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WO1997031096A1 - Procede de fabrication de pastilles d'agent detergent pour lave-vaisselle - Google Patents

Procede de fabrication de pastilles d'agent detergent pour lave-vaisselle Download PDF

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Publication number
WO1997031096A1
WO1997031096A1 PCT/EP1997/000700 EP9700700W WO9731096A1 WO 1997031096 A1 WO1997031096 A1 WO 1997031096A1 EP 9700700 W EP9700700 W EP 9700700W WO 9731096 A1 WO9731096 A1 WO 9731096A1
Authority
WO
WIPO (PCT)
Prior art keywords
salts
acids
surfactants
weight
mixture
Prior art date
Application number
PCT/EP1997/000700
Other languages
German (de)
English (en)
Inventor
Hans-Friedrich Kruse
Volker Bauer
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1997031096A1 publication Critical patent/WO1997031096A1/fr

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Classifications

    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • 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
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof

Definitions

  • the invention relates to a method for producing low-alkaline dishwasher tablets from a builder component based on polycarboxylic acids and their salts.
  • European dishwashing detergents are known from European application EP 530635, which contain sodium citrate and citric acid as the builder system and non-ionic surfactants, enzymes and thickeners as additives but no alkalinity carriers such as soda or hydrogen carbonate.
  • low alkaline agents for machine cleaning of dishes which contain sodium citrate, alkali hydrogen carbonate, a bleaching agent as an essential component. tel, a bleach activator and common additives such as enzymes and the like.
  • the agents mentioned there are described as granulated powders.
  • the application also provides for the use of citric acid (for the partial replacement of sodium citrate). However, since water is present in the manufacturing process described, a chemical reaction takes place during the manufacturing process, so that ultimately citric acid is not present in the agents described there in addition to the bicarbonate.
  • a water softener tablet is known from European patent application EP 628627 A1, which contains citrate and / or citric acid in addition to a polymer which acts as a softener and further auxiliaries. Sodium carbonate or sodium hydrogen carbonate is mentioned among the other auxiliaries. It is intended that the neutralization reaction which begins upon ingress of water will destroy the tablet and dissolve it rapidly.
  • the tablet can also contain paraffin in amounts of up to 0.2% by weight, however the person skilled in the art will infer from this document that poor dissolution behavior must be prevented, i.e. the tablet is also soluble in cold water and would dissolve completely in the pre-wash cycle of a dishwasher and then no longer be available for the main wash cycle.
  • a machine dishwashing detergent which contains citric acid as well as percarbonate.
  • the citric acid is coated twice.
  • the aim of the process according to this application is to adjust the dishwashing detergent which is used as granules in the main wash cycle so that the alkaline constituents dissolve faster than the acid constituents and thus the washing liquor undergoes a gradual shift in pH from strongly alkaline to neutral.
  • tablets are required to be unbreakable and easy to manufacture. Since tablets of the type mentioned are not used in the detergent dispenser, but are freely placed in the interior of the dishwasher, they must be such that only a small part of the detergent dissolves in the pre-rinse cycle operated with cold water.
  • the surfactants in cooperation with the hydrophobizing agent, protect the polycarboxylic acid or its sodium salt against the ingress of water at low temperatures, but that this protection no longer exists when warm water is admitted and that the tablet disintegrates the onset of reaction of the polycarboxylic acid with alkali carbonate or alkali hydrogen carbonate is accelerated.
  • the invention therefore relates to a process for the production of a machine dishwashing detergent in tablet form, containing polycarboxylic acids and their salts as a builder component, alkalinity carriers, bleaching agents, surfactants and water repellents and, if desired, customary additives, characterized in that the polycarboxylic acid and its salts are in encloses a first treatment stage with a liquid phase of surfactants and hydrophobicizing agent, then adds the remaining constituents in a second treatment stage and finally compresses the mixture into tablets.
  • the polycarboxylic acid or its sodium salt and, if desired, further components for example: a bleaching agent based on chlorine or on oxygen, initially with a liquid preparation, which in any case is a hydrophobizing agent, if desired also contains a surfactant.
  • a liquid preparation which in any case is a hydrophobizing agent, if desired also contains a surfactant.
  • the solid constituents are expediently placed in a mixer and the liquid constituents are added individually or in succession in any order.
  • a liquid mixture of surfactant and hydrophobic agent can be used, but the individual components can also be melted and then added.
