EP0203523B1 - Composés sous forme de blocs fondus contenant de l'hydroxyde de métaux alcalins pour le lavage de la vaisselle en machine et leur procédé de préparation - Google Patents

Composés sous forme de blocs fondus contenant de l'hydroxyde de métaux alcalins pour le lavage de la vaisselle en machine et leur procédé de préparation Download PDF

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Publication number
EP0203523B1
EP0203523B1 EP86106942A EP86106942A EP0203523B1 EP 0203523 B1 EP0203523 B1 EP 0203523B1 EP 86106942 A EP86106942 A EP 86106942A EP 86106942 A EP86106942 A EP 86106942A EP 0203523 B1 EP0203523 B1 EP 0203523B1
Authority
EP
European Patent Office
Prior art keywords
acid
sodium salt
organic complexing
weight
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP86106942A
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German (de)
English (en)
Other versions
EP0203523A3 (en
EP0203523A2 (fr
Inventor
Klaus Dr. Schumann
Theodor Dr. Altenschöpfer
Peter Dr. Jeschke
Jochen Dr. Jacobs
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT86106942T priority Critical patent/ATE60353T1/de
Publication of EP0203523A2 publication Critical patent/EP0203523A2/fr
Publication of EP0203523A3 publication Critical patent/EP0203523A3/de
Application granted granted Critical
Publication of EP0203523B1 publication Critical patent/EP0203523B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D17/0052—Cast detergent compositions
    • 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
    • C11D3/06—Phosphates, including polyphosphates
    • C11D3/062—Special methods concerning phosphates
    • 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
    • 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
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen

