicht erforderlich, d. h. auf solche Verdickungsmittel kann verzichtet werden.Although in addition thickeners such. B. swellable phyllosilicates of Montmorillonite type, bentonite, kaolin, talc or carboxymethylcellulose optional can be used to vary the strength, they are to achieve the desired controllable solids properties and the consistency of Cleaning agent according to the invention not required, d. H. on such Thickener can be dispensed with.
Auch der Einsatz hochschmelzender Paraffine oder hochschmelzender Polyethylenglycole zur Verfestigung von Mischungen ist hier zur Erzielung des erfindungsgemäßen Erfolges nicht notwendig. Zusätzlich können solche Mittel jedoch enthalten sein. 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. In der Regel sind solche Substanzen aber dem erfindungsgemäßen Erfolg nicht abträglich. Ebenfalls ist die Erzeugung von flüssigkristallinen Strukturen zur Verdickung nicht notwendig.The use of high-melting paraffins or high-melting polyethylene glycols for the solidification of mixtures is here to achieve the inventive Success not necessary. In addition, however, such funds may be included. 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 sufficient to achieve the strength according to the invention required. In general, however, such substances are the inventive Success not detrimental. Also is the production of liquid crystalline structures not necessary for thickening.
Weitere Erfindungsgegenstände ergeben sich aus der verfestigenden Wirkung der Alkoholate in Kombination mit festem Alkalihydroxid, bevorzugt Kalium- oder Natriumhydroxid, besonders bevorzugt Natriumhydroxid gegenüber Alkalilauge, bevorzugt Kali- und Natronlauge, besonders bevorzugt Natronlauge, mit der nachfolgenden Verzögerung der Aushärtung durch die Zugabe von Tensiden und/oder Paraffinölen.Other subjects of the invention result from the strengthening effect the alcoholates in combination with solid alkali hydroxide, preferred Potassium or sodium hydroxide, more preferably sodium hydroxide Alkali, preferably potassium and caustic soda, more preferably caustic soda, with the subsequent delay of cure by the addition of surfactants and / or paraffin oils.
So wird die Verwendung von Alkoholaten als Verfestigungsmittel für wasserhaltige Reinigungsmittel zum maschinellen Spülen von Geschirr oder zum Waschen von Textilien, enthaltend Alkalihydroxid, bevorzugt Natriumhydroxid, mit nachfolgender sequentieller Zugabe verschiedener Komponenten, insbesondere von Paraffinöl und/oder Tensiden in Kombination mit der nachfolgenden Zugabe von festem NaOH beansprucht.Thus, the use of alcoholates as solidifying agents for water-based detergents for the automatic rinsing of dishes or for washing textiles containing alkali metal hydroxide Sodium hydroxide, with subsequent sequential addition of various Components, in particular of paraffin oil and / or surfactants in combination claimed with the subsequent addition of solid NaOH.
Weiterhin wird ein Verfahren zum Verfestigen von wäßriger 42 bis 55 Gew.%iger Alkalilauge, bevorzugt Kali- und Natronlauge, besonders bevorzugt Natronlauge beansprucht. Das Verfahren ist dadurch qekennzeichnet, daß man einer solchen Alkalilauge unter Rühren ein Alkoholat zugibt und so eine pastenförmige Zubereitung erhält, der im Anschluß eine oder mehrere Komponenten aus den Klassen der Paraffin-Schauminhibitoren und/oder Buildersubstanzen und/oder Paraffinöl und/oder Tenside zugegeben werden, ehe festes Alkalihydroxid, bevorzugt Kalium- oder Natriumhydroxid, besonders bevorzugt Natriumhydroxid oder ein Gemisch dieser Substanzen zugesetzt wird, um eine verzögerte, kontrollierte und variierbare Aushärtung des Reinigungsmaterials zu erreichen. Im allgemeinen wird das Verfahren bei 20°C bis 50°C bevorzugt bei 30 bis 48°C besonders bevorzugt bei 38 bis 42°C durchgeführt. 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.Furthermore, a method for solidifying aqueous 42 to 55 wt.% Iger Alkali solution, preferably potassium and sodium hydroxide, more preferably sodium hydroxide claimed. The method is characterized in that one such Alkali solution with stirring an alkoxide is added and so a paste-like preparation, which is followed by one or more components from the classes of paraffin foam inhibitors and / or builders and / or paraffin oil and / or surfactants are added before solid Alkali hydroxide, preferably potassium or sodium hydroxide, more preferably Sodium hydroxide or a mixture of these substances is added to a delayed, controlled and variable curing of the cleaning material too to reach. In general, the process at 20 ° C to 50 ° C is preferred at 30 to 48 ° C particularly preferably carried out at 38 to 42 ° C. Because at higher Temperatures increase the solubility of NaOH in water, then the content NaOH in the aqueous solution also be more than 55 wt .-%. Accordingly, at lower temperatures, the NaOH content is also below 42 wt .-% are. The restriction to 42 to 55% by weight NaOH solutions is therefore limited essentially to temperatures of 20 ° C to 25 ° C.