  • the liquid component can expediently be used in molten form and solidify under normal conditions.
  • the purpose of this process step is to encase the solid material with the liquid, which means that the components are enclosed, hydrophobicized and thus not easily accessible to water.
  • Water-insoluble, oily or solid non-toxic organic substances are used as water repellents in the process according to the invention.
  • Particularly suitable here are paraffins with melting points below the working temperature of dishwashers, but also triglycerides and / or M oleochemical derivatives such as fatty alcohols, fatty alcohol ethers and the like.
  • the melting range of these substances is preferably between 40 and 60 ° C.
  • the mixture of the surfactants with the hydrophobizing agents has a melting point above room temperature. Therefore, surfactants with melting points above 20 ° C can be used, in particular between 40 and 60 C C.
  • the process according to the invention provides that the mixture treated in this way by the other constituents, e.g. due to the alkaline components such as alkali carriers and the small quantities such as e.g. Bleach activators, enzymes, corrosion protection agents, silver protection agents, foam inhibitors and the like, and to compress the mixture thus obtained into tablets in a manner known per se.
  • the alkaline components such as alkali carriers
  • the small quantities such as e.g. Bleach activators, enzymes, corrosion protection agents, silver protection agents, foam inhibitors and the like
  • polycarboxylic acids are primarily polyfunctional hydroxycarboxylic acids, in particular citric acid.
  • suitable polycarboxylic acids are sugar acids, mono- or dihydroxysuccinic acids, tartaric acids and related low molecular weight organic polycarboxylic acids.
  • copolymers based on unsaturated mono- or dicarboxylic acids such as acrylic acid, methacrylic acid or maleic anhydride, as are generally known in the field of detergents and cleaning agents.
  • the sodium or potassium salts are occasionally used as salts, and ammonium salts are also occasionally used. These salts can be anhydrous or as a hydrate.
  • a particularly preferred mixture in the sense of the invention consists of citric acid or its hydrate with trisodium citrate, which can be present in particular as a dihydrate. These mixtures should contain an acid fraction of more than 5% by weight, in particular more than 30% by weight of anhydrous acid. Instead of the mixture mentioned, mono- or disodium salt of citric acid and mixtures of these salts with citric acid can also be used.
  • the person skilled in the art must ensure that he chooses the amounts of polycarboxylic acids, their sodium salts and of the alkali metal carbonates or bicarbonates so that the resulting agent has a pH in the solution in percent by weight alkaline (from 8 to 9.5). If the salt of the polycarboxylic acid is completely dispensed with, corresponding amounts of alkali carbonate or alkali hydrogen carbonate must be present.
  • the agents according to the invention can also contain nitrogen-containing polycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid or triethylenetetraminehexaacetic acid or methylglycinediacetic acid and the like.
  • nitrogen-containing polycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid or triethylenetetraminehexaacetic acid or methylglycinediacetic acid and the like.
  • the oxidation products of polyglucosans mentioned in DE-A 4228786 can also be used.
  • the process according to the invention is usually carried out in a mixer, preferably in order to be able to carry out individual mixing steps in succession, as required, in a batch mixer. It is preferred not to add water.
  • the mixer has the task of producing an intimate mixture of the individual components. Suitable mixers are, for example, Eirich (R> mixers of the R or RV series, manufactured by Maschinenfabrik Gustav Eirich, Hardheim, Germany, the Fukae (R) FS-G mixers, manufactured by Fukal Powertech Kogyo Co. Japan, the Lödige (R) FM , KM or CB mixer, manufactured by Lödige Maschinenbau GmbH, Paderborn, Germany or the Drais (R) series T or KT, manufactured by Drais Maschinene GmbH, Mannheim, Germany.
  • Alkali metal carriers are alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates and mixtures of the aforementioned substances.
  • Sodium sequicarbonates While the carbonts or bicarbonates mentioned are compulsory constituents in the process according to the invention, silicates such as, for example, metasilicates are only used if the pH value needs to be raised. You can therefore only find them in quantities from 0 to 15, preferably from 2 to 10% by weight. Hydroxides can also be used, but only in the amount that the total pH of the preparation does not rise above 10 and preferably not above 9.5.
  • the preparations according to the invention also contain surfactants.
  • surfactants in principle, anionic surfactants, amphoteric surfactants or also cationic surfactants can be used, but nonionic surfactants are preferred, and among them nonionic surfactants which are liquid at room temperature.