Definitions

  • Solid detergents for automatic dishwashing are mainly offered in powder or granular form (agglomerates).
  • the individual particles of these agents have a preferred diameter between 0.01 and 3 mm.
  • a serious disadvantage of this type of solid cleaning agents, especially those used in the field of large-scale commercial use with a content of 10 to 60% by weight of alkali metal hydroxides, is that, due to the hygroscopicity of individual raw materials, small amounts of moisture have a strong tendency to Baked or clumped.
  • a disadvantage is the use of cleaning agents that tend to clump or cake when exposed to moisture, especially in automatic, stocking dosing devices that are used in large numbers in the area of large-scale commercial use of single-tank and multi-tank dishwashers.
  • cleaning agents that tend to clump or cake when exposed to moisture
  • the only remedy is to prevent the entry of moisture into the storage container, but this cannot be guaranteed in a damp kitchen atmosphere or after cleaning the device with water without drying the parts of the storage container and the dosing device.
  • the clumping or caking of alkaline cleaning agents can be avoided, inter alia, by producing them in block form from the outset and packaging, distributing and using them in a moisture-proof manner.
  • melt-block detergents for machine dishwashing have already been described, which are mixed together by mixing all alkaline-reacting, preferably hydrate-containing active substances, such as. B. sodium silicates, pentasodium triphosphate, sodium hydroxide and optionally water, if the preferred water of hydration of the compounds mentioned is not sufficient, and then mild heating of the mixture with stirring to 90 to 100 ° C until reaching a uniformly molten mass and pouring it into molds and solidifying a dense crystal aggregate.
  • active substances such as. B. sodium silicates, pentasodium triphosphate, sodium hydroxide and optionally water
  • melt-block-shaped, alkali hydroxide-containing detergents for the mechanical cleaning of dishes with not only good mechanical strength but also high dissolving speed can be obtained when they are used, if they are alkali silicate, water, preferably in the form of water of crystallization, and, if appropriate, pentaalkali metal phosphate and additionally contain organic complexing agents which cause a strong increase in the dissolution rate.
  • the invention therefore relates to melt-block-shaped, alkali hydroxide-containing agents for the mechanical cleaning of dishes containing alkali silicates, water, preferably in the form of water of crystallization, and optionally pentaalkali metal phosphate, which has a further content of 0.1 to 10% by weight, based on the total agent , organic complexing agents are marked.
  • alkali hydroxide potassium and, for reasons of price, preferably sodium hydroxide are suitable preferably in solid form, ie as flakes, flakes or prills, practically anhydrous or as a monohydrate.
  • the amounts which are used are advantageously 2 to 70, preferably 5 to 50% by weight, anhydrous, based on the total composition.
  • Preferred alkali silicates are alkali metal silicates, anhydrous, but advantageously in the form of sodium metasilicate. 9 H2O, sodium metasilicate. 6 H2O and sodium metasilicate. 5 H2O used.
  • the amounts used in the particular form are expediently 2 to 60, preferably 5 to 50,% by weight, based on the total composition.
  • they can also be partially or completely replaced by water glass solutions, the ratio of Na2O: SiO2 being 1: 1 to 1: 4, preferably 1: 2 to 1: 3.5. Because of the higher silicate content of the water glass, its solutions are used in amounts of 2 to 30, preferably 5 to 15,% by weight, based on the total agent.
  • pentaalkali metal triphosphate which is used in anhydrous form, as a hexahydrate or as a mixture of hexahydrate with small amounts of anhydrous pentasodium triphosphate, so that a total water content of 5.5 moles is calculated.
  • Possible solubility-improving organic complexing agents which are part of the melt-block-shaped cleaning agents according to the invention are polycarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, carboxyalkyl ethers, polyanionic polymers, in particular polymeric carboxylic acids and phosphonic acids, these compounds in the form of their water-soluble salts be used.
  • hydroxymono- or polycarboxylic acids examples include glycolic acid, lactic acid, malic acid, tartronic acid, methyltartronic acid, gluconic acid, glyceric acid, citric acid, tartaric acid, salicylic acid.
  • aminocarboxylic acids are glycine, glycylglycine, alanine, asparagine, glutamic acid, aminobenzoic acid, iminodiacetic or triacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminetetraacetic acid, hydroxyethyl-ethylenediamine-triacetic acid, diethylenetriamine pentaacetic acid and higher homologs, obtained by polymerization of a N-Aziridylcarbonklates, z.
  • acetic acid, succinic acid, tricarballylic acid and subsequent saponification or by condensation of polyamines with a molecular weight of 500 to 10,000 with chloroacetic or bromoacetic salts can be prepared.
  • carboxyalkyl ethers are 2,2-oxydisuccinic acid and other ether polycarboxylic acids, in particular those containing carboxymethyl ether groups
  • Polycarboxylic acids which include corresponding derivatives of the following polyhydric alcohols or hydroxycarboxylic acids, which can be fully or partially etherified with the glycolic acid: glycol, di- or triglycols, glycerol, di- or triglycerol, glycerol monomethyl ether, 2,2-dihydroxymethylpropanol 1,1,1 -Trihydroxymethylethane, 1,1,1-trihydroxymethylpropane, erythritol, pentaerythritol, glycolic acid, lactic acid, tartronic acid, methyl tartronic acid, glyceric acid, erythronic acid, malic acid, citric acid, tartaric acid, trihydroxyglutaric acid, sugar acid, mucic acid.
  • carboxymethyl ethers of sugar, starch and cellulose can be mentioned as transition types to the polymeric carboxylic acids.
  • polymeric carboxylic acids z. B. the polymers of acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid, methylene malonic acid, citraconic acid and the like, the copolymers of the above-mentioned carboxylic acids with one another or with ethylenically unsaturated compounds, such as ethylene, propylene, isobutylene, vinyl alcohol, vinyl methyl ether, furan, acrolein , Vinyl acetate, acrylamide, acrylonitrile, methacrylic acid, crotonic acid etc., such as.
  • the 1: 1 copolymers of maleic anhydride and ethylene or propylene or furan play a special role.
  • polymeric carboxylic acids of the type of polyhydroxypolycarboxylic acids or polyaldehydopolycarboxylic acids are essentially substances composed of acrylic acid and acrolein units or acrylic acid and vinyl alcohol units, which are obtained by copolymerizing acrylic acid and acrolein or by polymerizing Acrolein and subsequent Cannizzaro reaction, optionally in the presence of formaldehyde, are available.
  • Examples of phosphorus-containing organic complexing agents are alkane polyphosphonic acids, amino and hydroxyalkane polyphosphonic acids and phosphonocarboxylic acids, such as. B. the compounds methane diphosphonic acid, propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 2-amino-1-phenyl-1, 1-diphosphonic acid, aminotrimethylene triphosphonic acid, methylamino- or ethylaminodimethylene diphosphonic acid, ethylene diaminotetramethylene tetraphosphonic acid, diethylene triamine pentamethylene pentaphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, phosphonoacetic acid, phosphonopropionic acid, 1-phosphonoethanoic acid-1,2-dodisposphonic acid , 2-phosphonobutane-1,2,4-
  • the amount of organic complexing agent is preferably 0.5 to 5% by weight, based on the total agent.
  • the total water content of the melting block-shaped, alkali hydroxide-containing cleaning agents from dense crystal aggregates is 10 to 40, preferably 15 up to 30% by weight. It is preferably introduced by the crystal water content of the alkaline reacting substances, but optionally also via water glass solutions. The calculations of the water content must therefore be based on these compounds.
  • the alkali silicate as a metasilicate hydrate or as a water glass solution alone or together with solid alkali hydroxide is used or its monohydrate is heated to 45 to 48 ° C without affecting the automatic heating to 60 to 65 ° C that occurs, then with stirring or kneading all other components, preferably hydrate water, of which the last when the melting temperature is about 50 to 55 ° C has dropped, pentasodium triphosphate and / or its hexahydrate and the organic complexing agent are stirred in, and the still liquid melt is poured into arbitrarily designed, preferably flexible, molds and solidifies to form blocks therein.
  • the solidification process takes a few minutes to about an hour depending on the size of the mold.
  • the melting blocks are very hard, hard or less hard, but in all cases through and through consistently composed and quickly soluble when used.
  • the rate of dissolution of the cleaning agent after solidification was determined in a laboratory apparatus.
  • 15 g of the cleaning agent to be tested which was in the form of a solid, compact cylinder which had been freed from its shape (diameter 2 cm, height about 3 cm)
  • the wash bottle was then closed with a Drechsel wash bottle insert and secured with a cut holder.
  • a water mixture of 50% by volume at 14 ° C. and 16 ° C. was passed through the bottle at a rate of 20 liters per hour and the time in which the shaped body was completely dissolved was determined has been.
  • the dissolution rate was defined in grams per hour. In the composition according to Example 1, it was 24 grams per hour.
  • Example 2 Melting blocks of the following composition were produced analogously to Example 1, the pentasodium triphosphate and / or the PBS in each case being stirred into the still liquid melt below a temperature of 55 ° C.
  • the dissolution behavior was determined as indicated in Example 1.
  • the results are shown in Table 2. They show that the addition of PBS to melts of any composition leads to a significant improvement in the dissolution behavior:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Claims (4)