Ein besonderer Vorteil der Erfindung liegt darin, daß die Rührbarkeit und die damit verbundenen Vorteile bereits bei Raumtemperatur gegeben sind. In manchen Fällen, z.B. bei stark erhöhter Viskosität der verdickten Alkalilauge, 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 erfindungsgemäßen Reinigungsmittel eingearbeitet werden können.A particular advantage of the invention is that the stirrability and thus associated benefits are already given at room temperature. In some Cases, e.g. at greatly increased viscosity of the thickened alkali, preferred Potassium and caustic soda, particularly preferably sodium hydroxide, may be added before addition the solid ingredients are low, to reduce the viscosity slightly to go up with the temperature. The consistency of the invention can but in almost all cases below 42 ° C, preferably between 38 ° C and 42 ° C be realized, so that less temperature-stable components, such as Example, chlorine-containing bleach in the detergents of the invention can be incorporated.
Insbesondere wird einer frühen Aushärtung des Reinigungsmittels infolge der Zugabe von festem Alkalihydroxid dadurch entgegengewirkt, daß zuvor andere Komponenten, beispielsweise Schauminhibitoren, Buildersubstanzen, Paraffinöle und/oder Tenside 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 Alkalihydroxid zur Verfestigung beigemischt wird. In einer bevorzugten Ausführungsform wird nach Beendigung der Zugabe der Alkoholate noch mindestens 3 Minuten bevorzugt 10 bis 20 Minuten lang nachgerührt, bevor man die anderen Komponenten zusetzt, nach deren Zugabe jeweils auch mindestens 3 Minuten bevorzugt 8 bis 15 Minuten gerührt wird.In particular, an early hardening of the cleaning agent as a result of Addition of solid alkali hydroxide counteracted by previously other Components, for example foam inhibitors, builders, paraffin oils and / or surfactants are added. Depending on the desired curing time all or only certain substances of these classes can be added. A maximum curing time is achieved if all of the above Substances are added in this order, before firm Alkali hydroxide is mixed for solidification. In a preferred Embodiment becomes after completion of the addition of the alcoholates for at least 3 minutes, preferably for 10 to 20 minutes before stirring you add the other components, after their addition, respectively is stirred for at least 3 minutes, preferably 8 to 15 minutes.
So kann die Herstellung des Reinigungsmittels 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 Vekaufsgebinde 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.Thus, the preparation of the cleaning agent, for example, in a stirred tank at 20 to 50 ° C, preferably at 30 to 48 ° C, more preferably at 38 - 42 ° C take place. The detergent has procedurally by the sequence-bound Addition of paraffin oils and / or surfactants has the advantage that the curing of the detergent can be delayed so long that it no solid deposits can occur in the production equipment. Afterwards, the detergent can be stored at approx. 40 ° C in the sales container be bottled and e.g. via a cooling tunnel to about 20 ° C to reach the be cooled according to the invention consistency. But also other methods the filling and return to room temperature are conceivable.
Die Anwendung der erfindungsgemäßen 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 Firma Henkel Hygiene GmbH unter der Bezeichnung Topmater® P40 vertriebenes Dosiergerät oder ein von der Firma Henkel-Ecolab vertriebenes Feststoffdosiergerät V/VT-2000 an. Pastenförmige Reinigungsmittel können mit Hilfe von geigneten, starken Druck ausübenden Geräten direkt in die Anwendungsflotte dosiert werden oder ebenfalls zunächst mit Wasser in eine flüssige Form gebracht und in dieser Form dosiert werden. The application of the solid detergent according to the invention can, for. B. in the Make sure that in a container (capacity, for example, 0.5 to 10 kg) of controllable strength sprayed with water sprayed is and the so-dissolved detergent is used, for. In a dishwasher is metered. Here, for example, offers a from the company Henkel Hygiene GmbH under the name Topmater® P40 sold dosing device or a marketed by Henkel-Ecolab Solid Dosing Unit V / VT-2000 on. Pasty cleaners can be used with Help of suitable, strong pressure exerting devices directly into the Application liquor are dosed or also first with water in one brought liquid form and dosed in this form.