  • nonionic surfactants are adducts of preferably 2 to 20 moles of ethylene oxide with 1 mole of an aliphatic compound having essentially 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, long-chain alkylamines, carboxamides or alkylsulfonamides.
  • nonionic surfactants non-complete or incomplete water-soluble polyglycol ethers of long-chain alcohols with 2 to 7 ethylene glycol ether residues in the molecule are particularly important when they are used together with water-soluble nonionic or anionic surfactants.
  • alkyl polyglycosides of the general formula RO- (G) x can be used as nonionic surfactants, in which R denotes a primary straight-chain or branched aliphatic radical having 8 to 22, in particular 8 to 14, 12 to 18 carbon atoms , G stands for a glycose unit with 5 to 6 carbon atoms and the degree of oligomerization x is between 1 and 10, preferably between 1.1 and 1.7.
  • Alkyl glucamides can also be used. These are the amides of carboxylic acids with 8 to 22 carbon atoms and N-alkylamino sugars, especially N-methylglucamide.
  • bleaching agents that can be used are, for example, peroxyearbonate (Na 2 CO 3 .1, 5 H 2 O 2 ) or peracidic salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid.
  • peroxyearbonate Na 2 CO 3 .1, 5 H 2 O 2
  • peracidic salts of organic acids such as perbenzoates or salts of diperdodecanedioic acid.
  • the bleaches mentioned are preferably used directly in the process according to the invention with the polycarboxylic acid salts at the start of the process.
  • Suitable bleach activators for these oxidizing agents are in particular the N-acrylic or O-acyl compounds forming with H 2 O 2 organic peracids, preferably N, N'-tetraacylated diamines such as N, N, N ', N'- Tetraacetylethylenediamine.
  • the preliminary products are usually mixed with the bleaching agents and other constituents in amounts of about 7: 3 to 9: 1.
  • the oxygen-based oxidizing agent content of the ready-made dishwashing agents is preferably about 5% by weight to 15% by weight, in particular in combination with 1% by weight to 10% by weight, in particular 2% by weight to 5 % By weight of a bleach activator.
  • a preferred embodiment of the tablets is prepared by enclosing 20 to 60 parts by weight of polycarboxylic acids or their salts with 2 to 5 parts of surfactants and water repellents in the presence of up to 20 parts by weight of oxygen bleach and then 5 to 50 parts of alkali metal carbonate and / or hydrogen carbonate as well as other usual components.
  • other active substances which are usually only present in small amounts, can be added to the pre-products according to the invention.
  • the total amount of all these substances is preferably 5 to 10% by weight, based on the final cleaning agent.
  • These small components include, for example, foam inhibitors, fragrances, dyes, stabilizers and enzymes of the type of proteases, amylases, lipases and / or cellulases and water which is not bound as water of crystallization or is associated with the constituents in a similarly solid form.
  • the enzymes can be adsorbed onto carrier substances in a conventional manner and / or embedded in coating substances and are preferably used in amounts of not more than 5% by weight, in particular 2 to 4% by weight.
  • Suitable non-surfactant-containing and preferably used foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally signed silica.
  • the foam-inhibiting use of long-chain soaps is also possible.
  • Mixtures of different foam inhibitors can also be suitable, for example those composed of silicones and paraffins or waxes. These foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • silver protection agents in particular inorganic transition metal salts, for example manganese salts such as manganese sulfate, if desired in combination with fluorides, potassium hexafluorotitanate and the like, inorganic transition metal complexes, nitrogen-containing heterocycles such as benzene triazole or isocyanuric acid, natural amino acids such as cystine, histidine reversible organic redox systems such as quinone / hydroquinone and / or reversible inorganic redox systems such as Fe 2+ / Fe 3+ .
  • substances to prevent glass corrosion can be used, for example zinc salts or zinc (hydroxide).
  • the preliminary products produced by the process according to the invention are usually processed into tablets.
  • the preliminary products with the other constituents mentioned as a mixture by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range of 200. 10 5 Pa to 1 500. 10 5 Pa pressed.
  • break-resistant tablets are obtained which, under application conditions, dissolve sufficiently quickly and have a beige strength of normally over 150 N.
  • a tablet produced in this way has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm up to 40 mm.
  • non-ionic surfactant (coconut fatty alcohol 4 EO) 0.75 kg
  • Enzymes prote, amlyase mixture 1: 1) 1.8 kg,
  • the approx. 950 g / l heavy mixture was compressed on a Korsch eccentric press type EKIV to cylindrical, 25 g heavy tablets with a diameter of 34 mm and a height of 17.6 mm with a compressive force of 48 KN. Immediately after production, the tablets could be broken under a wedge-shaped load of 135 N. After 1 day of storage, the load leading to breakage increased to 600 N.