1. Produits sous forme de blocs de masse fondue pour le lavage de la vaisselle en machine, contenant des hydroxydes alcalins, ayant une teneur en silicate alcalin, ou eau, de préférence sous forme d'eau de cristallisation, ainsi qu'éventuellement en triphosphate penta(métal alcalin), cractérisés par une teneur supplémentaire en un complexant organique allant de 0,1 à 10% en poids, par rapport à la composition totale.
2. Produits selon la revendication 1, caractérisés par une teneur en un complexant organique choisi parmi les composés citrate de sodium dihydraté, sel de sodium de l'acide nitrilotriacétique, sel de sodium de l'acide éthylènediaminetétraacétique, sel de sodium de l'acide éthylènediaminetétraméthylènetétra­phosphonique, sel de sodium de l'acide diéthylènetri­aminepentaphosphonique, sel de sodium de l'acide 1-hy­droxyéthane-1,1-diphosphonique et sel de sodium de l'acide 2-phosphonobutane-1,2,4-tricarboxylique.
3. Produit selon les revendications 1 et 2, caractérisé en ce que la teneur en complexant organique va de 0,5 à 5% en poids, par rapprort à la composition totale.
4. Procédé pour la préparation de produits de lavage sous forme de blocs de masse fondue selon la revendication 1, caractérisé en ce que d'abord on chauffe à 45-48°C le silicate alcalin, sous forme de métasilicate hydraté ou d'une solution de verre soluble, seul ou conjointement avec un hydroxyde alcalin solide ou son monohydrate, sans influencer l'échauffement spontané à 60-65°C apparaissant à cette occasion, ensuite on délaie sous agitation ou avec malaxage tous les autres composants, contenant de préférence de l'eau d'hydratation, dont en dernier, lorsque la température de la masse fondue s'est abaissée aux environs de 50 à 55°C, le triphosphate pentasodique et/ou son hexahydrate et le complexant organique, puis on verse la masse fondue encore liquide dans des moules de forme quelconque, de préférence flexibles, et on la laisse se solidifier en blocs dans ceux-ci.
EP86106942A 1985-05-30 1986-05-22 Composés sous forme de blocs fondus contenant de l'hydroxyde de métaux alcalins pour le lavage de la vaisselle en machine et leur procédé de préparation Expired - Lifetime EP0203523B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86106942T ATE60353T1 (de) 1985-05-30 1986-05-22 Schmelzblockfoermige, alkalihydroxidhaltige mittel fuer das maschinelle reinigen von geschirr und verfahren zu ihrer herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853519353 DE3519353A1 (de) 1985-05-30 1985-05-30 Schmelzblockfoermige, alkalihydroxidhaltige mittel fuer das maschinelle reinigen von geschirr und verfahren zu ihrer herstellung
DE3519353 1985-05-30

Publications (3)