Claims (12)
- A pasty to solid, hydrous alkaline cleaning agent containinga) thickened, aqueous alkali solution, preferably potassium and/or sodium hydroxide solution, preferably having 42-55%, in an amount of from 21 to 70 wt.-%, preferably from 35 to 55 wt.-%, relative to the cleaning agent, for developing increased viscosity;b) an alcoholate or a plurality of alcoholates of ethanol, propanol, isopropanol, glycerol and butylene glycol, preferably in the form of potassium or sodium alcoholate, in an overall amount of from 0.5 to 40 wt.-%, preferably from 1 to 10 wt.-%, more preferably from 2 to 8 wt.-%, all weight percentages relative to the overall cleaning agent; andc) optionally the alcohols corresponding to the alcoholate of b) and/or foam inhibitors and/or builder components and/or paraffin oil and/or surfactants and/or alkali hydroxide in the form of a solid and/or other ingredients customary in detergents and cleaning agents, the water content ranging from 10 to 35 wt.-%.
- The agent according to claim 1, characterized in that it additionally contains solid alkali hydroxide with up to 35 wt.-%, preferably 2 to 25 wt.-%, relative to the overall agent.
- The agent according to claim 1 or 2, characterized in that it contains surfactants in amounts of up to 30 wt.-%, preferably from 0.1 to 15 wt.-%, more preferably between 1 and 10 wt.-%, and especially preferably between 2 and 4 wt.-%, relative to the overall agent.
- The agent according to claim 1, 2 or 3, characterized in that the surfactants are selected from the group of non-ionic surfactants, alkylbenzenesulfonates, fatty alcohol sulfates, fatty alcohol ether sulfates and mixtures thereof.
- The agent according to any of claims 1 to 4, characterized in that it contains paraffin oil in amounts of up to 10 wt.-%, preferably between 0.1 and 8 wt.-%, and particularly between 0.5 and 5 wt.%, relative to the overall agent.
- The agent according to any of claims 1 to 5, characterized in that it contains builder substance in an amount of up to 60 wt.%, preferably from 15 to 40 wt.-%, relative to the overall agent.
- The agent according to claim 6, characterized in that the builder substance is selected from the group of pentasodium triphosphate, trisodium citrate, nitrilotriacetate, ethylenediaminetetraacetate, sodium salts of polyacrylic acid and of maleic acid/acrylic acid copolymers, soda, alkali silicate and mixtures thereof.
- A method for the production of cleaning agents according to any of claims 1 to 7, characterized in that the aqueous alkali hydroxide solution is added with stirring with an alcoholate or a plurality of alcoholates of ethanol, propanol, isopropanol, glycerol and butylene glycol, preferably in the form of potassium or sodium alcoholate and/or the corresponding alcohols, optionally followed by foam inhibitors and/or builder components, thereafter surfactants and/or paraffin oil, and finally solid alkali hydroxide with 0.1 to 35 wt.-%, preferably 2 to 25 wt.-%, relative to the overall agent.
- The method according to claim 8, characterized in that the addition of one or more alcoholates of ethanol, propanol, isopropanol, glycerol and butylene glycol, preferably in the form of potassium or sodium alcoholate or the corresponding alcohol, is followed by stirring for at least 3 minutes, preferably between 10 and 20 minutes.
- The method according to any of claims 8 or 9, characterized in that each further addition of material is followed by stirring for at least 3 minutes, preferably between 8 and 15 minutes.
- Use of a hydrous solid agent according to any of claims 1 to 7 for cleaning surfaces and crockery.