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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)
  • Detergent Compositions (AREA)

Abstract

Procédé de fabrication d'un agent détergent, sous forme de pastilles, pour lave-vaisselle, renfermant des acides polycarboxyliques et leurs sels en tant qu'adjuvants, des supports d'alcalinité, des agents de blanchiment, des agents tensioactifs et des agents hydrophobes et, le cas échéant, des additifs courants, procédé pour lequel on cherche à améliorer la solubilité à température élevée et à réduire la friabilité des pastilles. Ce but est atteint grâce au fait qu'on entoure, dans une première étape du traitement, les acides carboxyliques et leurs sels, d'une phase liquide d'agents tensioactifs et d'agents hydrophobes, qu'on ajoute ensuite, dans une deuxième étape, les composants restants, et qu'on compresse finalement le mélange en pastilles.
PCT/EP1997/000700 1996-02-23 1997-02-14 Procede de fabrication de pastilles d'agent detergent pour lave-vaisselle WO1997031096A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19606765.0 1996-02-23
DE1996106765 DE19606765A1 (de) 1996-02-23 1996-02-23 Verfahren zur Herstellung von Geschirrspülmitteltabletten

Publications (1)

Publication Number Publication Date
WO1997031096A1 true WO1997031096A1 (fr) 1997-08-28

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0903405A3 (fr) * 1997-09-23 1999-08-11 Unilever Plc Composition pour lave-vaisselle
EP0915957A4 (fr) * 1996-07-31 2001-12-12 Procter & Gamble Procede et composition relatifs a des detergents

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2320254A (en) * 1996-12-12 1998-06-17 Procter & Gamble Process for making tabletted detergent compositions
US6177398B1 (en) 1996-12-12 2001-01-23 The Procter & Gamble Company Process for making tabletted detergent compositions
US6177393B1 (en) * 1996-12-12 2001-01-23 The Procter & Gamble Company Process for making tabletted detergent compositions
GB2320255A (en) * 1996-12-12 1998-06-17 Procter & Gamble Process for making tabletted detergent compositions
DE19752601C1 (de) * 1997-11-28 1998-12-10 Henkel Kgaa Verfahren zur Herstellung von Geschirrspülmitteltabletten
EP0933421B1 (fr) * 1997-12-18 2006-11-22 Mifa Ag Frenkendorf Produits de nettoyage en comprimés compacts sans phosphate

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0466484A2 (fr) * 1990-07-13 1992-01-15 Unilever Plc Compositions détergentes
EP0481547A1 (fr) * 1990-10-17 1992-04-22 Unilever N.V. Comprimés détergents pour le lavage de la vaisselle en machine
EP0504091A1 (fr) * 1991-03-15 1992-09-16 Cleantabs A/S Composition pour le lavage machinal de la vaisselle sans phosphate
EP0522766A2 (fr) * 1991-07-01 1993-01-13 Unilever Plc Compositions détergentes sous forme de tablettes
DE4232170A1 (de) * 1992-09-25 1994-03-31 Henkel Kgaa Schwachalkalische Geschirreinigungsmittel
DE4315048A1 (de) * 1993-04-01 1994-10-06 Henkel Kgaa Verfahren zur Herstellung stabiler, bifunktioneller, phosphat-, metasilikat- und polymerfreier niederalkalischer Reinigungsmitteltabletten für das maschinelle Geschirrspülen
DE4318902A1 (de) * 1993-06-07 1994-12-08 Benckiser Gmbh Joh A Wasserlöslicher, wasserenthärtender Builder
DE4408718A1 (de) * 1994-03-15 1995-09-21 Henkel Kgaa Bruch- und lagerstabile, polyfunktionelle Reinigungstabletten, Verfahren zu ihrer Herstellung und ihre Verwendung

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0466484A2 (fr) * 1990-07-13 1992-01-15 Unilever Plc Compositions détergentes
EP0481547A1 (fr) * 1990-10-17 1992-04-22 Unilever N.V. Comprimés détergents pour le lavage de la vaisselle en machine
EP0504091A1 (fr) * 1991-03-15 1992-09-16 Cleantabs A/S Composition pour le lavage machinal de la vaisselle sans phosphate
EP0522766A2 (fr) * 1991-07-01 1993-01-13 Unilever Plc Compositions détergentes sous forme de tablettes
DE4232170A1 (de) * 1992-09-25 1994-03-31 Henkel Kgaa Schwachalkalische Geschirreinigungsmittel
DE4315048A1 (de) * 1993-04-01 1994-10-06 Henkel Kgaa Verfahren zur Herstellung stabiler, bifunktioneller, phosphat-, metasilikat- und polymerfreier niederalkalischer Reinigungsmitteltabletten für das maschinelle Geschirrspülen
DE4318902A1 (de) * 1993-06-07 1994-12-08 Benckiser Gmbh Joh A Wasserlöslicher, wasserenthärtender Builder
DE4408718A1 (de) * 1994-03-15 1995-09-21 Henkel Kgaa Bruch- und lagerstabile, polyfunktionelle Reinigungstabletten, Verfahren zu ihrer Herstellung und ihre Verwendung

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0915957A4 (fr) * 1996-07-31 2001-12-12 Procter & Gamble Procede et composition relatifs a des detergents
EP0903405A3 (fr) * 1997-09-23 1999-08-11 Unilever Plc Composition pour lave-vaisselle

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Publication number Publication date
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