Publication Number Publication Date
EP0203523A2 EP0203523A2 (fr) 1986-12-03
EP0203523A3 EP0203523A3 (en) 1988-03-23
EP0203523B1 true EP0203523B1 (fr) 1991-01-23

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Family Applications (1)

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EP86106942A Expired - Lifetime EP0203523B1 (fr) 1985-05-30 1986-05-22 Composés sous forme de blocs fondus contenant de l'hydroxyde de métaux alcalins pour le lavage de la vaisselle en machine et leur procédé de préparation

Country Status (3)

Country Link
EP (1) EP0203523B1 (fr)
AT (1) ATE60353T1 (fr)
DE (2) DE3519353A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3156475B1 (fr) 2015-10-16 2018-06-06 Hans Georg Hagleitner Concentré de nettoyage liquide

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE8613092U1 (de) * 1986-05-14 1987-08-06 Henkel KGaA, 40589 Düsseldorf Vorratspackung eines in einer gewerblichen Geschirrspülmaschine einzusetzenden Reinigers
DE3634812A1 (de) * 1986-10-13 1988-04-14 Henkel Kgaa Verfahren zur herstellung schmelzblockfoermiger, alkalihydroxid- und gegebenenfalls auch aktivchlorhaltiger mittel fuer das maschinelle reinigen von geschirr
DE3721461A1 (de) * 1987-06-30 1989-01-12 Hoechst Ag Formstabile und spezifisch leichte alkalische reinigungsmittel sowie ein verfahren zu ihrer herstellung
US5066416A (en) * 1987-08-31 1991-11-19 Olin Corporation Process for producing moldable detergents having a stable available chlorine concentration
WO1989011753A2 (fr) * 1988-05-27 1989-11-30 Ecolab Incorporated Article moule contenant un detergent a basse temperature
NZ239112A (en) * 1991-01-29 1994-12-22 Ecolab Inc Solid alkaline compositions containing the reaction product in water of alkali metal hydroxide and alkali metal silicate; process of manufacture
DE4223807A1 (de) * 1992-07-20 1994-01-27 Basf Ag N,O-Acetal- oder Carbonamidstrukturen enthaltende Kondensationsprodukte, Verfahren zu ihrer Herstellung und ihre Verwendung und Acetallactonstrukturen enthaltende Kondensationsprodukte
DE4318902C2 (de) * 1993-06-07 1996-10-24 Benckiser Gmbh Joh A Wasserlösliches, wasserenthärtendes Mittel
DE4338626A1 (de) * 1993-11-12 1995-05-18 Henkel Kgaa Additiv für die Glasflaschenreinigung und seine Verwendung zur Verringerung der Glaskorrosion
US5425895A (en) * 1994-07-22 1995-06-20 Monsanto Co. Block detergent containing nitrilotriacetic acid
US5665694A (en) * 1994-07-22 1997-09-09 Monsanto Company Block detergent containing nitrilotriacetic acid
US5419850A (en) * 1994-07-22 1995-05-30 Monsanto Company Block detergent containing nitrilotriacetic acid
US5490949A (en) * 1994-07-22 1996-02-13 Monsanto Company Block detergent containing nitrilotriacetic acid
DE4440142C2 (de) 1994-11-10 1999-03-11 Iscon Hygiene Gmbh Verfahren zur Herstellung von Reinigungsmitteln in Schaumblockform
US6017864A (en) * 1997-12-30 2000-01-25 Ecolab Inc. Alkaline solid block composition
DE19933607A1 (de) * 1999-07-17 2001-01-18 Henkel Ecolab Gmbh & Co Ohg Alkalische, blockförmige Reinigungsmittelformulierungen
GB0522659D0 (en) * 2005-11-07 2005-12-14 Reckitt Benckiser Nv Delivery cartridge

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US2412819A (en) * 1945-07-21 1946-12-17 Mathieson Alkali Works Inc Detergent briquette
DE2062465B2 (de) * 1970-12-18 1976-11-25 Henkel & Cie GmbH, 4000 Düsseldorf Geschirrspuelmittel
DE2963759D1 (en) * 1978-02-07 1982-11-11 Economics Lab Cast detergent-containing article and method of making and using

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3156475B1 (fr) 2015-10-16 2018-06-06 Hans Georg Hagleitner Concentré de nettoyage liquide

Also Published As

Publication number Publication date
ATE60353T1 (de) 1991-02-15
DE3677057D1 (de) 1991-02-28
EP0203523A3 (en) 1988-03-23
DE3519353A1 (de) 1986-12-04
EP0203523A2 (fr) 1986-12-03

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