- Use of a hydrous solid agent according to any of claims 1 to 7 for washing laundry.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19741874A DE19741874A1 (en) | 1997-09-23 | 1997-09-23 | Alcoholic cleaner |
DE19741874 | 1997-09-23 | ||
PCT/EP1998/005811 WO1999015613A1 (en) | 1997-09-23 | 1998-09-12 | Cleaning agent containing alcoholate |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1017772A1 EP1017772A1 (en) | 2000-07-12 |
EP1017772B1 true EP1017772B1 (en) | 2005-11-23 |
Family
ID=7843292
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98954274A Expired - Lifetime EP1017772B1 (en) | 1997-09-23 | 1998-09-12 | Cleaning agent containing alcoholate |
Country Status (15)
Country | Link |
---|---|
US (1) | US6800600B1 (en) |
EP (1) | EP1017772B1 (en) |
JP (1) | JP2001517729A (en) |
AT (1) | ATE310793T1 (en) |
AU (1) | AU740019B2 (en) |
CA (1) | CA2304595C (en) |
CZ (1) | CZ20001052A3 (en) |
DE (2) | DE19741874A1 (en) |
HU (1) | HUP0003891A3 (en) |
NO (1) | NO20001460L (en) |
NZ (1) | NZ504116A (en) |
PL (1) | PL188588B1 (en) |
SK (1) | SK4192000A3 (en) |
TR (1) | TR200000768T2 (en) |
WO (1) | WO1999015613A1 (en) |
Families Citing this family (5)
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JP4015779B2 (en) * | 1999-06-17 | 2007-11-28 | ディバーシー・アイピー・インターナショナル・ビー・ヴイ | Detergent composition for dishwasher |
DE10002710A1 (en) * | 2000-01-22 | 2001-08-02 | Henkel Ecolab Gmbh & Co Ohg | Production of creamy alkaline-aqueous cleaning agents containing complexing agents |
WO2009034932A1 (en) * | 2007-09-14 | 2009-03-19 | Kao Corporation | Alkaline nonionic surfactant composition |
JPWO2010140561A1 (en) * | 2009-06-01 | 2012-11-22 | ユケン工業株式会社 | Degreasing composition and method for producing the same |
US10184097B2 (en) * | 2013-02-08 | 2019-01-22 | Ecolab Usa Inc. | Protective coatings for detersive agents and methods of forming and detecting the same |
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US3607764A (en) | 1968-01-31 | 1971-09-21 | Grace W R & Co | Glass washing compound and process |
US3637509A (en) * | 1970-02-10 | 1972-01-25 | Grace W R & Co | Chlorinated machine dishwashing composition 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 |
PT71309A (en) | 1980-05-27 | 1980-06-01 | Hovione Sociedade Quimica Lda | Process of selective |
DE3138425A1 (en) | 1981-09-26 | 1983-04-14 | Henkel KGaA, 4000 Düsseldorf | "USE OF A PASTOESE CLEANER IN DISHWASHER" |
JPS59182870A (en) | 1983-04-01 | 1984-10-17 | Nitto Kagaku Kk | Pasty cleaning and polishing agent |
DE3400008A1 (en) | 1984-01-02 | 1985-07-11 | Henkel KGaA, 4000 Düsseldorf | FOAM REGULATORS SUITABLE FOR USE IN SURFACTANT AGENTS |
JPS61296098A (en) | 1985-06-25 | 1986-12-26 | ティーポール株式会社 | Solid detergent |
US4753755A (en) * | 1986-08-25 | 1988-06-28 | Diversey Wyandotte Corporation | Solid alkaline detergent and process for making the same |
DE3633518A1 (en) | 1986-10-02 | 1988-04-14 | Philips Patentverwaltung | CLOCKED DC CONVERTER |
AU609012B2 (en) * | 1987-02-09 | 1991-04-18 | Atofina Chemicals, Inc. | High solids liquid alkaline cleaners |
DE4117032A1 (en) | 1991-05-24 | 1992-11-26 | Henkel Kgaa | SILICONE-CONTAINING DECORATIVE GRANULATE |
DE4216405A1 (en) * | 1992-05-18 | 1993-11-25 | Henkel Kgaa | Pumpable alkaline cleaner concentrates |
DE4228786A1 (en) | 1992-08-29 | 1994-03-03 | Henkel Kgaa | Dishwashing liquid with selected builder system |
JPH06108092A (en) * | 1992-09-28 | 1994-04-19 | Lion Corp | Strongly alkaline liquid detergent composition |
DE4323410A1 (en) | 1993-07-13 | 1995-01-19 | Henkel Kgaa | Pourable, phosphate-free foam control agent |
DE69402867T2 (en) | 1993-07-30 | 1997-12-18 | Unilever N.V., Rotterdam | TRIGLYCERIDOIL FACTIONING |
WO1995004124A1 (en) | 1993-08-02 | 1995-02-09 | Henkel Kommanditgesellschaft Auf Aktien | Foam regulating granulate and process for producing the same |
DE19507532C2 (en) * | 1995-03-03 | 2000-01-05 | Henkel Ecolab Gmbh & Co Ohg | Pasty detergent |
DE19519176A1 (en) * | 1995-05-24 | 1996-11-28 | Guenter Klockner | Cleaning metal articles such as bakeware contaminated with burnt-on organic residues |
DE19620249A1 (en) | 1996-05-21 | 1997-11-27 | Henkel Kgaa | Silicone free anti foaming agents for washing powders |
DE19616770A1 (en) | 1996-04-26 | 1997-11-06 | Henkel Kgaa | Acyl lactams as bleach activators for detergents and cleaning agents |
DE19617215A1 (en) * | 1996-04-30 | 1997-11-06 | Henkel Ecolab Gmbh & Co Ohg | Compact cleaner for commercial dishwashers |
US5777324A (en) * | 1996-09-19 | 1998-07-07 | Sequenom, Inc. | Method and apparatus for maldi analysis |
BR9713218A (en) * | 1996-09-24 | 2000-04-04 | Henkel Ecolab Gmbh & Co Ohg | Compact cleaner containing surfactant |
-
1997
- 1997-09-23 DE DE19741874A patent/DE19741874A1/en not_active Ceased
-
1998
- 1998-09-12 EP EP98954274A patent/EP1017772B1/en not_active Expired - Lifetime
- 1998-09-12 HU HU0003891A patent/HUP0003891A3/en not_active Application Discontinuation
- 1998-09-12 WO PCT/EP1998/005811 patent/WO1999015613A1/en not_active Application Discontinuation
- 1998-09-12 PL PL98339560A patent/PL188588B1/en not_active IP Right Cessation
- 1998-09-12 SK SK419-2000A patent/SK4192000A3/en unknown
- 1998-09-12 NZ NZ504116A patent/NZ504116A/en unknown
- 1998-09-12 AT AT98954274T patent/ATE310793T1/en not_active IP Right Cessation
- 1998-09-12 TR TR2000/00768T patent/TR200000768T2/en unknown
- 1998-09-12 JP JP2000512908A patent/JP2001517729A/en active Pending
- 1998-09-12 DE DE59813232T patent/DE59813232D1/en not_active Expired - Lifetime
- 1998-09-12 AU AU11463/99A patent/AU740019B2/en not_active Ceased
- 1998-09-12 CZ CZ20001052A patent/CZ20001052A3/en unknown
- 1998-09-12 CA CA002304595A patent/CA2304595C/en not_active Expired - Lifetime
-
2000
- 2000-03-21 NO NO20001460A patent/NO20001460L/en unknown
- 2000-07-07 US US09/509,123 patent/US6800600B1/en not_active Expired - Lifetime
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CA2304595C (en) | 2009-10-27 |
CZ20001052A3 (en) | 2001-08-15 |
WO1999015613A1 (en) | 1999-04-01 |
US6800600B1 (en) | 2004-10-05 |
NO20001460D0 (en) | 2000-03-21 |
PL339560A1 (en) | 2000-12-18 |
DE59813232D1 (en) | 2005-12-29 |
TR200000768T2 (en) | 2000-09-21 |
PL188588B1 (en) | 2005-02-28 |
NO20001460L (en) | 2000-03-21 |
SK4192000A3 (en) | 2000-09-12 |
CA2304595A1 (en) | 1999-04-01 |
JP2001517729A (en) | 2001-10-09 |
HUP0003891A3 (en) | 2003-02-28 |
NZ504116A (en) | 2001-09-28 |
ATE310793T1 (en) | 2005-12-15 |
AU1146399A (en) | 1999-04-12 |
DE19741874A1 (en) | 1999-04-01 |
EP1017772A1 (en) | 2000-07-12 |
AU740019B2 (en) | 2001-10-25 |
HUP0003891A2 (en) | 2001-03-28 |
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